1,4-Butanediol (1,4-BDO; Butane-1,4-diol) [C4H10O2] by Asch

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Query Query OH

1. Query

Results

Date

281 reactions in Reaxys

2018-07-13 16h:27m:29s (UTC)

Search as: Product, As drawn, No mixtures ) AND (IDE.RN='110-63-4') AND (IDE.INCHI='WERYXYBDKMZEQL-UHFFFAOYSA-N') NOT (RX.RXRN=1633445))

1/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Rx-ID: 39105 View in Reaxys 1/281 Yield <= 98.3 %

Conditions & References 1 :Comparative Example; Technical-Grade 1,4-butynediol; 190 ml of an Ni catalyst as described in example 1 of U.S. Pat. No. 5,068,468 were introduced into a hydrogenation reactor having a length of 1.2 m. Technical-grade 1,4-butynediol in the form of a 54percent strength by weight aqueous solution was fed into the reactor at a feed rate of 100 g/h. Hydrogenation was carried out for 2 weeks at a temperature of 140° C., a hydrogen pressure of 200 bar and a liquid circulation of 800 ml/h.Within the time of the experiment (2 weeks), the butynediol conversion was always quantitative. The average increase in n-butanol was about 0.06percent per day. After the catalyst was removed from the reactor, solid deposits were present on the catalyst. The yield of 1,4-butanediol, based on butynediol used, was 98.3percent by weight at the beginning but was reduced by 0.06percent by weight each day.; Example 1; Purification of 1,4-butynediol; Purification:Technical-grade butynediol in the form of a 54percent strength by weight aqueous solution was sheared by means of a mixing apparatus as described in FIG. 1 of DE-C 42 20 239 having a gap width of 0.05 mm and a rotor diameter of 48 mm at 80° C. for 10 minutes and was subsequently calmed at 80° C. for 22 hours until phase separation occurred. It was then cooled to 25° C. and the bottom phase was separated off by decantation. The butynediol which had been purified in this way was fed to the hydrogenation reactor.Hydrogenation:The hydrogenation was carried out in a manner analogous to the comparative example using the 1,4-butynediol which had been prepurified according to the invention. The average increase in n-butanol was only about 0.035percent per day. After removal of the catalyst from the reactor, no deposits were found. The yield of 1,4-butanediol, based on butynediol used, was 98.3percent by weight at the beginning and was reduced by 0.035percent by weight each day. With hydrogen, Ni catalyst as described in example 1 of U.S. Pat. No. 5,068,468, Time= 336h, T= 140 °C , p= 150015Torr , Conversion of starting material Patent; BASF SE; US2008/242897; (2008); (A1) English View in Reaxys

<= 98.3 %

1 :Comparative Example; Technical-grade 1,4-butynediol; 190 ml of an Ni catalyst as described in example 1 of U.S. Pat. No. 5,068,468 were introduced into a hydrogenation reactor having a length of 1.2 m. Technical-grade 1,4-butynediol in the form of a 54percent strength by weight aqueous solution was fed into the reactor at a feed rate of 100 g/h. Hydrogenation was carried out for 2 weeks at a temperature of 140° C., a hydrogen pressure of 200 bar and a liquid circulation of 800 ml/h.Within the time of the experiment (2 weeks), the butynediol conversion was always quantitative. The average increase in n-butanol was about 0.06percent per day. After the catalyst was removed from the reactor, solid deposits were present on the catalyst. The yield of 1,4-butanediol, based on butynediol used, was 98.3percent by weight at the beginning but was reduced by 0.06percent by weight each day.; Hydrogenation:; The hydrogenation was carried out in a manner analogous to the comparative example using the 1,4butynediol which had been prepurified according to the invention. The average increase in n-butanol was only about 0.04percent per day. After removal of the catalyst from the reactor, no deposits were found. The yield of 1,4-butanediol, based on butynediol used, was 98.3percent by weight at the beginning and was reduced by 0.04percent by weight each day. With hydrogen, Ni catalyst as described in example 1 of U.S. Pat. No. 5,068,468 in water, Time= 24 - 336h, T= 140 °C , p= 150015Torr , Product distribution / selectivity Patent; BASF SE; US2008/221371; (2008); (A1) English View in Reaxys

90 %

2 : Example 2: A catalyst was prepared as described in example 1, wherein the wet-chemical post-treatment was carried out with 10percent by weight aqueous sodium hydroxide solution at 60°C for a period of 60minutes. Analysis by ICP-OES gave a composition of the resulting catalytically active bulk material (catalyst C) of 89percent by weight nickel and 11percent by weight aluminium. The material had a bulk density of dsch = 0.3 kgIL. The bulk density was determined according to the procedure described inexample 1.Catalyst C was also investigated for its catalytic efficacy in the hydrogenation of butyne-1 ,4-diol(BYD) to 1 ,4-butanediol (BDO) in a stirred tank reactor. Experimental setup, procedure andevaluation were carried out as described in example 1.The results are compiled in the following table: With hydrogen in water, Time= 6h, T= 100 - 135 °C , p= 60006Torr , Reagent/catalyst, Temperature, Pressure Patent; EVONIK DEGUSSA GMBH; BERWEILER, Monika; GÖTTLINGER, Markus; ROOS, Meike; SCHWARZ, Matthias; POSS, René; (19 pag.); WO2018/60269; (2018); (A1) English View in Reaxys

89 %

in water, T= 50 - 60 °C , p= 760.051Torr

2/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Pyatnitsyna; El'Chaninov; Russian Journal of Applied Chemistry; vol. 86; nb. 3; (2013); p. 394 - 397; Zh. Prikl. Khim. (S.Peterburg, Russ. Fed.); vol. 86; nb. 3; (2013); p. 425 - 428,4 View in Reaxys 72 %

With hydrogen, platinum(IV) oxide in ethyl acetate, Time= 3h, p= 7757.2Torr Kingsbury, Celia L.; Smith, Robin A. J.; Journal of Organic Chemistry; vol. 62; nb. 22; (1997); p. 7637 - 7643 View in Reaxys With nickel, T= 25 °C , p= 110326Torr , Hydrogenation Johnson; Journal of the Chemical Society; (1946); p. 1013 View in Reaxys With water, nickel, T= 40 - 60 °C , p= 147102Torr , Hydrogenation Reppe et al.; Justus Liebigs Annalen der Chemie; vol. 596; (1955); p. 65 View in Reaxys With nickel-copper-chromium, T= 70 - 140 °C , p= 147102 - 220652Torr , Hydrogenation Patent; I.G.Farbenind.; DE734881; (1939); View in Reaxys Schneiders; ; vol. 4; (1953); p. 755 View in Reaxys Reppe,W.; View in Reaxys Reppe,W.; View in Reaxys Patent; General Aniline and Film Corp.; US2319707; (1939) View in Reaxys Reppe; Experientia; vol. 5; (1949); p. 93,108; Justus Liebigs Annalen der Chemie; vol. 582; (1953); p. 1,16, 35 View in Reaxys With hydrogen, platinum Lespieau; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 150; (1910); p. 1761; Annales de Chimie (Cachan, France); vol. <8>27; (1912); p. 176 View in Reaxys 2 :Examples 1 -6 below were carried out using pure 1 ,4-butynediol as 40percent strength by weight aqueous solution at atmospheric pressure. The butynediol solution was pumped continuously into an externally heated tube (diameter 2.7 cm). The tube was charged with glass rings (30 ml) in the upper region. This zone served as vaporization section in which 1 ,4-butynediol/ water and hydrogen (300 liter/h) were heated and passed in gaseous form into a second zone in the reactor tube in which the catalyst was located (20 ml). After the reactor tube, the gaseous reactor output was cooled to about 20°C and product which condensed out was collected. The offgas was passed through a cold trap at -78°C and further product was condensed out in this way. The two condensates were combined for the purposes of analysis. The catalysts were activated in a stream of hydrogen before the reaction. The results are shown in table 1 With hydrogen in water, T= 220 °C , p= 760.051Torr , Product distribution / selectivity Patent; BASF SE; PINKOS, Rolf; OSETSKA, Olga; KOeNIGSMANN, Lucia; BASF JAPAN LTD.; WO2012/95777; (2012); (A1) English View in Reaxys

99.9 %Chromat.

The typical procedure for hydrogenation of unsaturated carbon-carbon bonds using the H2-MNB-basedstrategy General procedure: The hydrogenation was carried out in a 100 mL vial equipped with an MNB-generator withoutadditional stirring. Alkene or alkyne 1 (20 mmol) was dissolved in MeOH (80 mL), and then warmed to 30 °C.Using the MNB-generator (MA3-FS), H2-MNBs were introduced into the reactor in the presence of palladium onalumina spheres (0.5percentPd, 2–4 mm, 0.1 mmol, 0.5 molpercent) at an H2-flow rate of 5 mL/min. The samples of thereaction mixture were taken out periodically to monitor the reaction progress using the GC analysis. After thecompletion of the hydrogenation reaction, MeOH was evaporated in vacuo to afford the desired alkane 1 withexcellent purity. With hydrogen in methanol, Time= 4h, T= 30 °C

3/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Mase, Nobuyuki; Isomura, Shogo; Toda, Mitsuo; Watanabe, Naoharu; Synlett; vol. 24; nb. 17; (2013); p. 2225 - 2228 View in Reaxys 33 : Typical Procedure for Example 23 to Example 38 The 50 mg 1percent Pd-MgO modified with HF as prepared in Example 10 was activated for the period up to 0.5 h under the constant flow of hydrogen of 10 mE/mm in the methanol (10 mE) with constant stirring at mentioned temperature. To this solution was added 0.5 g of various substrates as given in table 2. The reaction was continued for specified time. The samples were collected intermittently and analyzed by GC and GCMS. The product was also confirmed by FTIR analysis which shows absence ofolefinic CrrrC bond frequency. The reaction conditions and results are given in table 2. With hydrogen in methanol, Time= 6h, T= 20 °C Patent; Council of Scientific and Industrial Research; Umbarkar, Shubhangi Bhalchandra; Dongare, Mohan Keraba; Acham, Vaibhav Ravindrakumar; US2015/239821; (2015); (A1) English View in Reaxys 1 : Example 1 The first hydrogenation step: In a 500 ml autoclave, add 150 ml of 37percent by weight aqueous butynediol solution.2 g of the amorphous nickel alloy catalyst prepared in Preparation Example 1, and a 5 wtpercent NaOH solution was added dropwise to make the butynediol water solutionThe pH was 9, the autoclave was sealed, replaced with 1 MPa hydrogen three times, and then charged with hydrogen to press the hydrogen to 2.0 MPa. At 600 rpmUnder stirring with a bell, a hydrogenation reaction is performed at 50° C. for 2 hours, and the amorphous nickel alloy catalyst is separated by pressure release to obtain a period of time.The hydrogenated product serves as a raw material for the second stage of hydrogenation.Second stage hydrogenation step: using Pt-Rh/TiO2-Al2O3 prepared in Preparation Example 4 as a second stage hydrogenation catalystAgent, in a fixed bed reactor at a hydrogen pressure of 5 MPa, a reaction temperature of 120°C, and a liquid hourly space velocity of 3 hours-1.A twostage hydrogenation of a portion of the hydrogenation product results in a two-stage hydrogenation product containing 1,4-butanediol. Two-stage hydrogenation productThe composition and carbonyl values were determined and the results are shown in Table 1. The secondary hydrogenation product is subjected to distillation, and the fractionated product after distillation is divided intoThe product purity and chroma were analyzed. The results are shown in Table 1. Stage 1: With Ni87.4Al6.8Ti5.8, hydrogen, sodium hydroxide in water, Time= 2h, T= 50 °C , p= 7500.75 - 15001.5Torr , pH= 9, Autoclave Stage 2: With hydrogen, T= 120 °C , p= 37503.8Torr , Reagent/catalyst, Temperature Patent; Sinopec Corporation; Sinopec Corporation Petrochemical Sciences Institute; Zhang Xiaoxin; Wang Xuan; Mu Xuhong; Zong Baoning; (11 pag.); CN107778138; (2018); (A) Chinese View in Reaxys 1.3 : (3) Preparation of 1,4-butanediol by hydrogenation of 1,4-butynediol In a 500 mL autoclave, add 150 mL of a 37percent aqueous solution of butyne diol, 2 g of amorphous nickel alloy catalyst,The catalyst composition is Ni87.4Al6.8Ti5.8, 0.05g copper alloy catalyst, the catalyst composition is Cu86.5Al10.5Mo3, dropping 5percentThe NaOH solution was brought to pH 9, the autoclave was sealed, replaced with 1 MPa hydrogen three times, and then hydrogen was charged to press hydrogen to 2.0 Ma. inThe reaction was performed at 70°C for 2 hours with stirring at 600 rpm. The catalyst was separated by pressure release and the product was analyzed by gas chromatography. The results were obtained.See Table 1. With Ni87.4Al6.8Ti5.8, Cu86.5Al10.5Mo3.0, hydrogen, sodium hydroxide, Time= 2h, T= 70 °C , p= 7500.75Torr , pH= 9, Autoclave, Reagent/catalyst, Pressure, Temperature Patent; Sinopec Corporation; Sinopec Corporation Petrochemical Sciences Institute; Zhang Xiaoxin; Wang Xuan; Mu Xuhong; Zong Baoning; (11 pag.); CN107778137; (2018); (A) Chinese View in Reaxys O O

Rx-ID: 836740 View in Reaxys 2/281 Yield 97 %

Conditions & References With C24H38Cl2N3PRu, hydrogen, sodium methylate in isopropyl alcohol, Time= 6h, T= 25 °C , p= 38002.6Torr , Autoclave Li, Wei; Xie, Jian-Hua; Yuan, Ming-Lei; Zhou, Qi-Lin; Green Chemistry; vol. 16; nb. 9; (2014); p. 4081 - 4085

4/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

View in Reaxys 97 %

With C13H34BFeNOP2, hydrogen in tetrahydrofuran, Time= 18h, T= 100 °C , p= 22502.3Torr , Autoclave, Inert atmosphere Elangovan, Saravanakumar; Wendt, Bianca; Topf, Christoph; Bachmann, Stephan; Scalone, Michelangelo; Spannenberg, Anke; Jiao, Haijun; Baumann, Wolfgang; Junge, Kathrin; Beller, Matthias; Advanced Synthesis and Catalysis; vol. 358; nb. 5; (2016); p. 820 - 825 View in Reaxys

97%

10 : Example 10 General procedure: Hydrogenation of Other Ester Compounds Catalyzed by Synthetic Preparation of Bipyridine Tetradshed Ruthenium Complex 5 The results are shown in Table 2:Table 2 Hydrogenation of other ester compounds a; A Reaction conditions: S / C = 1000,3.0 mmol Substrate, 3.0 μmol 5, 3.0 mL lPrOH, 0.3 mmol NaOMe, 5 MPa H2, 25 ° C.#10; With C24H38Cl2N3PRu, hydrogen, sodium methylate in isopropyl alcohol, Time= 6h, T= 25 °C , p= 37503.8Torr Patent; Nankai University; Zhou, Qilin; Li, Wei; Xie, Jianhua; Wang, Lixin; (22 pag.); CN103980317; (2017); (B) Chinese View in Reaxys

89 %

With [RuHCl(CO)(NH(C2H4PPh2)2)], hydrogen, sodium methylate in methanol, Time= 16h, T= 100 °C , p= 37503.8Torr , Autoclave, Inert atmosphere Kuriyama, Wataru; Matsumoto, Takaji; Ogata, Osamu; Ino, Yasunori; Aoki, Kunimori; Tanaka, Shigeru; Ishida, Kenya; Kobayashi, Tohru; Sayo, Noboru; Saito, Takao; Organic Process Research and Development; vol. 16; nb. 1; (2012); p. 166 - 171 View in Reaxys

75 %

With [iPrPN(H)P]2Fe(H)(CO)(BH4), hydrogen in toluene, Time= 24h, T= 115 °C , p= 8517.48Torr , Glovebox, Sealed tube Chakraborty, Sumit; Dai, Huiguang; Bhattacharya, Papri; Fairweather, Neil T.; Gibson, Michael S.; Krause, Jeanette A.; Guan, Hairong; Journal of the American Chemical Society; vol. 136; nb. 22; (2014); p. 7869 - 7872 View in Reaxys With sodium hydroxide, T= 260 °C , p= 147102Torr , Hydrogenation Patent; Vereinigte Glanzstoff-Fabr.; US2863928; (1956) View in Reaxys 15 : Hydrogenation of Dimethyl Succinate Example 15 Hydrogenation of Dimethyl Succinate Dimethyl succinate (8 mmol), a ruthenium complex 1 (0.016 mmol), and tetrahydrofuran (3.2 mL) were charged into a 100-mL autoclave equipped with a stirrer. Then, the mixture was subjected to hydrogenation at a hydrogen pressure of 5 MPa at 80° C. for 16 hours. The reaction liquid was analyzed by gas chromatography. As a result, 1.4-butanediol was obtained at a conversion rate of 50percent and a selectivity of 71percent. With hydrogen, C40H39BN2P2Ru in tetrahydrofuran, Time= 16h, T= 80 °C , p= 37503.8Torr , Product distribution / selectivity Patent; TAKASAGO INTERNATIONAL CORPORATION; US2010/63294; (2010); (A1) English View in Reaxys With lithium aluminium tetrahydride in diethyl ether, T= 0 - 20 °C Colonna, Martino; Berti, Corrado; Fiorini, Maurizio; Binassi, Enrico; Mazzacurati, Marzia; Vannini, Micaela; Karanam, Sreepadaraj; Green Chemistry; vol. 13; nb. 9; (2011); p. 2543 - 2548 View in Reaxys

82 %Chromat.

With C33H32Cl2N2P2Ru, potassium tert-butylate, hydrogen in toluene, Time= 5h, T= 80 °C , p= 38002.6Torr , Autoclave, Catalytic behavior Tan, Xuefeng; Wang, Yan; Liu, Yuanhua; Wang, Fangyuan; Shi, Liyang; Lee, Ka-Ho; Lin, Zhenyang; Lv, Hui; Zhang, Xumu; Organic Letters; vol. 17; nb. 3; (2015); p. 454 - 457 View in Reaxys

5/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

99 %Spectr. With [Ru(1,1,1-tris(diphenylphosphinomethyl)ethane)(trimethylenemethane)], hydrogen in 1,4-dioxane, Time= 16h, T= 140 °C , p= 37503.8Torr , Autoclave, Inert atmosphere Vom Stein, Thorsten; Meuresch, Markus; Limper, Dominik; Schmitz, Marc; Hölscher, Markus; Coetzee, Jacorien; ColeHamilton, David J.; Klankermayer, Jürgen; Leitner, Walter; Journal of the American Chemical Society; vol. 136; nb. 38; (2014); p. 13217 - 13225 View in Reaxys 66 %Chromat.

With C15H29MnNO3P2 (1+)*Br(1-), potassium tert-butylate, hydrogen in 1,4-dioxane, Time= 48h, T= 120 °C , p= 22502.3Torr , Inert atmosphere, Autoclave Elangovan, Saravanakumar; Garbe, Marcel; Jiao, Haijun; Spannenberg, Anke; Junge, Kathrin; Beller, Matthias; Angewandte Chemie - International Edition; vol. 55; nb. 49; (2016); p. 15364 - 15368; Angew. Chem.; nb. 128; (2016); p. 15590 15594,5 View in Reaxys

87 %Chromat.

With dichlorido-bis[(2-diphenylphosphino)ethyl]amine-cobalt(II), hydrogen, sodium methylate in 1,4-dioxane, Time= 6h, T= 120 °C , p= 37503.8Torr , Autoclave Junge, Kathrin; Wendt, Bianca; Cingolani, Andrea; Spannenberg, Anke; Wei, Zhihong; Jiao, Haijun; Beller, Matthias; Chemistry - A European Journal; vol. 24; nb. 5; (2018); p. 1046 - 1052 View in Reaxys 5 : Example 5 According to the process shown in Figure 1 dimethyl succinate hydrogenation.The reaction conditions for controlling the prehydrogenation catalyst bed are:Pressure 5.5MPa, temperature 190 , space velocity 0.8h-1,Hydrogen and dimethyl succinate volume ratio of 800: 1. The reaction conditions for controlling the main hydrogenation catalyst bed are:Pressure 5.5MPa, temperature 230 , volume airspeed 0.8h-1,The volume ratio of hydrogen to the reaction mass from the prehydrogenation catalyst bed is 900: 1.The reaction conditions for controlling the replenishment of the refined catalyst bed are:Pressure 5.5MPa, temperature 220 ,The space velocity 4.0 h-1,Dissolved hydrogen and reaction volume from the hot high-grade tank volume ratio of 9: 1.The conversion of dimethyl succinate obtained in this example,The selectivity and purity index of 1,4-butanediol are shown in Table 1. With hydrogen, T= 230 °C , p= 41254.1Torr , Temperature, Pressure Patent; Sinopec Yangzi Petrochemical Co., Ltd.; Sinopec Corporation; Liu Bo; Wang Jiyuan; Meng Hai; Du Wenbin; Yang Aiwu; Bai Jiye; Liu Jianxin; Bian Botong; (9 pag.); CN105820038; (2016); (A) Chinese View in Reaxys

O OH

Rx-ID: 1522656 View in Reaxys 3/281 Yield 100 %

Conditions & References With sodium aluminum tetrahydride in tetrahydrofuran, Time= 0.0833333h, T= 0 °C Cha, Jin Soon; Brown, Herbert C.; Journal of Organic Chemistry; vol. 58; nb. 17; (1993); p. 4727 - 4731 View in Reaxys

100 %

With C31H33ClN2O3RuS, potassium tert-butylate, hydrogen in isopropyl alcohol, Time= 48h, T= 60 °C , p= 37503.8Torr , Inert atmosphere Touge, Taichiro; Hakamata, Tomohiko; Nara, Hideki; Kobayashi, Tohru; Sayo, Noboru; Saito, Takao; Kayaki, Yoshihito; Ikariya, Takao; Journal of the American Chemical Society; vol. 133; nb. 38; (2011); p. 14960 - 14963 View in Reaxys

100 %

With C39H39N6ORu(1+)*Br(1-), potassium methanolate, hydrogen in tetrahydrofuran, Time= 16h, T= 100 °C , p= 37503.8Torr , Reagent/catalyst Filonenko, Georgy A.; Cosimi, Elena; Lefort, Laurent; Conley, Matthew P.; Coperet, Christophe; Lutz, Martin; Hensen, Emiel J.M.; Pidko, Evgeny A.; ACS Catalysis; vol. 4; nb. 8; (2014); p. 2667 - 2671

6/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

View in Reaxys 100 %

With C56H70Cl3N10Ru2 (1+)*F6P(1-), potassium tert-butylate, hydrogen in tetrahydrofuran, dodecane, Time= 16h, T= 70 °C , p= 37503.8Torr , Inert atmosphere, Glovebox, Autoclave Filonenko, Georgy A.; Aguila, Mae Joanne B.; Schulpen, Erik N.; Van Putten, Robbert; Wiecko, Jelena; Müller, Christian; Lefort, Laurent; Hensen, Emiel J. M.; Pidko, Evgeny A.; Journal of the American Chemical Society; vol. 137; nb. 24; (2015); p. 7620 - 7623 View in Reaxys

99 %

With [(η6-C6H6)Ru(μ-Cl)Cl]2, 2-((dicyclohexylphosphino)methyl)-1-methyl-1H-imidazole, potassium tert-butylate, hydrogen in tetrahydrofuran, Time= 4.5h, T= 100 °C , p= 37503.8Torr Junge, Kathrin; Wendt, Bianca; Westerhaus, Felix Alexander; Spannenberg, Anke; Jiao, Haijun; Beller, Matthias; Chemistry - A European Journal; vol. 18; nb. 29; (2012); p. 9011 - 9018 View in Reaxys

99 %

With C13H34BFeNOP2, hydrogen in tetrahydrofuran, Time= 18h, T= 60 °C , p= 22502.3Torr , Autoclave, Inert atmosphere Elangovan, Saravanakumar; Wendt, Bianca; Topf, Christoph; Bachmann, Stephan; Scalone, Michelangelo; Spannenberg, Anke; Jiao, Haijun; Baumann, Wolfgang; Junge, Kathrin; Beller, Matthias; Advanced Synthesis and Catalysis; vol. 358; nb. 5; (2016); p. 820 - 825 View in Reaxys

96 %

With C24H38Cl2N3PRu, hydrogen, sodium methylate in isopropyl alcohol, Time= 6h, T= 25 °C , p= 38002.6Torr , Autoclave Li, Wei; Xie, Jian-Hua; Yuan, Ming-Lei; Zhou, Qi-Lin; Green Chemistry; vol. 16; nb. 9; (2014); p. 4081 - 4085 View in Reaxys

96%

10 : Example 10 General procedure: Hydrogenation of Other Ester Compounds Catalyzed by Synthetic Preparation of Bipyridine Tetradshed Ruthenium Complex 5 The results are shown in Table 2:Table 2 Hydrogenation of other ester compounds a; A Reaction conditions: S / C = 1000,3.0 mmol Substrate, 3.0 μmol 5, 3.0 mL lPrOH, 0.3 mmol NaOMe, 5 MPa H2, 25 ° C With C24H38Cl2N3PRu, hydrogen, sodium methylate in isopropyl alcohol, Time= 6h, T= 25 °C , p= 37503.8Torr Patent; Nankai University; Zhou, Qilin; Li, Wei; Xie, Jianhua; Wang, Lixin; (22 pag.); CN103980317; (2017); (B) Chinese View in Reaxys

95.3 %

10-2 : Hydrogenation of gamma butyrolactone 1,4-BDO was prepared by hydrogenation reaction from GBL. Specifically, H2 and GBL were supplied to the reactor under the following conditions, and the catalyst was prepared according to Example 1 of Korean Patent Registration No. 10-0538979CuO (72.2) MnO2 (2.5) ZnO (0.3) SiO2 (25) (parenthesized represents weight percent) was used. Reaction conditions: 170 [deg.] C, 40 atm. Supply conditions: H2 / GBL = 32/1 m / m, WHSV = 0.6 h-1 The product was partially recovered according to the elapsed time of the reaction, and the components were analyzed. The results are shown in Table 31 below. With hydrogen, Time= 2h, T= 170 °C , p= 30402Torr , Temperature, Pressure Patent; CJ CHEILJEDANG CORPORATION; KOREA RESEARCH INSTITUTE OF CHEMICAL TECHNOLOGY; YANG, YOUNG RYEOL; KIM, BYUNG SIK; KIM, JEONG HYUN; LEE, JUNG HO; SHIN, HYUN KWAN; KIM, JU NAM; CHO, KYUNG HO; (40 pag.); KR2015/118287; (2015); (A) Korean View in Reaxys

93 %

2 :General procedure: in25 mL of the autoclave was added0.5 mmol of different reactants, 50 mg of Co / ZrO2 La2O3 as catalyst,Add 10mL of deionized water, pass 2MPa hydrogen, heated to 60 , stirring conditions, the reaction after 8 hours,Cooling, deflating, and transferring the reaction solution with ethanol. After centrifugation, the catalyst and the reaction solution were separated and analyzed by gas chromatography.Gas chromatographic conditions are as follows: GC1690 gas chromatography, FID detector, capillary column (HP-5.30m × 0.250mm × 0.25μm), take the program temperature, the starting column temperature is 40 ,And the temperature was raised to 250 ° C for 3 minutes at a rate of 10 ° C / min. Carrier gas is 99.99percent high purity nitrogen,The flow rate was 1 mL / min. With hydrogen in water, Time= 8h, T= 60 °C , p= 15001.5Torr , Autoclave Patent; University of Science and Technology of China; Zhang Ying; Ma Yanfu; Wang Hao; Xu Guangyue; (9 pag.); CN107011107; (2017); (A) Chinese

7/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

View in Reaxys 87 %

With dimethylsulfide borane complex in tetrahydrofuran, Time= 0.5h, Heating, other lactones, Product distribution Brown, Herbert C.; Moon Choi, Yong; Narasimhan, S.; Journal of Organic Chemistry; vol. 47; nb. 16; (1982); p. 3153 - 3163 View in Reaxys

86 %

With lithium borohydride in diethyl ether, toluene, Time= 0.25h, T= 100 °C Brown, Herbert C.; Narasimhan, S.; Choi, Yong Moon; Journal of Organic Chemistry; vol. 47; nb. 24; (1982); p. 4702 - 4708 View in Reaxys

85 %

With sodium tetrahydroborate, cobalt(II) chloride hexahydrate, diisopropylamine in ethanol, Time= 24h, T= 50 °C , chemoselective reaction Jagdale, Arun R.; Paraskar, Abhimanyu S.; Sudalai, Arumugam; Synthesis; nb. 4; (2009); p. 660 - 664 View in Reaxys

81 %

73 %

Stage 1: With polyethylsiloxane, LiTi(OPr-i)4, Time= 24h, T= 100 °C Stage 2: With sodium hydroxide in tetrahydrofuran, Time= 3h, Heating Kozhukhova; Yatluk; Suvorov; Koryakova; Russian Journal of Organic Chemistry; vol. 40; nb. 6; (2004); p. 759 - 762 View in Reaxys

22 %

13 :Example 13Into a 100 mL autoclave equipped with a glass cylinder, 20 mg of the black green powder obtained from Example 12, 5 mg of sodium hydride-mineral oil dispersion (content 60percent), 200 mg of η-butyrolactone and 4 g of tetrahydrofuran were charged. The inside of the autoclave was replaced with nitrogen and then replaced with hydrogen, followed by increasing the hydrogen pressure to 1.0 MPa. Then, upon increasing the temperature to 120° C., the inner pressure became 1.4 MPa. Upon stirring the contents of the autoclave at 120° C. for 6 hours, the inner pressure became 1.3 MPa. When the contents of the autoclave were cooled to room temperature and analyzed by gas chromatography (internal standard method), the yield of 1,4-butanediol was 22percent. Also, η-butyrolactone recovery was 77percent. With hydrogen, sodium hydride, black green powder in tetrahydrofuran, Time= 6h, T= 120 °C , p= 7500.75 - 10501.1Torr , Autoclave, Inert atmosphere, Product distribution / selectivity Patent; SUMITOMO CHEMICAL COMPANY, LIMITED; US2012/10417; (2012); (A1) English View in Reaxys With lithium triethylborohydride in various solvent(s), Time= 0.416667h, ΔH, Thermodynamic data Wiberg, Kenneth B.; Waldron, Roy F.; Journal of the American Chemical Society; vol. 113; nb. 20; (1991); p. 7697 - 7705 View in Reaxys With ammonium hexafluorophosphate, hydrogen, η(+)-tris(pentane-2,5-dionato)ruthenium, TOP in various solvent(s), Time= 3h, T= 200 °C , p= 37503Torr , reaction rate; other also cyclic esters, var. reagents and catalysts, Product distribution Hara, Yoshinori; Inagaki, Hiroko; Nishimura, Sugio; Wada, Keisuke; Chemistry Letters; nb. 10; (1992); p. 1983 - 1986 View in Reaxys

69 %Chromat.

10 :Example 10 Hydrogenation of η-butyrolactone [Ru2(μ-Cl)3(triphos)2]Cl (3.0 mg), potassium tert-butoxide (5.5 mg), and 1.5 ml of methanol were added into a 20-ml Schlenk tube under a nitrogen atmosphere, and the mixture was stirred for 20 minutes at room temperature. This solution and η-butyrolactone (0.11 g) were added into a 100-ml autoclave having a stirrer placed inside, under a nitrogen atmosphere. The autoclave was purged with hydrogen, and then hydrogen was further included in the autoclave up to 4.0 MPa. The contents of the autoclave were heated and stirred at 100°C for 13 hours. After cooling, the reaction liquid was analyzed by gas chromatography, and it was found that 1, 4-butanediol was produced at a yield of 69.0percent. With potassium tert-butylate, hydrogen, [Ru2(μ-Cl)3(triphos)2]Cl in methanol, Time= 13h, T= 100 °C , p= 30003Torr , Inert atmosphere, Autoclave Patent; Takasago International Corporation; EP2141142; (2010); (A1) English

8/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

View in Reaxys 36 %Chromat.

With methanol, η(+)-tris(pentane-2,5-dionato)ruthenium, hydrogen, zinc, [2-((diphenylphospino)methyl)-2-methyl-1,3-propanediyl]bis[diphenylphosphine], T= 20 - 120 °C , p= 60006Torr , Autoclave Rosi, Luca; Frediani, Marco; Frediani, Piero; Journal of Organometallic Chemistry; vol. 695; nb. 9; (2010); p. 1314 - 1322 View in Reaxys

7 %Chromat.

15 :Example 15; Into a 100 mL autoclave equipped with a glass cylinder, 13 mg of the grayish white powder obtained from Example 10, 65 mg of η-butyrolactone and 10 g of tetrahydrofuran were charged. The inside of the autoclave was replaced with nitrogen and then replaced with hydrogen, followed by increasing the hydrogen pressure to 1.0 MPa. Then, upon increasing the temperature to 100° C., the inner pressure became 1.4 MPa. Upon stirring the contents of the autoclave at 130° C. for 4 hours, the inner pressure became 1.3 MPa. When the contents of the autoclave were cooled to approximately 25° C. and analyzed by gas chromatography (internal standard method), the yield of 1,4-butanediol was 7percent. Also, η-butyrolactone recovery was 91percent. With hydrogen, carbonyl(dihydride)tris(triphenylphosphine)ruthenium/N,N'-[bis(8-quinolyl)]ethane-1,2-diamine complex in tetrahydrofuran, Time= 4h, T= 100 - 130 °C , p= 9750.98 - 10501.1Torr , Autoclave, Product distribution / selectivity Patent; SUMITOMO CHEMICAL COMPANY, LIMITED; US2012/29195; (2012); (A1) English View in Reaxys

64 %Chromat.

Stage 1: With iron (II) stearate, ethylenediamine in toluene, Time= 0.0833333h, T= 20 °C , Inert atmosphere, Schlenk technique Stage 2: in toluene, Time= 20h, T= 100 °C , Inert atmosphere, Schlenk technique Junge, Kathrin; Wendt, Bianca; Zhou, Shaolin; Beller, Matthias; European Journal of Organic Chemistry; nb. 11; (2013); p. 2061 - 2065 View in Reaxys With samarium diiodide, water in tetrahydrofuran, T= 29.9 - 30.1 °C , Inert atmosphere, Schlenk technique, Kinetics, chemoselective reaction Szostak, Michal; Spain, Malcolm; Choquette, Kimberly A.; Flowers, Robert A.; Procter, David J.; Journal of the American Chemical Society; vol. 135; nb. 42; (2013); p. 15702 - 15705 View in Reaxys

89 %Chromat.

With [Fe(H)(BH4)(CO)(HN{CH2CH2P(iPr)2}2)], hydrogen in tetrahydrofuran, Time= 19h, T= 120 °C , p= 22502.3Torr , Autoclave Werkmeister, Svenja; Junge, Kathrin; Wendt, Bianca; Alberico, Elisabetta; Jiao, Haijun; Baumann, Wolfgang; Junge, Henrik; Gallou, Fabrice; Beller, Matthias; Angewandte Chemie - International Edition; vol. 53; nb. 33; (2014); p. 8722 8726; Angew. Chem.; vol. 126; nb. 33; (2014); p. 8867 - 8871,5 View in Reaxys

59 %Chromat.

With 1,1'-methylenebis(3-benzylimidazol-2-ylidene) diiodide, [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μchloride)]2, potassium tert-butylate, hydrogen in 1,4-dioxane, Time= 6h, T= 100 °C , p= 37503.8Torr Westerhaus, Felix A.; Wendt, Bianca; Dumrath, Andreas; Wienhoefer, Gerrit; Junge, Kathrin; Beller, Matthias; ChemSusChem; vol. 6; nb. 6; (2013); p. 1001 - 1005 View in Reaxys 9 : Production of 1,4-Butanediol from Gamma-Butyrolactone Example 9 Production of 1,4-Butanediol from Gamma-Butyrolactone The gamma-butyrolactone obtained in Example 4 was hydrogenated with hydrogen gas (50 bar) using 0.25 mol percent of a ruthenium (Ru) catalyst and 1 mol percent of an imidazole ligand in a THF solvent at 100° C. to yield 1,4-butanediol (Chem. Eur. J. 2012. 18, 9011-9018). With hydrogen in tetrahydrofuran, T= 100 °C , p= 37503.8Torr Patent; Lee, Han Won; Yang, Young Lyeol; Kim, So Young; Shin, Yong Uk; Chang, Jin Sook; Um, Hye Won; Goh, Young Hyoung; Jhon, Sung Hoo; US2014/296466; (2014); (A1) English View in Reaxys With lithium triethylborohydride in dichloromethane, T= -78 - 20 °C

9/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Gonzalez, Cesar; Kavoosi, Sam; Sanchez, Andersson; Wnuk, Stanislaw F.; Carbohydrate Research; vol. 432; (2016); p. 17 22 View in Reaxys Example 2-6 : Example 2-6 Under nitrogen atmosphere, η-butyrolactone (11.3 mmol), complex 1 (0.0113 mmol) produced in Example 1-1, tetrahydrofuran (60 mL), and a solution of 1M potassium tert-butoxide in tetrahydrofuran (0.57 mL) were placed in a 100-mL autoclave equipped with an electromagnetic induction stirrer, and hydrogenation reduction was performed at a hydrogen pressure of 0.65 MPa at 100° C. for 40 hours. With C37H47N5OPRu(1+)*Cl(1-), potassium tert-butylate, hydrogen in tetrahydrofuran, Time= 40h, T= 100 °C , p= 4875.49Torr , Autoclave Patent; KURARAY CO., LTD.; MURATA, Yusuke; TORIHARA, Masahiro; (27 pag.); US2016/145282; (2016); (A1) English View in Reaxys 73 %Chromat.

With [RuCl2(N-heterocyclic carbene)(bis[2-(diphenylphosphino)ethyl]amine)], hydrogen, sodium methylate in tetrahydrofuran, Time= 5h, T= 50 °C , p= 7500.75Torr , Schlenk technique, Inert atmosphere Ogata, Osamu; Nakayama, Yuji; Nara, Hideki; Fujiwhara, Mitsuhiko; Kayaki, Yoshihito; Organic Letters; vol. 18; nb. 15; (2016); p. 3894 - 3897 View in Reaxys

99 %Chromat.

With C36H32Cl2N2P2Ru, hydrogen, sodium methylate in tetrahydrofuran, Time= 8h, T= 120 °C , p= 37503.8Torr , Reagent/catalyst Fang, Xiaolong; Zhang, Chunyan; Chen, Jin; Zhu, Hongping; Yuan, Youzhu; RSC Advances; vol. 6; nb. 51; (2016); p. 45512 - 45518 View in Reaxys

88 %Chromat.

With C15H29MnNO3P2 (1+)*Br(1-), potassium tert-butylate, hydrogen in 1,4-dioxane, Time= 24h, T= 110 °C , p= 22502.3Torr , Inert atmosphere, Autoclave Elangovan, Saravanakumar; Garbe, Marcel; Jiao, Haijun; Spannenberg, Anke; Junge, Kathrin; Beller, Matthias; Angewandte Chemie - International Edition; vol. 55; nb. 49; (2016); p. 15364 - 15368; Angew. Chem.; nb. 128; (2016); p. 15590 15594,5 View in Reaxys

99 %Spectr. A3 : Hydrogenation Reaction of Various Substrates A hydrogenation reaction was performed in the same manner as in Reaction Examples A1 and A2, except that the conditions specified in Table 1 were used. Table 1 shows the results. Reaction Example A1 is an example performed without preactivation of catalyst. Reaction Example A2 is an example performed with preactivation of catalyst. The step of Reaction Example A2 may be expressed as follows. Table 1 shows that a hydrogenation reaction with respect to Amide Compound 1a was not advanced at all with Compound 2a (Entry 1) disclosed in Patent Document 1 (International Publication WO2012/102247 (A1) pamphlet); however, it was revealed that a hydrogenation reaction was advanced with Compounds 2b to 2g (Entries 2 to 7). Among them, the hydrogenation reaction was advanced at a high yield with Compounds 2b, 2c, and 2d (Entries 2 to 4), particularly with Compounds 2b and 2c (Entries 2 and 3). Further, the results of Entries 8 to 16 confirmed that various substrates may be efficiently hydrogenated by using the metal complex of the present invention. With C38H54Cl2N2P2Ru, hydrogen, sodium hydride in toluene, Time= 23h, T= 160 °C , p= 60006Torr , Autoclave, Sealed tube Patent; National University Corporation Nagoya University; Saito, Susumu; Noyori, Ryoji; Miura, Takashi; Naruto, Masayuki; Iida, Kazuki; Takada, Yuki; Toda, Katsuaki; Nimura, Sota; Agrawal, Santosh; Lee, Sunkook; (42 pag.); US9463451; (2016); (B2) English View in Reaxys > 99 %Chromat.

42 : Example 42 Hydrogenation of y-Butyrolactone Example 41 Hydrogenation of η-Butyrolactone In a 100 mL stainless autoclave, 1.9 mg (0.0027 mmol/Ru) of ruthenium complex D produced in Example 5 was added, and after replacement with nitrogen gas, 0.25 mL (0.25 mmol) of 1 M KOtBu (solution in THF), 2 mL of toluene, and 0.19 mL (2.5 mmol) of a substrate were added, and then stirred at 1 MPa of hydrogen pressure at 80° C. for 6 hours. After cooling, the reactant was analyzed by GC, and 1-phenylethanol was obtained with a GC yield of >99percent.

10/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

With C5H9AgClN2, C56H58Cl4N2P4Ru2, potassium tert-butylate, hydrogen in tetrahydrofuran, toluene, Time= 6h, T= 80 °C , p= 7500.75Torr , Autoclave Patent; Takasago International Corporation; Ogata, Osamu; Nara, Hideki; Nakayama, Yuji; (38 pag.); US2017/44196; (2017); (A1) English View in Reaxys With hydrogen in 1,4-dioxane, Time= 24h, T= 100 °C , p= 25502.6Torr , Autoclave, Reagent/catalyst, Solvent Huang, Zhiwei; Barnett, Kevin J.; Chada, Joseph P.; Brentzel, Zachary J.; Xu, Zhuoran; Dumesic, James A.; Huber, George W.; ACS Catalysis; vol. 7; nb. 12; (2017); p. 8429 - 8440 View in Reaxys 94 %Chromat.

With dichlorido-bis[(2-diphenylphosphino)ethyl]amine-cobalt(II), hydrogen, sodium methylate in 1,4-dioxane, Time= 24h, T= 120 °C , p= 37503.8Torr , Autoclave Junge, Kathrin; Wendt, Bianca; Cingolani, Andrea; Spannenberg, Anke; Wei, Zhihong; Jiao, Haijun; Beller, Matthias; Chemistry - A European Journal; vol. 24; nb. 5; (2018); p. 1046 - 1052 View in Reaxys

OH HO

Rx-ID: 1567497 View in Reaxys 4/281 Yield 100 %

Conditions & References With sodium aluminum tetrahydride in tetrahydrofuran, Time= 24h, Ambient temperature Cha, Jin Soon; Brown, Herbert C.; Journal of Organic Chemistry; vol. 58; nb. 17; (1993); p. 4727 - 4731 View in Reaxys

95 %

3 : Comparative Example 3 The succinic anhydride from example 1 was hydrogenated as a 20percent by weight aqueous solution over a Re/10 Pt/C catalyst analogously to example 1 of DE10009817 A1 (feed rate 100 g/h, temperature 155° C., pressure 220 bar, 20 mol of 11 hydrogen/h, 120 mL of catalyst, tubular reactor, diameter 2 cm, trickle mode). At first, the 12 butane-1,4-diol yield was about 95percent with 100percent conversion (remainder: butanol, propanol, THF and gamma-butyrolactone). After only 100 h, the conversion decreased to 98percent and the 13 butanediol yield was only 90percent. With hydrogen in water, T= 155 °C , p= 165017Torr , Reagent/catalyst Patent; BASF SE; Duefert, Alexander; Pinkos, Rolf; Weissker, Wolf-Steffen; (9 pag.); US2018/2303; (2018); (A1) English View in Reaxys

78 %

With sodium tetrahydroborate, C36H30F6N10Ni4O10 (2+)*2C2F3O2 (1-), zinc(II) chloride in tetrahydrofuran, Time= 12h, T= 45 °C Tsai, Bing-Chen; Liu, Yi-Hung; Peng, Shie-Ming; Liu, Shiuh-Tzung; European Journal of Inorganic Chemistry; vol. 2016; nb. 17; (2016); p. 2783 - 2790 View in Reaxys With [Ru(1,1,1-tris(diphenylphosphinomethyl)ethane)(trimethylenemethane)], hydrogen in 1,4-dioxane, Time= 24h, T= 195 °C , p= 37503.8Torr , Autoclave, Inert atmosphere Vom Stein, Thorsten; Meuresch, Markus; Limper, Dominik; Schmitz, Marc; Hölscher, Markus; Coetzee, Jacorien; ColeHamilton, David J.; Klankermayer, Jürgen; Leitner, Walter; Journal of the American Chemical Society; vol. 136; nb. 38; (2014); p. 13217 - 13225 View in Reaxys

98 %Spectr. A3 : Hydrogenation Reaction of Various Substrates A hydrogenation reaction was performed in the same manner as in Reaction Examples A1 and A2, except that the conditions specified in Table 1 were used. Table 1 shows the results. Reaction Example A1 is an example performed without preactivation of catalyst. Reaction Example A2 is an example performed with preactivation of catalyst. The step of Reaction Example A2 may be expressed as follows. Table 1 shows that a hydrogenation reaction with respect to Amide Compound 1a was not advanced at

11/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

all with Compound 2a (Entry 1) disclosed in Patent Document 1 (International Publication WO2012/102247 (A1) pamphlet); however, it was revealed that a hydrogenation reaction was advanced with Compounds 2b to 2g (Entries 2 to 7). Among them, the hydrogenation reaction was advanced at a high yield with Compounds 2b, 2c, and 2d (Entries 2 to 4), particularly with Compounds 2b and 2c (Entries 2 and 3). Further, the results of Entries 8 to 16 confirmed that various substrates may be efficiently hydrogenated by using the metal complex of the present invention. With C38H54Cl2N2P2Ru, hydrogen, sodium hydride in toluene, Time= 23h, T= 160 - 190 °C , p= 60006Torr , Autoclave, Sealed tube Patent; National University Corporation Nagoya University; Saito, Susumu; Noyori, Ryoji; Miura, Takashi; Naruto, Masayuki; Iida, Kazuki; Takada, Yuki; Toda, Katsuaki; Nimura, Sota; Agrawal, Santosh; Lee, Sunkook; (42 pag.); US9463451; (2016); (B2) English View in Reaxys O O

OH HO

Rx-ID: 48308951 View in Reaxys 5/281 Yield

Conditions & References

12 %, 60 %

With water, hydrogen in 1,4-dioxane, Time= 4h, T= 139.84 °C , p= 60006Torr , Reagent/catalyst Wang, Tianmiao; Liu, Sibao; Tamura, Masazumi; Nakagawa, Yoshinao; Hiyoshi, Norihito; Tomishige, Keiichi; Green Chemistry; vol. 20; nb. 11; (2018); p. 2547 - 2557 View in Reaxys

OH HO

Rx-ID: 48308953 View in Reaxys 6/281 Yield

Conditions & References With hydrogen in 1,4-dioxane, Time= 24h, T= 139.84 °C , p= 60006Torr , Reagent/catalyst Wang, Tianmiao; Liu, Sibao; Tamura, Masazumi; Nakagawa, Yoshinao; Hiyoshi, Norihito; Tomishige, Keiichi; Green Chemistry; vol. 20; nb. 11; (2018); p. 2547 - 2557 View in Reaxys

OH O

OH HO

O O

Rx-ID: 48308957 View in Reaxys 7/281 Yield

Conditions & References With hydrogen in 1,4-dioxane, Time= 1h, T= 139.84 °C , p= 60006Torr , Time Wang, Tianmiao; Liu, Sibao; Tamura, Masazumi; Nakagawa, Yoshinao; Hiyoshi, Norihito; Tomishige, Keiichi; Green Chemistry; vol. 20; nb. 11; (2018); p. 2547 - 2557 View in Reaxys With hydrogen in 1,4-dioxane, Time= 4h, T= 139.84 °C , p= 60006Torr Wang, Tianmiao; Liu, Sibao; Tamura, Masazumi; Nakagawa, Yoshinao; Hiyoshi, Norihito; Tomishige, Keiichi; Green Chemistry; vol. 20; nb. 11; (2018); p. 2547 - 2557 View in Reaxys

12/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

OH HO

Rx-ID: 48308958 View in Reaxys 8/281 Yield

Conditions & References

90 %

With water, hydrogen in 1,4-dioxane, Time= 4h, T= 139.84 °C , p= 60006Torr , Reagent/catalyst, Solvent Wang, Tianmiao; Liu, Sibao; Tamura, Masazumi; Nakagawa, Yoshinao; Hiyoshi, Norihito; Tomishige, Keiichi; Green Chemistry; vol. 20; nb. 11; (2018); p. 2547 - 2557 View in Reaxys

OH HO

Rx-ID: 48308959 View in Reaxys 9/281 Yield

Conditions & References With hydrogen in 1,4-dioxane, Time= 24h, T= 139.84 °C , p= 60006Torr , Reagent/catalyst, Temperature Wang, Tianmiao; Liu, Sibao; Tamura, Masazumi; Nakagawa, Yoshinao; Hiyoshi, Norihito; Tomishige, Keiichi; Green Chemistry; vol. 20; nb. 11; (2018); p. 2547 - 2557 View in Reaxys O O

OH HO

Rx-ID: 48308960 View in Reaxys 10/281 Yield

Conditions & References

13 %, 80 %

Rx-ID: 48308961 View in Reaxys 11/281 Yield

Conditions & References

9 %, 8 %, 39 %

With water, hydrogen in 1,4-dioxane, Time= 4h, T= 139.84 °C , p= 60006Torr Wang, Tianmiao; Liu, Sibao; Tamura, Masazumi; Nakagawa, Yoshinao; Hiyoshi, Norihito; Tomishige, Keiichi; Green Chemistry; vol. 20; nb. 11; (2018); p. 2547 - 2557 View in Reaxys

OH HO

Rx-ID: 6868525 View in Reaxys 12/281 Yield 100%

Conditions & References 3 : Example 3 Example 3 In a 300 ml pressure reactor, 10 g of the Ru catalyst as described in the catalyst production example were placed in a catalyst basket insert and 150 g (0.87 mol) of a 50percent strength aqueous butynediol solution were added.

13/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

The hydrogenation was carried out using pure hydrogen at a constant pressure of 40 bar and a temperature of 80° C. Hydrogenation was continued until no more hydrogen was absorbed (3 hours). The reactor was subsequently vented. The conversion of the alkyne was 100percent and the yield of 1,4-butanediol was 92percent, based on the amount of butynediol used. Patent; BASF Aktiengesellschaft; US6130360; (2000); (A) English View in Reaxys 97%

1 : EXAMPLE 1 EXAMPLE 1 A 300 ml stirred autoclave is charged with: The autoclave is then sealed, pressurized with hydrogen and maintained at 1500 psig of hydrogen pressure at 90° C for 30 minutes. At the end of this time, gas chromatograph analysis shows that 95percent of the dioxane is converted to a mixture of glycols. A 97percent yield of 1,4-butanediol (BAD) is obtained and only trace amounts of tetrahydrofuran (THF) are present. Patent; E. I. Du Pont de Nemours and Company; US4044059; (1977); (A) English View in Reaxys

96.4%

2 : Synthesis of (R)-3HB/1,4-Butanediol Oligomer EXAMPLE 2 Synthesis of (R)-3HB/1,4-Butanediol Oligomer In a 500 m reactor were charged 250 g (2.12 mol) of (R)-3HB, 9.53 g (0.106 mol) of 1,4-butanediol, and 1.05 g (4.2 mmol) of dibutyltin oxide, and the mixture was allowed to react in the same manner as in Example 1 to obtain 181.6 g (percent yield: 96.4percent) of the titled oligomer. 1H-NMR (400 MHz, CDC ) η (ppm): 3 (R)-3HB Segment: 1.22-1.33 (60H, m), 2.35-2.70 (40H, m), 4.16 (2H, m), 5.28 (18H, m) 1,4-Butanediol Segment: 1.71 (4H, m), 4.11 (4H, m) IR (liquid film, cmmin 1): 3500, 2980, 1740, 1385, 1305, 1190 Mw: 1,640 Mn: 1,060 Tm: 120.0°C Patent; Takasago International Corporation; EP552896; (1993); (A1) English View in Reaxys

69 %

1 : Example 1 Hydrogenation of Aliphatic Diesters to Terminal Diols General procedure: Example 1 Hydrogenation of Aliphatic Diesters to Terminal Diols (0067) (0068) A 90 mL Fischer-Porter tube was charged under nitrogen with catalyst (0.01 mmol), tBuOK (0.01 mmol), dialkyl esters (1.0 mmol), and toluene (2 mL). The Fischer-Porter tube was purged by three successive cycles of pressurization/venting with H2 (15 psi), then pressurized with H2 (6.8 atm). The solution was heated at 110° C. (bath temperature) with stirring for 24 hr. After cooling to 5° C. (ice/water), the excess H2 was vented carefully and the products were determined by GC using m-xylene as an internal standard. (0069) The data comprising catalytic hydrogenation of aliphatic diesters to terminal diols is summarized in Table 2. With C17H38ClNORuS2, potassium tert-butylate, hydrogen in toluene, Time= 24h, T= 110 °C , p= 775.743Torr , Inert atmosphere Patent; Council of Scientific and Industrial Research; BALARAMAN, Ekambaram; SAHOO, Manoj Kumar; (9 pag.); US2017/349514; (2017); (A1) English View in Reaxys Enz,W.; Helvetica Chimica Acta; vol. 44; (1961); p. 206 - 212 View in Reaxys Zweifel,G. et al.; Journal of the American Chemical Society; vol. 84; (1962); p. 190 - 195 View in Reaxys Brown,H.C.; Keblys,K.A.; Journal of the American Chemical Society; vol. 86; (1964); p. 1791 - 1795 View in Reaxys Hudrlik,P.F. et al.; Journal of Organic Chemistry; vol. 40; (1975); p. 1116 - 1120 View in Reaxys Holtz et al.; Journal of Organic Chemistry; vol. 38; (1973); p. 3175,3178

14/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

View in Reaxys Rakhmankulov et al.; J. Appl. Chem. USSR (Engl. Transl.); vol. 48; (1975); p. 1410,1468 View in Reaxys Rakhmankulov; Maksimova; J. Appl. Chem. USSR (Engl. Transl.); vol. 48; (1975); p. 677,703 View in Reaxys Kraewskii et al.; Doklady Chemistry; vol. 146; (1962); p. 939; Doklady Akademii Nauk SSSR; vol. 146; (1962); p. 1349 View in Reaxys Mjagkowa et al.; Zhurnal Organicheskoi Khimii; vol. 2; (1966); p. 1998,1961 View in Reaxys Zweifel; Brown; Journal of the American Chemical Society; vol. 85; (1963); p. 2066,2071 View in Reaxys Zweifel et al.; Journal of the American Chemical Society; vol. 84; (1962); p. 183,188 View in Reaxys Brown et al.; Journal of the American Chemical Society; vol. 82; (1960); p. 681,682 View in Reaxys Gromova et al.; J. Appl. Chem. USSR (Engl. Transl.); vol. 40; (1967); p. 114,98,99 View in Reaxys Rylander; Cohn; ; (1960); p. 977 - 984; ; nb. 24516; (1961) View in Reaxys Taira; Bulletin of the Chemical Society of Japan; vol. 35; (1962); p. 840 View in Reaxys Ray et al.; Journal of the Indian Chemical Society; vol. 38; (1961); p. 705 View in Reaxys Patent; Exp.-Design Bureau of Synth. Prod. and Bolakhovo Chem. Combine; SU202913; (1966); ; vol. 69; nb. 51576z; (1968) View in Reaxys Patent; Farbwerke Hoechst AG; NL6600274; (1965); ; vol. 65; nb. 16863h; (1966) View in Reaxys Patent; Mitsubishi Chem. Ind. Co.; DE2144316; (1970); ; vol. 76; nb. 2144316; (1972) View in Reaxys Patent; du Pont de Nemours and Co.; US3060244; (1959); ; vol. 58; nb. 5572h; (1963) View in Reaxys Patent; Du Pont de Nemours and Co.; US3008997; (1961); ; vol. 57; nb. 12534i; (1962) View in Reaxys Patent; General Electric Co.; US3965152; (1976); ; vol. 85; nb. 93861 View in Reaxys Patent; Rakhmankulov et al.; SU591462; (1978); Ref. Zh., Khim.; vol. 3; nb. N106P; (1979) View in Reaxys Patent; Mistrik; CS106533; (1961); ; vol. 60; nb. 2786c; (1964) View in Reaxys Patent; General Anilin + Film Corp.; US2953605; (1960); ; vol. 55; nb. 3439g; (1961) View in Reaxys Patent; Du Pont; FR2346311; (1977); DE2714237; (1977); ; vol. 88; nb. 22132 View in Reaxys Patent; General Electric Co.; DE2504231; (1975); ; vol. 83; nb. 192590 View in Reaxys Ohya; Sano; Biomedical mass spectrometry; vol. 4; nb. 4; (1977); p. 241 - 247 View in Reaxys Patent; Movsesyan et al.; SU282306; (1970); Ref. Zh., Khim.; vol. 14; nb. N44P; (1971) View in Reaxys Patent; General Anilin and Film; US2967893; (1961); ; vol. 55; nb. 13319c; (1961) View in Reaxys Gasparic; Borecky; Journal of Chromatography; vol. 5; (1961); p. 466,467-499; ; vol. 56; nb. 9393; (1962) View in Reaxys Baschkirow et al.; Neftekhimiya; vol. 16; (1976); p. 230,231; ; vol. 85; nb. 77548; (1976) View in Reaxys Chi-San Chen; Journal of Organometallic Chemistry; vol. 156; (1978); p. 213,215 View in Reaxys Areshidze et al.; J. Appl. Chem. USSR (Engl. Transl.); vol. 43; (1970); p. 601,606 View in Reaxys Musavirov et al.; J. Appl. Chem. USSR (Engl. Transl.); vol. 51; (1978); p. 2295,2184,2185-2187

15/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

View in Reaxys 15 Product distribution / selectivity Patent; BASF AKTIENGESELLSCHAFT; WO2004/43890; (2004); (A2) German View in Reaxys II : Procedure for the Synthesis of Oligoesterdiol from DBE-3, DBE-5 and 1,4-Butanediol STR25 EXAMPLE II Procedure for the Synthesis of Oligoesterdiol from DBE-3, DBE-5 and 1,4-Butanediol STR25 Into a 2000-mL 4-necked reaction kettle equipped with a Dean-Stark condenser, a reflux condenser, a nitrogen inlet, a thermometer inlet and a motor driven stirrer, was added 432.5 g of DBE-3 (dimethyl adipate, 2.5 mol, MW 173), 400 g of DBE-5 (dimethyl glutarate, 2.5 mol, MW 160), 924.60 g of 1,4-butanediol (10.26 mol, MW 90.12) and 0.18 g zinc acetate (0.01percent of total weight). The reaction vessel was purged with nitrogen for 30 minutes. The contents of the reaction vessel were heated to 140° C. for 12 hours, 160° C. for 8 hours, 200° C. for 2 hours and 225° C. for 1 hour. The color of the reaction mixture turned light yellow upon heating to 180° C. About 390 mL of methanol distilled out of the reaction mixture during this heating process (theoretical amount of methanol to be distilled out=400 mL). The remaining methanol is assumed to have escaped. The reaction temperature was raised to 240° C. to distill the excess 1,4-butanediol. Meanwhile, Brookfield viscosity of the aliquots of the reaction mixture were performed at regular intervals of 10 minutes at 25° C. using spindle #31 at 6 rpm. In the meantime, nearly 20 mL of 1,4-butanediol was distilled out. Once the viscosity reached about 500-600 mPa.s, the reaction mixture was cooled to room temperature. Patent; Exxon Chemical Patents, Inc.; US5973072; (1999); (A) English View in Reaxys Representative preferred compounds include, but are not limited to: ... 1-Phenyl-1,2-Propanediol 2-Methyl-1,3-Propanediol 1,2-Butanediol 1,3-Butanediol 1,4-Butanediol 2,3-Butanediol (2R,3R)-(-)-2,3-Butanediol (2S,3S)-(+)-2,3-Butanediol ... Patent; BROWN, DAVID A.; KHORLIN, ALEXANDER A.; LESIAK, KRYSTYNA; REN, WU YUN; US2002/141952; (2002); (A1) English View in Reaxys Patent; Codon Pharmaceuticals, Inc.; US5990177; (1999); (A) English View in Reaxys 2 : EXAMPLE 2 EXAMPLE 2 A further experimental test rig, similar to that used in Example 1 but with provision for recycle of product butane-1,4-diol from the exit end of the hydrogenation zone for dilution of the crude butane-1,4-diol feed, was used in this example. It was charged with 250 ml (237.4 g) of the same catalyst as used in Example 1 which was activated in the same way. A series of 12 Runs was carried out. The analysis of the wet feed butane-1,4-diol, obtained by adding water to a crude butane-1,4-diol of the type used in Example 1, was as set out in Table II. In the first 4 Runs the effects of liquid recycle were investigated using an LHSV of 1.0 h-1, a temperature of 110° C., a pressure of 900 psia (62.05 bar), and a hydrogen flow rate of 24 NLPH. In Run 1 the recycle rate was 2 kg h-1, in Run 2 1 kg h-1, in Run 3 0.6 kg h-1, and in Run 4 0 kg h-1. In Runs 5 to 12 the effects of hydrogen flow rate were investigated. Run 9 repeated the conditions of Run 8 after a weekend shutdown of the rig.

16/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Runs 10 to 12 used lower hydrogen flow rates. The results are summarised in Table III below. Patent; Kvaerner Process Technology Limited; US6137016; (2000); (A) English View in Reaxys Examples of suitable diols are: Ethylene glycol, diethylene glycol, triethylene glycol, ... propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,5-pentanediol, ... Patent; Henkel Kommanditgesellschaft auf Aktien; US5277900; (1994); (A) English View in Reaxys Table 3 lists the compounds that I have found to be effective. ... 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, dipropylene glycol, 1,5-pentanediol, 3-methyl-2,4-pentanediol, ... Patent; Berg; Lloyd; US5425854; (1995); (A) English View in Reaxys triethylene glycol (Example 10) 1,4-butanediol (Example 11) 1,5-pentanediol (Example 12) neopentylglycol (Example 13) 1-methoxy-2-propanol (Example 14) diethylene glycol monobutyl ether (Example 15) Patent; BASF Aktiengesellschaft; US5770708; (1998); (A) English View in Reaxys 6 : 1,4-butanediol monomontanate EXAMPLE 6 1,4-butanediol monomontanate 57.2 g 1,4-butanediol (0.636 mole), 254.2 g montanic acid and 0.4 g tin powder were heated to 210° C. as in Example 1 with application of a gentle vacuum. The vacuum was increased to 152 mbar over a period of 3 hours. The mixture had an acid value of 1.5. A brownish-yellow wax having a dropping point of 77° C. was obtained after cooling to 100° C., bleaching and filtering. Patent; Neynaber Chemie GmbH; US4962145; (1990); (A) English View in Reaxys 3 : EXAMPLE 3 EXAMPLE 3 The hydrogenation reaction was conducted in the same manner as in Example 1 except that 70 ml of m-xylene was used instead of tetraethylene glycol dimethyl ether solvent used in Example 1.

17/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

After completion of the reaction, the autoclave was opened, and two separated layers were observed. The upper layer was composed mainly of m-xylene, and the lower layer was composed mainly of the product 1,4-butanediol. The reaction product was analyzed, whereby the conversion of η-butyrolactone was 50.4percent, and the amount of 1,4-butanediol formed was 158.2 mmol. The yield of 1,4-butanediol was 40.3percent, and the selectivity was 80.0percent. Patent; Mitsubishi Kasei Corporation; US5077442; (1991); (A) English View in Reaxys C.1 : COMPARATIVE EXAMPLE 1 COMPARATIVE EXAMPLE 1 The operation was conducted in the same manner as in Example 1 except that phosphoric acid used in Example 1 was not employed, whereby the conversion of η-butyrolactone was 25.5percent, and the amount or 1,4-butanediol formed was 80.5 mmol. The yield of 1,4-butanediol was 20.5percent, and the selectivity was 80.4percent. Patent; Mitsubishi Kasei Corporation; US5077442; (1991); (A) English View in Reaxys Representative but non-exhausted examples of various polyhdric alcohols which can be alkoxylated according to the present invention are ethylene glycol 1,2-propylene glycol 1,4-butanediol 1,6-hexanediol 1,10-decanediol 1,3-butylene glycol diethylene glycol monobutyl ether diethylene glycol monomethyl ether diethyl glycol monoethyl ether dipropylene glycol ... Patent; Vista Chemical Company; US4568774; (1986); (A) English View in Reaxys ...ay be considered as being derived from dihydroxy compounds of the formula HO--R4 --OH, especially dihydroxyaromatic compounds and preferably bisphenols of the formula HO--A2 --Y3 --A3 --OH. The following dihydroxy compounds are illustrative: Ethylene glycol Propylene glycol 1,3-Propanediol 1,4-Butanediol 1,6-Hexanediol 1,12-Dodecanediol 2-Ethyl-1,10-decanediol 2-Butene-1,4-diol 1,3-Cyclopentanedoil 1,3-Cyclohexanediol ... Patent; General Electric Company; US4757150; (1988); (A) English View in Reaxys VI.d : EXAMPLE VI The procedure described in Example II was again repeated but using the 61 grams from the preceding step plus 45 grams of KOH dissolved in 50 grams of H2 O. After hydrolysis there was obtained by distillation 27.4 grams of 1,4-butanediol and 68 grams of residue which is assumed to be essentially KOOCCH3. Patent; Phillips Petroleum Co.; US4297506; (1981); (A) English View in Reaxys Representative but non-exhaustive examples of various polyols which can be alkoxylated according to the present invention are: ethylene glycol

18/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

1,2-propylene glycol 1,4-butanediol 1,6-hexanediol 1,10-decanediol 1,3-butylene glycol diethylene glycol monobutyl ether diethylene glycol monomethyl ether diethyl glycol monoethyl ether dipropylene glycol ... Patent; Vista Chemical Company; US4540828; (1985); (A) English View in Reaxys whereas optimum results have been obtained with 1,2-ethanediol 1,4-butanediol 1,4-cyclohexanedimethanol 1,2-cyclohexanediol 2,2-dimethyl-1,3-propanediol thioglycerol bis(2-hydroxyethyl)ether bis(3-hydroxy-n-propyl)ether Patent; Akzo N.V.; US4546136; (1985); (A) English View in Reaxys 3 : Manufacture of 1,4-butanediol EXAMPLE 3 Manufacture of 1,4-butanediol The 108 g of the oxo product from Example 2 are hydrogenated with 400 ml of methanol, 100 ml of water and 40 g of Raney nickel (which has been carefully washed until neutral) for 5 hours at 280 atmospheres and a maximum temperature of 140° C. The catalyst is then filtered off, the solvent is stripped off and the butanediols are distilled at from 93° to 96°C/2mm. 105 g of diols are obtained, containing 60percent of 2-methyl-1,3-propanediol and 40percent of 1,4-butanediol, according to gas-chromatographic analysis of the diacetates. Patent; BASF Aktiengesellschaft; US4017550; (1977); (A) English View in Reaxys 7 : EXAMPLE 7 EXAMPLE 7 Into a 1 liter magnedrive stirred autoclave was placed 200 g. of dibutyl maleate (reagent grade, Matheson Coleman and Bell) and 30 g. of copper chromite hydrogenation catalyst (Calsicat PC 108-80, Mallinckrodt Chemical Works). The autoclave was charged and pressured to 2,900 psig with hydrogen. Heat was then applied and the temperature was slowly brought to approximately 100° C. at which point an exothermic reaction ensued at a temperature increase to 250° C. Cooling water was passed through the internal coils of the autoclave to control the temperature and not to permit it to exceed about 250° C. After about 5 to 10 minutes the internal temperature had returned to approximately 120° C. and the contents of the autoclave were again heated to a temperature of 200° C. and maintained at this temperature and a hydrogen partial pressure of 2,900 psig for a period of 2.5 hours at which time the reaction appeared to be complete. The contents of the autoclave were then cooled and the hydrogen partial pressure was vented to the atmosphere. The catalyst was separated from the liquid autoclave contents by filtration and the filter was washed with n-butanol. Distillation of the filtrate yielded 1,4-butanediol containing a trace of η-butyrolactone. Patent; Petro-Tex Chemical Corporation; US4032458; (1977); (A) English View in Reaxys 5 : EXAMPLE 5 EXAMPLE 5 Following the procedure of Example 1, 0.224 mole of 1,4-butanediol and 1.11 moles of water were reacted at 250° C with a nitrogen flow rate of 175 cc/min. This resulted in a complete conversion of the 1,4-butanediol and produced 0.209 moles of tetrahydrofuran. The STY of tetrahydrofuran was 452 grams per liter of catalyst per hour.

19/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Patent; E. I. Du Pont de Nemours and Company; US4124600; (1978); (A) English View in Reaxys IX : EXAMPLE IX EXAMPLE IX In the same manner Example VII, allyl alcohol (10 grams) benzene (40 grams), tributyl phosphine (50 grams) and dicobalt octa carbonyl (0.1 gram) are sealed in a 300 ml "Magnadrive" autoclave. The vessel is pressurized to 300 psig with a mixture of carbon monoxide and hydrogen (1:1 mole ratio), and the gas pressure is held constant while the hydroformylation reaction medium is maintained at a temperature of 100° C for 1 hour. The temperature is then increased to 200° C and maintained until the conversion of the 4-hydroxybutanal intermediate to 1,4butanediol is completed. Patent; Celanese Corporation; US4083882; (1978); (A) English View in Reaxys The diols and diphenols used preferentially are the following: Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 4,4'-(p-phenylenedisulphonyl)-dibutanol, 1,4-bis-(η-hydroxybutyl)-cyclohexane, 1,4-bis-(η-hydroxyethyl)-benzene, resorcinol, ... Patent; Rhone-Poulenc Industries; US4088670; (1978); (A) English View in Reaxys 34 : EXAMPLE 34 EXAMPLE 34 Operating with the procedure of Example 23, 1 millimol of 4-butyrolactone in toluene (1 ml of a 1 M soln.) is reacted with 0.75 millimols of Mg [AlH2 (OC6 H11)2 ]2..2THF in toluene (2.78 mls of a 0.27 M soln.) for 1 hr at room temperature. After having treated the reaction mixture according to the method of Example 23, the solution thus obtained is gaschromatographed. The yield of 1.4-butanediol, which is the product of the reduction of 4-butyrolactone, is quantitative. Patent; Anic S.p.A.; US4219491; (1980); (A) English View in Reaxys Examples of particularly preferred alkane diols are: ethane diol propane-1,2-diol propane-1,3-diol butane-1,3-diol butane-1,4-diol butane-2,3-diol pentane-1,5-diol hexane-1,6-diol octane-1,8-diol, and ... Patent; Chesebrough-Pond's USA Co., Division of Conopco, Inc.; US5196187; (1993); (A) English View in Reaxys Patent; UNILEVER PLC; UNILEVER N.V.; EP435483; (1991); (A2) English View in Reaxys 6 : Butane-1,4-diol/trimethylolpropane mixed acrylate EXAMPLE 6 Butane-1,4-diol/trimethylolpropane mixed acrylate

20/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

4.03 kg of trimethylolpropane, 2.7 kg of butane-1,4-diol and 10.8 kg of acrylic acid were esterified, as described in Example 1, in the presence of 22 g of phenothiazine, 1.3 kg of an acid ion exchanger and 3 l of a light benzine fraction which boils at 60°-70° C., under a water separator. 150 g of η-methylstyrene were added as a costabiliser to the esterification mixture. 14.5 kg of a stabilised mixed acrylate with an acid number of 25 were obtained. Patent; Bayer Aktiengesellschaft; US4053504; (1977); (A) English View in Reaxys Examples of particularly preferred alkane diols are: ... propane-1,3-diol butane-1,3-diol butane-1,4-diol butane-2,3-diol ... Patent; UNILEVER PLC; UNILEVER N.V.; EP458600; (1991); (A1) English View in Reaxys Illustrative examples of polyol starters are as follows: ... 2,2-dimethyl-1,3-propanediol (neopentyl glycol) 1,4-butanediol 2,3-butanediol ... Patent; ARCO Chemical Technology, L.P.; CPC INTERNATIONAL INC.; EP506424; (1992); (A1) English View in Reaxys Representative but non-exhaustive examples of various polyhydric alcohols which can be alkoxylated according to the present invention are ethylene glycol 1,2-propylene glycol 1,4-butanediol 1,6-hexanediol 1,10-decanediol 1,3-butylene glycol diethylene glycol monobutyl ether diethylene glycol monomethyl ether diethyl glycol monoethyl ether dipropylene glycol ... Patent; Vista Chemical Company; US4593142; (1986); (A) English View in Reaxys For certain products according to the present invention are preferred which in addition comprise one, two or more compounds of the group consisting of: glycerol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, ... Patent; SYMRISE GmbH and Co. KG; US2010/80761; (2010); (A1) English View in Reaxys Patent; Symrise GmbH and Co. KG; EP2168570; (2010); (A2) English

21/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

View in Reaxys Patent; SYMRISE GmbH and Co. KG; US2010/143267; (2010); (A1) English View in Reaxys Patent; Symrise GmbH and Co. KG; EP2193785; (2010); (A2) English View in Reaxys Patent; Dong, Guangbin; Grubbs, Robert H.; Teo, Peili; Wickens, Zach K.; US2012/172634; (2012); (A1) English View in Reaxys O

OH HO

Rx-ID: 9931633 View in Reaxys 13/281 Yield

Conditions & References With hydrogenchloride in water-d2, T= 270 °C , Kinetics, Further Variations: Reagents, Temperatures Nagai, Yasuharu; Matubayasi, Nobuyuki; Nakahara, Masaru; Bulletin of the Chemical Society of Japan; vol. 77; nb. 4; (2004); p. 691 - 697 View in Reaxys in water, T= 200 °C , pH= 5.7, Kinetics, Equilibrium constant, Further Variations: pH-values, Temperatures Hunter, Shawn E.; Ehrenberger, Carolyn E.; Savage, Phillip E.; Journal of Organic Chemistry; vol. 71; nb. 16; (2006); p. 6229 - 6239 View in Reaxys With carbon dioxide, water, T= 299.84 °C , Inert atmosphere, Equilibrium constant, Concentration Yamaguchi, Aritomo; Hiyoshi, Norihito; Sato, Osamu; Bando, Kyoko K.; Masuda, Yoshio; Shirai, Masayuki; Journal of Chemical and Engineering Data; vol. 54; nb. 9; (2009); p. 2666 - 2668 View in Reaxys With water, hydrogen, Time= 4h, T= 120 °C , p= 22502.3Torr , chemoselective reaction Zhang, Bin; Zhu, Yulei; Ding, Guoqiang; Zheng, Hongyan; Li, Yongwang; Green Chemistry; vol. 14; nb. 12; (2012); p. 3402 - 3409 View in Reaxys 1 : Example 1 Catalysts were evaluated in a four-barrel microflow unit that consists of 4 parallel Hastelloy HC 276 reactor (1 cm ID) . The reactors had an isothermal zone of 25 cm length and an internal volume of 41 mL . The reactors can be operated between 40 and 500°C under 0.15 to 14 MPa pressure. The liquid feed was fed to the reactor by 1000 mL ISCO 1000D pumps with a maximum flow rate of 100 mL/h. Hydrogen was applied to the reactor through a mass flow controller with a maximum flow rate of 5 NL/h. The catalysts were loaded as crushed (30-80 mesh) particles, as 3 g load, and diluted in an equal weight of SiC (0.2 mm) . The catalysts used in each reactor comprised an active carbon support (RX3, commercially available from Norrit) that was impregnated with 4 wtpercent of Re and 0.04 wtpercent of Pd. The initial catalyst reduction was carried at 275°C for 16 h under atmospheric pressure and 1 Nl/h flow of 50 vol percent H2 in N2 and, subsequently, for 2 h at 4 bara and a 1 NL/h flow of pure 100 percent H2. After reduction the temperature was lowered to 200°C, the hydrogen flow and pressure were set to target and the furan-containing liquid flow was admitted to the reactor. The reaction was then carried out over a wide operation window for some 900 h time on stream, which is abbreviated herein as TOS . The window covered temperatures of 130-200°C, pressures of 30-130bar, WHSV of 0.2-2/h, and feed concentrations of 12-30wpercent for furan and 27-34 wpercent for water with EtOH as balance. in ethanol, water, Time= 48h, T= 150 °C , p= 97509.8Torr , Catalytic behavior, Reagent/catalyst, Solvent, Temperature, Pressure Patent; SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.; SHELL OIL COMPANY; LANGE, Jean, Paul, Andre, Marie, Joseph, Ghislain; HAAN, Rene, Johan; (24 pag.); WO2017/1376; (2017); (A1) English View in Reaxys

22/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

O O

OH HO

Rx-ID: 23052162 View in Reaxys 14/281 Yield

Conditions & References 1a; 1b; 1c; 2; 3; 4; 5; 6; 7; 8; 9; 10; A; B : Example 1; Examples 2-10; Comparative Example A To a 300-cc autoclave was added 0.4 g of Degussa P25 TiO2 powder, 0.03 g of RuCl3.xH2O and 0.005 g of MoO3, for an overall composition of 2.5 wt percent Ru and 0.83 wt percent Mo. Then, 125 g of 20percent aqueous gamma butyrolactone (GBL) was added. The autoclave was heated to 250° C. and then pressurized to 2000 psig with H2 while stirring. The conditions were maintained for 45 minutes, after which it was rapidly cooled down. The products were analyzed by gas chromatography to determine the net molar production rate (STY) and selectivity. The STY was 63.6 mol/Kg of catalyst-hour, where mols=the sum of 1,4-butanediol (BDO) and tetrahydrofuran (THF). The selectivity was 0.56, measured by dividing the sum of the (BDO+THF) STY by the sum of (BDO+THF+byproducts) STY. In terms of the two desired products only, the molar proportion of THF was 87percent and the BDO was 13percent. This trial is called Example 1a. A repeat scouting test (Example 1b) gave an STY of 35.7 and a selectivity of 0.61. The reason for the lower STY was not determined. A third trial (Example 1 c) essentially confirmed the first set of results, with an STY of 58.1, a selectivity of 0.64, and a proportion for the two desired products of 82percent THF and 18percent BDO The scouting tests described in Example 1a were repeated except for changing the amount of Ru and Mo added. The results for Examples 1 through 10, including any duplicate tests and comparative examples with no added Mo, are summarized in Table 1 below. Comparative Example A The test described in Example 1 was repeated except for omitting the molybdenum. The first trial is called Comparative Example A and the second Comparative Example B. With hydrogen, Ru-Mo Catalysts on TiO2 Support, 2.5-5.00 wtpercent Ru, 0.00-3.33 wtpercent Mo in water, Time= 0.75h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; Campos, Daniel; US2004/122242; (2004); (A1) English View in Reaxys 11; 12; 13; 14; 15; 16a; 16b; 17; 18; 19; 20; 21a; 21b; 22; 23; 24; 25; C; D; E; F; G; H; I : Examples 11-25 and Comparative Examples C-F To a 300-cc autoclave was added 0.4 g of Degussa P25 TiO2 powder, 0.03 g of RuCl3.xH2O and 0.005 g of MoO3, for an overall composition of 2.5 wt percent Ru and 0.83 wt percent Mo. Then, 125 g of 20percent aqueous gamma butyrolactone (GBL) was added. The autoclave was heated to 250° C. and then pressurized to 2000 psig with H2 while stirring. The conditions were maintained for 45 minutes, after which it was rapidly cooled down. The products were analyzed by gas chromatography to determine the net molar production rate (STY) and selectivity. The STY was 63.6 mol/Kg of catalyst-hour, where mols=the sum of 1,4-butanediol (BDO) and tetrahydrofuran (THF). The selectivity was 0.56, measured by dividing the sum of the (BDO+THF) STY by the sum of (BDO+THF+byproducts) STY. In terms of the two desired products only, the molar proportion of THF was 87percent and the BDO was 13percent. This trial is called Example 1a. A repeat scouting test (Example 1b) gave an STY of 35.7 and a selectivity of 0.61. The reason for the lower STY was not determined. A third trial (Example 1 c) essentially confirmed the first set of results, with an STY of 58.1, a selectivity of 0.64, and a proportion for the two desired products of 82percent THF and 18percent BDO. The tests of Example 1 were repeated, except that 0.4 g of KBB carbon was used as the catalyst support in place of TiO2, and the catalyst composition changed as shown in Table 2. With hydrogen, Ru-Mo Catalysts on KBB carbon Support, 0.83-5.78 wtpercent Ru, 0.00-2.33 wtpercent Mo in water, Time= 0.75h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; Campos, Daniel; US2004/122242; (2004); (A1) English View in Reaxys 1a; 1b; 1c; 2; J; K : Comparative Examples with Re To a 300-cc autoclave was added 0.4 g of Degussa P25 TiO2 powder, 0.03 g of RuCl3.xH2O and 0.005 g of MoO3, for an overall composition of 2.5 wt percent Ru and 0.83 wt percent Mo. Then, 125 g of 20percent aqueous gamma butyrolactone (GBL) was added. The autoclave was heated to 250° C. and then pressurized to 2000 psig with H2 while stirring. The conditions were maintained for 45 minutes, after which it was rapidly cooled down. The products were analyzed by gas chromatography to determine the net molar production rate (STY) and selectivity. The STY was 63.6 mol/Kg of catalyst-hour, where mols=the sum of 1,4-butanediol (BDO) and tetrahydrofuran (THF). The selectivity was 0.56, measured by dividing the sum of the (BDO+THF) STY by the sum of (BDO+THF+byproducts) STY. In terms of the two desired products only, the molar proportion of THF was 87percent and the BDO was 13percent. This trial is called Example 1a. A repeat scouting test (Example 1b) gave an STY of 35.7 and a selectivity of 0.61. The reason for the lower STY was not determined. A third trial (Example 1 c) essentially confirmed the first set of results, with an STY of 58.1, a selectivity of 0.64, and a proportion for the two desired products of 82percent THF and 18percent BDO. The tests of Example 1 were repeated, except that Re2O7 was added to the comparative examples in the

23/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

amounts shown in place of MoO3 in order to compare the performance of Ru-Re and Ru-Mo. TiO2 was used as catalyst support. Results are given in Table 3. With hydrogen, Ru-Re-Mo Catalysts on TiO2 Support, 2.50 wtpercent Ru, 0.00-1.54 wtpercent Re, 0.00-1.67 wtpercent Mo in water, Time= 0.75h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; Campos, Daniel; US2004/122242; (2004); (A1) English View in Reaxys 21a; 21b; 29; 30; 31a; 31b; 32a; 32b; 33; 34 : Examples 29-34 To a 300-cc autoclave was added 0.4 g of Degussa P25 TiO2 powder, 0.03 g of RuCl3.xH2O and 0.005 g of MoO3, for an overall composition of 2.5 wt percent Ru and 0.83 wt percent Mo. Then, 125 g of 20percent aqueous gamma butyrolactone (GBL) was added. The autoclave was heated to 250° C. and then pressurized to 2000 psig with H2 while stirring. The conditions were maintained for 45 minutes, after which it was rapidly cooled down. The products were analyzed by gas chromatography to determine the net molar production rate (STY) and selectivity. The STY was 63.6 mol/Kg of catalyst-hour, where mols=the sum of 1,4-butanediol (BDO) and tetrahydrofuran (THF). The selectivity was 0.56, measured by dividing the sum of the (BDO+THF) STY by the sum of (BDO+THF+byproducts) STY. In terms of the two desired products only, the molar proportion of THF was 87percent and the BDO was 13percent. This trial is called Example 1a. A repeat scouting test (Example 1b) gave an STY of 35.7 and a selectivity of 0.61. The reason for the lower STY was not determined. A third trial (Example 1 c) essentially confirmed the first set of results, with an STY of 58.1, a selectivity of 0.64, and a proportion for the two desired products of 82percent THF and 18percent BDO. The tests of Example 1 were repeated, except that SnC2O4 was added to Examples 29-34 in addition to the amounts shown of Ru and Mo., and that 0.4 g of KBB carbon was used as catalyst support in place of TiO2. Results are given in Table 5. With hydrogen, Ru-Sn-Mo Catalysts on KBB carbon Support, 4.13 wtpercent Ru, 0.00-1.72 wtpercent Sn; 1.33 wtpercent Mo in water, Time= 0.75h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; Campos, Daniel; US2004/122242; (2004); (A1) English View in Reaxys 8; 26; 27; 28 : Examples 26-28 To a 300-cc autoclave was added 0.4 g of Degussa P25 TiO2 powder, 0.03 g of RuCl3.xH2O and 0.005 g of MoO3, for an overall composition of 2.5 wt percent Ru and 0.83 wt percent Mo. Then, 125 g of 20percent aqueous gamma butyrolactone (GBL) was added. The autoclave was heated to 250° C. and then pressurized to 2000 psig with H2 while stirring. The conditions were maintained for 45 minutes, after which it was rapidly cooled down. The products were analyzed by gas chromatography to determine the net molar production rate (STY) and selectivity. The STY was 63.6 mol/Kg of catalyst-hour, where mols=the sum of 1,4-butanediol (BDO) and tetrahydrofuran (THF). The selectivity was 0.56, measured by dividing the sum of the (BDO+THF) STY by the sum of (BDO+THF+byproducts) STY. In terms of the two desired products only, the molar proportion of THF was 87percent and the BDO was 13percent. This trial is called Example 1a. A repeat scouting test (Example 1b) gave an STY of 35.7 and a selectivity of 0.61. The reason for the lower STY was not determined. A third trial (Example 1 c) essentially confirmed the first set of results, with an STY of 58.1, a selectivity of 0.64, and a proportion for the two desired products of 82percent THF and 18percent BDO. The tests of Example 1 were repeated, except that SnC2O4 was added to Examples 26-28 in addition to the amounts shown of Ru and Mo. Results are given in Table 4. With hydrogen, Ru-Sn-Mo Catalysts on TiO2 Support, 5.00 wtpercent Ru, 0.00-0.72 wtpercent Sn, 1.67 wtpercent Mo in water, Time= 0.75h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; Campos, Daniel; US2004/122242; (2004); (A1) English View in Reaxys 1.c; 2; 2 With water, hydrogen, activated CuO/ZnO/Al2O3/Cu catalyst, T= 190 °C , p= 45004.5Torr , Conversion of starting material Patent; BASF Aktiengesellschaft; WO2005/44768; (2005); (A1) German View in Reaxys With hydrogen in 1,4-dioxane, Time= 12h, T= 170 °C , p= 37503.8Torr Wu, Jun; Gao, Guang; Sun, Peng; Long, Xiangdong; Li, Fuwei; ACS Catalysis; vol. 7; nb. 11; (2017); p. 7890 - 7901 View in Reaxys

24/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Rx-ID: 34777469 View in Reaxys 15/281 Yield 25 %, 5 %

Conditions & References With water, hydrogen, T= 160 °C , p= 22502.3Torr , Autoclave Pan, Tao; Deng, Jin; Xu, Qing; Zuo, Yong; Guo, Qing-Xiang; Fu, Yao; ChemSusChem; vol. 6; nb. 1; (2013); p. 47 - 50 View in Reaxys

27.9 %Chromat., 14.2 %Chromat., 11 %Chromat.

9 :Examples 1 to 20 A number of catalysts were evaluated in a 16-reactor testing unit that can operate at up to 80 bar and 500°C. The testing unit can be fed with up to 5 gases (hydrogen, CO, N2, argon and air) and two liquids. The unit allowed for on-line GC analysis of gases and semi-automated off FontWeight="Bold" FontSize="10" line GC analysis of the liquid product. Gas and liquid product yields were determined in reference to a gas standard (He) and a liquid standard (diethylene-glycol diethyl ether) that were fed together with the gas and liquid feed and were selectively collected in the gas and liquid samples, respectively. The reactor consisted of SS316 tubes of 4.6 mm ID and 35.5 cm long, of which the central 10 cm length is isothermal. The reactor tubes were loaded with about 1 mL of catalyst, centered in the middle of the reactor while the remaining upper and lower void was filled with inert material such as SiC particles and/or porous SS316 cyclinders . The catalysts were prepared by incipient wetness impregnation of the support with solutions of the following salts: Pd (NH3) 4 (N03) 2 , Pt (NH3) 4 (N03) 2 , HRe04 , Co (N03) 2 · 6H20, Ru(N03)3NO. The solutions were prepared with the concentration required to achieve the targeted metal loading. The catalysts were dried at 120°c for 2 h in air and for half an hour at 225°C temperature. The catalysts supports consisted 30-80 mesh powders of monoclinic zirconia, anatase-rich titania (P25 from Degussa) and active carbon (RX-3 from Norit) . Their properties are the following: Table 1 - Support Properties The catalysts were dried and reduced for 1 h at 75°C, 4 h 120°C and more than 4 h at 275°C under a 30percent H2/70percent N2 flow of GHSV=625 NL/L/h at nearly atmospheric pressure. Subsequently, the temperature was lowered to 120°C, the pressure was raised to 50 atmosphere and the gas flow set to about GHSV=280 Nl/L/h and 100percent H2 to be ready for start-up. The gas feed consisted of a mixture of 10percent He and 90percent H2 and was fed at a rate of about 280 Nl per liter catalyst bed per hour. The liquid feed consisted of a mixture of 24 wpercent furan, 21 wpercent water, 50 wpercent ethanol and 4 wpercent standard. The liquid feed was introduced at a rate of about 0.8 litre per litre catalyst bed per hour. The run was carried out at a pressure of 50 bars. The temperature was ramped from 140 to 200°C by steps of 20°C and back to 160°C. The run lasted for 200-250 hours in total . The average yields measured at 160°C are reported in tables 2 and 3. The yields are expressed as fraction of the carbon of furan that is converted into the desired concerned. The yield may occasionally add up to slightly more than 100Cpercent as results of experimental inaccuracies. As shown in these tables, Pd-doped catalysts show a lower co-production of NBA than the correpsonding non-Pd catalysts supported on C. The same is observed for the catalysts supported in Zr02 or Ti02: The various Pd-doped catalysts show lower NBA co-production than the non-Pd doped catalysts, though these catalysts are more selective for THF and much less for BDO. In general, the NBA yields are below 5 Cpercent for Pd- based catalysts and >10 Cpercent for Co, Pt, and Ru-based catalysts . It should be clear to the skilled person that total yields above 100percent can be attributed to experimental errors . Table 2 - Pd Catalysts Operating at 160°C Table 3 - Non-Pd Based Catalysts Operating at 160°C When comparing the different metals combined with rhenium on each support, it can clearly be seen that the inventive catalysts provide good overall yields and a desirably low NBA/BDO ratio. With Co,Re/C, water, hydrogen in ethanol, T= 160 °C , p= 37503.8Torr , Reagent/catalyst Patent; SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.; SHELL OIL COMPANY; LANGE, Jean, Paul, Andre, Marie, Joseph, Gishlain; WADMAN, Sipke, Hidde; (14 pag.); WO2016/87508; (2016); (A1) English View in Reaxys

66 %Chromat., 12.1 %Chromat., 15.6 %Chromat.

15 :Examples 1 to 20 A number of catalysts were evaluated in a 16-reactor testing unit that can operate at up to 80 bar and 500°C. The testing unit can be fed with up to 5 gases (hydrogen, CO, N2, argon and air) and two liquids. The unit allowed for on-line GC analysis of gases and semi-automated off FontWeight="Bold" FontSize="10" line GC analysis of the liquid product. Gas and liquid product yields were determined in reference to a gas standard (He) and a liquid standard (diethylene-glycol diethyl ether) that were fed together with the gas and liquid feed and were selectively collected in the gas and liquid samples, respectively. The reactor consisted of SS316 tubes of 4.6 mm ID and 35.5 cm long, of which the central 10 cm length is isothermal. The reactor tubes were loaded with about 1 mL of catalyst, centered in the middle of the reactor while the remaining upper and lower void was filled with inert material such as SiC particles and/or porous SS316 cyclinders . The catalysts were prepared by incipient wetness impregnation of the support with solutions of the following salts: Pd (NH3) 4 (N03) 2 , Pt (NH3) 4 (N03) 2 , HRe04 , Co (N03) 2 · 6H20, Ru(N03)3NO. The solutions were prepared with the concentration required to achieve the targeted metal loading. The catalysts were dried at 120°c for 2 h in air and for half an hour at 225°C temperature. The catalysts supports consisted 30-80 mesh powders of monoclinic zirconia, anatase-rich titania (P25 from Degussa) and active carbon (RX-3 from Norit) . Their properties are the following: Table 1 - Support Properties The catalysts were dried and reduced for 1 h at 75°C, 4 h 120°C and more than 4 h at 275°C under a 30percent H2/70percent N2 flow of GHSV=625 NL/L/h at nearly atmospheric pressure. Subsequently, the temperature was lowered to 120°C, the pressure was raised to 50 atmosphere and the gas flow set to about

25/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

GHSV=280 Nl/L/h and 100percent H2 to be ready for start-up. The gas feed consisted of a mixture of 10percent He and 90percent H2 and was fed at a rate of about 280 Nl per liter catalyst bed per hour. The liquid feed consisted of a mixture of 24 wpercent furan, 21 wpercent water, 50 wpercent ethanol and 4 wpercent standard. The liquid feed was introduced at a rate of about 0.8 litre per litre catalyst bed per hour. The run was carried out at a pressure of 50 bars. The temperature was ramped from 140 to 200°C by steps of 20°C and back to 160°C. The run lasted for 200-250 hours in total . The average yields measured at 160°C are reported in tables 2 and 3. The yields are expressed as fraction of the carbon of furan that is converted into the desired concerned. The yield may occasionally add up to slightly more than 100Cpercent as results of experimental inaccuracies. As shown in these tables, Pd-doped catalysts show a lower co-production of NBA than the correpsonding non-Pd catalysts supported on C. The same is observed for the catalysts supported in Zr02 or Ti02: The various Pd-doped catalysts show lower NBA co-production than the non-Pd doped catalysts, though these catalysts are more selective for THF and much less for BDO. In general, the NBA yields are below 5 Cpercent for Pd- based catalysts and >10 Cpercent for Co, Pt, and Ru-based catalysts . It should be clear to the skilled person that total yields above 100percent can be attributed to experimental errors . Table 2 - Pd Catalysts Operating at 160°C Table 3 - Non-Pd Based Catalysts Operating at 160°C When comparing the different metals combined with rhenium on each support, it can clearly be seen that the inventive catalysts provide good overall yields and a desirably low NBA/BDO ratio. With Ru,Re/C, water, hydrogen in ethanol, T= 160 °C , p= 37503.8Torr , Reagent/catalyst Patent; SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.; SHELL OIL COMPANY; LANGE, Jean, Paul, Andre, Marie, Joseph, Gishlain; WADMAN, Sipke, Hidde; (14 pag.); WO2016/87508; (2016); (A1) English View in Reaxys An Aspen simulation of the process shown in Figureand described above was carried out using an appropriate data deck. In this case a solvent system of 1:1:1 NBA:1,4—BDO:THF was used in a process for the production of 1,4—BDO and THF from furan. In this process, furancontacted with hydrogen and water in a reactor in the presence of a catalytic composition and a portion of the furan was converted to 1,4—BDO, NBA and THF. The resultant reactor product stream was subjected to gas liquid separation such that stream 4 had the compositionshown in Table 1.The separation set up shown in Figure 1 was applied and the resultant isolated product stream compositions are also shown in Table 1.The results demonstrate a facile separation system in which the three products can each be isolatedseparately in a pure stream. Only a portion of the THF, 1,4—BDO and NBA present need to be isolated, with the rest recycled and re—used. This allows a much lesscomplex set up and a much reduced distillation duty for this system compared with a process in which a solvent not selected from NBA, THF and/or 1,4—BDO is used. With water, hydrogen Patent; SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.; SHELL OIL COMPANY; WADMAN, Sipke, Hidde; LANGE, Jean Paul, Andre, Marie, Joseph, Ghislain; (19 pag.); WO2017/42289; (2017); (A1) English View in Reaxys

OH HO

Rx-ID: 42756510 View in Reaxys 16/281 Yield

Conditions & References With hydrogen in ethanol, T= 30 °C , Reagent/catalyst Huang, Gang; Yang, Qihao; Xu, Qiang; Yu, Shu-Hong; Jiang, Hai-Long; Angewandte Chemie - International Edition; vol. 55; nb. 26; (2016); p. 7379 - 7383; Angew. Chem.; vol. 128; nb. 26; (2016); p. 7505 - 7509,5 View in Reaxys With hydrogen in water, T= 50 °C Yin, Dongdong; Li, Chuang; Ren, Hangxing; Shekhah, Osama; Liu, Jinxuan; Liang, Changhai; RSC Advances; vol. 7; nb. 3; (2017); p. 1626 - 1633 View in Reaxys Rx-ID: 46862930 View in Reaxys 17/281

Yield

Conditions & References With hydrogen in water, Time= 24h, T= 200 °C , p= 60006Torr , Autoclave, Reagent/catalyst Said, Achraf; Da Silva Perez, Denilson; Perret, Noémie; Pinel, Catherine; Besson, Michèle; ChemCatChem; vol. 9; nb. 14; (2017); p. 2768 - 2783

26/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

View in Reaxys Rx-ID: 46862931 View in Reaxys 18/281 Yield

Conditions & References With hydrogen in water, Time= 24h, T= 200 °C , p= 60006Torr , Autoclave Said, Achraf; Da Silva Perez, Denilson; Perret, Noémie; Pinel, Catherine; Besson, Michèle; ChemCatChem; vol. 9; nb. 14; (2017); p. 2768 - 2783 View in Reaxys

OH O

Rx-ID: 46862932 View in Reaxys 19/281 Yield

Conditions & References With hydrogen in water, Time= 25h, T= 200 °C , p= 60006Torr , Autoclave Said, Achraf; Da Silva Perez, Denilson; Perret, Noémie; Pinel, Catherine; Besson, Michèle; ChemCatChem; vol. 9; nb. 14; (2017); p. 2768 - 2783 View in Reaxys

OH HO

OH OH

HO OH

OH H

Rx-ID: 46862933 View in Reaxys 20/281 Yield

Conditions & References With hydrogen in water, Time= 31h, T= 200 °C , p= 60006Torr , Autoclave Said, Achraf; Da Silva Perez, Denilson; Perret, Noémie; Pinel, Catherine; Besson, Michèle; ChemCatChem; vol. 9; nb. 14; (2017); p. 2768 - 2783 View in Reaxys Rx-ID: 46862934 View in Reaxys 21/281

Yield

Conditions & References With hydrogen in water, Time= 31h, T= 200 °C , p= 60006Torr , Autoclave, Pressure, Reagent/catalyst Said, Achraf; Da Silva Perez, Denilson; Perret, Noémie; Pinel, Catherine; Besson, Michèle; ChemCatChem; vol. 9; nb. 14; (2017); p. 2768 - 2783 View in Reaxys

27/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

OH OH

Rx-ID: 46862936 View in Reaxys 22/281 Yield

OH OH

Rx-ID: 46862937 View in Reaxys 23/281 Yield

Conditions & References With hydrogen in water, Time= 31h, T= 200 °C , p= 22502.3Torr , Autoclave, Pressure Said, Achraf; Da Silva Perez, Denilson; Perret, Noémie; Pinel, Catherine; Besson, Michèle; ChemCatChem; vol. 9; nb. 14; (2017); p. 2768 - 2783 View in Reaxys

H OH HO

Rx-ID: 46862939 View in Reaxys 24/281 Yield

O HO

OH HO

Rx-ID: 47136020 View in Reaxys 25/281 Yield

Conditions & References With 5% active carbon-supported ruthenium, hydrogen in 1,4-dioxane, Time= 24h, T= 100 °C , p= 25502.6Torr , Autoclave Huang, Zhiwei; Barnett, Kevin J.; Chada, Joseph P.; Brentzel, Zachary J.; Xu, Zhuoran; Dumesic, James A.; Huber, George W.; ACS Catalysis; vol. 7; nb. 12; (2017); p. 8429 - 8440 View in Reaxys

O O

HO O

Rx-ID: 47136021 View in Reaxys 26/281

28/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Yield

Conditions & References With hydrogen, Time= 24h, T= 100 °C , p= 25502.6Torr , Autoclave, Reagent/catalyst, Solvent Huang, Zhiwei; Barnett, Kevin J.; Chada, Joseph P.; Brentzel, Zachary J.; Xu, Zhuoran; Dumesic, James A.; Huber, George W.; ACS Catalysis; vol. 7; nb. 12; (2017); p. 8429 - 8440 View in Reaxys O

OH HO

Rx-ID: 47136022 View in Reaxys 27/281 Yield

Conditions & References With hydrogen in 1,4-dioxane, Time= 0.5h, T= 100 °C , p= 25502.6Torr , Reagent/catalyst, Solvent Huang, Zhiwei; Barnett, Kevin J.; Chada, Joseph P.; Brentzel, Zachary J.; Xu, Zhuoran; Dumesic, James A.; Huber, George W.; ACS Catalysis; vol. 7; nb. 12; (2017); p. 8429 - 8440 View in Reaxys O

OH OH

Rx-ID: 236235 View in Reaxys 28/281 Yield 83 %

Conditions & References With hydrogen in 1,4-dioxane, Time= 48h, T= 159.84 °C , p= 112511Torr , Autoclave, Catalytic behavior, Reagent/catalyst, Pressure, Time, Temperature Takeda, Yasuyuki; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi; Catalysis Science and Technology; vol. 6; nb. 14; (2016); p. 5668 - 5683 View in Reaxys With ruthenium, T= 150 - 200 °C , p= 529566 - 698732Torr , Hydrogenation Carnahan et al.; Journal of the American Chemical Society; vol. 77; (1955); p. 3766 View in Reaxys 14.2 : 14-2) Production of 1,4-Butanediol Succinic acid was hydrogenated with hydrogen in water in the presence of the catalyst comprising palladium, silver and rhenium metals on the carbon support under pressure of 2500 psig at 160° C., a GHSV of 2760 hr−1 and a LHSV of 0.55 hr−1 to yield 1,4butanediol. With hydrogen, T= 160 °C , p= 130050Torr Patent; Lee, Han Won; Yang, Young Lyeol; Kim, So Young; Shin, Yong Uk; Chang, Jin Sook; Um, Hye Won; Goh, Young Hyoung; Jhon, Sung Hoo; US2014/296466; (2014); (A1) English View in Reaxys With [Ru(1,1,1-tris(diphenylphosphinomethyl)ethane)(trimethylenemethane)], hydrogen in 1,4-dioxane, Time= 24h, T= 195 °C , p= 37503.8Torr , Autoclave, Inert atmosphere Vom Stein, Thorsten; Meuresch, Markus; Limper, Dominik; Schmitz, Marc; Hölscher, Markus; Coetzee, Jacorien; ColeHamilton, David J.; Klankermayer, Jürgen; Leitner, Walter; Journal of the American Chemical Society; vol. 136; nb. 38; (2014); p. 13217 - 13225 View in Reaxys With lithium aluminium tetrahydride in tetrahydrofuran, T= 0 - 20 °C Pea-Lpez, Miguel; Neumann, Helfried; Beller, Matthias; ChemCatChem; vol. 7; nb. 5; (2015); p. 865 - 871 View in Reaxys

41 %Chromat.

With tin(II) trifluoromethanesulfonate, [Ru(acetylacetonate)3], hydrogen, [2-((diphenylphospino)methyl)-2-methyl-1,3-propanediyl]bis[diphenylphosphine] in water, toluene, Time= 48h, T= 160 °C , p= 45004.5Torr , Autoclave

29/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Cui, Xinjiang; Li, Yuehui; Topf, Christoph; Junge, Kathrin; Beller, Matthias; Angewandte Chemie - International Edition; vol. 54; nb. 36; (2015); p. 10596 - 10599; Angew. Chem.; vol. 127; (2015); p. 10742 - 10745,4 View in Reaxys 90.4 %Chromat.

17A : Example 17A (Synthesis of 1,4-butanediol from succinic acid) In an autoclave equipped with a 50 ml glass inner tube,0.60 g (5.0 mmol) of succinic acid, 0.10 g (0.10 mmol) of 1.0 mol / l aqueous sodium hydroxide solution, the residue obtained in Example 17 (Zr - Ru - Re / AC catalyst (1) Was added, and the volume was made up with water so that the succinic acid amounted to 15percent. The mixture was pressurized to 8 MPa with hydrogen gas at room temperature and reacted at 120 ° C. for 18 hours with stirring. After completion of the reaction, the obtained reaction solution was cooled to room temperature, and then filtered with a syringe equipped with a membrane filter (0.45 μm). Analysis of the obtained filtrate by gas chromatography revealed that the conversion of succinic acid was 100percent (confirmed by esterification with trimethylsilyldiazomethane), the yield of 1,4-butanediol was 90.4percent, the same selection The yield was 90.4percent, the yield of 1-butanol was 9.1percent, the selectivity was 9.1percent, and η-butyrolactone was not observed With hydrogen, sodium hydroxide in water, Time= 18h, T= 120 °C , p= 60006Torr , Autoclave, Reagent/catalyst Patent; UBE INDUSTRIES LIMITED; YOSHII, KIYOTAKA; YAMADA, ATSUSHI; WADA, NOBUHIRO; (27 pag.); JP2015/74619; (2015); (A) Japanese View in Reaxys O

O O

OH OH

Rx-ID: 23662962 View in Reaxys 29/281 Yield 0.2 %, 3.1 %, 89 %, 7.6 %

Conditions & References With hydrogen in 1,4-dioxane, Time= 96h, T= 139.84 °C , p= 60006Torr , Autoclave, Catalytic behavior, Reagent/catalyst, Time, Temperature, Overall yield = 100 percent Takeda, Yasuyuki; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi; Catalysis Science and Technology; vol. 6; nb. 14; (2016); p. 5668 - 5683 View in Reaxys

2.95 - 5.79 %, 0.00 6.79 %, 81.5 - 88.7 %, 3.35 14.1 %

7 :The catalyst of Example 7 is made by the same procedure as the catalyst of Example 1(a) except that the amounts of palladium and rhenium are adjusted to give a catalyst containing 1.0 wt percent palladium and 3.0 wt percent rhenium. Table 7 shows the results of the second stage hydrogenation of succinic acid to 1,4-Butanediol (BDO). In this reaction the first stage reaction wherein maleic acid was converted to succinic acid was conducted using a standard carbon catalyst, such as Carbon Catalyst B, and the second stage reaction was conducted using a catalyst comprising 1.0percent Pd and 3percent Re on a 1/16 rutile titanium dioxide support. With hydrogen, 1.0percent Pd/ 3.0percent Re on Rutile TiO2, Time= 21 - 237h, T= 164 - 185 °C , Product distribution / selectivity Patent; Bhattacharyya, Alakananda; Manila, Maynard D.; US2006/4212; (2006); (A1) English View in Reaxys

3.38 - 8.83 %, 0.00 25.74 %, 64.14 89.15 %, 2.86 - 6.28 %

6 :The catalyst of Example 6 is made by the same procedure as the catalyst of Example 1(a) except that palladium is not used and the amount of rhenium is adjusted to give a catalyst containing and 5.0 wt percent rhenium. Table 6 shows the results of the second stage hydrogenation of succinic acid to 1,4-Butanediol (BDO). In this reaction the first stage reaction wherein maleic acid was converted to succinic acid was conducted using a standard carbon catalyst, such as Carbon Catalyst B, and the second stage reaction was conducted using a catalyst comprising 0percent Pd and 5percent Re on a 1/16 rutile titanium dioxide support. With hydrogen, 0percent Pd/5.0percent Re on Rutile TiO2, Time= 90 - 825h, T= 170 - 185 °C , Product distribution / selectivity Patent; Bhattacharyya, Alakananda; Manila, Maynard D.; US2006/4212; (2006); (A1) English View in Reaxys

12.52 19.39 %, 4.72 - 13.82 %, 62.45 71.99 %,

8 :(A) Rutile TiO2 Support (94percent Rutile, 6percent Anatase, 1/16) rutile titanium dioxide 93.0 g (dry) (B) Pd/HNO3 Impregnation Solution 9.48 g of Pd (NO3)2 Solution (21.1percent Pd) 10.07 g of concentrated nitric acid (70 wt percent) (C) Re/HNO3 Impregnation Solution 9.09 g HReO4 Solution (54.98percent Re) 10.46 g of concentrated nitric acid (70 wt percent) Preparation Procedure: Step 1: The rutile TiO2 support (A) is gradually impregnated with solution (B) and allowed to stand for 1 hour. The material is then dried in an oven at 130° C. for 2 hours. Step 2: The palladium-impregnated TiO2 rutile support (A) from Step 1

30/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

4.14 - 4.66 %

is gradually impregnated with solution (C) and allowed to stand for 1 hour. The material is then dried in an oven at 130° C. for 2 hours. The results for the stage 1 reaction converting maleic acid to succinic acid are shown in Table 8(a), in which a sample was taken at 139 hours. The results for the second stage reaction converting succinic acid to BDO, THF, and GBL or mixtures thereof over several hours is shown in Table 8(b). Table 8a shows the results of the first stage hydrogenation of maleic acid to succinic acid (SAC) using a catalyst comprising 2.0percent Pd and 5.0percent Re on a 1/16 rutile titanium dioxide support. Table 8b shows the results of the second stage hydrogenation of succinic acid to 1,4-Butanediol (BDO) using a catalyst comprising 2.0percent Pd and 5.0percent Re on a 1/16 rutile titanium dioxide support. With hydrogen, 2.0percent Pd/ 5.0percent Re on Rutile TiO2, Time= 68 - 281h, T= 165 °C , Product distribution / selectivity Patent; Bhattacharyya, Alakananda; Manila, Maynard D.; US2006/4212; (2006); (A1) English View in Reaxys

1.84 - 14.75 %, 0.12 66.42 %, 18.8 - 78.24 %, 0.89 16.02 %

5 : 0.5percent Pd/5.0percent Re on 1/16" Rutile Titanium Dioxide Support (94percent Rutile/6percent Anatase Crystalline Phase The Example 5(a) is made by the same procedure as the catalyst of Example 1(a) except that the amounts of palladium and rhenium are adjusted to give a catalyst containing 0.5 wt percent palladium and 5.0 wt percent rhenium. Example 5(b) 0.5percent Pd/5.0percent Re on 1/16 Rutile Titanium Dioxide Support (98percent Rutile/2percent Anatase Crystalline Phase) The catalyst of Example 5(b) is made by the procedure of Example 5(a) except that a 1/16 diameter rutile TiO2 support (98percent Rutile/ 2percent Anatase Crystalline Phase) is used. Table 5 shows the results of the second stage hydrogenation of succinic acid to 1,4Butanediol (BDO). The first stage reaction (not shown) wherein maleic acid was converted to succinic acid was conducted using a catalyst comprising 0.5percent palladium on a rutile TiO2 support, such as the catalyst of Example 2, and the second stage reaction was conducted using a catalyst made by the process of Example 5 comprising 0.5percent Pd and 5percent Re on a 1/16 rutile titanium dioxide support. With hydrogen, 0.5percent Pd/5.0percent Re on Rutile TiO2, Time= 112 - 495h, T= 165 - 185 °C , Product distribution / selectivity Patent; Bhattacharyya, Alakananda; Manila, Maynard D.; US2006/4212; (2006); (A1) English View in Reaxys

12.98 39.38 %, 0 13.72 %, 14.44 77.13 %, 4.21 - 40.85 %

4 : 2.0percent Pd/5.0percent Re on 1/16" Rutile Titanium Dioxide Support (94percent Rutile/6percent Anatase Crystalline Phase) The catalyst of Example 4 is made by the same procedure as the catalyst of Example 1(a) except that the amounts of palladium and rhenium are adjusted to give a catalyst containing 2.0 wt percent palladium and 5.0 wt percent rhenium. Table 4 shows the results of the second stage hydrogenation of succinic acid to 1,4-Butanediol (BDO). The first stage reaction (not shown) wherein maleic acid was converted to succinic acid was conducted using a catalyst comprising 0.5percent palladium on a rutile TiO2 support, such as the catalyst of Example 2, and the second stage reaction was conducted using a catalyst made by the process of Example 4, comprising 2.0percent Pd and 5percent Re on a 1/16 rutile titanium dioxide support. With hydrogen, 2.0percent Pd/5.0percent Re on Rutile TiO2, Time= 90 - 945h, T= 165 - 188 °C , Product distribution / selectivity Patent; Bhattacharyya, Alakananda; Manila, Maynard D.; US2006/4212; (2006); (A1) English View in Reaxys O

O HO

OH OH

Rx-ID: 29114781 View in Reaxys 30/281 Yield 5 %, 95 %

Conditions & References F3 : Reduction of Carboxylic Acid A stirrer, an iridium(I)complex (Compound 2n) (10.9 mg, 0.01 mmol), sodium hydride (1.4 mg, 0.06 mmol), and succinic acid (118.1 mg, 1 mmol) were placed in a dried fluororesin tube (30 mL). The tube containing the mixture was rapidly inserted into an autoclave. Thereafter, dehydrated toluene (2 mL) was added to the mixture in the tube while introducing argon gas into the autoclave; then, the autoclave was rapidly hermetically sealed. Hydrogen gas was introduced into the autoclave from a hydrogen compressed gas cylinder connected via a stainless-steel pipe, thereby substituting the inside of the autoclave with hydrogen gas. More specifically, 1-MPa hydrogen gas pressure was applied inside the autoclave, and then the hydrogen gas pressure was removed through a leak valve. This operation was repeated three times. Finally, the hydrogen gas pressure inside the autoclave was set to 6 MPa, and the mixture was stirred for 18 hours using a constant-temperature bath at 180° C. (0362) After the reaction was

31/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

completed, the autoclave was cooled to substantially room temperature by being immersed in an icy bath. Then, the leak valve of the autoclave was opened and the hydrogen gas inside the autoclave was released into the air. Subsequently, the tube was taken out of the autoclave, thereby obtaining a reaction product (solution). An internal standard substance (mesitylene) was added to the solution. Based on the integration value of the hydrogen atom amount of the internal standard substance, the yield of the reaction product was calculated. 1,4-butane diol and η-butyrolactone were obtained at yields of 95percent and 5percent, respectively. With C36H54IrN2P2 (1+)*C24H20B(1-), hydrogen, sodium hydride in toluene, Time= 18h, T= 180 °C , p= 7500.75 - 45004.5Torr , Autoclave, Sealed tube, Reagent/catalyst, Temperature, Pressure Patent; National University Corporation Nagoya University; Saito, Susumu; Noyori, Ryoji; Miura, Takashi; Naruto, Masayuki; Iida, Kazuki; Takada, Yuki; Toda, Katsuaki; Nimura, Sota; Agrawal, Santosh; Lee, Sunkook; (42 pag.); US9463451; (2016); (B2) English View in Reaxys 64.7 %

2.3. Hydrogenation of succinic acid to BDO BDOHydrogenation of succinic acid was conducted in a high pressureautoclave reactor of 200 ml equipped with an electrically heatedjacket and an agitator with a magnetic driver. Before the experi-ment, the reactor was purged with N2gas to remove air. The reactorwas loaded with 50 ml of 1,4-dioxane (an inert aprotic solvent) and0.25 g of succinic acid. Then, 0.1 g of catalyst reduced at 500C for4 h was charged in the reaction vessel. After additional purging withN2gas, the reactor was heated to 200C and H2gas was injected to80 bar. The reaction was done at 700 rpm for 5 h. After the reaction,the aqueous samples taken from the reactor were analyzed witha gas chromatograph equipped with a capillary column (DB-624)and a flame ionization detector (FID). Catalytic performance wasevaluated by the following equations. Stage 1: in 1,4-dioxane, Time= 4h, T= 500 °C Stage 2: With hydrogen in 1,4-dioxane, Time= 5h, T= 200 °C , p= 60006Torr , Catalytic behavior, Reagent/catalyst Kang, Ki Hyuk; Han, Seung Ju; Lee, Jong Won; Kim, Tae Hyeop; Song, In Kyu; Applied Catalysis A: General; vol. 524; (2016); p. 206 - 213 View in Reaxys With hydrogen in ethanol, water, Time= 24h, T= 100 °C , p= 7500.75Torr Luque, Rafael; Clark, James H.; Yoshida, Kenta; Gai, Pratibha L.; Chemical Communications; nb. 35; (2009); p. 5305 5307 View in Reaxys With hydrogen in ethanol, water, Time= 24h, T= 100 °C , p= 7500.75Torr Luque, Rafael; Clark, James H.; Catalysis Communications; vol. 11; nb. 10; (2010); p. 928 - 931 View in Reaxys With hydrogen in water, T= 160 °C , p= 112511Torr , Reagent/catalyst Corbel-Demailly, Louis; Ly, Bao-Khanh; Minh, Doan-Pham; Tapin, Benoit; Especel, Catherine; Epron, Florence; Cabiac, Amandine; Guillon, Emmanuelle; Besson, Michèle; Pinel, Catherine; ChemSusChem; vol. 6; nb. 12; (2013); p. 2388 2395 View in Reaxys Hydrogenation of succinic acid to BDO Liquid-phase hydrogenation of succinic acid to BDO was con-ducted in a stainless steel autoclave reactor with a volume of200 ml. Prior to the reaction, the catalysts were reduced using anex situ reduction system at 500C for 4 h with a heating rate of5C/min under 5percent H2/N2flow (50 ml/min). In order to avoid airexposure, reduced catalyst (0.1 g), succinic acid (0.25 g), and 1,4-dioxane (50 ml, an inert aprotic solvent) were charged into thereactor in an argon atmosphere glove box. The closed reactor filledwith argon was then mounted to the autoclave chamber as quicklyas possible. After purging the reactor with nitrogen, it was pressur-ized up to 50 bar using hydrogen. The sealed autoclave was heatedto the reaction temperature (200C), and then pressurized up to80 bar using hydrogen. Catalytic reaction was conducted with con-stant stirring (700 rpm) for 7 h. After the reaction, the reactor wascooled to room temperature and depressurized. Reaction productswere analyzed with a gas chromatograph (Younglin, ACME-6100)equipped with a flame ionization detector (FID). Conversion ofsuccinic acid, selectivity for product, and yield for product werecalculated according to the following equations. With hydrogen in 1,4-dioxane, Time= 7h, T= 200 °C , p= 60006Torr , Inert atmosphere, Autoclave, Glovebox

32/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Kang, Ki Hyuk; Hong, Ung Gi; Bang, Yongju; Choi, Jung Ho; Kim, Jeong Kwon; Lee, Jong Kwon; Han, Seung Ju; Song, In Kyu; Applied Catalysis A: General; vol. 490; (2015); p. 153 - 162 View in Reaxys With hydrogen in 1,4-dioxane, Time= 30h, T= 240 °C , p= 22502.3 - 45004.5Torr , Autoclave You, Chenjia; Zhang, Chi; Chen, Lifang; Qi, Zhiwen; Applied Organometallic Chemistry; vol. 29; nb. 10; (2015); p. 653 660 View in Reaxys 61 %Chromat., 23 %Chromat.

With cobalt(II) tetrafluoroborate hexahydrate, hydrogen, [2-((diphenylphospino)methyl)-2-methyl-1,3-propanediyl]bis[diphenylphosphine] in tetrahydrofuran, Time= 22h, T= 100 °C , p= 60006Torr Korstanje, Ties J.; Van Der Vlugt, Jarl Ivar; Elsevier, Cornelis J.; De Bruin, Bas; Science; vol. 350; nb. 6258; (2015); p. 298 - 302 View in Reaxys 2.3. Hydrogenation of succinic acid to BDO Liquid-phase hydrogenation of succinic acid to BDO was conducted in a stainless steel autoclave reactor with a volume of 200 ml. Prior to the reaction, the catalysts were reduced using an ex situ reduction system at 500 °C for 4 h with a heating rate of 5 °C/min under 5percent H2/N2 flow (50 ml/min). In order to avoid air exposure, reduced catalyst (0.1 g), succinic acid (0.25 g), and 1,4-dioxane (50 ml, an inert aprotic solvent) were charged into the reactor in an argon atmosphere glove box. The closed reactor filled with argon was then mounted to the autoclave chamber as quickly as possible. After purging the reactor with nitrogen, it was pressurized up to 50 bar using hydrogen. The sealed autoclave was heated to the reaction temperature (200 °C), and then pressurized up to 80 bar using hydrogen. Catalytic reaction was conducted with constant stirring (700 rpm) for 7 h. After the reaction, the reactor was cooled to room temperature and depressurized. Reaction products were analyzed with a gas chromatograph (Younglin, ACME-6100) equipped with a flame ionization detector (FID). With hydrogen in 1,4-dioxane, Time= 7h, T= 200 °C , p= 60006Torr , Glovebox, Inert atmosphere, Autoclave, Catalytic behavior Kang, Ki Hyuk; Hong, Ung Gi; Bang, Yongju; Choi, Jung Ho; Kim, Jeong Kwon; Lee, Jong Kwon; Han, Seung Ju; Song, In Kyu; Applied Catalysis A: General; vol. 490; nb. 1; (2015); p. 153 - 162 View in Reaxys With hydrogen in 1,4-dioxane, Time= 4h, T= 99.84 °C , p= 60006Torr , Autoclave, Catalytic behavior, Overall yield = 2.0 percent Takeda, Yasuyuki; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi; Catalysis Science and Technology; vol. 6; nb. 14; (2016); p. 5668 - 5683 View in Reaxys O

OH OH

Rx-ID: 36932016 View in Reaxys 31/281 Yield 94 %, 6 %

Conditions & References With perrhenic acid anhydride, hydrogen in 1,4-dioxane, Time= 4h, T= 209.84 °C , p= 187519Torr , Autoclave, Catalytic behavior, Overall yield = 100 percent Takeda, Yasuyuki; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi; Catalysis Science and Technology; vol. 6; nb. 14; (2016); p. 5668 - 5683 View in Reaxys The reaction was carried out in a 316 L stainless steel tubular flow reactor described in literature [22]. Before the reaction, the catalysts were reduced in-situ in the reactor by hydrogen (160 mL min−1) at 473 K and 6 MPa for 2 h. After cooling down to reaction temperature (373 K), the aqueous solution of carboxylic acid was feed into the reactor from the bottom by a HPLC pump along with hydrogen at a flow rateof 60 mL min−1. The products from the reactor passed through a gas–liquid separator, and became two phases. The gaseous products flowed through a back pressure regulator to maintain the pressure in reaction system at 6 MPa and were analyzed on-line by an Agilent 6890N GC. CO2 in the gaseous products was analyzed by a Thermal Conductivity Detector (TCD) equipped with an Alltech HAYESEP DB 100/120 packed column (30 ft, 1/8 in. O.D., 2.0 mm I.D.). Alkanes in the gaseous products were analyzed by a Flame Ionized Detector (FID) equipped withan Rt®-Q-BOND capil-

33/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

lary column (30 m, 0.32 mm I.D., 10 μm film). Liquid products were drained from the gas–liquid separator after reaction for 6 h and analyzed by another Agilent 6890N GC equipped with a HP-INNOWAX capillary column (30 m, 0.25 mm I.D., 0.5 μm film) and a FID detector. With hydrogen in water, T= 99.84 °C , p= 45004.5Torr Wang, Zhiqiang; Li, Guangyi; Liu, Xiaoyan; Huang, Yanqiang; Wang, Aiqin; Chu, Wei; Wang, Xiaodong; Li, Ning; Catalysis Communications; vol. 43; (2014); p. 38 - 41 View in Reaxys

O O

OH O

O O

Rx-ID: 38841233 View in Reaxys 32/281 Yield 6.34 %Chromat., 5.33 %Chromat., 83.96 %Chromat.

Conditions & References 3 :In this example 3 the conditions of example 2 have been repeated, with the only difference of a small addition of water to the feed to simulate the conditions of an industrial plant, where the recycle gas is saturated by water. The main results of the analytical test are shown in Table 4 [TABLE-US-00004] TABLE 4 DMM Hydrogenation and Hydrogenolysis-Wet conditions DMM conversion 100percent Selectivity to 95.6 BDO/GBL/THF Composition (*) percent THF 6.34 BuOH 0.69 2Me THF less than 0.01 Me-butyrate 0.22 2-Metoxy-THF less than 0.01 4-Metoxy-BuOH 0.31 GBL 5.33 1,4 BDO 83.96 DMS 2.20 Unknown 1 0.95 Other unknown less than 0.01 (*) net of water and methanol [0117] This example 3 shows that in wet conditions the overall results are very similar to the dry conditions ones, with the main difference in the yields in THF which drops from 13percent to around 6percent, being this difference compensated by an equivalent increased yield in BDO. [0118] The overall yield in the three valuable products, BDO, GBL and THF, is 95.6percent. Considering that the unreacted DMS may be separated by distillation, alone or in mixture with GBL, and recycled back to the reaction system, the actual overall yield is around 97.8percent. Stage 1: With 10% palladium on activated charcoal, hydrogen in water, T= 130 - 135 °C , p= 52505.3Torr Stage 2: With hydrogen in water, T= 178 - 182 °C , p= 52505.3Torr Patent; CONSER SPA; Simola, Flavio; Scarsella, Marco; De Filippis, Paolo; US2014/316146; (2014); (A1) English View in Reaxys 1 : Example 1 In a process to produce 1 ,4 butanediol from maleic anhydride the maleic anhydride is esterified first in an autocatalytic reactor in contact with methanol, in a near to stoichiometric ratio to produce a stream of mono methyl maleate and heated to a temperature of about 1 10°C. This stream is fed near to the top of a reaction column containing a solid esterification catalyst suspended on the column reaction trays. Dry methanol is fed to the bottom of the reaction column at a feed rate equivalent to about 3mols of methanol to each mol of maleic anhydride feed. The methanol is vaporised in the reboiler which is heated by steam at a pressure of about 20 barg. This methanol travels up the column as a vapour, mixing and suspending the resin on the reaction trays, stripping water from the reaction trays and partially condensing on the trays to react with the mono methyl maleate to form dimethyl maleate and water. The conversion to dimethyl maleate is >99percent. The bottom offtake liquid is heated up to about 160°C in the reboiler which reduces the methanol content of the bottom liquid to <5wtpercent. The overhead vapour from the reaction column containing the excess methanol and water from the esterification reaction is fed to a distillation column (the methanol column) to remove the water from this stream and produce a dry methanol stream for recycle to the reaction column bottom. The dimethyl maleate is fed to a hydrogenation reaction system for conversion to a mixture of 1 ,4 butanediol and coproducts of tetrahydrofuran and [gammaj-butyroactone. These are separated from each other, from other impurities and from methanol and water produced in hydrogenation in a series of distillation columns to produce product grade 1 ,4 butanediol , tetrahydrofuran and [gamma]- butyrolactone. In this arrangement the steam requirement for the reaction column reboiler is about 0.7 ton of steam per ton of total products. With hydrogen, Industrial scale Patent; JOHNSON MATTHEY DAVY TECHNOLOGIES LIMITED; HILES, Andrew George; ANDERSSON, Rikard Umberto; WILLIAMS, Michael Gavin John; (24 pag.); WO2016/151289; (2016); (A1) English View in Reaxys

34/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Rx-ID: 40651056 View in Reaxys 33/281 Yield

Conditions & References

12 %, 79 %

With hydrogen in 1,4-dioxane, Time= 24h, T= 159.84 °C , p= 60006Torr , Autoclave Ota, Nobuhiko; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi; Angewandte Chemie International Edition; vol. 54; nb. 6; (2015); p. 1897 - 1900; Angew. Chem.; vol. 127; nb. 6; (2015); p. 1917 - 1920 View in Reaxys With hydrogen in 1,4-dioxane, Time= 4h, T= 139.84 °C , p= 60006Torr , Autoclave Ota, Nobuhiko; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi; ACS Catalysis; vol. 6; nb. 5; (2016); p. 3213 - 3226 View in Reaxys O

OH OH

O O

Rx-ID: 41670127 View in Reaxys 34/281 Yield

Conditions & References

70 %

With hydrogen, Time= 10h, T= 200 °C , p= 37503.8Torr , Autoclave Liu, Xiaoran; Wang, Xicheng; Xu, Guoqiang; Liu, Qiang; Mu, Xindong; Liu, Haichao; Journal of Materials Chemistry A; vol. 3; nb. 46; (2015); p. 23560 - 23569 View in Reaxys With hydrogen in 1,4-dioxane, Time= 4h, T= 119.84 °C , p= 60006Torr , Autoclave, Catalytic behavior, Reagent/catalyst, Temperature, Overall yield = 26 percent Takeda, Yasuyuki; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi; Catalysis Science and Technology; vol. 6; nb. 14; (2016); p. 5668 - 5683 View in Reaxys O

O O

Rx-ID: 42987760 View in Reaxys 35/281 Yield

Conditions & References With hydrogen in ethanol, T= 210 °C , p= 1875.19Torr , Green chemistry, Catalytic behavior, Temperature, Pressure Hu, Qi; Yang, Lan; Fan, Guoli; Li, Feng; Journal of Catalysis; vol. 340; (2016); p. 184 - 195 View in Reaxys 11 : Preparation of 1,4-BDO from dialkyl succinate 1,4-BDO was prepared via hydrogenation from DMS (dimethyl succinate). Specifically, methanol / DMS (50/50 vol percent) was used and the catalyst was prepared according to Example 1 of Korean Patent Registration No. 10-0538979CuO (72.2) MnO2 (2.5) ZnO (0.3) SiO2 (25) (in parentheses represents wtpercent) was used and reacted under the conditions shown in Table 32 below. The product was partially recovered and the components were analyzed. The results are shown in Table 32 below. With hydrogen in methanol, Time= 151h, T= 185 °C , p= 30402Torr , Temperature

35/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Patent; CJ CHEILJEDANG CORPORATION; KOREA RESEARCH INSTITUTE OF CHEMICAL TECHNOLOGY; YANG, YOUNG RYEOL; KIM, BYUNG SIK; KIM, JEONG HYUN; LEE, JUNG HO; SHIN, HYUN KWAN; KIM, JU NAM; CHO, KYUNG HO; (40 pag.); KR2015/118287; (2015); (A) Korean View in Reaxys

OH HO O

Rx-ID: 43071025 View in Reaxys 36/281 Yield

Conditions & References With sodium tetrahydroborate, C36H30F6N10Ni4O10 (2+)*2C2F3O2 (1-), zinc(II) chloride in tetrahydrofuran, Time= 12h, T= 45 °C

87 %

Tsai, Bing-Chen; Liu, Yi-Hung; Peng, Shie-Ming; Liu, Shiuh-Tzung; European Journal of Inorganic Chemistry; vol. 2016; nb. 17; (2016); p. 2783 - 2790 View in Reaxys O HO OH O

O O

HO OH

Rx-ID: 44253534 View in Reaxys 37/281 Yield

Conditions & References With hydrogen in 1,4-dioxane, Time= 2h, T= 179.84 °C , p= 60006Torr , Autoclave, Catalytic behavior, Reagent/catalyst, Temperature, Time, Overall yield = 34 percent Takeda, Yasuyuki; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi; Catalysis Science and Technology; vol. 6; nb. 14; (2016); p. 5668 - 5683 View in Reaxys O O

HO OH O

O HO OH

Rx-ID: 44253535 View in Reaxys 38/281 Yield

Conditions & References

0.2 %, 3.1 %, 89 %, 7.6 %

With hydrogen in 1,4-dioxane, Time= 24h, T= 139.84 °C , p= 60006Torr , Autoclave, Catalytic behavior, Reagent/catalyst, Time, Overall yield = > 99 percent Takeda, Yasuyuki; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi; Catalysis Science and Technology; vol. 6; nb. 14; (2016); p. 5668 - 5683 View in Reaxys O

HO OH O

36/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

O O

Rx-ID: 44253536 View in Reaxys 39/281 Yield

Conditions & References

1.2 %, 4 %, 32 %, 6.8 %, 54 %

With hydrogen in 1,4-dioxane, Time= 48h, T= 139.84 °C , p= 60006Torr , Autoclave, Catalytic behavior, Reagent/catalyst, Time, Overall yield = 100 percent Takeda, Yasuyuki; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi; Catalysis Science and Technology; vol. 6; nb. 14; (2016); p. 5668 - 5683 View in Reaxys O

HO HO

OH OH

O O

Rx-ID: 44253537 View in Reaxys 40/281 Yield

Conditions & References With hydrogen in 1,4-dioxane, Time= 4h, T= 159.84 °C , p= 60006Torr , Autoclave, Catalytic behavior, Reagent/catalyst, Temperature, Time, Overall yield = 31 percent Takeda, Yasuyuki; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi; Catalysis Science and Technology; vol. 6; nb. 14; (2016); p. 5668 - 5683 View in Reaxys O

O O

Rx-ID: 44253544 View in Reaxys 41/281 Yield

Conditions & References With hydrogen in 1,4-dioxane, Time= 4h, T= 139.84 °C , p= 60006Torr , Autoclave, Catalytic behavior, Reagent/catalyst, Overall yield = 10 percent Takeda, Yasuyuki; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi; Catalysis Science and Technology; vol. 6; nb. 14; (2016); p. 5668 - 5683 View in Reaxys O O

Rx-ID: 828200 View in Reaxys 42/281 Yield 100 %

Conditions & References With C56H70Cl3N10Ru2 (1+)*F6P(1-), potassium tert-butylate, hydrogen in tetrahydrofuran, dodecane, Time= 16h, T= 70 °C , p= 37503.8Torr , Inert atmosphere, Glovebox, Autoclave Filonenko, Georgy A.; Aguila, Mae Joanne B.; Schulpen, Erik N.; Van Putten, Robbert; Wiecko, Jelena; Müller, Christian; Lefort, Laurent; Hensen, Emiel J. M.; Pidko, Evgeny A.; Journal of the American Chemical Society; vol. 137; nb. 24; (2015); p. 7620 - 7623 View in Reaxys With ethanol, sodium Bennett; Mosses; Journal of the Chemical Society; (1931); p. 1699 View in Reaxys Vogel; Journal of the Chemical Society; (1934); p. 339; Journal of the Chemical Society; (1948); p. 640

37/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

View in Reaxys Steele; Journal of the American Chemical Society; vol. 53; (1931); p. 286 View in Reaxys Englund; Journal fuer Praktische Chemie (Leipzig); vol. <2> 129; (1931); p. 1,10, 11; ; vol. <4> 8; nb. 3; (1932); p. 33,38, 41, 45, 52, 60 View in Reaxys With copper chromite, T= 250 °C , p= 161812 - 220652Torr , Hydrogenation Patent; Roehm and Haas Co.; US2091800; (1931) View in Reaxys Adkins; Folkers; Journal of the American Chemical Society; vol. 53; (1931); p. 1096 View in Reaxys Wojcik; Adkins; Journal of the American Chemical Society; vol. 55; (1933); p. 4943 View in Reaxys With ethanol, T= 150 °C , p= 257428Torr , Hydrogenation Adkins; Billica; Journal of the American Chemical Society; vol. 70; (1948); p. 3121 View in Reaxys durch Reduktion Boeeseken; Recueil des Travaux Chimiques des Pays-Bas; vol. 34; (1915); p. 96; Chemische Berichte; vol. 46; (1913); p. 2616 View in Reaxys Mueller,A.; Monatshefte fuer Chemie; vol. 49; (1928); p. 28 View in Reaxys With ethanol, sodium Boeeseken; Recueil des Travaux Chimiques des Pays-Bas; vol. 34; (1915); p. 96; Chemische Berichte; vol. 46; (1913); p. 2616 View in Reaxys 99 %Spectr. With C27H37BrN4ORu, potassium tert-butylate, hydrogen in toluene, Time= 2h, T= 105 °C , p= 3975.4Torr , Inert atmosphere Sun, Yunshan; Koehler, Christian; Tan, Runyu; Annibale, Vincent T.; Song, Datong; Chemical Communications; vol. 47; nb. 29; (2011); p. 8349 - 8351 View in Reaxys

O H HO

OH H

OH HO

OH OH

Rx-ID: 1892358 View in Reaxys 43/281 Yield

Conditions & References With phosphate buffer, Bacillus sp. C-105, Time= 45h, T= 30 °C , fermentation, other carbon sources (D-xylose, D-fructose, maltose) Kobayashi, Morio; Ohishi, Michio; Asaoka, Sachio; Kitazato, Hajime; Noguchi, Masaaki; Agricultural and Biological Chemistry; vol. 51; nb. 6; (1987); p. 1689 - 1690 View in Reaxys II : Production of BDO from Glucose Production of BDO from Glucose. (0252) The final step of pathway corroboration is to express both the 4-HB and BDO segments of the pathway in E. coli and demonstrate production of BDO in glucose minimal medium. New plasmids were constructed so that all the required genes fit on two plasmids. In general, cat1, adhE, and sucD genes were expressed from pZE13, and cat2 and 4-HBd were expressed from pZA33. Various combinations of gene source and gene order were tested in the MG1655 lacIQ background. Cells were grown anaerobically in M9 minimal medium (6.78 g/L Na2HPO4, 3.0 g/L KH2PO4, 0.5 g/L NaCl, 1.0 g/L NH4Cl, 1 mM MgSO4, 0.1 mM CaCl2) supplemented with 20 g/L glucose, 100 mM 3-(N-morpholino)propanesulfonic

38/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

acid (MOPS) to improve the buffering capacity, 10 μg/mL thiamine, and the appropriate antibiotics. 0.25 mM IPTG was added approximately 15 hours following inoculation, and culture supernatant samples taken for BDO, 4-HB, and succinate analysis 24 and 48 hours following induction. The production of BDO appeared to show a dependency on gene order (Table 12). The highest BDO production, over 0.5 mM, was obtained with cat2 expressed first, followed by 4-HBd on pZA33, and cat1 followed by P. gingivalis sucD on pZE13. The addition of C. acetobutylicum adhE2 in the last position on pZE13 resulted in slight improvement. 4-HB and succinate were also produced at higher concentrations. With 3-(N-morpholino)propanesulfonic acid, vitamin B1, isopropyl η-D-thiogalactopyranoside in aq. buffer, Microbiological reaction, Reagent/catalyst Patent; Genomatica, Inc.; Burk, Mark J.; Burgard, Anthony P.; Osterhout, Robin E.; Sun, Jun; US9175297; (2015); (B2) English View in Reaxys O

O O

OH OH

Rx-ID: 23662963 View in Reaxys 44/281 Yield

Conditions & References The catalyst testing unit is comprised of a two-reactor system connected in series where maleic acid is first converted to succinic acid (SAC) in the first reactor at about 110° C. The effluent from the first stage reactor is delivered to the second stage reactor for the conversion of succinic acid to mainly BDO. Operating pressure is at 2500 to 4000 psi and internal reactor temperature is initially set at 165° C. Thereafter, temperature is adjusted closer to the temperature where a high conversion of SAC (about 99.7percent) is obtained. This temperature generally may vary from about 130° C. to about 175° C. At the lower end of the temperature range BDO selectivity is higher (80percent or higher) whereas THF is favored at higher temperatures (over 5percent). The results of the activity evaluation of a catalysts made according to the procedure of catalyst Example 1(a) is shown in Table 1a. Activity evaluation of a catalyst made according to the procedure of catalyst Example 2 is shown in Table 1(b). Catalyst results of the activity evaluation of a catalysts made according to the procedure of catalyst Example 3 is shown in Table 1(c). Tables 1a, 1b and 1c show that catalysts of Example 1(a), comprising Pd/Re on a rutile titanium dioxide support, and catalysts of Example 2 and Example 3, comprising Pd on a rutile titanium dioxide support, completely convert maleic acid to succinic acid with high selectivity to succinic acid and low amounts of other by-products. The Catalyst Testing Unit (CTU) results for Catalyst Example 1 and Catalyst Example 2 show that (a) Both 1/16 inch and inch Rutile extrudates can be used for hydrogenation. For carbon, inch was found to be less effective. (b) For maleic to succinic hydrogenation there is no need for other co-catalysts such as Ag, Fe, Na, etc., (c) 0.5percent Pd alone on a rutile TiO2 support gives good conversion of maleic acid to succinic acid. With hydrogen, 0.4percent Fe, 1.9percent Na, 2.66percent Ag, 2.66percent Pd, 10.0percent Re on carbon, T= 130 - 175 °C , p= 129290 - 206865Torr , Product distribution / selectivity Patent; Bhattacharyya, Alakananda; Manila, Maynard D.; US2006/4212; (2006); (A1) English View in Reaxys The catalyst testing unit is comprised of a two-reactor system connected in series where maleic acid is first converted to succinic acid (SAC) in the first reactor at about 110° C. The effluent from the first stage reactor is delivered to the second stage reactor for the conversion of succinic acid to mainly BDO. Operating pressure is at 2500 to 4000 psi and internal reactor temperature is initially set at 165° C. Thereafter, temperature is adjusted closer to the temperature where a high conversion of SAC (about 99.7percent) is obtained. This temperature generally may vary from about 130° C. to about 175° C. At the lower end of the temperature range BDO selectivity is higher (80percent or higher) whereas THF is favored at higher temperatures (over 5percent). The results of the activity evaluation of a catalysts made according to the procedure of catalyst Example 1(a) is shown in Table 1a. Activity evaluation of a catalyst made according to the procedure of catalyst Example 2 is shown in Table 1(b). Catalyst results of the activity evaluation of a catalysts made according to the procedure of catalyst Example 3 is shown in Table 1(c). Tables 1a, 1b and 1c show that catalysts of Example 1(a), comprising Pd/Re on a rutile titanium dioxide support, and catalysts of Example 2 and Example 3, comprising Pd on a rutile titanium dioxide support, completely convert maleic acid to succinic acid with high selectivity to succinic acid and low amounts of other by-products. The Catalyst Testing Unit (CTU) results for Catalyst Example 1 and Catalyst Example 2 show that (a) Both 1/16 inch and inch Rutile extrudates can be used for hydrogenation. For carbon, inch was found to be less effective. (b) For maleic to succinic hydrogenation there is no need for other co-catalysts such as Ag, Fe, Na, etc., (c) 0.5percent Pd alone on a rutile TiO2 support gives good conversion of maleic acid to succinic acid. With hydrogen, 0.5percent Pd/ 5percent Re on Rutile TiO2, T= 130 - 175 °C , p= 129290 - 206865Torr , Product distribution / selectivity

39/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Patent; Bhattacharyya, Alakananda; Manila, Maynard D.; US2006/4212; (2006); (A1) English View in Reaxys With hydrogen in ethanol, water, Time= 24h, T= 100 °C , p= 7500.75Torr Luque, Rafael; Clark, James H.; Yoshida, Kenta; Gai, Pratibha L.; Chemical Communications; nb. 35; (2009); p. 5305 5307 View in Reaxys Succinic acid hydrogenation was performed in a Hastelloy Parr 4560 high pressure reactor of 300 mL equipped with an electrically heated jacket, a turbine agitator with a magnetic driver, and a liquid sample line. The reactor was loaded with 100 mL of a 5 wt.percent SUC aqueous solution (420 mmol L−1) and 1 g catalyst (molar ratio SUC/Pd = 225). After purging with Ar, the reactor was heated to 160 °C. At 160 °C, hydrogen is added at a pressure of 150 bar to start the reaction. The aqueous samples taken from the reactor at regular intervals were analyzed using both gas chromatography (HP-5 column, 30 m × 0.25 mm column, thickness 0.25 μm) and a high performance liquid chromatography instrument equipped with UV and RI detection (ICSep Coregel 107H column at 40 °C, 0.005 N H2SO4 as mobile phase at a flow rate of 0.5 mL min−1). The main reaction products consisted of GBL, THF and BDO. By-products analyzed in the liquid phase were n-butanol, n-propanol, butyric acid, and propionic acid (Scheme 1). The mass balance was checked by measuring Total Organic Carbon (TOC) in the liquid phase using a Shimadzu TOC-VCSH analyzer. With hydrogen in water, Time= 48h, T= 160 °C , p= 112511Torr , Inert atmosphere, Reagent/catalyst Tapin, Benoit; Epron, Florence; Especel, Catherine; Ly, Bao Khanh; Pinel, Catherine; Besson, Michele; Catalysis Today; vol. 235; (2014); p. 127 - 133 View in Reaxys Hydrogenation of succinic acid to BDO Liquid-phase hydrogenation of succinic acid to BDO was con-ducted in a stainless steel autoclave reactor with a volume of200 ml. Prior to the reaction, the catalysts were reduced using anex situ reduction system at 500C for 4 h with a heating rate of5C/min under 5percent H2/N2flow (50 ml/min). In order to avoid airexposure, reduced catalyst (0.1 g), succinic acid (0.25 g), and 1,4-dioxane (50 ml, an inert aprotic solvent) were charged into thereactor in an argon atmosphere glove box. The closed reactor filledwith argon was then mounted to the autoclave chamber as quicklyas possible. After purging the reactor with nitrogen, it was pressur-ized up to 50 bar using hydrogen. The sealed autoclave was heatedto the reaction temperature (200C), and then pressurized up to80 bar using hydrogen. Catalytic reaction was conducted with con-stant stirring (700 rpm) for 7 h. After the reaction, the reactor wascooled to room temperature and depressurized. Reaction productswere analyzed with a gas chromatograph (Younglin, ACME-6100)equipped with a flame ionization detector (FID). Conversion ofsuccinic acid, selectivity for product, and yield for product werecalculated according to the following equations. With hydrogen in 1,4-dioxane, Time= 7h, T= 200 °C , p= 60006Torr , Inert atmosphere, Autoclave, Glovebox, Reagent/catalyst Kang, Ki Hyuk; Hong, Ung Gi; Bang, Yongju; Choi, Jung Ho; Kim, Jeong Kwon; Lee, Jong Kwon; Han, Seung Ju; Song, In Kyu; Applied Catalysis A: General; vol. 490; (2015); p. 153 - 162 View in Reaxys 2.3. Hydrogenation of succinic acid to BDO Liquid-phase hydrogenation of succinic acid to BDO was conducted in a stainless steel autoclave reactor with a volume of 200 ml. Prior to the reaction, the catalysts were reduced using an ex situ reduction system at 500 °C for 4 h with a heating rate of 5 °C/min under 5percent H2/N2 flow (50 ml/min). In order to avoid air exposure, reduced catalyst (0.1 g), succinic acid (0.25 g), and 1,4-dioxane (50 ml, an inert aprotic solvent) were charged into the reactor in an argon atmosphere glove box. The closed reactor filled with argon was then mounted to the autoclave chamber as quickly as possible. After purging the reactor with nitrogen, it was pressurized up to 50 bar using hydrogen. The sealed autoclave was heated to the reaction temperature (200 °C), and then pressurized up to 80 bar using hydrogen. Catalytic reaction was conducted with constant stirring (700 rpm) for 7 h. After the reaction, the reactor was cooled to room temperature and depressurized. Reaction products were analyzed with a gas chromatograph (Younglin, ACME-6100) equipped with a flame ionization detector (FID). With hydrogen in 1,4-dioxane, Time= 7h, T= 200 °C , p= 60006Torr , Glovebox, Inert atmosphere, Autoclave, Catalytic behavior, Reagent/catalyst Kang, Ki Hyuk; Hong, Ung Gi; Bang, Yongju; Choi, Jung Ho; Kim, Jeong Kwon; Lee, Jong Kwon; Han, Seung Ju; Song, In Kyu; Applied Catalysis A: General; vol. 490; nb. 1; (2015); p. 153 - 162 View in Reaxys With water, hydrogen, Time= 48h, T= 160 °C , p= 112511Torr

40/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Ly, Bao Khanh; Tapin, Benoît; Aouine, Mimoun; Delichere, Pierre; Epron, Florence; Pinel, Catherine; Especel, Catherine; Besson, Michèle; ChemCatChem; vol. 7; nb. 14; (2015); p. 2161 - 2178 View in Reaxys With hydrogen, Time= 10h, T= 300 °C , p= 37503.8Torr , Autoclave, Catalytic behavior, Temperature, Pressure Liu, Xiaoran; Wang, Xicheng; Xu, Guoqiang; Liu, Qiang; Mu, Xindong; Liu, Haichao; Journal of Materials Chemistry A; vol. 3; nb. 46; (2015); p. 23560 - 23569 View in Reaxys O O

Rx-ID: 29820748 View in Reaxys 45/281 Yield

Conditions & References

9.6 %, 10.8 %, 6 %, 17.8 %

With ZnCuO2, hydrogen, T= 260 °C , p= 15001.5Torr Ding, Guoqiang; Zhu, Yulei; Zheng, Hongyan; Zhang, Wei; Li, Yongwang; Catalysis Communications; vol. 11; nb. 14; (2010); p. 1120 - 1124 View in Reaxys With hydrogen, T= 180 °C , p= 75007.5Torr , Kinetics, Temperature, Pressure Timofeev; Bazanov; Zubritskaya; Russian Journal of Organic Chemistry; vol. 46; nb. 10; (2010); p. 1537 - 1541 View in Reaxys With hydrogen in water, Time= 10h, T= 240 °C , p= 60006Torr , Autoclave, Catalytic behavior Di, Xin; Shao, Zhengfeng; Li, Chuang; Li, Wenzhen; Liang, Changhai; Catalysis Science and Technology; vol. 5; nb. 4; (2015); p. 2441 - 2448 View in Reaxys O

HO OH O

O O

Rx-ID: 31708211 View in Reaxys 46/281 Yield

Conditions & References 6 :A series of batch hydrogenation reactions are performed to evaluate the effectiveness of the catalysts in the hydrogenation of fermentation-derived SA. The reactions are conducted in a stirrable 125 ml autoclave rated up to 2,500 psig.Hydrogenation experiments are conducted by reducing the catalysts in situ for determination of catalyst compositions suitable for hydrogenation of fermentation-derived SA. The experiments are conducted in the 125 ml autoclave as follows: (1) 0.5100 grams of a 1percent ruthenium solution derived from RuCl3.xH2O, 0.2780 g of a HReO4 solution (7.7percent Re from Re2O7), 0.5035 g of particulate acidic carbon (BET 1,500 m2/g), an appropriate amount of 12.5percent Sn solution prepared from 5 nCl4;5H2O, and 35 g of 7percent aqueous SA solution are mixed in the autoclave; (2) Hydrogen is charged to the reactor to 1,200 psig; (3) The reactor contents are heated to 250° C. at 700 rpm and maintained at 250° C. for 3 hours; (4) The reactor is cooled and vented; and (5) A sample of the slurry in the reactor is filtered and analyzed for BDO, THF, GBL, 1-propanol, and n-butanol using gas chromatography.Hydrogenation experiments are also conducted by pre-reducing the catalysts deposited on a support to determine catalysts compositions and supports suitable for hydrogenation of fermentation-derived SA. The catalyst is prepared as follows: (1) 2.0305 grams of 1percent ruthenium solution derived from RuCl3.xH2O, 1.104 grams of 7.7percent rhenium solution derived from HReO4, appropriate amount of 12.5percent Sn solution prepared from SnCl4;5H2O, and 2.03 grams of particulate carbon support (average particle size about 20 micron) characterizes as intrinsically acidic (pH=4-4.5) with BET surface area of about 1,500 m2/g are slurried; (2) The slurry is dried at about 100-120° C., under vacuum and nitrogen purge; (3) The catalysts is reduced under hydrogen-helium flow for about 8 hours at about 300° C.; (4) The catalysts is cooled under helium to about 50° C. and passivated for 30 minutes under 1percent O2 in N2. The hydrogenation experiments are conducted in the 125 ml autoclave

41/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

as follows: (1) About 0.1 to 0.5 g of the catalyst and 35 g of 7percent aqueous SA solution are mixed in the autoclave; (2) Hydrogen is charged to the reactor to 1,200 psig; (3) The reactor contents are heated to 250° C. at 700 rpm and maintained at 250° C. for 3 hours; (4) The reactor is cooled and vented; and (5) A sample of the slurry in the reactor is filtered and analyzed for BDO, THF, GBL, 1-propanol, and n-butanol using gas chromatography.Hydrogenation of SA crystallized from simulated broth composed of reagent grade chemicals and de-ionized water is conducted to determine the effectiveness of the catalysts for SA hydrogenation. SA for hydrogenation is prepared as follows: (1) an aqueous solution consisting of 25percent (wt.) SA, 2.5percent (wt.) acetic acid, 0.25percent (wt.) formic acid, and 0.25percent (wt.) lactic acid is prepared at 80° C. in a jacketed kettle equipped with a reflux condenser; (2) The hot solution is cooled to 20° C. by cooling the solution over a 3 hour period following a linear cooling profile; (3) The solution is seeded with 0.1 g of SA crystals at 75° C.; (4) The slurry is allowed to equilibrate at 20° C. for 1 hour; (5) The slurry is filtered with vacuum filtration and washed with 20 g of water; (6) 50 g of the cake (10percent wt. moisture) is dissolved in 593 g of deionized water (7percent wt. solution).Hydrogenation of SA crystallized from fermentation-derived broth is conducted to establish the effect of carryover impurities from fermentation. Fermentation-derived SA for hydrogenation is prepared as follows: (1) A fermentation-derived broth containing 4.5percent (wt.) DAS, 0.45percent (wt.) ammonium acetate, 0.05percent (wt.) ammonium formate, and 0.05percent (wt.) ammonium lactate is deammoniated and concentrated resulting in a greater than 25percent SA solution; (2) The hot solution is cooled to 20° C. by cooling the solution over a 3 hour period following a linear cooling profile; (3) The solution is seeded with 0.1 g of SA crystals at 75° C.; (4) The slurry is allowed to equilibrate at 20° C. for 1 hour; (5) The slurry is filtered with vacuum filtration and washed with 20 g of water; (6) 50 g of the cake (10percent wt. moisture) is dissolved in 593 g of deionized water (7percent wt. solution).Representative results are presented in Examples 6-13 in Table 3. TABLE 3 Representative hydrogenation results Ex. Catalysts SA BDO THF GBL PrOH BuOH 61percent Ru:4percent Re(a) S 0.08 16.9 0.08 1.45 1.21 71percent Ru:4percent Re(a) F 0.08 16.9 0.08 1.45 1.21 81percent Ru:0.8percent Re:0.4percent(a) S 91percent Ru:0.8percent Re:0.4percent(a) F 101percent Ru:4percent Re(b) S 0.88 14.8 0.29 2.16 1.59 111percent Ru:4percent Re(b) F 0.88 14.8 0.29 2.16 1.59 121percent Ru:0.8percent Re:0.4percent(b) S 131percent Ru:0.8percent Re:0.4percent(b) F S = succinic acid derived from simulated broth derived from reagent chemicals, F = succinic acid derived from fermentation broth,(a) = catalyst reduced in situ,(b) = Pre-reduced catalytst, PrOH = propanol, and BuOH = butanol. With water, hydrogen, T= 250 °C , p= 62819.5Torr , Product distribution / selectivity Patent; BIOAMBER S.A.S.; US2011/245514; (2011); (A1) English View in Reaxys 15 :Hydrogenation experiments conducted by reducing the catalysts in situ for determination of catalyst compositions suitable for hydrogenation of fermentation-derived SA. The experiments are conducted in the 125 ml autoclave as follows: (1) 0.5100 grams of a 1percent ruthenium solution derived from RuCl3.xH2O, 0.2780 g of a HReO4 solution (7.7percent Re from Re2O7), 0.5035 g of particulate acidic carbon (BET 1,500 m2/g), an appropriate amount of 12.5percent Sn solution prepared from SnCl4;5H2O, and 35 g of 7percent aqueous SA solution are mixed in the autoclave; (2) Hydrogen is charged to the reactor to 1,200 psig; (3) The reactor contents are heated to 250° C. at 700 rpm and maintained at 250° C. for 3 hours; (4) The reactor is cooled and vented; and (5) A sample of the slurry in the reactor is filtered and analyzed for BDO, THF, GBL, 1-propanol, and nbutanol using gas chromatography. With hydrogen, 1percentRu:4percentRe, Time= 3h, T= 250 °C , Product distribution / selectivity Patent; BIOAMBER S.A.S.; US2011/245515; (2011); (A1) English View in Reaxys With hydrogen in water, Time= 10h, T= 240 °C , p= 60006Torr , Autoclave, Catalytic behavior, Kinetics, Reagent/catalyst, Concentration, Pressure, Temperature Di, Xin; Shao, Zhengfeng; Li, Chuang; Li, Wenzhen; Liang, Changhai; Catalysis Science and Technology; vol. 5; nb. 4; (2015); p. 2441 - 2448 View in Reaxys O

OH HO

Rx-ID: 34449402 View in Reaxys 47/281 Yield

Conditions & References With water, hydrogen, Time= 4h, T= 120 °C , p= 22502.3Torr , chemoselective reaction Zhang, Bin; Zhu, Yulei; Ding, Guoqiang; Zheng, Hongyan; Li, Yongwang; Green Chemistry; vol. 14; nb. 12; (2012); p. 3402 - 3409

42/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

View in Reaxys 1 :In a further particularly preferred, but non- limiting, embodiment of the invention illustrated in Figure 2, the furan stream 210 is contacted with a gaseous stream comprising hydrogen 219 in a vessel 212 and carbon monoxide present in the furan stream 210 is removed into the gaseous stream comprising hydrogen. The resultant (CO-depleted) furan stream 213 is contacted with hydrogen 214 in a hydrogenation reactor 215 containing a hydrogenation catalyst. The resultant hydrogenation reaction product stream 216 is separated in a column 217 to provide a product stream 218 containing 1,4-BDO and/or THF and the resultant postseparation hydrogen-containing stream 219, a portion of which is then recycled for use in removing carbon monoxide from the furan stream and the remainder can be recycled to provide hydrogen for the hydrogenation reaction . Examples Example 1 (Comparative) A process line-up was developed in ASPEN, using a fit for purpose thermodynamic data deck. The product stream ex-decarbonylation reactor consisted of 98 kmol/h furan, 2 kmol/h furfural, 18 kmol/h H2 and 98 kmol/h CO, at 5 barA and 50 °C. Two stage compression of this stream to 15 and 40 barA, respectively, with cooling to 10°C resulted in the condensation of furan and furfural. After separation of the liquid streams, the gaseous stream contains 2.2 kmol/h furan and 1.2xl0~7 kmol/h of furfural. Accordingly, 2.2 molpercent of the furan is lost in the gas phase. With hydrogen Patent; SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.; SHELL OIL COMPANY; LANGE, Jean Paul, Andre, Marie, Joseph, Gishlain; WADMAN, Sipke, Hidde; WO2015/150241; (2015); (A1) English View in Reaxys

HO O

OH HO O

Rx-ID: 39585900 View in Reaxys 48/281 Yield 46 %

Conditions & References General procedure for the deprotection of the PMB ethers and ester by (COCl)2 (General Method D) To a solution of the PMB ether or ester (1 equiv.) in dichloroethane (5 mL), (COCl)2 (0.5 equiv.) was added and stirred at room temperature. After completion of the reaction, it was quenched in ice water and the organic layer was separated and the aqueous layer was extracted with dichloroethane (2 x 5 mL). Combined organic layer was washed with brine solution, dried (Na2SO4), concentrated under reduced pressure and the residue was purified by column chromatography (silica gel, EtOAc: Hexane) to afford the corresponding alcohol With oxalyl dichloride in 1,2-dichloro-ethane, Time= 2.66667h, T= 20 °C Ilangovan, Andivelu; Anandhan, Karnambaram; Kaushik, Mahabir Prasad; Tetrahedron Letters; vol. 56; nb. 9; (2015); p. 1081 - 1084 View in Reaxys

Rx-ID: 39633244 View in Reaxys 49/281 Yield

Conditions & References With D-Glucose, Escherichia coli P450pyr I83M/I82T monooxygenase mutant in aq. phosphate buffer, Time= 4h, T= 30 °C , pH= 8, Enzymatic reaction, Reagent/catalyst, regioselective reaction Yang, Yi; Chi, Yu Tse; Toh, Hui Hung; Li, Zhi; Chemical Communications; vol. 51; nb. 5; (2015); p. 914 - 917 View in Reaxys OH

HO HO

Rx-ID: 39699349 View in Reaxys 50/281

43/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Yield

Conditions & References

80 %Chromat., Ca. 5 %Chromat.

With iridium, hydrogen in ethanol, Time= 5h, T= 25 °C Mekhaev; Pervova; Kazakov; Bratskaya; Pestov; Russian Journal of Organic Chemistry; vol. 51; nb. 2; (2015); p. 279 - 280; Zh. Org. Khim.; vol. 51; nb. 2; (2015); p. 289 - 290,2 View in Reaxys

Rx-ID: 40091232 View in Reaxys 51/281 Yield

Conditions & References With hydrogen in water, Time= 10h, T= 240 °C , p= 60006Torr , Autoclave, Catalytic behavior Di, Xin; Shao, Zhengfeng; Li, Chuang; Li, Wenzhen; Liang, Changhai; Catalysis Science and Technology; vol. 5; nb. 4; (2015); p. 2441 - 2448 View in Reaxys With hydrogen, Time= 20h, T= 200 °C , p= 37503.8Torr , Autoclave Liu, Xiaoran; Wang, Xicheng; Xu, Guoqiang; Liu, Qiang; Mu, Xindong; Liu, Haichao; Journal of Materials Chemistry A; vol. 3; nb. 46; (2015); p. 23560 - 23569 View in Reaxys O

O O

Rx-ID: 40275632 View in Reaxys 52/281 Yield

Conditions & References 2 :A hydrogenation reactor was charged with 250 mL of catalyst of 1.45 for catalyst DRD- 92/89-A and 1.35 for PG-85/1. Both catalysts are available from Johnson Matthey Davy Technologies Ltd Distilled bio~dimethyi succinate made from bio-succinic acid samples A & B, with a low sulphur concentration (ppb) was introduced. The feed composition was 85 wtpercent DMS and 15 wtpercent methanol. The reactor was operated at the following conditions: Exit Temperature, Pressure, psi(g) LHSV, hf1 H2: Ester (molar) This process gave a dimethyl succinate conversion of 99.67 molpercent, with selectivity to tetrahydrofuran, butanol, η-butyrolactone and butanediol of 3.91 mopercent, 0.97 molpercent, 11.77 molpercent and 83.24 moipercent respectively. With hydrogen in methanol, Time= 197h, T= 190 °C , p= 45717.1Torr , Temperature Patent; JOHNSON MATTHEY DAVY TECHNOLOGIES LIMITED; SMIDT, Martin Lucas; CAMPBELL, Ian; GORDON, Paul; FERGUSON, Christopher; REED, Graham; WO2015/82916; (2015); (A1) English View in Reaxys 11 : Preparation of 1,4-BDO from dialkyl succinate 1,4-BDO was prepared via hydrogenation from DMS (dimethyl succinate). Specifically, methanol / DMS (50/50 vol percent) was used and the catalyst was prepared according to Example 1 of Korean Patent Registration No. 10-0538979CuO (72.2) MnO2 (2.5) ZnO (0.3) SiO2 (25) (in parentheses represents wtpercent) was used and reacted under the conditions shown in Table 32 below. The product was partially recovered and the components were analyzed. The results are shown in Table 32 below. With hydrogen in methanol, Time= 72h, T= 180 °C , p= 30402Torr , Temperature, Pressure Patent; CJ CHEILJEDANG CORPORATION; KOREA RESEARCH INSTITUTE OF CHEMICAL TECHNOLOGY; YANG, YOUNG RYEOL; KIM, BYUNG SIK; KIM, JEONG HYUN; LEE, JUNG HO; SHIN, HYUN KWAN; KIM, JU NAM; CHO, KYUNG HO; (40 pag.); KR2015/118287; (2015); (A) Korean View in Reaxys

44/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

O OH

Rx-ID: 41316981 View in Reaxys 53/281 Yield

Conditions & References

92 %, 90 %

With oxygen, hydrazine hydrate in acetonitrile, Time= 4h, T= 32 °C , p= 760.051Torr , Schlenk technique Santra, Surojit; Guin, Joyram; European Journal of Organic Chemistry; vol. 2015; nb. 33; (2015); p. 7253 - 7257 View in Reaxys

O OH

Rx-ID: 41490372 View in Reaxys 54/281 Yield

Conditions & References 3 : Reductive Hydrogenation of the Oxidized Butyl Butyrate to Form 1,4-butanediol EXAMPLE 3 Reductive Hydrogenation of the Oxidized Butyl Butyrate to Form 1,4-butanediol 740 mg of lithium aluminium hydride are charged in 50 mL of dry diethyl ether and 10 g of the oxidized ester from Example 2 are slowly added dropwise at 0° C. After addition is complete, the mixture is heated to boiling and stirred under reflux until complete conversion. The resulting alcohols are separated by distillation. 7.41 g of 1,4-butanediol and 1.77 g of 1-butanol are obtained. The butanol is recycled to Example 1d and esterified therein. in diethyl ether Patent; HAAS, Thomas; ENGEL, Philip; PFEFFER, Jan Christoph; THUM, Oliver; GEHRING, Christian; ENGEL, Phillip; US2015/353963; (2015); (A1) English View in Reaxys

B Cl

Rx-ID: 41596786 View in Reaxys 55/281 Yield

Conditions & References With dihydrogen peroxide, Alkaline conditions Khusainova; Khafizova; Tyumkina; Dzhemilev; Russian Journal of Organic Chemistry; vol. 51; nb. 11; (2015); p. 1517 1523; Zh. Org. Khim.; vol. 51; nb. 11; (2015); p. 1551 - 1557,7 View in Reaxys HO

H OH

Rx-ID: 41631645 View in Reaxys 56/281 Yield

Conditions & References 1 : Example 1 Example 1 [00043] Into a high pressure liquid phase fixed bed reactor system containing 60,000 kg of Ni (Raney) on Al203 (40/60 by weight) catalyst is passed 26,000 kg/hour of liquid feedstock comprising 54 percent BYD and 3,000 kg/hour of hydrogen at a pressure of 300 bar. The hydrogen feedstock is from a compressed hydrogen supply system involving a hydrogen booster compressor and other unit operations required to provide quality high pressure hydrogen for the reaction. Reaction conditions maintained in the fixed bed reactor include a pressure of 300 bar and temperature of 135 C. Vent gas comprised of 96 percent hydrogen is removed from the reactor and recycled to the hydrogen supply system at about 2,300kg/hour. Liquid phase product comprising approximately 54 percent BDO is recovered from the reactor and passed to a first liquid phase iet down vessel via an isenthalpic pressure let down, maintained at a pressure of 80 bar at 26,000 kg/hour, along with about 50 to 100 kg/hour of hydro-

45/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

gen. [00044] From the first liquid phase let down vessel is recovered a first stream liquid bottoms comprising product BDO and a second stream overhead vent gas comprising mainly water vapor plus residual light organics and hydrogen. The recovered first stream liquid bottoms is passed to a second liquid phase iet down vessel, maintained at a pressure of 8 bar, at approximately 20,000 kg/hour. The recovered second stream overhead vent gas is passed to a vent gas cooler maintained at a pressure of 75 bar and temperature of 35 °C. The gas from the vent gas cooler is passed to a hydrogen recovery zone comprising a MEDAL™ membrane filter unit. Permeate recovered from the hydrogen recovery zone, comprising 97 percent hydrogen gas of 99 percent hydrogen purity (water free basis), is recycled to the hydrogen supply system. The retentate recovered from the hydrogen recovery zone comprises contaminants, such as, for example, carbon dioxide, methane, and methanol. With hydrogen, T= 135 °C , p= 60006 - 225023Torr , Large scale, Pressure, Temperature Patent; INVISTA TECHNOLOGIES S.À R.L.; WARD, Philip N.; WO2015/164379; (2015); (A1) English View in Reaxys

HO OH

OH HO O

Rx-ID: 41650878 View in Reaxys 57/281 Yield

Conditions & References II : Production of BDO from 4-HB The production of BDO from 4-HB required two reduction steps, catalyzed by dehydrogenases. Alcohol and aldehyde dehydrogenases (ADH and ALD, respectively) are NAD+/H and/or NADP+/H-dependent enzymes that together can reduce a carboxylic acid group on a molecule to an alcohol group, or in reverse, can perform the oxidation of an alcohol to a carboxylic acid. This biotransformation has been demonstrated in wild-type Clostridium acetobutylicum (Jewell et al., Current Microbiology, 13:215-19 (1986)), but neither the enzymes responsible nor the genes responsible were identified. In addition, it is not known whether activation to 4-HB-CoA is first required (step 9 in FIG. 1), or if the aldehyde dehydrogenase (step 12) can act directly on 4-HB. We developed a list of candidate enzymes from C. acetobutylicum and related organisms based on known activity with the non-hydroxylated analogues to 4-HB and pathway intermediates, or by similarity to these characterized genes (Table 6). Since some of the candidates are multifunctional dehydrogenases, they could potentially catalyze both the NAD(P)H-dependent reduction of the acid (or CoA-derivative) to the aldehyde, and of the aldehyde to the alcohol. Before beginning work with these genes in E. coli, we first validated the result referenced above using C. acetobutylicum ATCC 824. Cells were grown in Schaedler broth (Accumedia, Lansing, Mich.) supplemented with 10 mM 4-HB, in an anaerobic atmosphere of 10percent CO2, 10percent H2, and 80percent N2 at 30° C. Periodic culture samples were taken, centrifuged, and the broth analyzed for BDO by GCMS as described below. BDO concentrations of 0.1 mM, 0.9 mM, and 1.5 mM were detected after 1 day, 2 days, and 7 days incubation, respectively. No BDO was detected in culture grown without 4-HB addition. To demonstrate that the BDO produced was derived from glucose, we grew the best BDO producing strain MG1655 lacIQ pZE13-0004-0035-0002 pZA33-0034-0036 in M9 minimal medium supplemented with 4 g/L uniformly labeled 13C-glucose. Cells were induced at OD of 0.67 with 1 mM IPTG, and a sample taken after 24 hours. Analysis of the culture supernatant was performed by mass spectrometry. (0245) Gene candidates for the 4-HB to BDO conversion pathway were next tested for activity when expressed in the E. coli host MG1655 lacIQ. Recombinant strains containing each gene candidate expressed on pZA33 were grown in the presence of 0.25 mM IPTG for four hours at 37° C. to fully induce expression of the enzyme. Four hours after induction, cells were harvested and assayed for ADH and ALD activity as described above. Since 4-HB-CoA and 4-hydroxybutyraldehyde are not available commercially, assays were performed using the non-hydroxylated substrates (Table 9). The ratio in activity between 4-carbon and 2-carbon substrates for C. acetobutylicum adhE2 (0002) and E. coli adhE (0011) were similar to those previously reported in the literature a Atsumi et al., Biochim. Biophys. Acta. 1207:1-11 (1994). For the BDO production experiments, cat2 from Porphyromonas gingivalis W83 (gene 0034) was included on pZA33 for the conversion of 4-HB to 4-HB-CoA, while the candidate dehydrogenase genes were expressed on pZE13. The host strain was MG1655 lacIQ. Along with the alcohol and aldehyde dehydrogenase candidates, we also tested the ability of CoA-dependent succinic semialdehyde dehydrogenases (sucD) to function in this step, due to the similarity of the substrates. Cells were grown to an OD of about 0.5 in LB medium supplemented with 10 mM 4-HB, induced with 1 mM IPTG, and culture broth samples taken after 24 hours and analyzed for BDO as described below. The best BDO production occurred using adhE2 from C. acetobutylicum, sucD from C. kluyveri, or sucD from P. gingivalis (FIG. 5). Interestingly, the absolute amount of BDO produced was higher under aerobic conditions; however, this is primarily due to the lower cell density achieved in anaerobic cultures. When normalized to cell OD, the BDO production per unit biomass is higher in anaerobic conditions (Table 10). As discussed above, it may be advantageous to use a route for converting 4-HB to 4-HB-CoA that does not generate acetate as a byproduct. To this aim, we tested the use of phosphotransbutyrylase (ptb) and butyrate kinase (bk) from C. acetobutylicum to carry out this conversion via steps 10 and 11 in FIG. 1. The native ptb/bk operon from C. acetobutylicum (genes 0020 and 0021) was cloned and expressed in pZA33. Extracts from cells containing the resulting construct were taken and assayed for the two enzyme activities as described herein. The specific activity of BK was approximately 65 U/mg, while the specific activity of PTB was approximately 5 U/mg. One unit (U) of activity is defined as conversion of 1 μM substrate in 1 minute at room temperature. Finally, the construct was tested for participation in the conversion of 4-HB to BDO.

46/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Host strains were transformed with the pZA33-0020-0021 construct described and pZE13-0002, and compared to use of cat2 in BDO production using the aerobic procedure used above in FIG. 5. The BK/PTB strain produced 1 mM BDO, compared to 2 mM when using cat2 (Table 11). Interestingly, the results were dependent on whether the host strain contained a deletion in the native adhE gene. With E. coli strain MG1655 lacIQ, containing pZA33-0020-0021, adhE2 from C. acetobutylicum in aq. buffer, Microbiological reaction, Reagent/catalyst Patent; Genomatica, Inc.; Burk, Mark J.; Burgard, Anthony P.; Osterhout, Robin E.; Sun, Jun; US9175297; (2015); (B2) English View in Reaxys O O

Rx-ID: 41670128 View in Reaxys 58/281 Yield

Conditions & References With hydrogen, Time= 20h, T= 200 °C , p= 37503.8Torr , Autoclave Liu, Xiaoran; Wang, Xicheng; Xu, Guoqiang; Liu, Qiang; Mu, Xindong; Liu, Haichao; Journal of Materials Chemistry A; vol. 3; nb. 46; (2015); p. 23560 - 23569 View in Reaxys

O O

HO OH HO

Rx-ID: 41670129 View in Reaxys 59/281 Yield

Conditions & References With 10% palladium on activated charcoal, hydrogen, Time= 20h, T= 200 °C , p= 37503.8Torr , Autoclave Liu, Xiaoran; Wang, Xicheng; Xu, Guoqiang; Liu, Qiang; Mu, Xindong; Liu, Haichao; Journal of Materials Chemistry A; vol. 3; nb. 46; (2015); p. 23560 - 23569 View in Reaxys O

OH HO

Rx-ID: 44038096 View in Reaxys 60/281 Yield 2.8 mol, 22 mol

Conditions & References 2-1 : Comparative Example 2-1 (Synthesis of 1,5-pentanediol) To the aqueous dispersion of the catalyst (Ir - Ru - Re / SiO 2 catalyst (2)) obtained by the same method as in Example 1-2,0.250 g (2.60 mmol) of furfural was charged at room temperature, pressurized to 8 MPa with hydrogen gas, and stirred at 40 ° C. for 2 hours,Reaction at 80 ° C for 2 hours(At this point, furfural was converted to furfuryl alcohol or tetrahydrofurfuryl alcohol), and the mixture was further reacted at 120 ° C. for 2 hours. The resulting reaction solution was cooled to room temperature and then filtered through a syringe equipped with a membrane filter (pore diameter: 0.45 μm). Analysis of the filtrate by gas chromatography showed that the conversion of furfural was 100 molpercent, the yield of 1,5-pentanediol was 2.8 molpercent, the yield of tetrahydrofurfuryl alcohol was 45.0 molpercent The yield of 1,4-butanediol was 22.0percent. With hydrogen, sodium hydroxide in water, Time= 6h, T= 40 - 120 °C , p= 60006Torr Patent; Ube Industries, Ltd.; Yoshii, Kiyotaka; Yamada, Atsushi; (17 pag.); JP2015/3892; (2015); (A) Japanese View in Reaxys

47/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

OH HO

H HO

HO OH

Rx-ID: 44192470 View in Reaxys 61/281 Yield

Conditions & References 1 :As a catalyst, the iridium · rhenium-supported silica (1) obtained in Preparation Example 2 (Re / Ir = 1) was used. 1 g of water, 4 g of erythritol, 1percent sulfuric acid 15 0 mg (0.5 molar times with respect to iridium, 1 equivalent) was added, the reaction temperature was 80 ° C., the hydrogen pressure The reaction was carried out for 24 hours at 8 MPa. The conversion of erythritol was 28.5percent, the proportion of 1,2,3-butanetriol was 21.1percent , 29.5percent 1,2,4-butanetriol, 25.2percent 1,4 butanediol, 1 , 7.5percent 3-butanediol, 2.5percent 1,2-butanediol, 2,3-butane 2.3percent of diol, 5.9percent of 1-butanol and 5.3percent of 2-butanol were obtained. With sulfuric acid in water, Time= 24h, T= 80 °C , p= 60006Torr , Reagent/catalyst Patent; DAICEL CORPORATION; TOMISHIGE, KEIICHI; NAKAGAWA, YOSHINAO; KAJIKAWA, YASUTERU; (23 pag.); JP5827925; (2015); (B2) Japanese View in Reaxys

OH H

OH HO

Rx-ID: 44192471 View in Reaxys 62/281 Yield

Conditions & References 13 :As a catalyst, the iridium · rhenium-supported silica (1) obtained in Preparation Example 2 (Re / Ir = 1) was used. 1 g of water, 4 g of erythritol, 1percent sulfuric acid 15 0 mg (0.5 molar times with respect to iridium, 1 equivalent) was added, the reaction temperature was 80 ° C., the hydrogen pressure The reaction was carried out for 24 hours at 8 MPa. The conversion of erythritol was 28.5percent, the proportion of 1,2,3-butanetriol was 21.1percent , 29.5percent 1,2,4-butanetriol, 25.2percent 1,4 butanediol, 1 , 7.5percent 3-butanediol, 2.5percent 1,2-butanediol, 2,3-butane 2.3percent of diol, 5.9percent of 1-butanol and 5.3percent of 2-butanol were obtained. With sulfuric acid in water, Time= 24h, T= 80 °C , p= 60006Torr Patent; DAICEL CORPORATION; TOMISHIGE, KEIICHI; NAKAGAWA, YOSHINAO; KAJIKAWA, YASUTERU; (23 pag.); JP5827925; (2015); (B2) Japanese View in Reaxys

H H

OH HO

Rx-ID: 44241665 View in Reaxys 63/281 Yield

Conditions & References 2 : Reference Example 1 (Hydrocracking Reaction)

48/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

7200 parts by weight of erythritol, 10 parts by weight of sulfuric acid and 1,800 parts by weight of water were mixed and heated to 90 ° C. to prepare a raw material liquid of erythritol 80percent by weight.In a trickle bed reactor (fixed bed continuous reactor, content of iron component: 0percent by weight, content of nickel component: 0percent by weight) made of titanium (Ti) having a reaction tube with an inside diameter of 9 mm, 1.2 kg (0.8 L) of the obtained catalyst (1) was charged and the catalyst packed part was heated to 100 ° C. (reaction temperature: 100 ° C.). The raw material liquid was supplied at 900 g / hr (LHSV = 1.0 hr -1) to the catalyst filled portion, and hydrogen was supplied at 2 L / min to start the reaction (molar ratio of supplying hydrogen to erythritol: hydrogen / Erythritol = 4.0). During the reaction, the pressure inside the reaction tube was maintained at 12 MPa (gauge pressure). Then, the reaction mixture (reaction solution) was continuously discharged (discharged) from the reactant withdrawal line, and after 5 hours from the start of supply of the raw material liquid and hydrogen, the reaction mixture flowing out from the reactant withdrawal line was collected over 1 hour The collected solution (including the reaction product) was analyzed. As a result, the conversion of erythritol was 65.4percent, and the selectivity of each product was17.3percent of 1,2,3butanetriol,4.9percent of 1,2,4-butanetriol,35.4percent of 1,4-butanediol,13.5percent of 1,3-butanediol,2.1percent of 1,2-butanediol,2.1percent of 2,3-butanediol,1.1percent 1-butanol,2-butanol was 1.5percent. With sulfuric acid, hydrogen in water, Time= 5h, T= 90 - 100 °C , p= 90009Torr Patent; Daicel Co., Ltd.; Tomishige, Keiichi; Nakagawa, Yoshinao; Kajikawa, Yasuteru; Matsuda, Hirokazu; Uchida Noriyuki, Noriyuki; Hirai, Yuichiro; (15 pag.); JP5684657; (2015); (B2) Japanese View in Reaxys O O

Rx-ID: 47843127 View in Reaxys 64/281 Yield

Conditions & References

8.3 %

With 10% palladium on activated charcoal, water, hydrogen, Time= 2h, T= 170 °C , p= 52505.3Torr , Autoclave Hu, Xun; Westerhof, Roel J. M.; Wu, Liping; Dong, Dehua; Li, Chun-Zhu; Green Chemistry; vol. 17; nb. 1; (2015); p. 219 224 View in Reaxys

OH O

HO O

Rx-ID: 4882413 View in Reaxys 65/281 Yield 100 % Spectr.

Conditions & References With hydrogen, triethylamine, η(+)-tris(pentane-2,5-dionato)ruthenium, [2-((diphenylphospino)methyl)-2-methyl-1,3-propanediyl]bis[diphenylphosphine] in various solvent(s), Time= 16h, T= 120 °C , p= 63755.1Torr Teunissen, Herman T.; Elsevier, Cornells J.; Chemical Communications; nb. 13; (1998); p. 1367 - 1368 View in Reaxys 1-4 :Comparative Example 1; A butane oxidation reactor produces 100 moles per hour of maleic anhydride, of which 40 kmols are condensed by cooling the gases in condensers. The remaining 60 moles per hour are recovered as a 50 wtpercent aqueous solution of maleic acid from an absorber. This is fed to an evaporation system to concentrate the solution of maleic acid. The concentrated solution is fed to a dehydration reactor system to produce a stream of crude maleic anhydride. This maleic anhydride, together with the crude maleic anhydride from the partial condensers is fed to an esterification unit. The crude maleic acid is mixed with recycle methanol from the refining section and fed to a plug flow, mono-ester reactor. The product from this is fed to a reaction column to react the mono-methyl maleate with methanol to produce di-methyl maleate. 300 mols per hour of methanol are fed to the bottom of the reaction column. Essentially dry, fully converted di-methyl maleate is fed to hydrogenation. Recycle methanol from the refining section is fed to the top of the reaction column as washed to minimise the di-methyl maleate in the overhead of the column. Methanol and water from the overhead of the reaction column is fed to the methanol column where the methanol is separated and recycled to the reaction column; Example 1 This example is particularly relevant to the arrangement of Figure 2. A butane oxidation reactor (not shown) produces 100 moles per hour of maleic anhydride, of which 40 kmols are condensed by cooling the gases in condensers (not shown). The remaining 60 moles per hour are recovered as a 50 wtpercent aqueous solution of maleic acid from an absorber (2) in line (5). This is fed to an evaporator system (6) and the maleic acid is concentrated (line 5a/37) and mixed together with the crude maleic anhydride from the partial condensers (line 8') to

49/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

form a 95 wtpercent solution of maleic acid. The aqueous maleic acid feed is mixed with recycled methanol from the refining section (line 38/16a') and fed to a plug flow, mono-ester reactor (36), where more than 80 percent of the maleic acid is converted to mono-methyl maleate. The product from this is fed to a reaction column (19') to react the mono-methyl maleate with methanol to produce di-methyl maleate. 540 mols per hour of methanol (lines 42 and 41) are fed to the bottom of the reaction column (19'). Di-methyl maleate (line 26') is fed to hydrogenation (20). Recycle methanol from the refining section is fed to the top of the reaction column as wash (line 16b') to minimise the di-methyl maleate and maleic acid in the overhead of the column. Methanol and water from the overhead (line 31') of the reaction column is fed to the methanol column (25') where the methanol is separated and recycled to the reaction column (line 39). Water and a small amount of recovered maleic acid and di-methyl maleate from the bottom of the methanol column are recycled to absorber (2) in line 3'. Thus this example clearly illustrates that the esterification can be carried out using a carboxylic acid starting material in the presence of water of solution that is additional to the water of esterification.; Example 2 This example relates particularly to Figure 3 and illustrates use of a side heater in the reaction column. In this example a 95 wtpercent solution of aqueous maleic acid is provided as described in Example 1. The aqueous maleic acid feed is mixed with recycle methanol from the refining section (line 38/16a') and fed to a plug flow, monoester reactor (36), where more than 80percent of the maleic acid is converted to mono-methyl maleate. The product from this is fed to reaction column (19') to react to the mono-methyl maleate with methanol to produce di-methyl maleate. This reaction column includes a heater near the feed point. The heater helps to drive off water from the column. 350 moles per hour of methanol (lines 42 and 41) are fed to the bottom of the reaction column (19'). Essentially water free, fully converted di-methyl maleate (line 26') is fed to hydrogenation (20). Recycle methanol from the refining section is fed to the top of the reaction column as wash (line 16b') to minimize the di-methyl maleate and maleic acid in the overhead of the column. Methanol or water from the overhead (line 31') of the reaction column is fed to the methanol column (25') where the methanol is separated and recycled to the reaction column (line 39). Water and a small amount of recovered maleic acid and di-methyl maleate from the bottom of the methanol column are recycled to the absorber (2) in line 3'.; This example relates to Figure 1. In this example a 95 wt percent solution of aqueous maleic acid is provided as described in Example 1. The aqueous maleic acid is fed to the mono-ester reactor column (9). Recycled methanol from the refining section (line 16a) is fed to the bottom of the column 9. More than 80 percent of the maleic acid is converted to mono-methyl maleate from the bottom product line (line 17) contains less than 10 mole percent water. Mainly water and methanol and a small amount of maleic acid in the overhead (line 14) are fed to the methanol column (line 25). The bottom product from column (9) is fed to a reaction column (19) to react the mono-methyl maleate with methanol to produce di-methyl maleate. 300 mols per hour of methanol (line 24) are fed to the bottom of the reaction column (19). Essentially water free, fully converted di-methyl maleate is fed (line 26) to hydrogenation in reactor (20). Recycle methanol from the refining section is fed to the top of the reaction column as wash (line 16b) to minimise the di-methyl maleate and maleic acid in the overhead of the column. Methanol and water from the overhead (line 31) of the reaction column is fed to the methanol column (25) where the methanol is separated and recycled to the reaction column (line 24). Water and a small amount of recovered maleic acid and dimethyl maleate from the bottom of the methanol column are recycled to the absorber (2) in line 3.; This example also refers to Figure 1. A butane oxidation reactor (not shown) produces 100 moles per hour of maleic anhydride, of which 40 kmols are condensed by cooling the gases in condensers (not shown). The remaining 60 moles per hour are recovered as a 50 wtpercent aqueous solution of maleic acid from an absorber (2) in line 5 and mixed together with the crude maleic anhydride from the partial condensers (line 8). The aqueous maleic acid is fed to the mono-ester reaction column (9). Recycle methanol from the refining section is fed (line 16a) to the bottom of the column (9). More than 80percent of the maleic acid is converted to mono-methyl maleate and the bottom product (line 17) contains less than 20 molpercent water. Mainly water and methanol and a small amount of maleic acid in the overhead are fed (line 14) to the methanol column (25). The bottom product from the mono-ester reaction column (9) is fed to a reaction column (19) to react the mono-methyl maleate with methanol to produce di-methyl maleate. 300 moles per hour of methanol are fed (line 24) to the bottom of the reaction column (19). Essentially water free, fully converted di-methyl maleate is fed (line 26) to hydrogenation. Recycle methanol from the refining section is fed to the top of the reaction column as wash (line 16b) to minimise the di-methyl maleate and maleic acid in the overhead of the column. Methanol and water from the overhead (line 31) of the reaction column is fed to the methanol column (25) where the methanol is separated and recycled to the reaction column (line 24). Water and a small amount of recovered maleic acid and di-methyl maleate from the bottom of the methanol column are recycled to the absorber (2) in line 3. Thus in this arrangement the evaporator and the mono-ester reaction column duties are combined in a single unit which will reduce the equipment costs by eliminating the evaporation equipment. With hydrogen, Product distribution / selectivity Patent; DAVY PROCESS TECHNOLOGY LIMITED; WO2005/51885; (2005); (A1) English View in Reaxys EXAMPLES 8 to 12 EXAMPLES 8 to 12 The general procedure of Examples 1 to 7 is repeated using dimethyl maleate, diethyl, maleate, diethyl succinate, dimethyl fumarate, or gamma-butyrolactone in place of dimethyl 1,4-cyclohexane-dicarboxylate, resulting in each case in production of butane-1,4-diol. A similar improvement in catalyst activity is observed following the reactivation procedure.

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

50/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Patent; Eastman Chemical Company; US5395991; (1995); (A) English View in Reaxys With hydrogen in methanol, T= 170 °C , p= 45004.5Torr , Inert atmosphere Hu, Qi; Fan, Guoli; Yang, Lan; Li, Feng; ChemCatChem; vol. 6; nb. 12; (2014); p. 3501 - 3510 View in Reaxys O

OH OH

Rx-ID: 29349146 View in Reaxys 66/281 Yield

Conditions & References

8 %, 5.7 %, 86.3 %

Hydrogenation of Succinic Acid Liquid-phase hydrogenation of succinic acid (SA) to 1,4-butanediol (BDO) was carried out over Re/XCu-MC catalysts(X =80, 12.7, 15.9, 23.3, and 26.8) in a batch reactorat 200 °C and 80 bar (H2). Succinic acid (0.5 g), methanol(25 ml), and a reduced catalyst (0.2 g) were charged intoan autoclave (150 ml). 1,4-Dioxane (25 ml) was used asa solvent for the reaction. The reactor was purged withnitrogen to remove air, and it was then pressurized up to40 bar using hydrogen. After heating the reactor to reactiontemperature (200 C), hydrogen pressure was raisedup to 80 bar. The catalytic reaction was carried out for20 h. The reaction mixture was stirred at 700 rpm in orderto avoid mass transfer limitation. Reaction products wereanalyzed using a gas chromatograph (Younglin, ACME-6100) equipped with a FID (flame ionization detector). With hydrogen in 1,4-dioxane, methanol, Time= 20h, T= 200 °C , p= 60006Torr , Inert atmosphere, Autoclave, Reagent/catalyst Hong, Ung Gi; Kim, Jeong Kwon; Lee, Joongwon; Lee, Jong Kwon; Yi, Jongheop; Song, In Kyu; Journal of Nanoscience and Nanotechnology; vol. 14; nb. 11; (2014); p. 8867 - 8872 View in Reaxys

76 %Chromat., 6 %Chromat., 14 %Chromat.

With η(+)-tris(pentane-2,5-dionato)ruthenium, hydrogen, zinc, [2-((diphenylphospino)methyl)-2-methyl-1,3-propanediyl]bis[diphenylphosphine], T= 20 - 120 °C , p= 60006Torr , Autoclave Rosi, Luca; Frediani, Marco; Frediani, Piero; Journal of Organometallic Chemistry; vol. 695; nb. 9; (2010); p. 1314 - 1322 View in Reaxys O

O O

Rx-ID: 29820755 View in Reaxys 67/281 Yield

Conditions & References With ZnCuO2, hydrogen, Time= 0.0005h, T= 170 °C , p= 30003Torr Ding, Guoqiang; Zhu, Yulei; Zheng, Hongyan; Zhang, Wei; Li, Yongwang; Catalysis Communications; vol. 11; nb. 14; (2010); p. 1120 - 1124 View in Reaxys Example: Hydrogenolysis The esters, resulting from the fermeatation extraction described above is then hydrogesoiyxed over a catalyst (e.g., reduced CnO/ ZnO), which should obtain high conversions (>98percent) and sekeiicities (e.g., International Patent Application No. WO 82/03854). Alternatively, one can proceed according to a process such as described in U.S. Patent No. 4,584,419. A stainless steel with an oil jacket maintained at 231 °€ was used for this reaction. Hydrogen was introduced by w ay of a pressure regulator and Oow controller (not shown) through line to the bottom end of a vaporiser containing a number of steel bails. Ester w as metered as a liquid to vaporiser through a line. The resulting vaporous mixture of ester and hydrogen w as passed through preheating coil to reactor. This contained a layer of glass balls, on which rested the catalyst bed. The remainder of the reactor was filled with glass balls and the upper end of the reactor was fitted with as exit tube which led to a condenser (not downstream from the condenser usin a wet gas m er. A charge of 30 ml of a granulated copper chromlte catalyst: was placet in the reactor hich as then purged with nitrogen at 42 bar. The oil bath was raised to a temperature of 231. degree. C. A 2percent M.sul>,2 I NufcJ aseous mi ture at 42 bar was then passed over the catalyst for 8 hours* followed by 10percent H.suh.2 in .sah.2 (stiU at 42 bar) for a further 16 h urs, and then by pn e H,sfe,2 (also at 42 har) for an additional 12 hours. Diethyl succinate was then introduced into the vaporizer corresponding to a liquid ho rly space velocity of 0.2/hr. The hydrogen gastester molar ratio in the va-

51/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

porous mixture was 313;. The temperature of the sand bat was maintained at 23i°C The condensate was analyzed by gas chromatography using a 1.82 meter long stainless steel column with an interna diameter of 3.18 mm containing 10percent dielhylene glycol succinate on Chromusorfe F 'W, a helium gas f ow rate of 3 ml/minute and a liaise iouisation detector. The n trumen was fitted with a chart recorder having a peak integrator and was calibrated asing a mixture of diethyl inaleafe, dialkyl succinate, bntyrelactsne, butane- 1, 4-dioi, teirahydrofuran and water of known composition. The exit gas was also sampled and analyzed by gas chromatography using the same tech usque. The identity of the peaks was confirmed by comparison of the retention times observed with those of authentic specimens of the materials in question and fey .mass spectroscopy. The following compounds were detected in the reaction mixture: diethyl succinate, hutyroiactone, butane- i,4~dkd, teirahydrofuran and water. Trace amounts of minor byproducts, including 2-eihoxytetrahydrofyran and 2~ethoxybutane-l ,4-dio were also detected n the reaction mixture, From the results obtained it appeared that diethyl succinate had been smoothly converted to products with a selectivity to teirahydrofuran of 52.2mol percent, a selectivity to o-butanol of l l.6 moi , a selectivity to gamma-butyrolactene of 2o.i snol percent, and a selectivity to feta.ne-l,4~d5ol of 10.1 snol percent, the balance being minor byproducts. With hydrogen, T= 231 °C , Autoclave Patent; ARCHER DANIELS MIDLAND COMPANY; STENSRUD, Kenneth; VENKITASUBRAMANIAN, Padmesh; WO2014/99431; (2014); (A1) English View in Reaxys O

O O

OH OH

Rx-ID: 36869336 View in Reaxys 68/281 Yield 46.4 %Chromat.

Conditions & References 2.3. Hydrogenation of succinic acid to THF Liquid-phase hydrogenation of succinic acid (SA) to THF was carried out over Ru–XC catalysts (X = 200, 250, 300, 350, and 400°C) in a batch reactor at 240°C and 80 bar (H2). Succinic acid (0.5 g) and a reduced Ru–XC catalyst (0.2 g) were charged into an autoclave (150 ml). 1,4-Dioxane (50 ml) was used as a solvent for the reaction. The reactor was purged with nitrogen to remove air, and then it was pressurized up to 40 bar using hydrogen. After heating the reactor to reaction temperature (240°C), hydrogen pressure was raised up to 80 bar. The catalytic reaction was carried out for 4 h. During the reaction, reaction mixture was stirred at 500 rpm in order to avoid mass transfer limitation. Reaction products were analyzed using a gas chromatograph (Younglin, ACME-6100) equipped with a FID (flame ionization detector). In order to investigate the stability of the catalyst after the reaction, the amount of ruthenium leaching was measured by ICP-AES (PerkinElmer, Optima-4300DV) analyses. With 2% Ru/C, hydrogen in 1,4-dioxane, Time= 4h, T= 240 °C , p= 60006Torr , Autoclave, Reagent/catalyst Hong, Ung Gi; Kim, Jeong Kwon; Lee, Joongwon; Lee, Jong Kwon; Song, Ji Hwan; Yi, Jongheop; Song, In Kyu; Applied Catalysis A: General; vol. 469; (2014); p. 466 - 471 View in Reaxys OH

HO HO

Rx-ID: 36979229 View in Reaxys 69/281 Yield

Conditions & References 2.3 Catalytic reactions under continuous flow General procedure: In a typical experiment, a deaereated solution of alkyne in methanol (0.1M) was allowed to flow through the PdMonoBor column catalyst (29mg, reactor volume 176 μL) at 0.2mLmin−1 together with a H2 flow of 1.3mLmin−1 at r.t. This resulted in a H2 pressure at the reactor inlet of ca. 1.2bar (corresponding to a H2/alkyne molar ratio of ca. 2.8), while the hydrogen gas was released at atmospheric pressure at the outlet of the reactor. Therefore, the pressure drop generated by monolithic reactor was ca. 0.2bar. The attainment of the steady-state conditions (ca. 1h) was taken as the reaction start time. The reaction was typically monitored for 14h time-on-stream by periodically analyzing the product solution for conversion and selectivity by GC, while 5.0mL aliquots were sampled at 1h intervals for Pd leaching determination by ICP-OES. The amount of Pd in solution was below the detection limit in each sample (0.006ppm). With hydrogen in methanol, Time= 0.005h, T= 20 °C , p= 150.015 - 900.09Torr , Inert atmosphere, Schlenk technique, Green chemistry

52/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Liguori, Francesca; Barbaro, Pierluigi; Journal of Catalysis; vol. 311; (2014); p. 212 - 220 View in Reaxys O HO

Rx-ID: 37313430 View in Reaxys 70/281 Yield

Conditions & References With hydrogen in water, T= 79.84 °C , p= 45004.5Torr , Flow reactor Li, Mengxia; Li, Guangyi; Li, Ning; Wang, Aiqin; Dong, Wenjun; Wang, Xiaodong; Cong, Yu; Chemical Communications; vol. 50; nb. 12; (2014); p. 1414 - 1416 View in Reaxys O OH

OH HO

Rx-ID: 37727396 View in Reaxys 71/281 Yield

Conditions & References 1 With hydrogen, T= 100 °C , p= 26252.6Torr , Flow reactor, Catalytic behavior, Reagent/catalyst, Concentration Patent; MITSUBISHI CHEMICAL CORPORATION; IZAWA, Yusuke; UTSUNOMIYA, Masaru; KONISHI, Norikazu; TANAKA, Kouta; US2014/135511; (2014); (A1) English View in Reaxys O

OH O

Rx-ID: 37872301 View in Reaxys 72/281 Yield 85.2 %

Conditions & References 3.1. Catalytic conversion of furfural into BDO Furfural is oxidized with performic acid to give a mixture of2(5H)-furanone and its isomer (2(3H)-furanone) [28]. The directoxidation of furfural with formic acid/hydrogen peroxide canproceed without the catalyst and the yield of furanones is 43.2percentafter nine-hour reaction (Table 1). This conversion of furfural tofuranones is too slow to be synthetically useful. Supported Pt andPd show marked catalytic activity for improving the conversion(Fig. S1). The leaching of Pd in the acidic solution is serious andgradual deactivation is observed. In the oxidation of furfural withformic acid/hydrogen peroxide, supported Pt is the most suitablecatalysts. The residual peroxide after the oxidation is hazardous anddangerous to the following hydrogenation. Supported platinum cancatalyze the self-decomposition of peroxide under mild conditions.Table 1 lists experimental results about the conversion from fur-fural to BDO over supported platinum catalysts. The oxidation of furfural to furanones is performed by gradual addition of hydro-gen peroxide into the reaction mixture during 1.0 h. The residualperoxide is removed by self-decomposition over supported Pt cat-alysts. Pt/TiO2–ZrO2removes the residual peroxide within 25 min(Table 1). No residual peroxide is detected by a negative per-oxide test. The reaction mixture is further hydrogenated to giveBDO without any separation or purification. Pt/TiO2–ZrO2(Pt load:1.0 wtpercent) is the most active catalyst and the total yield of BDOreaches 85.2percent. Stage 1: With formic acid, dihydrogen peroxide in methanol, water, Time= 1h, T= 24.84 °C , Autoclave Stage 2: With hydrogen in methanol, water, Time= 6h, T= 119.84 °C , p= 26252.6Torr , Autoclave, Inert atmosphere, Reagent/ catalyst Li, Fengbo; Lu, Tao; Chen, Bingfeng; Huang, Zhijun; Yuan, Guoqing; Applied Catalysis A: General; vol. 478; (2014); p. 252 - 258 View in Reaxys

53/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

HO H

H H

Rx-ID: 38451436 View in Reaxys 73/281 Yield

Conditions & References With 5% Pd/C, hydrogen, sodium hydroxide in water, Time= 50h, T= 200 °C , p= 30003Torr , pH= 9 - 12, Inert atmosphere, Pressure, pH-value, Temperature, Concentration Auneau, Florian; Berchu, Maeva; Aubert, Guillaume; Pinel, Catherine; Besson, Michele; Todaro, Daniela; Bernardi, Marco; Ponsetti, Tiziano; Di Felice, Renzo; Catalysis Today; vol. 234; (2014); p. 100 - 106 View in Reaxys

OH O

OH HO

Rx-ID: 38680627 View in Reaxys 74/281 Yield

Conditions & References With hydrogen in water, T= 90 °C , p= 22502.3Torr , Temperature Chen, Xiao; Zhang, Mingming; Yang, Kaixuan; Williams, Christopher T.; Liang, Changhai; Catalysis Letters; vol. 144; nb. 7; (2014); p. 1118 - 1126 View in Reaxys

O O

OH O

HO O

Rx-ID: 38841234 View in Reaxys 75/281 Yield 13.09 %Chromat., 77 %Chromat.

Conditions & References 2 :In this example 2 both reactor stages, as described in the Experimental apparatus, were used. [0111] A stream of liquid DMM was fed to the first reactor with palladium on carbon catalyst, under the following conditions: Pressure: 70 barg Temperatures: [0112] First stage outlet 130 to 135° C. [0113] Second stage outlet 178 to 182° C. Molar ratio H2/DMM: 50 Liquid hourly Space Velocity: [0114] First stage 2.0 hr−1 [0115] Second stage 0.2 hr−1 The main results of the analytical test are shown in Table 3 [TABLE-US-00003] TABLE 3 DMM Hydrogenation and Hydrogenolysis-Dry conditions DMM conversion 100percent Selectivity to 95 BDO/GBL/THF Composition (*) percent THF 13.09 BuOH 1.61 2Me THF less than 0.01 Me-butyrate 0.47 2-Metoxy-THF less than 0.01 4-Metoxy-BuOH 0.44 GBL 4.86 1,4 BDO 77.00 DMS 2.36 Unknown 1 0.17 Other unknown less than 0.01 (*) net of water and methanol Stage 1: With 10% palladium on activated charcoal, hydrogen, T= 130 - 135 °C , p= 52505.3Torr Stage 2: With hydrogen, T= 178 - 182 °C , p= 52505.3Torr Patent; CONSER SPA; Simola, Flavio; Scarsella, Marco; De Filippis, Paolo; US2014/316146; (2014); (A1) English View in Reaxys

54/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Rx-ID: 39583641 View in Reaxys 76/281 Yield

Conditions & References With [Ru(1,1,1-tris(diphenylphosphinomethyl)ethane)(trimethylenemethane)], hydrogen in 1,4-dioxane, Time= 24h, T= 160 °C , p= 37503.8Torr , Autoclave, Inert atmosphere Vom Stein, Thorsten; Meuresch, Markus; Limper, Dominik; Schmitz, Marc; Hölscher, Markus; Coetzee, Jacorien; ColeHamilton, David J.; Klankermayer, Jürgen; Leitner, Walter; Journal of the American Chemical Society; vol. 136; nb. 38; (2014); p. 13217 - 13225 View in Reaxys

O HO

OH HO

Rx-ID: 223324 View in Reaxys 77/281 Yield

Conditions & References With aluminium amalgam, water Paul; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 215; (1942); p. 304 View in Reaxys Paul; Tchelitcheff; Bulletin de la Societe Chimique de France; (1948); p. 197,202 View in Reaxys With hydrogen Patent; LYONDELL CHEMICAL TECHNOLOGY, L.P.; MANDIMUTSIRA, Beaven, S.; WHITE, Daniel, F.; WO2013/181255; (2013); (A1) English View in Reaxys O

OH HO

Rx-ID: 1501994 View in Reaxys 78/281 Yield 89 %

Conditions & References With titanium(III)-tris-(tetrahydridoborate) in dichloromethane, Time= 6h, T= -20 °C Ravikumar; Chandrasekaran, Srinivasan; Tetrahedron; vol. 53; nb. 8; (1997); p. 2973 - 2978 View in Reaxys

73 %

With chloro-trimethyl-silane, Benzyltriethylammonium borohydride, oxygen in dichloromethane, Time= 8h, T= 0 °C , other enol ethers Baskaran, S.; Chidambaram, N.; Narasimhan, N.; Chandrasekaran, S.; Tetrahedron Letters; vol. 33; nb. 42; (1992); p. 6371 - 6374 View in Reaxys

73 %

With chloro-trimethyl-silane, Benzyltriethylammonium borohydride, oxygen in dichloromethane, Time= 8h, T= 0 °C Baskaran, S.; Chidambaram, N.; Narasimhan, N.; Chandrasekaran, S.; Tetrahedron Letters; vol. 33; nb. 42; (1992); p. 6371 - 6374 View in Reaxys With water, T= 5 °C Austad, Brian C.; Benayoud, Farid; Calkins, Trevor L.; Campagna, Silvio; Chase, Charles E.; Choi, Hyeong-Wook; Christ, William; Costanzo, Robert; Cutter, James; Endo, Atsushi; Fang, Francis G.; Hu, Yongbo; Lewis, Bryan M.; Lewis, Michael D.; McKenna, Shawn; Noland, Thomas A.; Orr, John D.; Pesant, Marc; Schnaderbeck, Matthew J.; Wilkie, Gordon D.; Abe, Taichi; Asai, Naoki; Asai, Yumi; Kayano, Akio; Kimoto, Yuichi; Komatsu, Yuki; Kubota, Man-

55/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

abu; Kuroda, Hirofumi; Mizuno, Masanori; Nakamura, Taiju; Omae, Takao; Ozeki, Naoki; Suzuki, Taeko; Takigawa, Teiji; Watanabe, Tomohiro; Yoshizawa, Kazuhiro; Synlett; vol. 24; nb. 3; (2013); p. 327 - 332; Art.No: ST-2012-Y0973-C View in Reaxys

Rx-ID: 8544477 View in Reaxys 79/281 Yield

Conditions & References With hydrogen, (1 percentPd+PV3Mo9)/C, T= 29.85 °C , p= 22501.8Torr , Catalytic hydrogenation, Product distribution, Further Variations: Catalysts Zakarina; Volkova; Russian Journal of Applied Chemistry; vol. 73; nb. 1; (2000); p. 74 - 77 View in Reaxys With hydrogen, 10 wt. % palladium on activated carbon in water, Time= 1.65h, T= 50 °C , atmospheric pressure, Product distribution, Further Variations: Catalysts, Temperatures Pyatnitsyna; El'chaninov; Savost'yanov; Russian Journal of Applied Chemistry; vol. 79; nb. 1; (2006); p. 89 - 92 View in Reaxys With 2% active carbon-supported palladium, hydrogen in water, Time= 7.16667h, p= 760.051Torr , Reagent/catalyst Pyatnitsyna; El'Chaninov; Russian Journal of Applied Chemistry; vol. 86; nb. 3; (2013); p. 394 - 397; Zh. Prikl. Khim. (S.Peterburg, Russ. Fed.); vol. 86; nb. 3; (2013); p. 425 - 428,4 View in Reaxys O O

OH HO

O O

Rx-ID: 35508445 View in Reaxys 80/281 Yield

Conditions & References

13.09 %, 77 2 :Example 2In this example 2 both reactor stages, as described in the Experimental apparatus, were used. A stream of liquid % DMM was fed to the first reactor with palladium on carbon catalyst, under the following conditions:Pressure: 70 bargTemperatures:First stage outlet 130 to 135Second stage outlet 178 to 182Molar ratio Hz/DMM: 50Liquid hourly Space Velocity:-1First stage 2.0 hr-1Second stage 0.2 hrThe main results of the analytical test are shown in Table 3Table 3 - DMM Hydrogenation and Hydrogenolysis -Dry conditionsDMS 2.36Unknown 1 0.17Other unknown less than 0.01(*) net of water and methanol With 10% palladium on activated charcoal, hydrogen, T= 130 - 182 °C , p= 52505.3Torr Patent; CONSER SPA; SIMOLA, Flavio; SCARSELLA, Marco; DE FILIPPIS, Paolo; WO2013/76747; (2013); (A1) English View in Reaxys O

O O

Rx-ID: 35508446 View in Reaxys 81/281 Yield 6.34 %, 5.33 %, 83.96 %

Conditions & References 3 :Example 3In this example 3 the conditions of example 2 have been repeated, with the only difference of a small addition of water to the feed to simulate the conditions of an industrial plant, where the recycle gas is saturated by water .The main results of the analytical test are shown in Table 4 Table 4 - DMM Hydrogenation and Hydrogenolysis - Wet conditionsUnknown 1 0.95Other unknown less than 0.01 (*) net of water and methanolThis example 3 shows that in wet conditions the overall results are very similar to the dry conditions ones, with the main difference in the yields in THF which drops from 13percent to around 6percent, being this difference compensated by an equivalent increased yield in BDO.The overall yield in the three valuable

56/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

products, BDO, GBL and THF, is 95.6percent. Considering that the unreacted DMS may be separated by distillation, alone or in mixture with GBL, and recycled back to the reaction system, the actual overall yield is around With 10% palladium on activated charcoal, hydrogen in water, T= 130 - 182 °C , p= 52505.3Torr Patent; CONSER SPA; SIMOLA, Flavio; SCARSELLA, Marco; DE FILIPPIS, Paolo; WO2013/76747; (2013); (A1) English View in Reaxys

Rx-ID: 35524940 View in Reaxys 82/281 Yield

Conditions & References With hydrogen in water, Time= 9.33333h, T= 50 °C , p= 760.051Torr , Reagent/catalyst, Temperature Pyatnitsyna; El'Chaninov; Russian Journal of Applied Chemistry; vol. 86; nb. 3; (2013); p. 394 - 397; Zh. Prikl. Khim. (S.Peterburg, Russ. Fed.); vol. 86; nb. 3; (2013); p. 425 - 428,4 View in Reaxys

Rx-ID: 35524941 View in Reaxys 83/281 Yield

Conditions & References With 2% active carbon-supported palladium, hydrogen in water, Time= 5.16667h, T= 40 °C , p= 760.051Torr , Reagent/catalyst Pyatnitsyna; El'Chaninov; Russian Journal of Applied Chemistry; vol. 86; nb. 3; (2013); p. 394 - 397; Zh. Prikl. Khim. (S.Peterburg, Russ. Fed.); vol. 86; nb. 3; (2013); p. 425 - 428,4 View in Reaxys O

O O

HO OH

HO HO

Rx-ID: 36543367 View in Reaxys 84/281 Yield

Conditions & References With hydrogen in water, Time= 50h, T= 160 °C , p= 112511Torr , Inert atmosphere, High pressure, Sonication, Reagent/catalyst Tapin, Benoit; Epron, Florence; Especel, Catherine; Ly, Bao Khanh; Pinel, Catherine; Besson, Michele; ACS Catalysis; vol. 3; nb. 10; (2013); p. 2327 - 2335 View in Reaxys OH

OH HO HO

Rx-ID: 38797866 View in Reaxys 85/281 Yield

Conditions & References With 10% palladium on activated charcoal, hydrogen in ethanol, T= 20 °C , p= 750.075Torr , chemoselective reaction Chung, Jooyoung; Kim, Chanhoi; Jeong, Hansaem; Yu, Taekyung; Binh, Do Huy; Jang, Jyongsik; Lee, Jaichan; Kim, B. Moon; Lim, Byungkwon; Chemistry - An Asian Journal; vol. 8; nb. 5; (2013); p. 919 - 925 View in Reaxys

57/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

OH HO

Rx-ID: 3323186 View in Reaxys 86/281 Yield

Conditions & References

68 %, 11 %, With 2-ethoxy-ethanol, dmap, hexarhodium hexadecacarbonyl in water, Time= 48h, T= 50 °C , p= 7600Torr 21 % Kaneda, Kiyotomi; Imanaka, Toshinobu; Teranishi, Shiichiro; Chemistry Letters; (1983); p. 1465 - 1466 View in Reaxys 10 %Chromat., 20 %Chromat., 31 %Chromat.

With 1-hydroxytetraphenylcyclopentadienyl(tetraphenyl-2,4-cyclopentadien-1-one)-μ-hydrotetracarbonyldiruthenium(II), dicarbonylacetylacetonato rhodium(I), hydrogen, 4,5-bis(diphenylphosphino)-9 ,9-dimethylxanthene in N,N-dimethyl acetamide, Time= 12.5h, T= 120 °C , p= 15001.5Torr Takahashi, Kohei; Yamashita, Makoto; Nozaki, Kyoko; Journal of the American Chemical Society; vol. 134; nb. 45; (2012); p. 18746 - 18757 View in Reaxys

O O

Rx-ID: 33106484 View in Reaxys 87/281 Yield

Conditions & References 17 :To a 100 mL round bottom flask equipped with a stir bar was added 4.990 g LA-BDO-LA prepared according to Example 16 and recrystallized twice to greater than 99percent purity by GC-FID. To this was added a solution of 0.88 g NaOH in 4.46 g H2O. The reaction mixture was then stirred at 80° C. for 210 minutes, at which point the reaction was cooled and the pH adjusted to approximately 4.5, according to the procedure described in Example 19. GC-FID analysis showed the complete disappearance of starting material and the appearance of peaks attributed to LA and 1,4-BDO, indicating near quantitative hydrolysis of the diester. Stage 1: With water, sodium hydroxide, Time= 3.5h, T= 80 °C Stage 2: With hydrogenchloride in water, pH= 4.5, Product distribution / selectivity Patent; SEGETIS, INC.; US2012/123147; (2012); (A1) English View in Reaxys O

Rx-ID: 33502255 View in Reaxys 88/281 Yield

Conditions & References 4 :In these examples, aqueous pure 1 ,4-butynediol or technical-grade 1 ,4-butynediol in example 5 (denoted by *) was vaporized in a stream of hydrogen under superatmospheric pressure in a vaporizer which comprised metal filling rings and was externally heated to 240°C by means of oil and hydrogenated in a reactor tube filled with catalyst (100 ml unless indicated otherwise in table 2) or catalysts. The reactor tube was configured as a double-walled tube which was heated or cooled externally by means of oil. The reaction output was cooled and the condensed product was depressurized via a valve to atmospheric pressure, while the gas phase was recirculated via a recycle gas fan to the vaporizer. A small part of the gas was discharged as offgas. Hydrogen was introduced by means of a fresh gas supply into the reaction in the amount corresponding to the hydrogen consumed by reaction and offgas. The reaction pressure was kept constant in this way. The experimental results are shown in table 2. The conversion of butynediol was in all cases quantitative. To calculate the selectivity, products such as1 ,4-butenediol and 4-hydroxybutanal and acetals thereof, gamma-butyrolactone (GBL) and butanediol (BDO) were included in the calculation as compounds still to be hydrogenated or reacted to form THF. With hydrogen, 0.5% Pd/Sibunit carbon material in water, T= 225 - 240 °C , p= 6750.68Torr , Product distribution / selectivity Patent; BASF SE; PINKOS, Rolf; OSETSKA, Olga; KOeNIGSMANN, Lucia; BASF JAPAN LTD.; WO2012/95709; (2012); (A1) English View in Reaxys

58/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

7 :Examples 7 to 9 below were carried out using technical-grade 1 ,4-butynediol at atmospheric pressure. The 1 ,4-butynediol solution was pumped continuously into a thin film evaporator with about 99.5percent by weight of the feed solution being fed in vapor form to the in each case about 50 ml of catalyst or mixture of two catalysts in a reactor tube having a diameter of 2.7 cm. Both reactor tube and thin film evaporator were operated together using recycle gas. The amount of fresh gas was 2.5 mol of hydrogen/mole of butynediol. After the reactor tube, the gaseous reactor output was cooled to about 20°C and product which condensed out was collected. The offgas was passed through a cold trap at -78°C and further product was condensed out in this way. The two condensates were combined for the purposes of analysis. The catalysts were activated in a stream of hydrogen before the reaction. The results are shown in table 2. With hydrogen, 5 weight% Pd/C in water, T= 180 °C , p= 760.051Torr , Product distribution / selectivity Patent; BASF SE; PINKOS, Rolf; OSETSKA, Olga; KOeNIGSMANN, Lucia; BASF JAPAN LTD.; WO2012/95777; (2012); (A1) English View in Reaxys 12 :In these examples, aqueous pure or technical-grade butynediol (denoted by *) was vaporized in a stream of hydrogen under superatmospheric pressure in a vaporizer which comprised metal packing rings and was externally heated by means of oil (about 240°C) and hydrogenated in a reactor tube filled with catalyst or catalyst mixture (100 ml unless indicated otherwise). The reactor tube was configured as a double-walled tube which was heated or cooled externally by means of oil. The reaction output was cooled and the product which condensed out was depressurized to atmospheric pressure through a valve, while the gas phase was recirculated via the vaporizer by means of a recycle gas blower. A small part of the gas was discharged as offgas. Hydrogen was introduced into the reaction in an amount corresponding to hydrogen consumed by reaction and offgas via a fresh gas supply. The reaction pressure was kept constant in this way. The experimental results are shown in table 2. The conversion of butynediol was quantitative in each case. To calculate the selectivity, products such as 1 ,4-butenediol and 4-hydroxybutanal and acetals thereof, gamma-butyrolactone (GBL) and butanediol (BDO) were included in the calculation as compounds still to be hydrogenated or reacted to form THF. The results are shown in table 3. With hydrogen, 0.5% Pd/Sibunit carbon material in water, T= 225 - 240 °C , p= 6750.68Torr , Product distribution / selectivity Patent; BASF SE; PINKOS, Rolf; OSETSKA, Olga; KOeNIGSMANN, Lucia; BASF JAPAN LTD.; WO2012/95777; (2012); (A1) English View in Reaxys O OH

Rx-ID: 33502257 View in Reaxys 89/281 Yield

Conditions & References 9 :Examples 7 to 9 below were carried out using technical-grade 1 ,4-butynediol at atmospheric pressure. The 1 ,4-butynediol solution was pumped continuously into a thin film evaporator with about 99.5percent by weight of the feed solution being fed in vapor form to the in each case about 50 ml of catalyst or mixture of two catalysts in a reactor tube having a diameter of 2.7 cm. Both reactor tube and thin film evaporator were operated together using recycle gas. The amount of fresh gas was 2.5 mol of hydrogen/mole of butynediol. After the reactor tube, the gaseous reactor output was cooled to about 20°C and product which condensed out was collected. The offgas was passed through a cold trap at -78°C and further product was condensed out in this way. The two condensates were combined for the purposes of analysis. The catalysts were activated in a stream of hydrogen before the reaction. The results are shown in table 2. With hydrogen, Ni/Cu/MnOx/ZrO2 in water, T= 180 °C , p= 760.051Torr , Product distribution / selectivity Patent; BASF SE; PINKOS, Rolf; OSETSKA, Olga; KOeNIGSMANN, Lucia; BASF JAPAN LTD.; WO2012/95777; (2012); (A1) English View in Reaxys 9 :Examples 7 to 9 below were carried out using technical-grade 1 ,4-butynediol at atmospheric pressure. The 1 ,4-butynediol solution was pumped continuously into a thin film evaporator with about 99.5percent by weight of the feed solution being fed in vapor form to the in each case about 50 ml of catalyst or mixture of two catalysts in a reactor tube having a diameter of 2.7 cm. Both reactor tube and thin film evaporator were operated together using recycle gas. The amount of fresh gas was 2.5 mol of hydrogen/mole of butynediol. After the reactor tube, the gaseous reactor output was cooled to about 20°C and product which condensed out was collected. The offgas was passed through a cold trap at -78°C and further product was condensed out in this

59/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

way. The two condensates were combined for the purposes of analysis. The catalysts were activated in a stream of hydrogen before the reaction. The results are shown in table 2. With hydrogen, Ni/Cu/MnOx/ZrO2 in water, T= 220 °C , p= 760.051Torr , Product distribution / selectivity Patent; BASF SE; PINKOS, Rolf; OSETSKA, Olga; KOeNIGSMANN, Lucia; BASF JAPAN LTD.; WO2012/95777; (2012); (A1) English View in Reaxys O

OH OH

Rx-ID: 33564678 View in Reaxys 90/281 Yield

Conditions & References 11 :[Example 11] Production of butyrolactone from the fumaric acid through the hydrogenation reaction [catalyst: CuO(80)SiO2(20)]The catalyst was produced by using the same method as Example 1. The fumaric acid was used instead of the levulinic acid as the reactant, the temperature and the pressure of the reactor were fixed to 265°C and 25 bar, respectively, and the reaction was performed by using the same method as Example 1. The results are described in the following Table 10.As confirmed through Table 10, the conversion of fumaric acid over CuO(80)SiO2(20) was 100percent, and the catalyst exhibited very high selectivity of 65percent to butyrolactone. With hydrogen in 1,4-dioxane, T= 265 °C , p= 18751.9Torr Patent; Korea Research Institute Of Chemical Technology; EP2476674; (2012); (A2) English View in Reaxys O O

Rx-ID: 33590016 View in Reaxys 91/281 Yield

Rx-ID: 34449401 View in Reaxys 92/281 Yield

60/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

View in Reaxys Rx-ID: 34575449 View in Reaxys 93/281 Yield

Conditions & References With sulfuric acid, hydrogen in water, Time= 24h, T= 99.84 °C , p= 60006Torr , Reagent/catalyst, Temperature Amada, Yasushi; Watanabe, Hideo; Hirai, Yuichirou; Kajikawa, Yasuteru; Nakagawa, Yoshinao; Tomishige, Keiichi; ChemSusChem; vol. 5; nb. 10; (2012); p. 1991 - 1999 View in Reaxys H

OH OH

H OH

Rx-ID: 34575450 View in Reaxys 94/281 Yield

Conditions & References With sulfuric acid, hydrogen in water, Time= 4h, T= 99.84 °C , p= 60006Torr Amada, Yasushi; Watanabe, Hideo; Hirai, Yuichirou; Kajikawa, Yasuteru; Nakagawa, Yoshinao; Tomishige, Keiichi; ChemSusChem; vol. 5; nb. 10; (2012); p. 1991 - 1999 View in Reaxys

O HO

O O

HO S

S O

Rx-ID: 30276008 View in Reaxys 95/281 Yield 99 - 100 %, 85 %

Conditions & References II-3 :EXAMPLE II-3Using methanol as a solvent, the concentration of the solution of the dicarbonate compound (0.045 mmol) shown below was adjusted to 2.0*10-2 M. The resulting solution was freeze-deaerated, and transferred to a reaction tube made of Pyrex. After light irradiation was performed for one hour at room temperature using a super-high pressure mercury lamp, the reaction solution was concentrated under reduced pressure. The residue was purified by silica gel column chromatography, and the monocarbonate compound in which only sulfone was deprotected was isolated in 98percent. Simultaneously, the tetracyclic compound was isolated in 88percent. Further, by using the same process as employed in Example II-2(3), the sulfur atom was oxidized to sulfone. Subsequently, the obtained compound (0.037 mmol) was dissolved in deuterated methanol, and the concentration thereof was adjusted to 2.0*10-2 M. The resulting solution was freeze-deaerated, and transferred to an NMR tube. After light irradiation was performed for one hour at room temperature using a super-high pressure mercury lamp, 1H-NMR confirmed that the target 1,4-butanediol was quantitatively obtained. Further, the reaction solution was concentrated under reduced pressure, and purification was performed to isolate a tetracyclic compound in 85percent. in d(4)-methanol, Time= 1h, T= 20 °C , light irradiation, Conversion of starting material Patent; National University Corporation Nara Institute of Science and Technology; US2011/28738; (2011); (A1) English View in Reaxys

61/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

O O O

Rx-ID: 30662001 View in Reaxys 96/281 Yield

Conditions & References 10 :Catalyst DRD 92/89 D obtained from Davy Process Technology Ltd and activated as detailed above was used in a process for the production of tetrahydrofuran from a feed comprising maleic anhydride. The reaction conditions are detailed in Table 1 and the results in Table 2. TABLE 1 Example 2 Example 3 Example 4 Example 5 Inlet Temperature ° C. 194 194 204 217 Exit Temperature ° C. 190 189 198 210 Pressure psig 885 900 900 900 Hydrogen:ester 352 246 246 246True LHSV, hr-1 0.344 0.344 0.344 0.344 TABLE 2 Selectivities, mole percent Example 2 Example 3 Example 4 Example 5 Tetrahydrofuran 83.21 82.69 92.78 97.43 n-butanol 0.15 0.15 0.25 0.52 η-butyrolactone 11.79 13.38 4.07 0.13 1,4-butanediol 1.63 1.85 0.70 0.00 Conversion, mole percent 67.72 67.48 91.59 99.28 With hydrogen, DRD 92/89 D, T= 197 °C , p= 47304.6Torr , Product distribution / selectivity Patent; DAVY PROCESS TECHNOLOGY LIMITED; US2011/92721; (2011); (A1) English View in Reaxys OH

HO HO

Rx-ID: 31215164 View in Reaxys 97/281 Yield

Conditions & References With 5% Pd(II)/C(eggshell), hydrogen in isopropyl alcohol, Time= 1h, T= 30 °C , p= 7500.75Torr , Autoclave, optical yield given as percent de Chan, Chun Wong Aaron; Xie, Yaling; Cailuo, Nick; Yu, Kai Man Kerry; Cookson, James; Bishop, Peter; Tsang, Shik Chi; Chemical Communications; vol. 47; nb. 28; (2011); p. 7971 - 7973 View in Reaxys H

OH OH

Rx-ID: 31641740 View in Reaxys 98/281 Yield

Conditions & References With hydrogen in water, Time= 4h, T= 119.84 °C , p= 25502.6Torr Chia, Mei; Pagan-Torres, Yomaira J.; Hibbitts, David; Tan, Qiaohua; Pham, Hien N.; Datye, Abhaya K.; Neurock, Matthew; Davis, Robert J.; Dumesic, James A.; Journal of the American Chemical Society; vol. 133; nb. 32; (2011); p. 12675 12689 View in Reaxys O O

Rx-ID: 31796445 View in Reaxys 99/281 Yield

Conditions & References 22 :Example 22Hydrogenation of methyl maleate was carried out according to the following reaction scheme. Methyl maleate (4.0 mmol), the complex 1a (0.01 mmol) produced in Example 1, sodium methoxide (0.2 mmol), and methanol (4 mL) were added to a 100 mL autoclave equipped with a stirrer, and the hydrogenation was carried out at 80° C. for 8 hrs with hydrogen pressure of 5 MPa. As a result of the analysis of the reaction for the reaction solution according to gas chromatography, it was found that the reaction conversion rate was 100percent and the selectivity was 100percent. With hydrogen, sodium methylate, [RuHCl(CO)(NH(C2H4PPh2)2)] in methanol, Time= 8h, T= 80 °C , p= 37503.8Torr

62/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Patent; Takasago International Corporation; US2011/237814; (2011); (A1) English View in Reaxys

OH HO

Rx-ID: 8991315 View in Reaxys 100/281 Yield

Conditions & References With hydrogen, [Rh(η4-C7H8)(PPh3)2][BF4] in water, Time= 2h, T= 80 °C , p= 45600Torr Dyson; Ellis; Welton; Canadian Journal of Chemistry; vol. 79; nb. 5-6; (2001); p. 705 - 708 View in Reaxys With hydrogen in water, T= 22 °C , p= 760.051Torr , chemoselective reaction Drelinkiewicz; Zieba; Krol; Sobczak; Grzywa; Polish Journal of Chemistry; vol. 82; nb. 9; (2008); p. 1717 - 1732 View in Reaxys 6 :The same continuous single tube bubble column up flow reactor as referred to in Example 1 was used for hydrogenation studies of pure Butynediol ('Aldrich* make) dissolved in demineralized water to make a 35percent solution and was operated at the same temperature and pressure conditions as mentioned in Example 1. The hydrogenation reactor was packed with standard industrial Pd/AkQj catalysts containing 0.002percent Pd contents, and was operated under the same range of GHSV and LHSV as mentioned in Examples 2 and 3. Hydrogenation was carried out just near complete conversion of butynediol. The catalyst activity achieved was 13,100 of butynediol/day-g palladium. Selectivities for the desired product (1,4 butenediol) and the undesired product (1,4 butanediol) are expressed. The results are tabulated in Table 6.Table 6Various runs on the 0.002percent Pd/ Al2Qj catalyst as illustrated by Examples 2,3,4,5 and 6 were carried out for a total duration of more than 5000 hours. The catalyst activity showed consistency during this period. With hydrogen, Pd/Al2O3 in water, T= 110 °C , p= 7500.75Torr , Product distribution / selectivity Patent; HINDUSTAN ORGANIC CHEMICALS LIMITED; SATHE, Amod, Madhukar; SHINDE, Bapurao, Sidram; WO2010/44092; (2010); (A1) English View in Reaxys With hydrogen in water, Time= 1h, T= 100 °C , p= 15001.5Torr , Kinetics, Temperature, Pressure, Concentration Rode; Tayade; Nadgeri; Jaganathan; Chaudhari; Organic Process Research and Development; vol. 10; nb. 2; (2006); p. 278 284 View in Reaxys

OH HO

Rx-ID: 23566630 View in Reaxys 101/281 Yield

Conditions & References With hydrogen, Reppe reaction Patent; BASF AKTIENGESELLSCHAFT; WO2005/87757; (2005); (A1) German View in Reaxys 1 :Example 1 In a reactor battery consisting of three cylindrical 10 m-long reactors with a diameter of 15 cm, filled with a catalyst (approx. 15percent CuO, approx. 4percent Bi2O3 on SiO2) in the form of 0.5-2 mm spall, prepared according to DE-A 26 02 418, which was operated both with cycle gas and with liquid circulation in upward mode (feed to circulation 10:1), 20 kg/h 32percent aqueous formaldehyde and 2.8 kg/h of acetylene were reacted at 5 bar and from 70 to 90° C. at a pH of 6. The reaction product of the first reactor was conveyed into the second reactor and that of the second reactor into the third reactor. In this way, >95percent of the formaldehyde and of the acetylene were converted to 1,4-butynediol. The pH of the reaction was controlled such that the pH was measured downstream of each reactor and, if required, small amounts of 1percent aqueous NaOH solution were metered in. The reaction effluent of the third reactor was separated into gas and liquid phase in a separator. The liquid phase comprised approx. 50percent by weight of butynediol, 1.3percent by weight of propynol, 0.5percent by weight of formaldehyde, 0.5percent by weight of methanol, dissolved acetylene and several 100 ppm of nonvolatile oligomers, polymers and catalyst constituents, and also <0.5percent other impurities and water. The gas phase, which comprised essentially acetylene, was recycled predominantly as cycle gas; 1percent of the gas stream was discharged. The liquid effluent of the separator was passed into a column in which water, formaldehyde, methanol and propynol were removed (approx. 1 kg) via the top at 0.2 bar absolute

63/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

and bottom temperature 90° C., and recycled into the reaction.The bottom effluent was passed continuously into an intermediate buffer in which the mean residence time was 10 h at 60° C. and 1 bar (absolute). The butynediol-containing solution was withdrawn from this intermediate buffer and hydrogenated in a two-stage reactor battery with hydrogen over an Ni catalyst according to EP-A 394 841 in the form of 3.x.3 mm tablets (approx. 38percent by weight of Ni, approx. 12percent by weight of Cu on ZrO2/MoO3). The molar ratio of fresh hydrogen to 1,4-butynediol was 2.1:1. The first hydrogenation reactor (length 10 m, diameter 10 cm) was operated with liquid circulation for cooling in upward mode at reactor inlet pressure 250 bar and 120-140° C. To adjust the pH to approx. 7.2, 1percent aqueous NaOH or gamma-butyrolactone was metered into the feed. The second reactor (length 10 m, diameter 5 cm) was operated in trickle mode of 140-160 to 140 to 175° C. at 250 bar. The effluent was separated in a separator into liquid phase and gas phase, and the gas phase was recycled by means of a cycle gas compressor. Approx. 1percent of the amount of the fresh gas was discharged continuously from the gas stream as offgas and incinerated. The hydrogenation effluent was decompressed to approx. 5 bar and the gas stream released was likewise sent to the combustion. Subsequently, the degassed hydrogenation effluent was separated into the individual constituents in a battery of columns. In a first column, low boilers such as methanol, propanol and n-butanol were removed via the top with water at approx. 5 bar and a bottom temperature of approx. 170° C. and sent to incineration. The bottom stream passed into a second column in which quite predominantly water was distilled off via the top, likewise at approx. 0.3 bar and bottom temperature approx. 130° C. The bottom stream of the second column was separated in a third column at approx. 0.15 bar and bottom temperature approx. 175° C. such that predominantly 1,4-butanediol together with gamma-butyrolactone, 2-methyl-1,4-butanediol, acetal, pentanediols and a few further, quantitatively insignificant components were distilled off via the top. This top stream was separated in a fourth column, which was operated at approx. 0.04 bar and bottom temperature approx. 165° C., into a top stream which, as well as 1,4butanediol, comprised predominantly gamma-butyrolactone, a sidde stream which consisted of predominantly 1,4-butanediol, and a bottom stream which likewise consisted of predominantly 1,4-butanediol and was fed into the bottom stream of the third column. The bottom stream of the third column, together with that of the fourth column, was separated in a fifth column at approx. 0.05 bar and bottom temperature 170° C. such that the top stream, which comprised predominantly 1,4-butanediol, was recycled into the feed of the third column, while the bottom stream, which, as well as a little 1,4-butanediol, comprised high boilers and salts, was discharged and incinerated.Course of the hydrogenation and purity of the 1,4-butanediol after purificationAfter 24 h, in the hydrogenation effluent of the first reactor (calculated without water), approx. 94percent 1,4-butanediol, 0.1percent 1,4-butenediol, 0.05percent gamma-butyrolactone, 0.05percent 2-methyl-1,4-butanediol, 1.5percent methanol, 2.5percent npropanol, 1.1percent n-butanol, 0.07percent acetal, 0.1percent pentanediols and a multitude of quantitatively minor components were found. The pressure drop (reactor outlet pressure minus reactor inlet pressure) was 2.5 bar. In the outlet of the post-hydrogenation reactor, (calculated without water), approx. 94.2percent 1,4-butanediol, 0.04percent gamma-butyrolactone, 0.06percent 2-methyl-1,4-butanediol, 1.6percent methanol, 2.5percent n-propanol, 1.2percent n-butanol, 0.04percent acetal and a multitude of quantitatively minor components were found.The pure 1,4-butanediol had the composition of 99.90percent 1,4-butanediol, 0.05percent 2-methyl-1,4-butanediol, 0.04percent acetal and several quantitatively insignificant components.After 12 weeks of operating time of the hydrogenation, in the hydrogenation effluent of the first reactor (calculated without water), approx. 91percent 1,4-butanediol, 1.1percent 1,4-butenediol, 0.05percent 1,4-butynediol, 0.08percent gamma-butyrolactone, 0.08percent 2methyl-1,4-butanediol, 1.5percent methanol, 2.3percent n-propanol, 2.9percent n-butanol, 0.15percent acetal and a multitude of quantitatively minor components were found. The pressure drop (reactor outlet pressure minus reactor inlet pressure) was 4.5 bar. In the outlet of the second reactor, (calculated without water), approx. 91.2percent 1,4-butanediol, 0.05percent gamma-butyrolactone, 0.09percent 2-methyl-1,4-butanediol, 1.7percent methanol, 2.5percent n-propanol, 3.0percent n-butanol, 0.13percent acetal and a multitude of quantitatively minor components were found.The pure 1,4-butanediol had the composition of 99.80percent 1,4-butanediol, 0.08percent 2-methyl-1,4-butanediol, 0.1percent acetal and several quantitatively minor components.After these 12 weeks of operating time, the first hydrogenation reactor was flushed with water and the catalyst was then deinstalled under water and washed to free it of adhering impurities with water and then reinstalled. Thereafter, virtually the same hydrogenation profile and 1,4-butanediol purity as before were established. It was possible to pass through a total of 4 wash cycles until the hydrogenation result slowly became poorer. Stage 1: With water, 15percent CuO/4percent Bi2O3 on SiO2, T= 70 - 90 °C , p= 3750.38Torr , pH= 6 Stage 2:, Time= 10h, T= 60 °C , p= 750.075Torr , Aqueous buffer Stage 3: With hydrogen, 38percent wt Ni/12percent wt Cu on ZrO2/MoO3 in water, T= 120 - 175 °C , p= 187519Torr , pH= 7.2 Patent; BASF SE; US2010/16643; (2010); (A1) English View in Reaxys

Rx-ID: 29140062 View in Reaxys 102/281 Yield

Conditions & References 1C :A solution of diphosphine (16 mmol) and triethylphosphine (16 mmol) in dry degassed solvent (4 mL) is added under a stream of argon or nitrogen to [Rh(CO)2(acac)] (8 mmol) under an argon atmosphere. The resulting solution is transferred in a

64/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

gastight syringe to a 25-mL autoclave under an argon atmosphere. The autoclave is flushed twice with a 1:1 CO/H2 mixture and then pressurized to 30 bar with the CO/H2 mixture. The autoclave is then heated to 120° C. with stirring, the pressure is increased to 39.5 bars, allyl alcohol (1 mL) is then injected from a sidearm, and the autoclave pressurized to 40 bar with the CO/H2 mixture. The autoclave is kept at a constant pressure of 40 bar, and the gas uptake of the reaction is monitored in a ballast vessel from which the gas is delivered. When there is no further gas uptake, the autoclave is cooled and depressurized. The resulting solution is analyzed by gas chromatography to determine the products of the reaction. The reaction produces BDO, MPDiol, HBA, HMPA, and C3 products (n-propanol and propionaldehyde). The BDO-MPDiol selectivity (i.e., moles BDO+MPDiol produced/moles allyl alcohol converted*100percent) and the ratio of BDO:MPDiol (l:b or linear:branched) is also measured.The results, shown in Table 1, demonstrate that the use of an alcohol solvent results in much higher BDO-MPDiol selectivity and the use of a diphosphine and trialkylphosphine unexpectedly results in significantly higher BDO:MPDiol (l:b) ratio than just using a trialkylphosphine With hydrogen, acetylacetonatobis(ethylene)rhodium(I), trans-1,2-bis(bis(3,5-dimethylphenyl)-phosphinomethyl)cyclobutane, triethylphosphine in ethanol, T= 120 °C , p= 22502.3 - 30003Torr , Inert atmosphere, Product distribution / selectivity Patent; Lyondell Chemical Technology, L.P.; US7655821; (2010); (B1) English View in Reaxys O

OH OH

Rx-ID: 29349147 View in Reaxys 103/281 Yield

Conditions & References

14 %Chromat., 56 %Chromat., 28 %Chromat.

O HO

OH OH

Rx-ID: 29349150 View in Reaxys 104/281 Yield

Conditions & References

11 %Chromat., 81 %Chromat.

With methanol, η(+)-tris(pentane-2,5-dionato)ruthenium, hydrogen, zinc, [2-((diphenylphospino)methyl)-2-methyl-1,3-propanediyl]bis[diphenylphosphine], T= 20 - 150 °C , p= 60006Torr , Autoclave Rosi, Luca; Frediani, Marco; Frediani, Piero; Journal of Organometallic Chemistry; vol. 695; nb. 9; (2010); p. 1314 - 1322 View in Reaxys

OH C

O O

OH HO

Rx-ID: 29593133 View in Reaxys 105/281 Yield 13 %Chromat., 6 %Chromat., 11 %Chromat., 58 %Chromat.

Conditions & References With acetylacetonatodicarbonylrhodium(l), C38H46P2, hydrogen, triethylphosphine, T= 120 °C , p= 30003Torr , Autoclave Boogaerts, Ine T.I. F.; White, Daniel F. S.; Cole-Hamilton, David J.; Chemical Communications; vol. 46; nb. 13; (2010); p. 2194 - 2196 View in Reaxys

65/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

OH C

O O

Rx-ID: 29593134 View in Reaxys 106/281 Yield

Conditions & References

7 %Chromat., 7 %Chromat., 11 %Chromat., 61 %Chromat., 9 %Chromat.

With acetylacetonatodicarbonylrhodium(l), DIOP, hydrogen, triethylphosphine, T= 120 °C , p= 30003Torr , Autoclave Boogaerts, Ine T.I. F.; White, Daniel F. S.; Cole-Hamilton, David J.; Chemical Communications; vol. 46; nb. 13; (2010); p. 2194 - 2196 View in Reaxys

OH C

O HO

Rx-ID: 29593136 View in Reaxys 107/281 Yield

Conditions & References

13 %Chromat., 56 %Chromat., 6 %Chromat., 15 %Chromat.

OH C

Rx-ID: 29593137 View in Reaxys 108/281 Yield

Conditions & References

7 %Chromat., 52 %Chromat., 11 %Chromat., 10 %Chromat., 6 %Chromat.

With acetylacetonatodicarbonylrhodium(l), hydrogen, 4,5-bis(diphenylphosphino)-9 ,9-dimethylxanthene, triethylphosphine, T= 120 °C , p= 30003Torr , Autoclave Boogaerts, Ine T.I. F.; White, Daniel F. S.; Cole-Hamilton, David J.; Chemical Communications; vol. 46; nb. 13; (2010); p. 2194 - 2196 View in Reaxys

OH C

OH HO

Rx-ID: 29593140 View in Reaxys 109/281 Yield

Conditions & References

31 %Chro- With acetylacetonatodicarbonylrhodium(l), C38H46P2, hydrogen, triethylphosphine, T= 120 °C , p= 30003Torr , Autoclave mat., 45 %Chromat., Boogaerts, Ine T.I. F.; White, Daniel F. S.; Cole-Hamilton, David J.; Chemical Communications; vol. 46; nb. 13; (2010); p. 2194 - 2196

66/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

8 %Chromat.

View in Reaxys

7 %Chromat., 12 %Chromat., 66 %Chromat.

With acetylacetonatodicarbonylrhodium(l), C38H46P2, hydrogen, triethylphosphine, T= 120 °C , p= 30003Torr , Autoclave Boogaerts, Ine T.I. F.; White, Daniel F. S.; Cole-Hamilton, David J.; Chemical Communications; vol. 46; nb. 13; (2010); p. 2194 - 2196 View in Reaxys

OH C

O O

Rx-ID: 29593142 View in Reaxys 110/281 Yield

Conditions & References

6 %Chromat., 6 %Chromat., 59 %Chromat., 11 %Chromat.

With acetylacetonatodicarbonylrhodium(l), hydrogen, 4,5-bis(diphenylphosphino)-9 ,9-dimethylxanthene, triethylphosphine, T= 120 °C , p= 30003Torr , Autoclave

6 %Chromat., 17 %Chromat., 56 %Chromat., 7 %Chromat.

With acetylacetonatodicarbonylrhodium(l), C38H46P2, hydrogen, triethylphosphine, T= 120 °C , p= 30003Torr , Autoclave

Boogaerts, Ine T.I. F.; White, Daniel F. S.; Cole-Hamilton, David J.; Chemical Communications; vol. 46; nb. 13; (2010); p. 2194 - 2196 View in Reaxys

OH C

Rx-ID: 29593143 View in Reaxys 111/281 Yield

Conditions & References

13 %Chromat., 7 %Chromat., 38 %Chromat., 20 %Chromat.

With 2,2'-bis<(diphenylphosphino)methyl>-1,1'-biphenyl, acetylacetonatodicarbonylrhodium(l), hydrogen, triethylphosphine, T= 120 °C , p= 30003Torr , Autoclave Boogaerts, Ine T.I. F.; White, Daniel F. S.; Cole-Hamilton, David J.; Chemical Communications; vol. 46; nb. 13; (2010); p. 2194 - 2196 View in Reaxys

OH C

Rx-ID: 29593144 View in Reaxys 112/281 Yield 12 %Chromat., 56 %Chromat., 9 %Chromat.

Conditions & References With acetylacetonatodicarbonylrhodium(l), hydrogen, 4,5-bis(diphenylphosphino)-9 ,9-dimethylxanthene, triethylphosphine, T= 120 °C , p= 30003Torr , Autoclave Boogaerts, Ine T.I. F.; White, Daniel F. S.; Cole-Hamilton, David J.; Chemical Communications; vol. 46; nb. 13; (2010); p. 2194 - 2196 View in Reaxys

67/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

8 %Chromat., 67 %Chromat., 10 %Chromat.

OH C

Rx-ID: 29593145 View in Reaxys 113/281 Yield

Conditions & References

15 %Chromat., 31 %Chromat., 23 %Chromat., 6 %Chromat.

Rx-ID: 29688277 View in Reaxys 114/281 Yield

Conditions & References 3 Product distribution / selectivity Patent; Lyondell Chemical Technology, L.P.; US7790932; (2010); (B1) English View in Reaxys

Rx-ID: 29688284 View in Reaxys 115/281 Yield

Conditions & References 3 :Allyl alcohol is hydroformylated using phosphines 1A-1D and 2A-2D according to the following procedure:A solution of phosphine (0.12 mmol) in dry degassed isopropanol solvent (4 mL) is added under a stream of argon or nitrogen to [Rh(CO)2(acac)] (0.04 mmol) under an argon atmosphere. The resulting solution is transferred in a gastight syringe to a 25-mL autoclave under an argon atmosphere. The autoclave is flushed twice with a 1:1 CO/H2 mixture and then pressurized to 30 bar with the CO/H2 mixture. The autoclave is then heated to 90° C. with stirring, the pressure is increased to 39 bars, allyl alcohol (1 mL) is then injected from a sidearm, and the autoclave pressurized to 40 bar with the CO/H2 mixture. The autoclave is kept at a constant pressure of 40 bar, and the gas uptake of the reaction is monitored in a ballast vessel from which the gas is delivered. When there is no further gas uptake, the autoclave is cooled and depressurized. The resulting solution is analyzed by gas chromatography to determine the products of the reaction.The reaction produces HBA, HMPA, and C3 products (n-propanol and propionaldehyde). Some of the reactions produce BDO and MPD, as well, showing that some reactions undergo hydrogenation under the present conditions in addition to the hydroformylation. In some cases when BDO if formed 1-butanol is also formed via BDO dehydration. In these cases 1-butanol is also defined as a linear alcohol product.The aldehyde selectivity (i.e., moles HBA +HMPA produced/moles allyl alcohol converted*100percent) and the aldehyde L:B ratio (linear:branched; HBA:HMPA) is measured. For those reactions that also produce BDO, 1-butanol and MPD, the alcohol selectivity (i.e., moles BDO+1-butanol +MPD produced/moles allyl alcohol converted*100percent) and the ratio of alcohol L:B (linear:branched) is also measured. The total selectivity (HBA, HMPA, BDO, 1-butanol, MPD) demonstrates the is effectiveness of the catalyst systems at hydroformylation. The results are shown in Table 1.

68/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

With hydrogen, acetylacetonatodicarbonylrhodium(l), 3-dicyclohexylphosphino-2H-isoquinolin-1-one in isopropyl alcohol, T= 90 °C , p= 22502.3 - 30003Torr , Inert atmosphere, Autoclave, Product distribution / selectivity Patent; Lyondell Chemical Technology, L.P.; US7790932; (2010); (B1) English View in Reaxys O O O O O

O O

OH HO

O HO O

Rx-ID: 29820754 View in Reaxys 116/281 Yield

Conditions & References With ZnCuO2, hydrogen, Time= 0.000361111h, T= 170 °C , p= 30003Torr Ding, Guoqiang; Zhu, Yulei; Zheng, Hongyan; Zhang, Wei; Li, Yongwang; Catalysis Communications; vol. 11; nb. 14; (2010); p. 1120 - 1124 View in Reaxys O O O O

O O

Rx-ID: 30147699 View in Reaxys 117/281 Yield

Conditions & References With hydrogen, T= 260 °C , p= 75007.5Torr , Kinetics, Temperature Timofeev; Bazanov; Zubritskaya; Russian Journal of Organic Chemistry; vol. 46; nb. 10; (2010); p. 1537 - 1541 View in Reaxys O

OH OH

Rx-ID: 31804555 View in Reaxys 118/281 Yield

Conditions & References

64 %

With hydrogen in water, Time= 10h, T= 160 °C , p= 97509.8Torr Tachibana, Yuya; Masuda, Takashi; Funabashi, Masahiro; Kunioka, Masao; Biomacromolecules; vol. 11; nb. 10; (2010); p. 2760 - 2765 View in Reaxys H 2 H

O OH HO

N H

OH HN

Rx-ID: 28426691 View in Reaxys 119/281

69/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Yield

Conditions & References

4.2 %, 3.7 %, 8.6 %

1 :Reference Example 1Experiments on the Direct Catalytic Hydrogenation of Succinic Salts to THFFor comparative purposes, various salts of succinic acid were subjected to a homogeneous or heterogeneous hydrogenation. Either no reaction (disodium salt) or the formation of various hydrogenation products, such as BDO, GBL or pyrrolidone, is observed, but not the formation of the desired THF product.; Homogeneous hydrogenation conditions: Ru(acac)3/Triphos, 150° C., 150 bar H2, 24 h; (b)The monosodium salt can be regarded as a 50:50 mixture of diacid and disodium salt. Only the diacid could in butanediol BDO and GBL. No conversion of a sodium carboxylate was observed. With hydrogen, [Ru(acetylacetonate)3], Time= 24h, T= 150 °C , p= 112511Torr , Product distribution / selectivity Patent; Bauduin, Christophe; Fischer, Wolfgang; Pinkos, Rolf; Scholten, Edzard; US2009/137825; (2009); (A1) English View in Reaxys O–

HO O

Na +

Rx-ID: 28426693 View in Reaxys 120/281 Yield

Conditions & References

26.2 %, 10 %

monosodium salt can be regarded as a 50:50 mixture of diacid and disodium salt. Only the diacid could in butanediol BDO and GBL. No conversion of a sodium carboxylate was observed. With hydrogen, 3% Sn/7% Pt on C, Time= 24h, T= 120 °C , p= 150015Torr , Product distribution / selectivity

Patent; Bauduin, Christophe; Fischer, Wolfgang; Pinkos, Rolf; Scholten, Edzard; US2009/137825; (2009); (A1) English View in Reaxys 3.3 %, 21.3 %

Si O

Rx-ID: 2292528 View in Reaxys 121/281 Yield 98 %

Conditions & References With sulfated SnO2 in methanol, Time= 0.166667h, T= 20 °C Bhure, Mahesh H.; Kumar, Indresh; Natu, Arun D.; Rode, Chandrashekhar V.; Synthetic Communications; vol. 38; nb. 3; (2008); p. 346 - 353 View in Reaxys

70 %

With sodium hydride in N,N,N,N,N,N-hexamethylphosphoric triamide, Time= 12h, T= 25 °C Shekhani, Mohammed Saleh; Khan, Mohammed Khalid; Mahmood, Khalid; Tetrahedron Letters; vol. 29; nb. 47; (1988); p. 6161 - 6162 View in Reaxys

70/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

O OH

OH HO

Rx-ID: 4477107 View in Reaxys 122/281 Yield

Conditions & References

45 %, 20 %

With tris-(4-bromophenyl)aminium hexachloroantimonate in methanol, Time= 1h, T= 20 °C Xu, Yanfen; Tang, Shouchu; Han, Junjie; She, Xuegong; Pan, Xinfu; Tetrahedron Letters; vol. 49; nb. 22; (2008); p. 3634 3637 View in Reaxys

61 % Chromat., 27 % Chromat.

With dichloro bis(acetonitrile) palladium(II) in water, N,N-dimethyl-formamide, acetone, Time= 9h, T= 120 °C , Title compound not separated from byproducts Wilson, Noel S.; Keay, Brian A.; Journal of Organic Chemistry; vol. 61; nb. 9; (1996); p. 2918 - 2919 View in Reaxys

OH C

OH HO

Rx-ID: 26011318 View in Reaxys 123/281 Yield

Conditions & References With hydrogen, acetylacetonatodicarbonylrhodium(l), Time= 2.5h, T= 125 °C , p= 30003Torr , Product distribution, Further Variations: reagent ratios Cheliatsidou, Paraskevi; White, Daniel F. S.; Slawin, Alexandra M. Z.; Cole-Hamilton, David J.; Dalton Transactions; nb. 18; (2008); p. 2389 - 2394 View in Reaxys

Rx-ID: 26011319 View in Reaxys 124/281 Yield

Conditions & References With hydrogen, triethylphosphine, acetylacetonatodicarbonylrhodium(l) in ethanol, Time= 2.5h, T= 125 °C , p= 30003Torr , Product distribution, Further Variations: Reagents Cheliatsidou, Paraskevi; White, Daniel F. S.; Slawin, Alexandra M. Z.; Cole-Hamilton, David J.; Dalton Transactions; nb. 18; (2008); p. 2389 - 2394 View in Reaxys

HO OH

Rx-ID: 28018949 View in Reaxys 125/281 Yield 10 %

71/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

perature at constant concentrations of alkali (sodium hydroxide) and constant LHSV on the amount of BDO formed was investigated. Higher temperatures resulted in greater formation of BDOs, thus the formation of BDOs was minimized when the reaction was operated at lower reaction temperatures (178-2050C, Table 4); Hydrogenolysis of a 40percent solution of the polyhydric alcohol glycerol was carried out substantially as described in Example 3. The effect of LHSV of the feed at constant concentration of alkali (sodium hydroxide) and constant on amount of BDO formed was investigated. Higher LHSV resulted in lower levels of formation of BDOs, thus the formation of BDOs was minimized when the reaction was operated at higher LHSV (1.5-2.3, Table 4). With sodium hydroxide, hydrogen, T= 166 °C , p= 51716.2Torr , Product distribution / selectivity Patent; ARCHER-DANIELS-MIDLAND COMPANY; WO2008/133939; (2008); (A1) English View in Reaxys HO

Rx-ID: 28018950 View in Reaxys 126/281 Yield

Conditions & References

21 - 24 %

4; 5; 6 :Examples 4-7 describe methods to reduce the formation of four- carbon product BDO and maximize the conversion of polyhydric alcohol glycerol to three-carbon product propylene glycol with a solid phase catalyst such as the <n="21"/>"G" catalyst as disclosed in US 6,479,713 or the "HC-1" catalyst available from Sd Chemie (Louisville, KY). Hydrogenolysis of a 40percent solution of glycerol was carried out substantially as described in Example 3. The effect of the concentration of alkali (sodium hydroxide) in the feed at constant temperature and constant LHSV on the amount of BDO formed was investigated. Higher levels of sodium hydroxide resulted in greater formation of BDOs, thus, the formation of BDOs was minimized when the reaction was operated at lower concentrations (1- 1.9 wt percent) of alkali promoter (Table 4); Hydrogenolysis of a 40percent solution of the polyhydric alcohol glycerol was carried out substantially as described in Example 3. The effect of the reaction temperature at constant concentrations of alkali (sodium hydroxide) and constant LHSV on the amount of BDO formed was investigated. Higher temperatures resulted in greater formation of BDOs, thus the formation of BDOs was minimized when the reaction was operated at lower reaction temperatures (178-2050C, Table 4); Hydrogenolysis of a 40percent solution of the polyhydric alcohol glycerol was carried out substantially as described in Example 3. The effect of LHSV of the feed at constant concentration of alkali (sodium hydroxide) and constant on amount of BDO formed was investigated. Higher LHSV resulted in lower levels of formation of BDOs, thus the formation of BDOs was minimized when the reaction was operated at higher LHSV (1.5-2.3, Table 4). With sodium hydroxide, hydrogen, T= 170 °C , p= 51716.2Torr , Product distribution / selectivity Patent; ARCHER-DANIELS-MIDLAND COMPANY; WO2008/133939; (2008); (A1) English View in Reaxys

OH OH

Rx-ID: 28018951 View in Reaxys 127/281 Yield 60 %

Conditions & References 4; 5; 6 :Examples 4-7 describe methods to reduce the formation of four- carbon product BDO and maximize the conversion of polyhydric alcohol glycerol to three-carbon product propylene glycol with a solid phase catalyst such as the <n="21"/>"G" catalyst as disclosed in US 6,479,713 or the "HC-1" catalyst available from Sd Chemie (Louisville, KY). Hydrogenolysis of a 40percent solution of glycerol was carried out substantially as described in Example 3. The effect of the concentration of alkali (sodium hydroxide) in the feed at constant temperature and constant LHSV on the amount of BDO formed was investigated. Higher levels of sodium hydroxide resulted in greater formation of BDOs, thus, the formation of BDOs was minimized when the reaction was operated at lower concentrations (1- 1.9 wt percent) of alkali promoter (Table 4); Hydrogenolysis of a 40percent solution of the polyhydric alcohol glycerol was carried out substantially as described in Example 3. The effect of the reaction temperature at constant concentrations of alkali (sodium hydroxide) and constant LHSV on the amount of BDO formed was investigated. Higher temperatures resulted in greater formation of BDOs, thus the formation of BDOs was minimized when the reaction was operated at lower reaction temperatures (178-2050C, Table 4); Hydrogenolysis of a 40percent solution of the polyhydric alcohol glycerol was carried out substantially as described in Example 3. The effect of LHSV of the feed at constant concentra-

72/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

tion of alkali (sodium hydroxide) and constant on amount of BDO formed was investigated. Higher LHSV resulted in lower levels of formation of BDOs, thus the formation of BDOs was minimized when the reaction was operated at higher LHSV (1.5-2.3, Table 4). With sodium hydroxide, hydrogen, T= 212 °C , p= 51716.2Torr , Product distribution / selectivity Patent; ARCHER-DANIELS-MIDLAND COMPANY; WO2008/133939; (2008); (A1) English View in Reaxys

Rx-ID: 28095608 View in Reaxys 128/281 Yield

Conditions & References EXAMPLECatalyst PreparationActivated carbon fibres of polyacrylonitrile origin in the form of plain woven fabrics (Taiwan Carbon Technology Co) were used as supports for catalyst preparation. The fabrics are woven from the long threads of ca. 0.5 mm in diameter. These threads consist of a bundle of elementary filaments of 3-5 μm. The palladium deposition on the fabric was carried out via ion-exchange from aqueous solution of Na2PdCl4 as described in Chem. Eng. Sci. 2002, 57, 3453-3460. The loading of palladium was 4 mass percent as determined by atomic absorption spectroscopy, and the catalysts were characterized via BET-method for specific surface area and pore size distribution. Pulse chemisorption of carbon monoxide was applied for the determination of Pd dispersion, see Chem. Eng. Sci., supra.Experimental Set-UpThe experimental set-up is described in detail in Chem. Eng. Sci., supra.The reaction was carried out in a batch reactor (150 ml autoclave, Buechiglas, Uster, CH), at isothermal conditions kept by a heating jacket. The autoclave was provided with a quantitative gas supply system.. The fibrous catalysts were placed between two metal gauzes (20.x.40 mm) fixed on the stirrer. The amount of catalyst placed in the reactor was varied between 150 and 35 mg. The agitation speed was kept at 1500 rpm to avoid mass transfer limitations. To achieve an efficient gas-liquid contact a self-gassing hollow shaft stirrer was used. The autoclave was fed with hydrogen (>99.99percent) under isobaric reaction conditions.Pure 2-butyne-1,4-diol was charged as a solid (mp 331K) and molten under Argon to prevent degradation of the reactant. After the required temperature was reached, the reactor was flushed with hydrogen and pressurized to the desired level. During the course of the reaction, the pressure of H2 in the reactor was maintained constant by supplying hydrogen from the reservoir at the rate of consumption. The pressure in the H2 reservoir was monitored continuously allowing in situ measurement of the instantaneous hydrogen consumption.Samples of liquids withdrawn from the loop are analysed by gas chromatography (Auto System XL, PERKIN ELMER) with He as a carrier gas and a FID-detector. Product separation was performed on a 30 m Perkin Elmer Elite Series 0.25 mm capillary column with a 0.25 micron coating, at temperature ramp of 20 K/min from 373 to 493K. Butan-1,3-diol was used as internal standard for quantitative GC analysis.The results of experiments under varying reaction conditions can be seen from FIGS. 1 to 3.FIG. 1 shows typical concentration time profiles for a reaction temperature of 352K. The measured and predicted selectivity for butenediol (B2) is ca. 98percent up to butynediol (B3) conversions of 90percent and drops to 95percent at 99percent conversion as shown in FIG. 2. The influence of temperature on the rate of reaction can be seen from FIG. 3, where the reactant concentration is shown as function of time. Based on the initial reaction rate, the dependence of the turnover frequency on temperature can be calculated. With hydrogen, Catalyst of Example (4percent palladium on polyacrylonitrile support), T= 78.84 - 118.84 °C , p= 11251.1Torr , Neat (no solvent), Product distribution / selectivity Patent; Joannet, Eric; Kiwi-Minsker, Lioubov; Renken, Albert; US2008/312475; (2008); (A1) English View in Reaxys

Rx-ID: 28166174 View in Reaxys 129/281 Yield

Conditions & References With hydrogen in water, T= 22 °C , p= 760.051Torr , chemoselective reaction Drelinkiewicz; Zieba; Krol; Sobczak; Grzywa; Polish Journal of Chemistry; vol. 82; nb. 9; (2008); p. 1717 - 1732 View in Reaxys

OH HO

Rx-ID: 4156061 View in Reaxys 130/281

73/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Yield

Conditions & References

78 %

With formic acid, tri-tert-butyl phosphine, palladium diacetate in tetrahydrofuran, Time= 12h, T= 20 - 60 °C Brunel, Jean Michel; Synlett; nb. 2; (2007); p. 330 - 332 View in Reaxys

78 %

With formic acid, tri-tert-butyl phosphine, palladium diacetate in tetrahydrofuran, Time= 12h, T= 20 °C Brunel, Jean Michel; Tetrahedron; vol. 63; nb. 18; (2007); p. 3899 - 3906 View in Reaxys With hydrogen, ruthenium palladium in propan-1-ol, T= 89.9 °C , Rate constant Karavanov, A. N.; Gryaznov, V. M.; Batyrev, I. G.; Olenina, E. G.; Russian Journal of Physical Chemistry; vol. 69; nb. 5; (1995); p. 739 - 743; Zhurnal Fizicheskoi Khimii; vol. 69; nb. 5; (1995); p. 816 - 821 View in Reaxys

Si O

OH Si

Si O

Rx-ID: 5103637 View in Reaxys 131/281 Yield

Conditions & References

3 %, 83 %

With MCM-41 in methanol, Time= 4h, Ambient temperature Itoh, Akichika; Kodama, Tomohiro; Masaki, Yukio; Synlett; nb. 3; (1999); p. 357 - 359 View in Reaxys

3 %, 83 %

With mesoporous silica MCM-41 in methanol, Time= 4h, T= 20 °C Itoh, Akichika; Kodama, Tomohiro; Masaki, Yukio; Chemical and Pharmaceutical Bulletin; vol. 55; nb. 6; (2007); p. 861 864 View in Reaxys

15 %, 80 %

With iron(III) chloride in methanol, Time= 0.25h, T= 23 °C Yang, Yong-Qing; Cui, Jia-Rong; Zhu, Lin-Gui; Sun, Ya-Ping; Wu, Yikang; Synlett; nb. 8; (2006); p. 1260 - 1262 View in Reaxys

2 %, 46 %

With MCM-41 in acetonitrile, Time= 4h, Ambient temperature, various additives and solvents, Product distribution Itoh, Akichika; Kodama, Tomohiro; Masaki, Yukio; Synlett; nb. 3; (1999); p. 357 - 359 View in Reaxys

Rx-ID: 10522101 View in Reaxys 132/281 Yield 83 %

Conditions & References With iron(III) chloride in methanol, Time= 3h, T= 23 °C Yang, Yong-Qing; Cui, Jia-Rong; Zhu, Lin-Gui; Sun, Ya-Ping; Wu, Yikang; Synlett; nb. 8; (2006); p. 1260 - 1262 View in Reaxys

74/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

HO O

Rx-ID: 10545012 View in Reaxys 133/281 Yield

Conditions & References

4 %, 90 %

With iron(III) chloride in methanol, Time= 4h, T= 23 °C Yang, Yong-Qing; Cui, Jia-Rong; Zhu, Lin-Gui; Sun, Ya-Ping; Wu, Yikang; Synlett; nb. 8; (2006); p. 1260 - 1262 View in Reaxys O

O O O

O O

HO OH

OH O O

Rx-ID: 23659042 View in Reaxys 134/281 Yield 0.77 %, 0.38 %, 0.24 %, 0.05 %, 98.28 %, 0.02 %, 0.26 %

Conditions & References 9 :1st-Stage Material 10 0.5percent Pd on 1/16 Rutile Catalvst Preparation Materials: Rutile TiO2 Support (94percent Rutile, 6percent Anatase 1/16 inch (1.5 mm) diameter) Titanium dioxide containing 96 wt percent of the rutile crystalline phase of titanium dioxide and 6 wt percent of the anatase crystalline phase of titanium dioxide, 49.5 g (dry). Pd Impregnation Solution 1.31 g of Pd (NO3)2 Solution (19.02 wt percent Pd) is mixed with 6.12 g concentrated nitric acid (70percent nitric acid). This solution is used to impregnate the 96percent rutile titanium dioxide support. Preparation Procedure: Step 1 The 96percent rutile titanium dioxide support is gradually impregnated with the Pd impregnation solution, and allowed to stand for 1 hr. The material is then dried in an oven at 130° C. for 3.5 hr. 2nd-Stage Material Carbon Catalyst-Aqueous Two-step Preparation of BDO Catalyst with 1.5 mm Carbon Support This procedure describes an aqueous two-step BDO catalyst preparation using Norit 1.5 mm carbon. Nominal Composition: 0.4percent Fe, 1.9percent Na, 2.66percent Ag, 2.66percent Pd, 1 0.0percent Re on 1.5 mm diameter carbon. Materials: (A) Carbon Support: 58.4 g of Norit 1.5 mm diameter Active Carbon extrudate (referred to herein as Standard C or standard carbon) (acquired from Norit Americas Inc. located in Atlanta, Ga.) (B) Ag/Fe/Na Impregnation Solution: 2.9 g of silver nitrate, 5.1 g of sodium nitrate and 2 g of [Fe(NO3)3.9H2O] are dissolved in 20 g of de-ionized water and then gradually mixed with 68.3 g of concentrated nitric acid (70 wt percent nitric acid). (C) Pd/Re Impregnation Solution 1: 9.1 g of Pd (NO3)2 solution (20.38percent Pd), 12.22 g of HReO4 solution (56.36 wt percent Re), 23.3 g of concentrated nitric acid (70 wt percent nitric acid), and 24 g of de-ionized water are mixed together. Preparation Procedure: Step 1 The carbon support (A) is gradually impregnated with the Ag/Fe/Na impregnation solution (B), and allowed to stand for 1 hr. The material is then dried in an oven at 130° C. for 4.5 hr. Step 2 The carbon support (A) which has been impregnated with Ag/Fe/Na is next gradually impregnated with the Pd/Re solution (C) and the mixture is allowed to stand for 3 hr. The catalyst is then dried for 5 hr at 130° C. The rutile titanium dioxide support is gradually impregnated with the Pd/Re impregnation solution, and allowed to stand for 1 hr. The material is then dried in an oven at 130° C. for 3.5 hr. With hydrogen, 0.5percent Pd on Rutile TiO2, T= 110 °C , Product distribution / selectivity Patent; Bhattacharyya, Alakananda; Manila, Maynard D.; US2006/4212; (2006); (A1) English View in Reaxys Rx-ID: 23659043 View in Reaxys 135/281

Yield 0.86 - 2.09 %, 4.34 7.98 %, 0.28 - 2.73 %, 1.24 2.95 %, 0 0.48 %,

Conditions & References Tables 2a and 2b show the results of hydrogenation of maleic acid to succinic acid over several sample time periods using catalysts prepared as described in Catalyst Example 1(a) and Catalyst Example 2. With hydrogen, 0.5percent Pd/0.2percent Re on Rutile TiO2, Time= 170 - 1009h, T= 110 °C , Product distribution / selectivity Patent; Bhattacharyya, Alakananda; Manila, Maynard D.; US2006/4212; (2006); (A1) English View in Reaxys

75/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

85.51 92.03 %, 0 0.01 %, 0.04 - 0.46 %, 0 - 0.06 %, 0 - 0.11 % O HO

O O O

HO OH

O O

Rx-ID: 23659044 View in Reaxys 136/281 Yield

Conditions & References

1.27 %, 4.78 %, 1.55 %, 1.24 %, 0.48 %, 90.6 %, 0.08 %

The catalyst testing unit is comprised of a two-reactor system connected in series where maleic acid is first converted to succinic acid (SAC) in the first reactor at about 110° C. The effluent from the first stage reactor is delivered to the second stage reactor for the conversion of succinic acid to mainly BDO. Operating pressure is at 2500 to 4000 psi and internal reactor temperature is initially set at 165° C. Thereafter, temperature is adjusted closer to the temperature where a high conversion of SAC (about 99.7percent) is obtained. This temperature generally may vary from about 130° C. to about 175° C. At the lower end of the temperature range BDO selectivity is higher (80percent or higher) whereas THF is favored at higher temperatures (over 5percent). The results of the activity evaluation of a catalysts made according to the procedure of catalyst Example 1(a) is shown in Table 1a. Activity evaluation of a catalyst made according to the procedure of catalyst Example 2 is shown in Table 1(b). Catalyst results of the activity evaluation of a catalysts made according to the procedure of catalyst Example 3 is shown in Table 1(c).Tables 1a, 1b and 1c show that catalysts of Example 1(a), comprising Pd/Re on a rutile titanium dioxide support, and catalysts of Example 2 and Example 3, comprising Pd on a rutile titanium dioxide support, completely convert maleic acid to succinic acid with high selectivity to succinic acid and low amounts of other by-products. The Catalyst Testing Unit (CTU) results for Catalyst Example 1 and Catalyst Example 2 show that (a) Both 1/16 inch and inch Rutile extrudates can be used for hydrogenation. For carbon, inch was found to be less effective. (b) For maleic to succinic hydrogenation there is no need for other cocatalysts such as Ag, Fe, Na, etc., (c) 0.5percent Pd alone on a rutile TiO2 support gives good conversion of maleic acid to succinic acid. With hydrogen, 0.5percent Pd/2.0percent Re on Rutile TiO2, T= 110 °C , Product distribution / selectivity Patent; Bhattacharyya, Alakananda; Manila, Maynard D.; US2006/4212; (2006); (A1) English View in Reaxys O

O O O

O O

OH O

Rx-ID: 23659045 View in Reaxys 137/281 Yield 0.60 - 2.77 %, 0.04 0.88 %, 0.62 - 4.29 %, 0.19 0.49 %, 88.49 98.29 %,

Conditions & References Tables 2a and 2b show the results of hydrogenation of maleic acid to succinic acid over several sample time periods using catalysts prepared as described in Catalyst Example 1(a) and Catalyst Example 2. With hydrogen, 0.5percent Pd on Rutile TiO2, Time= 96 - 238h, T= 110 °C , Product distribution / selectivity Patent; Bhattacharyya, Alakananda; Manila, Maynard D.; US2006/4212; (2006); (A1) English View in Reaxys

76/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

0.12 - 0.24 %, 0.11 2.91 % O HO

HO O O O

O O

OH O

Rx-ID: 23659046 View in Reaxys 138/281 Yield

Conditions & References

0.45 %, 0.06 %, 0.00 %, 0.21 %, 0.36 %, 98.73 %, 0.04 %, 0.08 %

The catalyst testing unit is comprised of a two-reactor system connected in series where maleic acid is first converted to succinic acid (SAC) in the first reactor at about 110° C. The effluent from the first stage reactor is delivered to the second stage reactor for the conversion of succinic acid to mainly BDO. Operating pressure is at 2500 to 4000 psi and internal reactor temperature is initially set at 165° C. Thereafter, temperature is adjusted closer to the temperature where a high conversion of SAC (about 99.7percent) is obtained. This temperature generally may vary from about 130° C. to about 175° C. At the lower end of the temperature range BDO selectivity is higher (80percent or higher) whereas THF is favored at higher temperatures (over 5percent). The results of the activity evaluation of a catalysts made according to the procedure of catalyst Example 1(a) is shown in Table 1a. Activity evaluation of a catalyst made according to the procedure of catalyst Example 2 is shown in Table 1(b). Catalyst results of the activity evaluation of a catalysts made according to the procedure of catalyst Example 3 is shown in Table 1(c).Tables 1a, 1b and 1c show that catalysts of Example 1(a), comprising Pd/Re on a rutile titanium dioxide support, and catalysts of Example 2 and Example 3, comprising Pd on a rutile titanium dioxide support, completely convert maleic acid to succinic acid with high selectivity to succinic acid and low amounts of other by-products. The Catalyst Testing Unit (CTU) results for Catalyst Example 1 and Catalyst Example 2 show that (a) Both 1/16 inch and inch Rutile extrudates can be used for hydrogenation. For carbon, inch was found to be less effective. (b) For maleic to succinic hydrogenation there is no need for other cocatalysts such as Ag, Fe, Na, etc., (c) 0.5percent Pd alone on a rutile TiO2 support gives good conversion of maleic acid to succinic acid. With hydrogen, 0.5percent Pd on Rutile TiO2, T= 110 °C , Product distribution / selectivity Patent; Bhattacharyya, Alakananda; Manila, Maynard D.; US2006/4212; (2006); (A1) English View in Reaxys O

O O

Rx-ID: 23659047 View in Reaxys 139/281 Yield 0.37 %, 0.28 %, 0.37 %, 98.89 %, 0.08 %

77/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Patent; Bhattacharyya, Alakananda; Manila, Maynard D.; US2006/4212; (2006); (A1) English View in Reaxys O O

OH HO

OH O

Rx-ID: 23662964 View in Reaxys 140/281 Yield

Conditions & References 9 :1st-Stage Material 10 0.5percent Pd on 1/16 Rutile Catalvst Preparation Materials: Rutile TiO2 Support (94percent Rutile, 6percent Anatase 1/16 inch (1.5 mm) diameter) Titanium dioxide containing 96 wt percent of the rutile crystalline phase of titanium dioxide and 6 wt percent of the anatase crystalline phase of titanium dioxide, 49.5 g (dry). Pd Impregnation Solution 1.31 g of Pd (NO3)2 Solution (19.02 wt percent Pd) is mixed with 6.12 g concentrated nitric acid (70percent nitric acid). This solution is used to impregnate the 96percent rutile titanium dioxide support. Preparation Procedure: Step 1 The 96percent rutile titanium dioxide support is gradually impregnated with the Pd impregnation solution, and allowed to stand for 1 hr. The material is then dried in an oven at 130° C. for 3.5 hr. 2nd-Stage Material Carbon Catalyst-Aqueous Two-step Preparation of BDO Catalyst with 1.5 mm Carbon Support This procedure describes an aqueous two-step BDO catalyst preparation using Norit 1.5 mm carbon. Nominal Composition: 0.4percent Fe, 1.9percent Na, 2.66percent Ag, 2.66percent Pd, 1 0.0percent Re on 1.5 mm diameter carbon. Materials: (A) Carbon Support: 58.4 g of Norit 1.5 mm diameter Active Carbon extrudate (referred to herein as Standard C or standard carbon) (acquired from Norit Americas Inc. located in Atlanta, Ga.) (B) Ag/Fe/Na Impregnation Solution: 2.9 g of silver nitrate, 5.1 g of sodium nitrate and 2 g of [Fe(NO3)3.9H2O] are dissolved in 20 g of de-ionized water and then gradually mixed with 68.3 g of concentrated nitric acid (70 wt percent nitric acid). (C) Pd/Re Impregnation Solution 1: 9.1 g of Pd (NO3)2 solution (20.38percent Pd), 12.22 g of HReO4 solution (56.36 wt percent Re), 23.3 g of concentrated nitric acid (70 wt percent nitric acid), and 24 g of de-ionized water are mixed together. Preparation Procedure: Step 1 The carbon support (A) is gradually impregnated with the Ag/Fe/Na impregnation solution (B), and allowed to stand for 1 hr. The material is then dried in an oven at 130° C. for 4.5 hr. Step 2 The carbon support (A) which has been impregnated with Ag/Fe/Na is next gradually impregnated with the Pd/Re solution (C) and the mixture is allowed to stand for 3 hr. The catalyst is then dried for 5 hr at 130° C. The rutile titanium dioxide support is gradually impregnated with the Pd/Re impregnation solution, and allowed to stand for 1 hr. The material is then dried in an oven at 130° C. for 3.5 hr. With hydrogen, 0.4percent Fe, 1.9percent Na, 2.66percent Ag, 2.66percent Pd, 10.0percent Re on carbon, Product distribution / selectivity Patent; Bhattacharyya, Alakananda; Manila, Maynard D.; US2006/4212; (2006); (A1) English View in Reaxys

HO O

OH HO

HO H

OH HO

OH H

Rx-ID: 23836266 View in Reaxys 141/281 Yield

Conditions & References

0 - 6 %, 0.1 5 - 41.8 %, 0 With hydrogen, ruthenium/ruthenium oxide/aluminium oxide in water, Time= 0.00138889h, T= 250 - 400 °C , p= 187519Torr , 17.2 % Product distribution / selectivity

78/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Patent; FRAUNHOFER-GESELLSCHAFT ZUR FOeRDERUNG DER ANGEWANDTEN FORSCHUNG E. V.; WO2006/61196; (2006); (A1) German View in Reaxys

HO O HO

HO OH

OH HO

HO H

Rx-ID: 23836267 View in Reaxys 142/281 Yield

Conditions & References

9.4 %, < 1.5 1; 2; 3; 4 - 21 %, 3.0 With hydrogen, ruthenium/ruthenium oxide/aluminium oxide in water, Time= 0.0416667 - 0.0833333h, T= 150 - 250 °C , p= 98 %, 9.2 %, 10.6 %, 187519Torr , pH= 6, Product distribution / selectivity 19.6 % Patent; FRAUNHOFER-GESELLSCHAFT ZUR FOeRDERUNG DER ANGEWANDTEN FORSCHUNG E. V.; WO2006/61196; (2006); (A1) German View in Reaxys

O O OH

HO OH

OH HO

HO H

Rx-ID: 23836526 View in Reaxys 143/281 Yield

Conditions & References

6.2 - 18 %, 7 5.1 - 64.5 % With hydrogen, ruthenium/ruthenium oxide/aluminium oxide in water, Time= 0.0833333h, T= 150 - 250 °C , p= 187519Torr , Product distribution / selectivity Patent; FRAUNHOFER-GESELLSCHAFT ZUR FOeRDERUNG DER ANGEWANDTEN FORSCHUNG E. V.; WO2006/61196; (2006); (A1) German View in Reaxys

79/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

OH O

Rx-ID: 23235033 View in Reaxys 144/281 Yield

Conditions & References 2 : Example 2; Hydroformylation of allyl alcohol: Chlorine moiety present in rhodium precursor 9.0 mg (0. 00383MOL/LITRE) of [RhCl (COD) 2] 2 was added to 18. 0 mg (0. 00383MOL/LITRE) of the bidentate phosphine ligand, 1,. 2-bis (di-tertbutylphosphinomethyl) BENZENE.. 10ML of toluene was then added to the mixture. 2.0 ml (29. Ommol) of allyl was then added and hydroformylation was performed for. 3hrs by the addition, at 80°C, of a 1. : 1 mixture of CO: H2 at a pressure of 30bar, and in the presence of 0. 072mmol of NAOAC. It was found that after 3hrs under these conditions, there was 86. 6percent conversion of allyl alcohol, with 73. 8percent selectivity to HYDROXYTETRAHYDROFURAN, 12.9percent to hydroxymethyl-propionaldehyde. These two products were then hydrogenated to give, respectively, 1,4-butanediol and 2-methyl-1, 3-PROPANEDIOL. The L : b ratio in this case was 5. 72: 1. Patent; LUCITE INTERNATIONAL UK LIMITED; WO2005/3070; (2005); (A1) English View in Reaxys

OH HO

OH OH

Rx-ID: 23310898 View in Reaxys 145/281 Yield 57.5 %, 28.5 %

80/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

num. Specifically, in this embodiment, the fuel alcohol synthesis catalyst preferably comprises one or more of Cu/ZnO/Cr2O3 and Cu/ZnO/Al2O3. In this embodiment, it is preferred that the fuel alcohol synthesis catalyst is alkali promoted. Thus, the fuel alcohol optionally is formed in this aspect of the invention by contacting syngas with a fuel alcohol synthesis catalyst comprising one or more of Cu/ZnO/Cr2O3 and Cu/ZnO/Al2O3, which fuel alcohol synthesis catalyst optionally is alkali promoted, under conditions effective to convert the syngas to the fuel alcohol. Additionally or alternatively, the fuel alcohol synthesis catalyst comprises an oxide of one or more of zinc, chromium, copper, cobalt, and nickel. In this embodiment, it is preferred that the fuel alcohol synthesis catalyst is alkali, lanthanum or cerium promoted. Thus, the fuel alcohol optionally is formed in this aspect of the invention by contacting syngas with a fuel alcohol synthesis catalyst under conditions effective to convert the syngas to the fuel alcohol, wherein the fuel alcohol synthesis catalyst comprises an oxide of one or more of zinc, chromium, copper, cobalt, and nickel, which fuel alcohol synthesis catalyst optionally is alkali, lanthanum or cerium promoted. Additionally or alternatively, the fuel alcohol synthesis catalyst comprises a compound comprising molybdenum and preferably sulfur. In this embodiment, it is preferred that the fuel alcohol synthesis catalyst is alkali promoted. Specifically, the fuel alcohol optionally is catalyzed by one or more of MoS2 and Co/MoS2. Thus, the fuel alcohol can be formed by contacting syngas with a fuel alcohol synthesis catalyst under conditions effective to convert the syngas to the fuel alcohol, wherein the fuel alcohol synthesis catalyst comprises one or more of MoS2 and Co/MoS2, and wherein the fuel alcohol synthesis catalyst optionally is alkali promoted. The alkali metal atom component of the catalyst system can come from any of the known ionic compounds of the alkali metals sodium, potassium, lithium, rubidium and cesium. Preferred alkali metal atom components are derived from sodium salts and potassium salts. Illustrative sources thereof include sodium iodide, sodium bicarbonate, sodium carbonate, sodium nitrate, sodium nitrite, sodium sulfate, sodium bisulfate, sodium chromate, sodium permanganate, sodium chlorate, sodium persulfate, sodium tetraborate, sodium bromide, sodium chloride, sodium fluoride, sodium sulfite, sodium hypochlorite, as well as any other ionic salt of sodium. Rather than repeat the individual compound names, the corresponding potassium, lithium, rubidium and cesium salts are illustrative of useful ionic compounds. The concentration of alkali metal atoms in the fuel alcohol synthesis zone optionally is from about 0.00013 to about 1 mole per liter; preferably from about 0.07 to about 0.6 mole per liter. Preferably, hydrogen and carbon monoxide are present in the syngas that is directed to the fuel alcohol synthesis zone. The molar ratio of H2:CO in the syngas that is directed to the fuel alcohol synthesis zone can vary from about 20:1 to about 1:20, from about 10:1 to about 1:10, and preferably from about 3:1 to about 1:3. Particularly in continuous operations, but also in batch experiments, the carbon monoxide-hydrogen gaseous mixture may also be used in conjunction with up to 50percent by volume of one or more other gases. These other gases may include one or more inert gases such as nitrogen, argon, neon and the like, or they may include gases that may, or may not, undergo reaction under CO hydrogenation conditions, such as carbon dioxide, hydrocarbons such as methane, ethane, propane and the like, ethers such as dimethyl ether, methylethyl ether and diethyl ether, alkanols such as methanol and acid esters such as methyl acetate. According to the present invention, a fuel alcohol-containing stream is formed, which comprises the fuel alcohol. The fuel alcohol-containing stream preferably comprises two or more alcohols in the C2 to C5 range. Higher alcohols and carboxylic acid esters may also be formed while carrying out the process of this invention. For example, the fuel alcohol-containing stream may include methyl formate, methyl acetate, ethyl acetate, ethyl ether. The major by-products of the process such as the higher molecular weight alcohols and carboxylic acid esters, are, of course, also useful compounds and major articles of commerce. The higher alcohols, the carboxylic acid esters and ethers can easily be separated from one another by conventional means, e.g., fractional distillation in vacuo, if desired. The precise amount and type of components contained in the fuel alcohol-containing stream will vary widely depending on catalyst type, reaction conditions, and syngas composition used. For example, Table I, below, provides three catalyst systems and indicates exemplary product yields and operating conditions. See El Sawy, A. H., DOE report DE90010325, pp. 3-17, 3-18. Product Yields (Wt. percent) and Reaction Conditions of Three Fuel Alcohol Synthesis Systems Process Product Slate Main Catalyst Constituents (anhydrous basis) Cu/Co/Al Zn/Cr/K Cu/ZnO/Al Methanol 57.5 70.0 64.5 Ethanol 28.5 2.5 11.5 C3 alcohols 7.1 3.4 5.2 C4 alcohols 2.8 12.5 7.4 C5+ alcohols 2.5 9.5 7.4 Hydrocarbons 0.3 - 0.02 Esters 0.7 0.1 0.8 Other Oxygenated 0.6 2.0 3.18 Products Total Alcohols 98.4 97.9 96.0 Operating T (Â° C.) 260-320 350-420 285-300 Operating Pressure 6-10 10-18 6-9 (MPa) Syngas Feed Ratio 2.0-2.5 1.5-2 0.5-1 (H2:CO)Syngas CO2 0.5-3.0 2-6 1.0 Content (Vol. percent) As indicated by Table I, the amount of ethanol contained in the fuel alcohol-containing stream may vary. The fuel alcohol-containing stream preferably comprises at least about 10 weight percent ethanol, more preferably at least about 25 weight percent ethanol and most preferably at least about 35 weight percent ethanol, based on the total weight of the fuel alcohol-containing stream. In terms of ranges, the fuel alcohol-containing stream optionally comprises on the order of from about 5 to about 60 weight percent ethanol, preferably from about 10 to about 50 weight percent ethanol, and most preferably from about 20 to about 40 weight percent ethanol, based on the total weight of the fuel alcoholcontaining stream. The fuel alcohol-containing stream also comprises one or more C3 alcohols, preferably on the order of from about 5 to about 80 weight percent C3 alcohols, preferably from about 10 to about 60 weight percent C3 alcohols, and most preferably from about 15 to about 40 weight percent C3 alcohols, based on the total weight of the fuel alcohol-containing stream. Optionally, the C3 alcohols comprise one or more of 1-propanol, 2-propanol, and/or 1,2-propadiol. Additionally or alternatively, the fuel alcohol-containing stream comprises one or more C4 alcohols, preferably on the order of from about 0.1 to about 20 weight percent C4 alcohols, preferably from about I to about 10 weight percent C4 alcohols, and most preferably from about 2 to about 5 weight percent C4 alcohols, based on the total weight of the fuel alcohol-containing stream. Optionally, the C4 alcohols comprise one or more of I -butanol; 2-butanol; 1,4-butanediol; 1,3-butanediol; 1,2-butanediol; isobutyl alcohol; secbutyl alcohol; and t-butyl alcohol. The fuel alcohol-containing stream preferably comprises at least about 5 weight percent C3C4 alcohols, more preferably at least about 10 weight percent C3-C4 alcohols, and most preferably at least about 15 weight percent C3-C4 alcohols. Optionally, the fuel alcohol-containing stream comprises one or more C5 alcohols, preferably on the

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

81/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

order of from about 0.01 to about 10 weight percent C5 alcohols, preferably from about 0.1 to about 5 weight percent C5 alcohols, and most preferably from about 0.1 to about 3 weight percent C5 alcohols, based on the total weight of the fuel alcoholcontaining stream. Optionally, the C5 alcohols comprise one or more of 1-pentanol; 2-pentanol; 3-pentanol; 1,5-pentanediol; 1,4-pentanediol; 1,3-pentanediol; and 1,2-pentanediol. Additionally, the fuel alcohol-containing stream optionally comprises one or more C6+ alcohols, preferably on the order of from about 0.01 to about 10 weight percent C6+ alcohols, preferably from about 0.1 to about 5 weight percent C6+ alcohols, and most preferably from about 0.1 to about 3 weight percent C6+ alcohols, based on the total weight of the fuel alcohol-containing stream. Ideally, the fuel alcohol-containing stream contains low amounts of methanol, if any. Preferably, the fuel alcohol-containing stream comprises less than 75 weight percent methanol, more preferably less than 65 weight percent methanol, and most preferably less than 60 weight percent methanol, based on the total weight of the fuel alcohol-containing stream. In terms of weight ratios, if the fuel alcohol-containing stream comprises methanol and ethanol, then the weight ratio of methanol to ethanol ranges from about 1 to about 6, more preferably from about 1.5 to about 5, and most preferably from about 2 to about 4. If the fuel alcohol-containing stream comprises ethanol and C3 alcohols, then the weight ratio of ethanol to C3 alcohols preferably ranges from about 1 to about 30, more preferably from about 5 to about 30, and most preferably from about 10 to about 20. The novel process of this invention can be conducted in a batch, semicontinuous or continuous fashion. The catalyst may be initially introduced into the fuel alcohol synthesis zone batchwise, or it may be continuously or intermittently introduced into such a zone during the course of the synthesis reaction. Operating conditions can be adjusted to optimize the formation of the fuel alcohol product, and after recovery of the alcohol and other products, a fraction rich in the catalyst composition may then be recycled to the reaction zone, if desired, and additional products generated. A non-limiting list of preferred reactor types for the synthesis of fuel alcohol includes fixed bed, slurry reactors and fluid bed reactors. One can additionally have an inert solvent present in the reaction mixture. A wide variety of substantially inert solvents are useful in the process of this invention including hydrocarbon and oxygenated hydrocarbon solvents. Suitable oxygenated hydrocarbon solvents are compounds comprising carbon, hydrogen and oxygen and those in which the only oxygen atoms present are in ether groups, ester groups, ketone carbonyl groups or hydroxyl groups of alcohols. Generally, the oxygenated hydrocarbon will contain 3 to 12 carbon atoms and preferably a maximum of 3 oxygen atoms. The solvent preferably is substantially inert under reaction conditions, is relatively non-polar and has a normal boiling point of at least 65Â° C. at atmospheric pressure, and preferably, the solvent will have a boiling point greater than that of ethanol and other oxygen-containing reaction products so that recovery of the solvent by distillation is facilitated. Preferred ester type solvents are the aliphatic and acylic carboxylic acid monoesters as exemplified by butyl acetate, methyl benzoate, isopropyl iso-butyrate, and propyl propionate as well as dimethyl adipate. Useful alcohol-type solvents include monohydric alcohols such as cyclohexanol, 1-hexanol, 2hexanol, neopentanol, 2-octanol, etc. Suitable ketone-type solvents include, for example, cyclic ketones such as cyclohexanone, 2-methylcyclohexanone, as well as acylic ketones such as 2-pentanone, butanone, acetophenone, etc. Ethers that may be utilized as solvents include cyclic, acyclic and heterocyclic materials. Preferred ethers are the heterocyclic ethers as illustrated by 1,4dioxane and 1,3-dioxane. Other suitable ether solvents include isopropyl propyl ether, diethylene glycol dibutyl ether, dibutyl ether, ethyl butyl ether, diphenyl ether, heptyl phenyl ether, anisole, tetrahydrofuran, etc. The most useful solvents of all of the above groups include the ethers as represented by monocyclic, heterocyclic ethers such a 1,4-dioxane or p-dioxane, etc. Hydrocarbon solvents, such as hexane, heptane, decane, dodecane, tetradecane, etc. are also suitable solvents for use in this invention. In the practice of this invention, it is also possible to add a small amount of water to the solvent and still obtain satisfactory results. The reaction time varies depending upon the reaction parameters, reactor size and charge, and the individual components employed at the specific process conditions. With hydrogen, Cu/Co/Al, T= 260 - 320 Â°C , p= 45004.5 - 75007.5Torr , Conversion of starting material Patent; Janssen, Marcel Johannes; Van Egmond, Cornelis F.; Martens, Luc R.M.; Sher, Jaimes; US2005/107481; (2005); (A1) English View in Reaxys 57.5 %, 28.5 %

C :As indicated above, the present invention, in one embodiment, provides for a combined process for forming methanol and fuel alcohol and converting the methanol and fuel alcohol to light olefins in an OTO reaction system. A non-limiting description of several fuel alcohol synthesis systems that may be incorporated into the present invention will now be described. As with methanol synthesis, there are numerous technologies available for producing fuel alcohol. The preferred embodiment for forming fuel alcohol according to the present invention comprises the reaction of carbon monoxide, hydrogen and optionally carbon dioxide in the presence of a fuel alcohol synthesis catalyst to form fuel alcohol and water. The synthesis of fuel alcohol occurs in a fuel alcohol synthesis zone. Without limiting the invention to a particular reaction mechanism, the synthesis of fuel alcohol may be illustrated as follows: nCO+2nH2-->CnH2n+1OH+(n-1)H2O (7) where n is a whole number. According to the present invention, the fuel alcohol synthesis reaction or reactions optionally are catalyzed using a fuel alcohol synthesis catalyst, preferably containing a metal atom, optionally with a halogen promoter. Many metal compounds and promoters can be used. Optionally, secondary activators or ligands may be used in conjunction with the metal catalysts and promoters. These secondary activators can be other metallic salts or compounds, amines, phosphorus compounds, as well as a multitude of other compounds that have been disclosed in the published literature. Thus, a typical catalyst system for the synthesis of fuel alcohol comprises a metal atom-containing catalyst, a promoter and optionally ligands, solvents and/or secondary activators. A variety of references disclose the synthesis of fuel alcohol from syngas. See, for example, (i) El Sawy, A. H., DOE report DE90010325 and references therein, the entireties of which are incorporated herein by reference; (ii) Courty, Charmette, Raimbault and Travers, Rev. De

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

82/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Institute du Petrole, vol. 45(4), 561-578 (1990), the entireties of which are incorporated herein by reference; and (iii) Klier, Herman, Simmons and Lyman, DOE report DE89009888 and references therein, the entireties of which are incorporated herein by reference. Fuel alcohol synthesis may occur at a variety of reaction conditions. In one embodiment, the fuel alcohol synthesis reaction temperature in the fuel alcohol synthesis zone ranges from about 200° C. to about 500° C., preferably from about 250° C. to about 450° C., and most preferably from about 300° C. to about 400° C. The pressure in the fuel alcohol synthesis zone also may vary widely, although the pressure preferably is in the range of the pressure of the syngas that is directed to the methanol synthesis unit, discussed above. Optionally, the pressure in the fuel alcohol synthesis zone ranges from about 5 to about 20 MPa, preferably from about 6 to about 18 MPa, and most preferably from about 10 to about 15 MPa. Although many different fuel alcohol synthesis catalysts may be utilized in the fuel alcohol synthesis zone to facilitate conversion of the syngas contained therein to fuel alcohol, the fuel alcohol synthesis catalyst preferably comprises a microporous zeolitic material. Thus, in one embodiment, the fuel alcohol is formed by contacting syngas with a fuel alcohol synthesis catalyst comprising a microporous zeolitic material under conditions effective to convert the syngas to fuel alcohol, which is contained in a fuel alcohol-containing stream. Additionally or alternatively, the fuel alcohol synthesis catalyst comprises copper and an oxide of zinc. Additionally, in this embodiment, the fuel alcohol synthesis catalyst preferably comprises an oxide of one or both of chromium and/or aluminum. Specifically, in this embodiment, the fuel alcohol synthesis catalyst preferably comprises one or more of Cu/ZnO/Cr2O3 and Cu/ZnO/Al2O3. In this embodiment, it is preferred that the fuel alcohol synthesis catalyst is alkali promoted. Thus, the fuel alcohol optionally is formed in this aspect of the invention by contacting syngas with a fuel alcohol synthesis catalyst comprising one or more of Cu/ZnO/Cr2O3 and Cu/ZnO/Al2O3, which fuel alcohol synthesis catalyst optionally is alkali promoted, under conditions effective to convert the syngas to the fuel alcohol. Additionally or alternatively, the fuel alcohol synthesis catalyst comprises an oxide of one or more of zinc, chromium, copper, cobalt, and nickel. In this embodiment, it is preferred that the fuel alcohol synthesis catalyst is alkali, lanthanum or cerium promoted. Thus, the fuel alcohol optionally is formed in this aspect of the invention by contacting syngas with a fuel alcohol synthesis catalyst under conditions effective to convert the syngas to the fuel alcohol, wherein the fuel alcohol synthesis catalyst comprises an oxide of one or more of zinc, chromium, copper, cobalt, and nickel, which fuel alcohol synthesis catalyst optionally is alkali, lanthanum or cerium promoted. Additionally or alternatively, the fuel alcohol synthesis catalyst comprises a compound comprising molybdenum and preferably sulfur. In this embodiment, it is preferred that the fuel alcohol synthesis catalyst is alkali promoted. Specifically, the fuel alcohol optionally is catalyzed by one or more of MoS2 and Co/MoS2. Thus, the fuel alcohol can be formed by contacting syngas with a fuel alcohol synthesis catalyst under conditions effective to convert the syngas to the fuel alcohol, wherein the fuel alcohol synthesis catalyst comprises one or more of MoS2 and Co/MoS2, and wherein the fuel alcohol synthesis catalyst optionally is alkali promoted. The alkali metal atom component of the catalyst system can come from any of the known ionic compounds of the alkali metals sodium, potassium, lithium, rubidium and cesium. Preferred alkali metal atom components are derived from sodium salts and potassium salts. Illustrative sources thereof include sodium iodide, sodium bicarbonate, sodium carbonate, sodium nitrate, sodium nitrite, sodium sulfate, sodium bisulfate, sodium chromate, sodium permanganate, sodium chlorate, sodium persulfate, sodium tetraborate, sodium bromide, sodium chloride, sodium fluoride, sodium sulfite, sodium hypochlorite, as well as any other ionic salt of sodium. Rather than repeat the individual compound names, the corresponding potassium, lithium, rubidium and cesium salts are illustrative of useful ionic compounds. The concentration of alkali metal atoms in the fuel alcohol synthesis zone optionally is from about 0.00013 to about 1 mole per liter; preferably from about 0.07 to about 0.6 mole per liter. Preferably, hydrogen and carbon monoxide are present in the syngas that is directed to the fuel alcohol synthesis zone. The molar ratio of H2:CO in the syngas that is directed to the fuel alcohol synthesis zone can vary from about 20:1 to about 1:20, from about 10:1 to about 1:10, and preferably from about 3:1 to about 1:3. Particularly in continuous operations, but also in batch experiments, the carbon monoxide-hydrogen gaseous mixture may also be used in conjunction with up to 50percent by volume of one or more other gases. These other gases may include one or more inert gases such as nitrogen, argon, neon and the like, or they may include gases that may, or may not, undergo reaction under CO hydrogenation conditions, such as carbon dioxide, hydrocarbons such as methane, ethane, propane and the like, ethers such as dimethyl ether, methylethyl ether and diethyl ether, alkanols such as methanol and acid esters such as methyl acetate. According to the present invention, a fuel alcohol-containing stream is formed, which comprises the fuel alcohol. The fuel alcohol-containing stream preferably comprises two or more alcohols in the C2 to C5 range. Higher alcohols and carboxylic acid esters may also be formed while carrying out the process of this invention. For example, the fuel alcohol-containing stream may include methyl formate, methyl acetate, ethyl acetate, ethyl ether. The major by-products of the process such as the higher molecular weight alcohols and carboxylic acid esters, are, of course, also useful compounds and major articles of commerce. The higher alcohols, the carboxylic acid esters and ethers can easily be separated from one another by conventional means, e.g., fractional distillation in vacuo, if desired. The precise amount and type of components contained in the fuel alcohol-containing stream will vary widely depending on catalyst type, reaction conditions, and syngas composition used. For example, Table I, below, provides three catalyst systems and indicates exemplary product yields and operating conditions. See El Sawy, A. H., DOE report DE90010325, pp. 3-17, 3-18. Product Yields (Wt. percent) and Reaction Conditions of Three Fuel Alcohol Synthesis Systems Process Product Slate Main Catalyst Constituents (anhydrous basis) Cu/Co/Al Zn/Cr/K Cu/ZnO/Al Methanol 57.5 70.0 64.5 Ethanol 28.5 2.5 11.5 C3 alcohols 7.1 3.4 5.2 C4 alcohols 2.8 12.5 7.4 C5+ alcohols 2.5 9.5 7.4 Hydrocarbons 0.3 - 0.02 Esters 0.7 0.1 0.8 Other Oxygenated 0.6 2.0 3.18 Products Total Alcohols 98.4 97.9 96.0 Operating T (° C.) 260-320 350-420 285-300 Operating Pressure 6-10 10-18 6-9 (MPa) Syngas Feed Ratio 2.0-2.5 1.5-2 0.5-1 (H2:CO)Syngas CO2 0.5-3.0 2-6 1.0 Content (Vol. percent) As indicated by Table I, the amount of ethanol contained in the fuel alcohol-containing stream may vary. The fuel alcohol-containing stream preferably comprises at least about 10 weight percent ethanol, more preferably at least about 25 weight percent ethanol and most preferably at least about 35 weight percent ethanol,

83/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

based on the total weight of the fuel alcohol-containing stream. In terms of ranges, the fuel alcohol-containing stream optionally comprises on the order of from about 5 to about 60 weight percent ethanol, preferably from about 10 to about 50 weight percent ethanol, and most preferably from about 20 to about 40 weight percent ethanol, based on the total weight of the fuel alcoholcontaining stream. The fuel alcohol-containing stream also comprises one or more C3 alcohols, preferably on the order of from about 5 to about 80 weight percent C3 alcohols, preferably from about 10 to about 60 weight percent C3 alcohols, and most preferably from about 15 to about 40 weight percent C3 alcohols, based on the total weight of the fuel alcohol-containing stream. Optionally, the C3 alcohols comprise one or more of 1-propanol, 2-propanol, and/or 1,2-propadiol. Additionally or alternatively, the fuel alcohol-containing stream comprises one or more C4 alcohols, preferably on the order of from about 0.1 to about 20 weight percent C4 alcohols, preferably from about I to about 10 weight percent C4 alcohols, and most preferably from about 2 to about 5 weight percent C4 alcohols, based on the total weight of the fuel alcohol-containing stream. Optionally, the C4 alcohols comprise one or more of I -butanol; 2-butanol; 1,4-butanediol; 1,3-butanediol; 1,2-butanediol; isobutyl alcohol; secbutyl alcohol; and t-butyl alcohol. The fuel alcohol-containing stream preferably comprises at least about 5 weight percent C3C4 alcohols, more preferably at least about 10 weight percent C3-C4 alcohols, and most preferably at least about 15 weight percent C3-C4 alcohols. Optionally, the fuel alcohol-containing stream comprises one or more C5 alcohols, preferably on the order of from about 0.01 to about 10 weight percent C5 alcohols, preferably from about 0.1 to about 5 weight percent C5 alcohols, and most preferably from about 0.1 to about 3 weight percent C5 alcohols, based on the total weight of the fuel alcoholcontaining stream. Optionally, the C5 alcohols comprise one or more of 1-pentanol; 2-pentanol; 3-pentanol; 1,5-pentanediol; 1,4-pentanediol; 1,3-pentanediol; and 1,2-pentanediol. Additionally, the fuel alcohol-containing stream optionally comprises one or more C6+ alcohols, preferably on the order of from about 0.01 to about 10 weight percent C6+ alcohols, preferably from about 0.1 to about 5 weight percent C6+ alcohols, and most preferably from about 0.1 to about 3 weight percent C6+ alcohols, based on the total weight of the fuel alcohol-containing stream. Ideally, the fuel alcohol-containing stream contains low amounts of methanol, if any. Preferably, the fuel alcohol-containing stream comprises less than 75 weight percent methanol, more preferably less than 65 weight percent methanol, and most preferably less than 60 weight percent methanol, based on the total weight of the fuel alcohol-containing stream. In terms of weight ratios, if the fuel alcohol-containing stream comprises methanol and ethanol, then the weight ratio of methanol to ethanol ranges from about 1 to about 6, more preferably from about 1.5 to about 5, and most preferably from about 2 to about 4. If the fuel alcohol-containing stream comprises ethanol and C3 alcohols, then the weight ratio of ethanol to C3 alcohols preferably ranges from about 1 to about 30, more preferably from about 5 to about 30, and most preferably from about 10 to about 20. The novel process of this invention can be conducted in a batch, semicontinuous or continuous fashion. The catalyst may be initially introduced into the fuel alcohol synthesis zone batchwise, or it may be continuously or intermittently introduced into such a zone during the course of the synthesis reaction. Operating conditions can be adjusted to optimize the formation of the fuel alcohol product, and after recovery of the alcohol and other products, a fraction rich in the catalyst composition may then be recycled to the reaction zone, if desired, and additional products generated. A non-limiting list of preferred reactor types for the synthesis of fuel alcohol includes fixed bed, slurry reactors and fluid bed reactors. One can additionally have an inert solvent present in the reaction mixture. A wide variety of substantially inert solvents are useful in the process of this invention including hydrocarbon and oxygenated hydrocarbon solvents. Suitable oxygenated hydrocarbon solvents are compounds comprising carbon, hydrogen and oxygen and those in which the only oxygen atoms present are in ether groups, ester groups, ketone carbonyl groups or hydroxyl groups of alcohols. Generally, the oxygenated hydrocarbon will contain 3 to 12 carbon atoms and preferably a maximum of 3 oxygen atoms. The solvent preferably is substantially inert under reaction conditions, is relatively non-polar and has a normal boiling point of at least 65Â° C. at atmospheric pressure, and preferably, the solvent will have a boiling point greater than that of ethanol and other oxygen-containing reaction products so that recovery of the solvent by distillation is facilitated. Preferred ester type solvents are the aliphatic and acylic carboxylic acid monoesters as exemplified by butyl acetate, methyl benzoate, isopropyl iso-butyrate, and propyl propionate as well as dimethyl adipate. Useful alcohol-type solvents include monohydric alcohols such as cyclohexanol, 1-hexanol, 2hexanol, neopentanol, 2-octanol, etc. Suitable ketone-type solvents include, for example, cyclic ketones such as cyclohexanone, 2-methylcyclohexanone, as well as acylic ketones such as 2-pentanone, butanone, acetophenone, etc. Ethers that may be utilized as solvents include cyclic, acyclic and heterocyclic materials. Preferred ethers are the heterocyclic ethers as illustrated by 1,4dioxane and 1,3-dioxane. Other suitable ether solvents include isopropyl propyl ether, diethylene glycol dibutyl ether, dibutyl ether, ethyl butyl ether, diphenyl ether, heptyl phenyl ether, anisole, tetrahydrofuran, etc. The most useful solvents of all of the above groups include the ethers as represented by monocyclic, heterocyclic ethers such a 1,4-dioxane or p-dioxane, etc. Hydrocarbon solvents, such as hexane, heptane, decane, dodecane, tetradecane, etc. are also suitable solvents for use in this invention. In the practice of this invention, it is also possible to add a small amount of water to the solvent and still obtain satisfactory results. The reaction time varies depending upon the reaction parameters, reactor size and charge, and the individual components employed at the specific process conditions. With hydrogen, Cu/ZnO/Al2O3, T= 285 - 300 Â°C , p= 45004.5 - 67506.8Torr , Conversion of starting material Patent; Janssen, Marcel Johannes; Van Egmond, Cornelis F.; Martens, Luc R.M.; Sher, Jaimes; US2005/107481; (2005); (A1) English View in Reaxys

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

84/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

HO OH

OH HO

OH OH

Rx-ID: 23310899 View in Reaxys 146/281 Yield 57.5 %, 28.5 %

Conditions & References C :As indicated above, the present invention, in one embodiment, provides for a combined process for forming methanol and fuel alcohol and converting the methanol and fuel alcohol to light olefins in an OTO reaction system. A non-limiting description of several fuel alcohol synthesis systems that may be incorporated into the present invention will now be described. As with methanol synthesis, there are numerous technologies available for producing fuel alcohol. The preferred embodiment for forming fuel alcohol according to the present invention comprises the reaction of carbon monoxide, hydrogen and optionally carbon dioxide in the presence of a fuel alcohol synthesis catalyst to form fuel alcohol and water. The synthesis of fuel alcohol occurs in a fuel alcohol synthesis zone. Without limiting the invention to a particular reaction mechanism, the synthesis of fuel alcohol may be illustrated as follows: nCO+2nH2-->CnH2n+1OH+(n-1)H2O (7) where n is a whole number. According to the present invention, the fuel alcohol synthesis reaction or reactions optionally are catalyzed using a fuel alcohol synthesis catalyst, preferably containing a metal atom, optionally with a halogen promoter. Many metal compounds and promoters can be used. Optionally, secondary activators or ligands may be used in conjunction with the metal catalysts and promoters. These secondary activators can be other metallic salts or compounds, amines, phosphorus compounds, as well as a multitude of other compounds that have been disclosed in the published literature. Thus, a typical catalyst system for the synthesis of fuel alcohol comprises a metal atom-containing catalyst, a promoter and optionally ligands, solvents and/or secondary activators. A variety of references disclose the synthesis of fuel alcohol from syngas. See, for example, (i) El Sawy, A. H., DOE report DE90010325 and references therein, the entireties of which are incorporated herein by reference; (ii) Courty, Charmette, Raimbault and Travers, Rev. De Institute du Petrole, vol. 45(4), 561-578 (1990), the entireties of which are incorporated herein by reference; and (iii) Klier, Herman, Simmons and Lyman, DOE report DE89009888 and references therein, the entireties of which are incorporated herein by reference. Fuel alcohol synthesis may occur at a variety of reaction conditions. In one embodiment, the fuel alcohol synthesis reaction temperature in the fuel alcohol synthesis zone ranges from about 200° C. to about 500° C., preferably from about 250° C. to about 450° C., and most preferably from about 300° C. to about 400° C. The pressure in the fuel alcohol synthesis zone also may vary widely, although the pressure preferably is in the range of the pressure of the syngas that is directed to the methanol synthesis unit, discussed above. Optionally, the pressure in the fuel alcohol synthesis zone ranges from about 5 to about 20 MPa, preferably from about 6 to about 18 MPa, and most preferably from about 10 to about 15 MPa. Although many different fuel alcohol synthesis catalysts may be utilized in the fuel alcohol synthesis zone to facilitate conversion of the syngas contained therein to fuel alcohol, the fuel alcohol synthesis catalyst preferably comprises a microporous zeolitic material. Thus, in one embodiment, the fuel alcohol is formed by contacting syngas with a fuel alcohol synthesis catalyst comprising a microporous zeolitic material under conditions effective to convert the syngas to fuel alcohol, which is contained in a fuel alcohol-containing stream. Additionally or alternatively, the fuel alcohol synthesis catalyst comprises copper and an oxide of zinc. Additionally, in this embodiment, the fuel alcohol synthesis catalyst preferably comprises an oxide of one or both of chromium and/or aluminum. Specifically, in this embodiment, the fuel alcohol synthesis catalyst preferably comprises one or more of Cu/ZnO/Cr2O3 and Cu/ZnO/Al2O3. In this embodiment, it is preferred that the fuel alcohol synthesis catalyst is alkali promoted. Thus, the fuel alcohol optionally is formed in this aspect of the invention by contacting syngas with a fuel alcohol synthesis catalyst comprising one or more of Cu/ZnO/Cr2O3 and Cu/ZnO/Al2O3, which fuel alcohol synthesis catalyst optionally is alkali promoted, under conditions effective to convert the syngas to the fuel alcohol. Additionally or alternatively, the fuel alcohol synthesis catalyst comprises an oxide of one or more of zinc, chromium, copper, cobalt, and nickel. In this embodiment, it is preferred that the fuel alcohol synthesis catalyst is alkali, lanthanum or cerium promoted. Thus, the fuel alcohol optionally is formed in this aspect of the invention by contacting syngas with a fuel alcohol synthesis catalyst under conditions effective to convert the syngas to the fuel alcohol, wherein the fuel alcohol synthesis catalyst comprises an oxide of one or more of zinc, chromium, copper, cobalt, and nickel, which fuel alcohol synthesis catalyst optionally is alkali, lanthanum or cerium promoted. Additionally or alternatively, the fuel alcohol synthesis catalyst comprises a compound comprising molybdenum and preferably sulfur. In this embodiment, it is preferred that the fuel alcohol synthesis catalyst is alkali promoted. Specifically, the fuel alcohol optionally is catalyzed by one or more of MoS2 and Co/MoS2. Thus, the fuel alcohol can be formed by contacting syngas with a fuel alcohol synthesis catalyst under conditions effective to convert the syngas to the fuel alcohol, wherein the fuel alcohol synthesis catalyst comprises one or more of MoS2 and Co/MoS2, and wherein the fuel alcohol synthesis catalyst optionally is alkali promoted. The alkali metal atom component of the catalyst system can come from any of the known ionic compounds of the alkali metals sodium, potassium, lithium, rubidium and cesium. Preferred alkali metal atom components are derived from sodium salts and potassium salts. Illustrative sources thereof include sodium iodide, sodium bicarbonate, sodium carbonate, sodium nitrate, sodium nitrite,

85/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

sodium sulfate, sodium bisulfate, sodium chromate, sodium permanganate, sodium chlorate, sodium persulfate, sodium tetraborate, sodium bromide, sodium chloride, sodium fluoride, sodium sulfite, sodium hypochlorite, as well as any other ionic salt of sodium. Rather than repeat the individual compound names, the corresponding potassium, lithium, rubidium and cesium salts are illustrative of useful ionic compounds. The concentration of alkali metal atoms in the fuel alcohol synthesis zone optionally is from about 0.00013 to about 1 mole per liter; preferably from about 0.07 to about 0.6 mole per liter. Preferably, hydrogen and carbon monoxide are present in the syngas that is directed to the fuel alcohol synthesis zone. The molar ratio of H2:CO in the syngas that is directed to the fuel alcohol synthesis zone can vary from about 20:1 to about 1:20, from about 10:1 to about 1:10, and preferably from about 3:1 to about 1:3. Particularly in continuous operations, but also in batch experiments, the carbon monoxide-hydrogen gaseous mixture may also be used in conjunction with up to 50percent by volume of one or more other gases. These other gases may include one or more inert gases such as nitrogen, argon, neon and the like, or they may include gases that may, or may not, undergo reaction under CO hydrogenation conditions, such as carbon dioxide, hydrocarbons such as methane, ethane, propane and the like, ethers such as dimethyl ether, methylethyl ether and diethyl ether, alkanols such as methanol and acid esters such as methyl acetate. According to the present invention, a fuel alcohol-containing stream is formed, which comprises the fuel alcohol. The fuel alcohol-containing stream preferably comprises two or more alcohols in the C2 to C5 range. Higher alcohols and carboxylic acid esters may also be formed while carrying out the process of this invention. For example, the fuel alcohol-containing stream may include methyl formate, methyl acetate, ethyl acetate, ethyl ether. The major by-products of the process such as the higher molecular weight alcohols and carboxylic acid esters, are, of course, also useful compounds and major articles of commerce. The higher alcohols, the carboxylic acid esters and ethers can easily be separated from one another by conventional means, e.g., fractional distillation in vacuo, if desired. The precise amount and type of components contained in the fuel alcohol-containing stream will vary widely depending on catalyst type, reaction conditions, and syngas composition used. For example, Table I, below, provides three catalyst systems and indicates exemplary product yields and operating conditions. See El Sawy, A. H., DOE report DE90010325, pp. 3-17, 3-18. Product Yields (Wt. percent) and Reaction Conditions of Three Fuel Alcohol Synthesis Systems Process Product Slate Main Catalyst Constituents (anhydrous basis) Cu/Co/Al Zn/Cr/K Cu/ZnO/Al Methanol 57.5 70.0 64.5 Ethanol 28.5 2.5 11.5 C3 alcohols 7.1 3.4 5.2 C4 alcohols 2.8 12.5 7.4 C5+ alcohols 2.5 9.5 7.4 Hydrocarbons 0.3 - 0.02 Esters 0.7 0.1 0.8 Other Oxygenated 0.6 2.0 3.18 Products Total Alcohols 98.4 97.9 96.0 Operating T (Â° C.) 260-320 350-420 285-300 Operating Pressure 6-10 10-18 6-9 (MPa) Syngas Feed Ratio 2.0-2.5 1.5-2 0.5-1 (H2:CO)Syngas CO2 0.5-3.0 2-6 1.0 Content (Vol. percent) As indicated by Table I, the amount of ethanol contained in the fuel alcohol-containing stream may vary. The fuel alcohol-containing stream preferably comprises at least about 10 weight percent ethanol, more preferably at least about 25 weight percent ethanol and most preferably at least about 35 weight percent ethanol, based on the total weight of the fuel alcohol-containing stream. In terms of ranges, the fuel alcohol-containing stream optionally comprises on the order of from about 5 to about 60 weight percent ethanol, preferably from about 10 to about 50 weight percent ethanol, and most preferably from about 20 to about 40 weight percent ethanol, based on the total weight of the fuel alcoholcontaining stream. The fuel alcohol-containing stream also comprises one or more C3 alcohols, preferably on the order of from about 5 to about 80 weight percent C3 alcohols, preferably from about 10 to about 60 weight percent C3 alcohols, and most preferably from about 15 to about 40 weight percent C3 alcohols, based on the total weight of the fuel alcohol-containing stream. Optionally, the C3 alcohols comprise one or more of 1-propanol, 2-propanol, and/or 1,2-propadiol. Additionally or alternatively, the fuel alcohol-containing stream comprises one or more C4 alcohols, preferably on the order of from about 0.1 to about 20 weight percent C4 alcohols, preferably from about I to about 10 weight percent C4 alcohols, and most preferably from about 2 to about 5 weight percent C4 alcohols, based on the total weight of the fuel alcohol-containing stream. Optionally, the C4 alcohols comprise one or more of I -butanol; 2-butanol; 1,4-butanediol; 1,3-butanediol; 1,2-butanediol; isobutyl alcohol; secbutyl alcohol; and t-butyl alcohol. The fuel alcohol-containing stream preferably comprises at least about 5 weight percent C3C4 alcohols, more preferably at least about 10 weight percent C3-C4 alcohols, and most preferably at least about 15 weight percent C3-C4 alcohols. Optionally, the fuel alcohol-containing stream comprises one or more C5 alcohols, preferably on the order of from about 0.01 to about 10 weight percent C5 alcohols, preferably from about 0.1 to about 5 weight percent C5 alcohols, and most preferably from about 0.1 to about 3 weight percent C5 alcohols, based on the total weight of the fuel alcoholcontaining stream. Optionally, the C5 alcohols comprise one or more of 1-pentanol; 2-pentanol; 3-pentanol; 1,5-pentanediol; 1,4-pentanediol; 1,3-pentanediol; and 1,2-pentanediol. Additionally, the fuel alcohol-containing stream optionally comprises one or more C6+ alcohols, preferably on the order of from about 0.01 to about 10 weight percent C6+ alcohols, preferably from about 0.1 to about 5 weight percent C6+ alcohols, and most preferably from about 0.1 to about 3 weight percent C6+ alcohols, based on the total weight of the fuel alcohol-containing stream. Ideally, the fuel alcohol-containing stream contains low amounts of methanol, if any. Preferably, the fuel alcohol-containing stream comprises less than 75 weight percent methanol, more preferably less than 65 weight percent methanol, and most preferably less than 60 weight percent methanol, based on the total weight of the fuel alcohol-containing stream. In terms of weight ratios, if the fuel alcohol-containing stream comprises methanol and ethanol, then the weight ratio of methanol to ethanol ranges from about 1 to about 6, more preferably from about 1.5 to about 5, and most preferably from about 2 to about 4. If the fuel alcohol-containing stream comprises ethanol and C3 alcohols, then the weight ratio of ethanol to C3 alcohols preferably ranges from about 1 to about 30, more preferably from about 5 to about 30, and most preferably from about 10 to about 20. The novel process of this invention can be conducted in a batch, semicontinuous or continuous fashion. The catalyst may be initially introduced into the fuel alcohol synthesis zone batchwise, or it may be continuously or intermittently introduced into such a zone during the course of the synthesis reaction. Operating conditions can be adjusted to optimize the formation of the fuel alcohol product, and after recovery of the alcohol and other products, a fraction rich in the catalyst composition may then be recycled to the reaction zone, if desired, and additional products gener-

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

86/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

ated. A non-limiting list of preferred reactor types for the synthesis of fuel alcohol includes fixed bed, slurry reactors and fluid bed reactors. One can additionally have an inert solvent present in the reaction mixture. A wide variety of substantially inert solvents are useful in the process of this invention including hydrocarbon and oxygenated hydrocarbon solvents. Suitable oxygenated hydrocarbon solvents are compounds comprising carbon, hydrogen and oxygen and those in which the only oxygen atoms present are in ether groups, ester groups, ketone carbonyl groups or hydroxyl groups of alcohols. Generally, the oxygenated hydrocarbon will contain 3 to 12 carbon atoms and preferably a maximum of 3 oxygen atoms. The solvent preferably is substantially inert under reaction conditions, is relatively non-polar and has a normal boiling point of at least 65° C. at atmospheric pressure, and preferably, the solvent will have a boiling point greater than that of ethanol and other oxygen-containing reaction products so that recovery of the solvent by distillation is facilitated. Preferred ester type solvents are the aliphatic and acylic carboxylic acid monoesters as exemplified by butyl acetate, methyl benzoate, isopropyl iso-butyrate, and propyl propionate as well as dimethyl adipate. Useful alcohol-type solvents include monohydric alcohols such as cyclohexanol, 1-hexanol, 2hexanol, neopentanol, 2-octanol, etc. Suitable ketone-type solvents include, for example, cyclic ketones such as cyclohexanone, 2-methylcyclohexanone, as well as acylic ketones such as 2-pentanone, butanone, acetophenone, etc. Ethers that may be utilized as solvents include cyclic, acyclic and heterocyclic materials. Preferred ethers are the heterocyclic ethers as illustrated by 1,4dioxane and 1,3-dioxane. Other suitable ether solvents include isopropyl propyl ether, diethylene glycol dibutyl ether, dibutyl ether, ethyl butyl ether, diphenyl ether, heptyl phenyl ether, anisole, tetrahydrofuran, etc. The most useful solvents of all of the above groups include the ethers as represented by monocyclic, heterocyclic ethers such a 1,4-dioxane or p-dioxane, etc. Hydrocarbon solvents, such as hexane, heptane, decane, dodecane, tetradecane, etc. are also suitable solvents for use in this invention. In the practice of this invention, it is also possible to add a small amount of water to the solvent and still obtain satisfactory results. The reaction time varies depending upon the reaction parameters, reactor size and charge, and the individual components employed at the specific process conditions. With hydrogen, Zn/Cr/K, T= 350 - 420 °C , p= 75007.5 - 135014Torr , Conversion of starting material Patent; Janssen, Marcel Johannes; Van Egmond, Cornelis F.; Martens, Luc R.M.; Sher, Jaimes; US2005/107481; (2005); (A1) English View in Reaxys O

OH HO

Rx-ID: 23336709 View in Reaxys 147/281 Yield

Conditions & References 1 With activated CuO/ZnO/Al2O3/Cu catalyst Patent; BASF Aktiengesellschaft; WO2005/44768; (2005); (A1) German View in Reaxys

O O

Rx-ID: 23487630 View in Reaxys 148/281 Yield

Conditions & References 1 :Comparative Example 1 demonstrates that under the preferred reaction conditions the addition of sodium salts of strong acids is detrimental to the reaction reducing both the conversion and the selectivity. Example 1 was repeated except that two molar equivalents of sodium-p-toluene sulphonate were added. At the end of the reaction a white solid (succinic acid, 3. 9g) was recovered and the liquid products (82. 5g) were analysed by gas chromatograph and found to be (wtpercent) water (95.90) propanol (0.10), tetrahydrofuran (0.09), propionic acid (1.478) y-butyrolactone (1.67), butanediol (0. 38) ; giving an overall molar selectivity to tetrahydrofuran of 2.43percent y-butyrolactone of 38. 25percent, and to butanediol of 8. 26percent. Thus conversion had fallen to 33. 49molpercent With hydrogen, sodium tosylate, η(+)-tris(pentane-2,5-dionato)ruthenium, [2-((diphenylphospino)methyl)-2-methyl-1,3-propanediyl]bis[diphenylphosphine] in water, T= 250 °C , p= 36201.3 - 51716.2Torr , Product distribution / selectivity

87/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Patent; DAVY PROCESS TECHNOLOGY LIMITED; WO2005/51875; (2005); (A1) English View in Reaxys 0.09 %Chromat., 1.67 %Chromat., 0.10 %Chromat., 0.38 %Chromat., 1.478 %Chromat.

4 :demonstrates that under the preferred reaction conditions the addition of sodium salts of strong acids is detrimental to the reaction reducing both the conversion and the selectivity. Example 1 was repeated except that two molar equivalents of sodiump-toluene sulphonate were added. At the end of the reaction a white solid (succinic acid, 13.9g) was recovered and the liquid products (82. 5g) were analysed by gas chromatography and found to be (wtpercent) : water (95.90), propanol (0.10), tetrahydrofuran (0.09), propionic acid (1.478) y-butyrolactone (1.67), butanediol (0. 38) ; giving an overall selectivity to tetrahydrofuran of 2. 43percent, to y-butyrolactone of 38.25percent, and to butanediol of 8.26percent. The conversion had fallen to 33.49 molpercent. With water, hydrogen, sodium tosylate, η(+)-tris(pentane-2,5-dionato)ruthenium, [2-((diphenylphospino)methyl)-2-methyl-1,3propanediyl]bis[diphenylphosphine], T= 241 °C , p= 36961.4 - 52476.2Torr , Product distribution / selectivity Patent; DAVY PROCESS TECHNOLOGY LIMITED; WO2003/93208; (2003); (A1) English View in Reaxys O

HO HO

OH HO

O O O

Rx-ID: 23487631 View in Reaxys 149/281 Yield

Conditions & References 1 :Example 1 illustrates that maleic acid may be successfully hydrogenated in the presence of water; Ruthenium (III) acetylacetonate (0.46 mmols, 0. 181g) and 1, 1, 1 tris (diphenylphosphinomethyl) ethane (triphos) (6. 1mmols, 0. 38g), water (71g) and maleic acid (ex Fluka, 20.2g) were transferred into a 300ml Hastelloy Parr autoclave. This was sealed and purged with hydrogen before being pressurised to 700 psig with hydrogen and heated to 250°C. Once 250°C had been achieved, the reactor was topped up with hydrogen to 1000 psig and this pressure was maintained throughout the reaction via a mass flow meter, which recorded the amount of hydrogen added. At the end of the reaction the hydrogen supply was isolated and the reactor cooled. At room temperature the headspace gas was analysed using a Pye-Unicam refinery gas analyser, before being vented. The product was removed from the reactor and weighed (91. 42g). The maleic conversion was determined by titration of the liquid product against 0.1 M sodium hydroxide (>99. 9percent). The water and organic analysis was determined using an HP gas chromatograph equipped with a micro TCD (wtpercent): water (86. 52), propanol (0.84), tetrahydrofuran (7.02) propionic acid (0.14), ybutyrolactone (2.47) butanediol (2.83) ; giving an overall molar selectivity to tetrahydrofuran of 5 1. 1 percent, to y-butyrolactone of 15. 1percent and to butanediol of 16.5percent. With hydrogen, η(+)-tris(pentane-2,5-dionato)ruthenium, [2-((diphenylphospino)methyl)-2-methyl-1,3-propanediyl]bis[diphenylphosphine] in water, T= 250 °C , p= 36201.3 - 51716.2Torr , Product distribution / selectivity Patent; DAVY PROCESS TECHNOLOGY LIMITED; WO2005/51875; (2005); (A1) English View in Reaxys 3 :Example 3 illustrates the use of other tridentate facially co-ordinated phosphines. Ru (acac) 3, (2.541g) tris-1, 1, l- (diethylphosphinomethyl) ethane (2. 00g) N- methylpyrrolidone (153g) were loaded under argon into a 300 ml Hastelloy C autoclave, then heated at 200°C for 30 minutes to preform the catalyst. The method of Example 1 was then repeated except that 15.89 Nmethylpyrrolidone were added instead of the ruthenium acetylacetonate and triphos. At the end of the reaction the products were analysed and found to be (wtpercent) water (61.43), propanol (0.14) tetrahydrofuran (3.69), propionic acid (0.15), y-butyrolactone (3.87), butanediol (5.22) ; giving an overall selectivity to tetrahydrofuran (30.49) to y-butyrolactone (26.81) and to butanediol of (34.57) and a conversion of>99percent With hydrogen in 1-methyl-pyrrolidin-2-one, water, T= 250 °C , p= 36201.3 - 51716.2Torr , Product distribution / selectivity Patent; DAVY PROCESS TECHNOLOGY LIMITED; WO2005/51875; (2005); (A1) English View in Reaxys

7.02 %Chromat., 0.14 %Chromat., 0.84 %Chromat., 2.83

1 :Ruthenium (III) acetylacetonate (0.46 mmols, 0. 181g) and 1,1, 1 tris (diphenylphosphinomethyl) ethane (triphos) (6. 1mmols, 0.38g), water (71g) and maleic acid (ex Fluka, 20.2g) were transferred into a 300ml Hastelloy Parr autoclave. This was sealed and purged with hydrogen before being pressurised to 700 psig with hydrogen and heated to 241°C. Once 241°C had been achieved, the reactor was topped up with hydrogen to 1000 psig and this pressure was maintained throughout the reaction via a mass flow meter, which recorded the amount of hydrogen added. At the end of the reaction the hydrogen supply was isolated and the reactor cooled. At room temperature the headspace gas was analysed using a Pye-Unicam refinery gas analyser, before being vented. The product was removed from the reactor and weighed (91.42g). The maleic conversion was determined by

88/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

%Chromat., titration of the liquid product against 0. 1M sodium hydroxide. (>99.9percent). The water and organic analysis was determined 0.14 using an HP gas chromatograph equipped with a micro TCD (wtpercent): water (86.52), propanol (0.84), tetrahydrofuran (7.02) %Chromat. propionic acid (0.14), y- butyrolactone (2.47) butanediol (2.83) ; giving an overall molar selectivity to tetrahydrofuran of 51. 1percent, to y-butylractone of 15. 1percent, and to butanediol of 16.5percent, others 17.3percent. With water, hydrogen, η(+)-tris(pentane-2,5-dionato)ruthenium, [2-((diphenylphospino)methyl)-2-methyl-1,3-propanediyl]bis[diphenylphosphine], T= 241 °C , p= 36961.4 - 52476.2Torr , Product distribution / selectivity Patent; DAVY PROCESS TECHNOLOGY LIMITED; WO2003/93208; (2003); (A1) English View in Reaxys O HO OH O

O O

HO HO

OH HO

Rx-ID: 23491962 View in Reaxys 150/281 Yield

Conditions & References 2 :Examples 2 illustrates the direct hydrogenation of succinic acid in the presence of a solvent. In Example 2, Example 1 was repeated using except that maleic acid was replaces with succinic acid (20.03g) 1-methyl-2-pyrrolidone (20.61g) was included as a solvent and the 49.86g water were used. At the end of the reaction the products were analysed and found to be (wtpercent) water (67.43), propanol (0.14) tetrahydrofuran (3.69), propionic acid (0.15) y-butyrolactone (3.87), butanediol (5.22) ; giving an overall selectivity to tetrahydrofuran (32. 55) y-butyrolactone (42.91) and to butanediol of (9.57) and a conversion of >88percent. With hydrogen, η(+)-tris(pentane-2,5-dionato)ruthenium, [2-((diphenylphospino)methyl)-2-methyl-1,3-propanediyl]bis[diphenylphosphine] in 1-methyl-pyrrolidin-2-one, water, T= 250 °C , p= 36201.3 - 51716.2Torr , Product distribution / selectivity Patent; DAVY PROCESS TECHNOLOGY LIMITED; WO2005/51875; (2005); (A1) English View in Reaxys

3.69 %Chromat., 3.87 %Chromat., 0.14 %Chromat., 5.22 %Chromat., 0.15 %Chromat.

8 :The method of Example 1 was repeated except that maleic acid was replaced with succinic acid (20. 03g), 1-methyl-2-pyrrolidinine (20. 61g) was included as a solvent and the amount of water (49.86g) included, was reduced. At the end of the reaction the products were analysed and found to be (wtpercent): water (61.43), propanol (0.14), tetrahydrofuran (3.69), propionic acid (0.15), y-butyrolactone (3.87), butanediol (5. 22) ; giving an overall selectivity to tetrahydrofuran of 30.49percent, to y-butyrolactone of 26.81percent, and to butanediol of 34.57percent, and a conversion of >99percent. With water, hydrogen, η(+)-tris(pentane-2,5-dionato)ruthenium, [2-((diphenylphospino)methyl)-2-methyl-1,3-propanediyl]bis[diphenylphosphine] in 1-methyl-pyrrolidin-2-one, T= 241 °C , p= 36961.4 - 52476.2Torr , Product distribution / selectivity Patent; DAVY PROCESS TECHNOLOGY LIMITED; WO2003/93208; (2003); (A1) English View in Reaxys O O

Rx-ID: 23511696 View in Reaxys 151/281 Yield 37.5 - 53.3 %Chromat., 21.0 - 47.4 %Chromat., 1.6 - 40.0 %Chromat., 1.4 - 9.8 %Chromat.

Conditions & References 6 With hydrogen, T= 180 - 260 °C , p= 7500.75 - 18751.9Torr , Gas phase, Product distribution / selectivity Patent; BASF Aktiengesellschaft; WO2005/58853; (2005); (A2) German View in Reaxys

89/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

OH OH

HO OH

Rx-ID: 23590952 View in Reaxys 152/281 Yield

Conditions & References 1 With hydrogen, catalyst 1 (Pd(NO3)2, sodium hypophosphite, Re2O7, Timrex.(R). HSAG 100; calcined) in water, Time= 38h, T= 100 - 270 °C , p= 45004.5 - 187519Torr , Product distribution / selectivity Patent; BASF Aktiengesellschaft; WO2005/77871; (2005); (A1) German View in Reaxys 7 With hydrogen, catalyst 10 (Rh(NO3)3, Re2O7, Timrex.(R). HSAG 100; calcined) in water, Time= 38h, T= 100 - 270 °C , p= 45004.5 - 187519Torr , Product distribution / selectivity Patent; BASF Aktiengesellschaft; WO2005/77871; (2005); (A1) German View in Reaxys 8 With hydrogen, catalyst 11 (Pd(NO3)2, Ir(CH3COO)3, Timrex.(R). HSAG 100; calcined) in water, Time= 38h, T= 100 - 270 °C , p= 45004.5 - 187519Torr , Product distribution / selectivity Patent; BASF Aktiengesellschaft; WO2005/77871; (2005); (A1) German View in Reaxys 2 With hydrogen, catalyst 2 (Rh(NO3)3, Re2O7, Timrex.(R). HSAG 100; calcined) in water, Time= 38h, T= 100 - 270 °C , p= 45004.5 - 187519Torr , Product distribution / selectivity Patent; BASF Aktiengesellschaft; WO2005/77871; (2005); (A1) German View in Reaxys 4 With hydrogen, catalyst 4 (Rh(NO3)3, Re2O7, Timrex.(R). HSAG 100; calcined) in water, Time= 38h, T= 100 - 270 °C , p= 45004.5 - 187519Torr , Product distribution / selectivity Patent; BASF Aktiengesellschaft; WO2005/77871; (2005); (A1) German View in Reaxys 11; 12 With hydrogen, catalyst 5 (Rh(NO3)3, Re2O7, Timrex.(R). HSAG 100; calcined) in water, T= 100 °C , p= 150015Torr , Product distribution / selectivity Patent; BASF Aktiengesellschaft; WO2005/77871; (2005); (A1) German View in Reaxys 5 With hydrogen, catalyst 8 (Pd(NO3)2, Re2O7, Timrex.(R). HSAG 100; calcined) in water, Time= 70h, T= 100 - 270 °C , p= 45004.5 - 150015Torr , Product distribution / selectivity Patent; BASF Aktiengesellschaft; WO2005/77871; (2005); (A1) German View in Reaxys 6

90/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

With hydrogen, catalyst 9 (Pt(NO3)2, Re2O7, Timrex.(R). HSAG 100; calcined) in water, Time= 38h, T= 100 - 270 °C , p= 45004.5 - 187519Torr , Product distribution / selectivity Patent; BASF Aktiengesellschaft; WO2005/77871; (2005); (A1) German View in Reaxys O

OH OH

HO OH

Rx-ID: 23590953 View in Reaxys 153/281 Yield

Conditions & References 3 With hydrogen, catalyst 3 (Pt(NO3)2, Re2O7, Timrex.(R). HSAG 100; calcined) in water, Time= 38h, T= 100 - 270 °C , p= 45004.5 - 187519Torr , Product distribution / selectivity Patent; BASF Aktiengesellschaft; WO2005/77871; (2005); (A1) German View in Reaxys

O O

H OH

HO O

Rx-ID: 9691791 View in Reaxys 154/281 Yield

Conditions & References

15 %, 55 %

With lithium aluminium tetrahydride in tetrahydrofuran, Time= 4h, T= 55 °C Huang, Pei-Qiang; Lan, Hong-Qiao; Zheng, Xiao; Ruan, Yuan-Ping; Journal of Organic Chemistry; vol. 69; nb. 11; (2004); p. 3964 - 3967 View in Reaxys

O O

Rx-ID: 22960932 View in Reaxys 155/281 Yield 20.3 %Chromat., 46.6 %Chromat., 15.3 %Chromat., 0.2 %Chromat.

Conditions & References 5 : Vergleichsbeispiel 5 25 ml des Katalysators V4 wurden in einen kontinuierlichen Rohrreaktor eingebaut. Der Feed bestand aus einer MALEINSaeURELoeSUNG (10 percent Maleinsaeure) und wurde mit 25 g/h dosiert. 50 NI/H Wasserstoff wurden zugegeben. Es wurde bei 160°C und 80 bar hydriert. Der Fluessigaustrag wurde mittels Gaschromatographie analysiert. Die Werte in Tabelle 5 sind jeweils als Ausbeuten in [percent] pro mol Maleinsaeure angegeben. With hydrogen, T= 160 °C , p= 60006Torr , Product distribution / selectivity Patent; BASF AKTIENGESELLSCHAFT; WO2004/43890; (2004); (A2) German View in Reaxys

91/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

O HO

O O

Rx-ID: 22960933 View in Reaxys 156/281 Yield

Conditions & References

0.1 - 0.9 %Chromat., 0.0 - 14.4 %Chromat., 58.6 - 72.5 %Chromat., 6.3 - 17.9 %Chromat.

1; 2; 3 : Beispiele 2 und 3, Vergleichsbeispiel 1 25 ml des Katalysators A wurden in einen kontinuierlichen Rohrreaktor eingebaut. Der Feed (Eduktgemisch) bestand aus einer Maleinsaeureloesung (10 GEW.-percent Maleinsaeure) und 50 NI/h Wasserstoff. Die Hydrierung wurde bei 160°C und 80 bar durchgefuehrt. Der Fluessigaustrag wurde mittels Gaschromatographie analysiert. Die Werte in Tabelle 1 sind jeweils als Ausbeuten in [percent] pro mol Maleinsaeure angegeben. With hydrogen, T= 160 °C , p= 60006Torr , Product distribution / selectivity Patent; BASF AKTIENGESELLSCHAFT; WO2004/43890; (2004); (A2) German View in Reaxys

1.1 %Chromat., 0.1 %Chromat., 60.1 %Chromat., 19.8 %Chromat.

10 : Beispiel 10 12 ml des Katalysators E wurden mit 80 mi waessriger Maleinsaeureloesung (5 Gew.-percent Maleinsaeure) in einen Autoklaven eingebaut. Es wurden bei Raumtemperatur 75 bar Wasserstoff aufgepresst. Die Temperatur wurde auf 160°C angehoben. Nach 1 h WUR- de die Reaktion abgebrochen. Der FLueSSIGAUSTRAG wurde mittels Gaschromatographie analysiert. Die Werte in Tabelle 7 sind jeweils als Ausbeuten in [percent] pro mol Maleinsaeure angegeben With hydrogen, Time= 1h, T= 160 °C , p= 56255.6Torr , Product distribution / selectivity Patent; BASF AKTIENGESELLSCHAFT; WO2004/43890; (2004); (A2) German View in Reaxys

0.5 - 1.0 %Chromat., 1.1 - 6.0 %Chromat., 73.3 - 93.1 %Chromat., 3.4 - 4.0 %Chromat.

12; 13 : Beispiele 12 und 13 Jeweils 25 mi Katalysator wurden in einen kontinuierlichen Rohrreaktor eingebaut. Der Feed bestand aus einer waessrigen Maleinsaeureloesung (10 Gew.-percent Maleinsaeure). 50 NI/h Wasserstoff wurden zugegeben. Der Fluessigaustrag wurde mittels Gaschromatographie analysiert. Die Werte in Tabelle 8 sind jeweils als Ausbeuten in [percent] pro mol Maleinsaeure angegeben.

0.1 - 0.3 %Chromat., 0.7 - 1.8 %Chromat., 91.1 - 91.4 %Chromat., 4.4 - 6.6 %Chromat.

5; 6 : Beispiele 5 und 6 25 ml des Katalysators B wurden in einen kontinuierlichen Rohrreaktor eingebaut. Der Feed bestand aus einer Maleinsaeureloesung (10 Gew.-percent Maleinsaeure) und wurde mit 25 g/h dosiert. Es wurde bei 160°C und 80 bar hydriert. Der FLueSSIGAUSTRAG wurde mittels Gaschromatographie analysiert. Die Werte in Tabelle 2 sind jeweils als Ausbeuten in [percent] pro mol Maleinsaeure angegeben.

With hydrogen, T= 160 - 180 °C , p= 60006Torr , Product distribution / selectivity Patent; BASF AKTIENGESELLSCHAFT; WO2004/43890; (2004); (A2) German View in Reaxys

With hydrogen, T= 160 °C , p= 60006Torr , Product distribution / selectivity Patent; BASF AKTIENGESELLSCHAFT; WO2004/43890; (2004); (A2) German View in Reaxys

HO O O

Rx-ID: 22960934 View in Reaxys 157/281 Yield 87.9 %Chromat., 3.1 %Chromat.

Conditions & References 8 : Beispiel 8 25 ml des Katalysators D wurden zu 0,1-1 mm grossem Splitt zerkleinert und in einen kontinuierlichen Rohrreaktor eingebaut. Der Feed bestand aus einer MALEINSaeURELoe- sung (10 Gew.-percent Maleinsaeure) und wurde mit 25 g/h dosiert. 50 NI/h Wasserstoff wurden zugegeben. Es wurde bei 140°C und 80 bar hydriert. Der FLueSSIGAUSTRAG wurde mittels Gaschromatographie analysiert. Die Werte in Tabelle 6 sind jeweils als Ausbeu- ten in [percent] pro mol Maleinsaeure angegeben. With hydrogen, T= 160 °C , p= 60006Torr , Product distribution / selectivity

92/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Patent; BASF AKTIENGESELLSCHAFT; WO2004/43890; (2004); (A2) German View in Reaxys

HO O O

Rx-ID: 22960935 View in Reaxys 158/281 Yield

Conditions & References

20.3 %Chromat., 19.7 %Chromat., 0.1 %Chromat.

3 : Vergleichsbeispiel 3 25 ml des Katalysators V2 wurden zu 0,1-1 mm grossem Splitt gebrochen und in einen kontinuierlichen Rohrreaktor eingebaut. Der Feed bestand aus einer Maleinsaeure- loesung (10 percent Maleinsaeure) und wurde mit 25 g/h dosiert. 50 NI/h Wasserstoff wurden zugegeben. Die Reaktionsbedingungen sind 160°C und 80 bar. Der Fluessigaustrag wurde mittels Gaschromatographie analysiert. Die Werte in Tabelle 4 sind jeweils als Ausbeuten in [percent] pro mol Maleinsaeure angegeben. With hydrogen, T= 160 °C , p= 60006Torr , Product distribution / selectivity Patent; BASF AKTIENGESELLSCHAFT; WO2004/43890; (2004); (A2) German View in Reaxys

OH HO O O

Rx-ID: 22960936 View in Reaxys 159/281 Yield 100 %

Conditions & References 19 : EXAMPLE 19 EXAMPLE 19 0.5g of the catalyst of Example 12, and then 50g of a 20 weight percent solution of maleic acid in water, were placed in the glass liner of a 300 ml autoclave, which was then sealed, purged several times with hydrogen and then pressurized with hydrogen to 1100 psig. The autoclave was heated to 170° C. and the pressure adjusted to 1850 psig. As the reaction proceeded, additional hydrogen was added when the pressure dropped 50 to 100 psi to bring the pressure back to or near the original pressure at reaction temperature. The reaction was effected for 175 minutes, the reactor and contents cooled to room temperature, and the gas volume measured. The gases were analyzed by gas chromatography. The liquid phase was also analyzed by gas chromatography after filtering out the solids. The conversion of maleic acid was 100 percent, and the yields of η-butyrolactone and 1,4-butanediol were 6.3percent and 50.9percent, respectively. With hydrogen in water Patent; The Standard Oil Company; US4827001; (1989); (A) English View in Reaxys

100 %

20 : EXAMPLE 20 EXAMPLE 20 0.5g of the catalyst of Example 15, and then 50g of a 20 weight percent solution of maleic acid in water, were placed in the glass liner of a 300 ml autoclave, which was then sealed, purged several times with hydrogen and then pressurized with hydrogen to 1100 psig. The autoclave was heated to 170° C. and the pressure adjusted to 1850 psig. As the reaction proceeded, additional hydrogen was added when the pressure dropped 50 to 100 psi to bring the pressure back to or near the original pressure at reaction temperature. The reaction was effected for 60 minutes, the reactor and contents cooled to room temperature, and the gas volume measured. The gases were analyzed by gas chromatography. The liquid phase was also analyzed by gas chromatography after filtering out the solids. The conversion of maleic acid was 100 percent, and the yields of η-butyrolactone and 1,4-butanediol were 46.6percent and 11.8percent, respectively. With hydrogen in water

93/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Patent; The Standard Oil Company; US4827001; (1989); (A) English View in Reaxys 100 %

21 : EXAMPLE 21 EXAMPLE 21 0.5g of the catalyst of Example 15, and then 50g of a 20 weight percent solution of maleic acid in water, were placed in the glass liner of a 300 ml autoclave, which was then sealed, purged several times with hydrogen and then pressurized with hydrogen to 1100 psig. The autoclave was heated to 170° C. and the pressure adjusted to 1850 psig. As the reaction proceeded, additional hydrogen was added when the pressure dropped 50 to 100 psi to bring the pressure back to or near the original pressure at reaction temperature. The reaction was effected for 115 minutes, the reactor and contents cooled to room temperature, and the gas volume measured. The gases were analyzed by gas chromatography. The liquid phase was also analyzed by gas chromatography after filtering out the solids. The conversion of maleic acid was 100 percent, and the yields of η-butyrolactone and 1,4-butanediol were 37.4percent and 24.2percent, respectively. With hydrogen in water Patent; The Standard Oil Company; US4827001; (1989); (A) English View in Reaxys

100 %

22 : EXAMPLE 22 EXAMPLE 22 0.5g of the catalyst of Example 15, and then 50g of a 20 weight percent solution of maleic acid in water, were placed in the glass liner of a 300 ml autoclave, which was then sealed, purged several times with hydrogen and then pressurized with hydrogen to 1100 psig. The autoclave was heated to 170° C. and the pressure adjusted to 1500 psig. As the reaction proceeded, additional hydrogen was added when the pressure dropped 50 to 100 psi to bring the pressure back to or near the original pressure at reaction temperature. The reaction was effected for 190 minutes, the reactor and contents cooled to room temperature, and the gas volume measured. The gases were analyzed by gas chromatography. The liquid phase was also analyzed by gas chromatography after filtering out the solids. The conversion of maleic acid was 100 percent, and the yields of η-butyrolactone and 1,4-butanediol were 2.7percent and 30.1percent, respectively. With hydrogen in water Patent; The Standard Oil Company; US4827001; (1989); (A) English View in Reaxys

100 %

23 : EXAMPLE 23 EXAMPLE 23 0.5g of the catalyst of Example 15, and then 50g of a 20 weight percent solution of maleic acid in water, were placed in the glass liner of a 300 ml autoclave, which was then sealed, purged several times with hydrogen and then pressurized with hydrogen to 1100 psig. The autoclave was heated to 160° C. and the pressure adjusted to 1850 psig. As the reaction proceeded, additional hydrogen was added when the pressure dropped 50 to 100 psi to bring the pressure back to or near the original pressure at reaction temperature. The reaction was effected for 170 minutes, the reactor and contents cooled to room temperature, and the gas volume measured. The gases were analyzed by gas chromatography. The liquid phase was also analyzed by gas chromatography after filtering out the solids. The conversion of maleic acid was 100 percent, and the yields of η-butyrolactone and 1,4-butanediol were 31.0percent and 38.0percent, respectively. With hydrogen in water Patent; The Standard Oil Company; US4827001; (1989); (A) English View in Reaxys

100 %

24 : EXAMPLE 24 EXAMPLE 24

94/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

0.5g of the catalyst of Example 15, and then 50g of a 30 weight percent solution of maleic acid in water, were placed in the glass liner of a 300 ml autoclave, which was then sealed, purged several times with hydrogen and then pressurized with hydrogen to 1100 psig. The autoclave was heated to 160° C. and the pressure adjusted to 1850 psig. As the reaction proceeded, additional hydrogen was added when the pressure dropped 50 to 100 psi to bring the pressure back to or near the original pressure at reaction temperature. The reaction was effected for 170 minutes, the reactor and contents cooled to room temperature, and the gas volume measured. The gases were analyzed by gas chromatography. The liquid phase was also analyzed by gas chromatography after filtering out the solids. The conversion of maleic acid was 100 percent, and the yields of η-butyrolactone and 1,4-butanediol were 28.9percent and 37.6percent, respectively. With hydrogen in water Patent; The Standard Oil Company; US4827001; (1989); (A) English View in Reaxys 100 %

25 : EXAMPLE 25 EXAMPLE 25 0.5g of the catalyst of Example 13, and then 50g of a 20 weight percent solution of maleic acid in water, were placed in the glass liner of a 300 ml autoclave, which was then sealed, purged several times with hydrogen and then pressurized with hydrogen to 1100 psig. The autoclave was heated to 170° C. and the pressure adjusted to 1850 psig. As the reaction proceeded, additional hydrogen was added when the pressure dropped 50 to 100 psi to bring the pressure back to or near the original pressure at reaction temperature. The reaction was effected for 115 minutes, the reactor and contents cooled to room temperature, and the gas volume measured. The gases were analyzed by gas chromatography. The liquid phase was also analyzed by gas chromatography after filtering out the solids. The conversion of maleic acid was 100 percent, and the yields of η-butyrolactone and 1,4-butanediol were 26.6percent and 45.7percent, respectively. With hydrogen in water Patent; The Standard Oil Company; US4827001; (1989); (A) English View in Reaxys

100 %

26 : EXAMPLE 26 EXAMPLE 26 0.5g of the catalyst of Example 14, and then 50g of a 20 weight percent solution of maleic acid in water, were placed in the glass liner of a 300 ml autoclave, which was then sealed, purged several times with hydrogen and then pressurized with hydrogen to 1100 psig. The autoclave was heated to 170° C. and the pressure adjusted to 1850 psig. As the reaction proceeded, additional hydrogen was added when the pressure dropped 50 to 100 psi to bring the pressure back to or near the original pressure at reaction temperature. The reaction was effected for 115 minutes, the reactor and contents cooled to room temperature, and the gas volume measured. The gases were analyzed by gas chromatography. The liquid phase was also analyzed by gas chromatography after filtering out the solids. The conversion of maleic acid was 100 percent, and the yields of η-butyrolactone and 1,4-butanediol were 50.0percent and 19.0percent, respectively. With hydrogen in water Patent; The Standard Oil Company; US4827001; (1989); (A) English View in Reaxys

100 %

C.A : COMPARATIVE EXAMPLE A COMPARATIVE EXAMPLE A 0.5g of the catalyst of Example 18, and then 50g of a 20 weight percent solution of maleic acid in water, were placed in the glass liner of a 300 ml autoclave, which was then sealed, purged several times with hydrogen and then pressurized with hydrogen to 1100 psig. The autoclave was heated to 170° C. and the pressure adjusted to 1850 psig. As the reaction proceeded, additional hydrogen was added when the pressure dropped 50 to 100 psi to bring the pressure back to or near the original pressure at reaction temperature.

95/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

The reaction was effected for 175 minutes, the reactor and contents cooled to room temperature, and the gas volume measured. The gases were analyzed by gas chromatography. The liquid phase was also analyzed by gas chromatography after filtering out the solids. The conversion of maleic acid was 100 percent, and the yields of η-butyrolactone and 1,4-butanediol were 18.8percent and 0.5percent respectively. With hydrogen in water Patent; The Standard Oil Company; US4827001; (1989); (A) English View in Reaxys 100 %

C.B : COMPARATIVE EXAMPLE B COMPARATIVE EXAMPLE B 0.5g of the catalyst of Example 17, and then 50g of a 20 weight percent solution of maleic acid in water, were placed in the glass liner of a 300 ml autoclave, which was then sealed, purged several times with hydrogen and then pressurized with hydrogen to 1100 psig. The autoclave was heated to 170° C. and the pressure adjusted to 1850 psig. As the reaction proceeded, additional hydrogen was added when the pressure dropped 50 to 100 psi to bring the pressure back to or near the original pressure at reaction temperature. The reaction was effected for 170 minutes, the reactor and contents cooled to room temperature, and the gas volume measured. The gases were analyzed by gas chromatography. The liquid phase was also analyzed by gas chromatography after filtering out the solids. The conversion of maleic acid was 100 percent, and the yields of η-butyrolactone and 1,4-butanediol were 30.9percent and 2.7percent, respectively. With hydrogen in water Patent; The Standard Oil Company; US4827001; (1989); (A) English View in Reaxys

100 %

C.C : COMPARATIVE EXAMPLE C COMPARATIVE EXAMPLE C 0.5g of the catalyst of Example 16, and then 50g of a 20 weight percent solution of maleic acid in water, were placed in the glass liner of a 300 ml autoclave, which was then sealed, purged several times with hydrogen and then pressurized with hydrogen to 1100 psig. The autoclave was heated to 170° C. and the pressure adjusted to 1850 psig. As the reaction proceeded, additional hydrogen was addd when the pressure dropped 50 to 100 psi to bring the pressure back to or near the original pressure at reaction temperature. The reaction was effected for 170 minutes, the reactor and contents cooled to room temperature, and the gas volume measured. The gases were analyzed by gas chromatography. The liquid phase was also analyzed by gas chromatography after filtering out the solids. The conversion of maleic acid was 100 percent, and the yields of η-butyrolactone and 1,4-butanediol were 6.8percent and 1.4percent, respectively. in water Patent; The Standard Oil Company; US4827001; (1989); (A) English View in Reaxys 14 : Beispiel 14 25 ml des Katalysators A wurden in einen kontinuierlich zu betreibenden Rohrreaktor eingebaut. Der Feed bestand aus ein 10 GEW.-percent IGEN waessrigen Maleinsaeureloesung und wurde mit 25 g/h zudosiert. Der Katalysator wurde mit dieser Loesung angefahren. Bei 160°C und 80 bar wurde mit 50 NI/h Wasserstoff hydriert. Der fluessige Reaktions- austrag wurde mittels Gaschromatographie nach verschiedenen Reaktionszeiten auf seinen 1, 4-Butandiol-Gehalt hier analysiert und in Auftragung 1 gegen die Zeit aufgetragen. With hydrogen, T= 160 °C , p= 60006Torr , Product distribution / selectivity Patent; BASF AKTIENGESELLSCHAFT; WO2004/43890; (2004); (A2) German View in Reaxys

96/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

O HO

HO OH

OH O

O O

HO OH

Rx-ID: 23050055 View in Reaxys 160/281 Yield

Conditions & References

73 - 98 %, 45 - 75 %Chromat., 72 - 96 %

1-14 : Production of a Diol Mixture by a Hydrogenation Reaction 10 g of water, 5.0 g of the dicarboxylic acid mixture and 0.3 g of the Ru-Sn-Re catalyst prepared in Reference Example 1 were charged into a 100 ml autoclave made of Hastelloy, which was equipped with a magnetic induction type stirrer. The atmosphere in the autoclave was replaced by nitrogen at room temperature and, then, pressurized hydrogen gas was introduced into the autoclave to increase the internal pressure thereof to 2 MPa, and the internal temperature of the autoclave was elevated to 180° C. After the internal temperature of the autoclave reached 180° C., pressurized hydrogen gas was further introduced into the autoclave to increase the internal pressure thereof to 15 MPa, and then a hydrogenation reaction was performed under the abovementioned internal pressure for 18 hours. After completion of the hydrogenation reaction, a hydrogenation reaction mixture containing a diol mixture was taken out from the autoclave, while leaving the catalyst in the autoclave. The diol mixture contained in the hydrogenation reaction mixture was analyzed by gas chromatography under the above-mentioned analysis conditions to determine the yields of the diols. As a result, it was found that the yields of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol were 75percent, 98percent and 96percent, respectively. [00215] Into the autoclave containing the catalyst therein were charged 5.0 g of the dicarboxylic acid mixture and 10 g of water, and a hydrogenation reaction was performed under substantially the same conditions as mentioned above to produce a diol mixture. This procedure for the hydrogenation of the dicarboxylic acid mixture was further repeated 6 times (i.e., 7 runs of the hydrogenation were performed). With respect to the catalyst used, the activity maintenance ratio (percent) was calculated by the formula: {(total amount of 1,4-butanediol, 1,5-pentanediol and 1,6hexanediol which were obtained in the 7th run of the hydrogenation)/(total amount of 1,4-butanediol, 1,5-pentanediol and 1,6hexanediol which were obtained in the 1st run of the hydrogenation)}.x.100. When the activity maintenance ratio is less than 100percent, it means that the catalytic activity is lowered. The results are shown in Table 1. With hydrogen, nitric acid, Ru-Sn-Re catalyst in water, Time= 18h, T= 180 °C , p= 15001.5 - 112511Torr Patent; Asahi Kasei Kabushiki Kaisha; US6706932; (2004); (B1) English View in Reaxys

OH HO

Rx-ID: 9420277 View in Reaxys 161/281 Yield

Conditions & References

76 %

With zirconium(IV) chloride in acetonitrile, Time= 0.75h, T= 20 °C Madhava Sharma, Gangavaram V.; Reddy, Ch. Govardhan; Krishna, Palakodety Radha; Journal of Organic Chemistry; vol. 68; nb. 11; (2003); p. 4574 - 4575 View in Reaxys O H

HO OH

Rx-ID: 9453480 View in Reaxys 162/281

97/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Yield

Conditions & References

11 %, 8 %, 74 %, 3 %

With hydrogen, Ru-carbon in water, Time= 10h, T= 135 °C , p= 258574Torr , Further byproducts given Niu, Wei; Molefe, Mapitso N.; Frost; Journal of the American Chemical Society; vol. 125; nb. 43; (2003); p. 12998 - 12999 View in Reaxys O

O O O

Rx-ID: 22842222 View in Reaxys 163/281 Yield

Conditions & References 1.c : 1 c) Hydrierapparatur Die zur Hydrierung verwendete Druckapparatur besteht aus einem Verdampfer, einem Reaktor, einem Kuehler mit Quenchzulauf, einer Wasserstoffzufuhr, einer Abgasleitung und einem Kreisgasgeblaese. Der Druck in der Apparatur wird konstant gehalten. Das aufgeschmolzene MSA wird von oben auf den vorgeheizten [(245°C)] Verdampfer gepumpt und verdampft. Auf den Verdampfer gelangt ebenfalls von oben eine Mischung aus frischem Wasserstoff und Kreisgas. Wasserstoff und MSA gelangen so von unten in den temperierten Reaktor. Der Reaktorinhalt besteht aus einem Gemisch aus Glasringen und Katalysator. Nach der Hydrierung verlaesst das entstandene GBL zusammen mit Wasser, anderen Reaktionsprodukten und Wasserstoff den Reaktor und wird im Kuehler durch Quenchen niedergeschlagen. Ein Teil des Kreisgases wird ausgeschleust, bevor der Rest, mit Frischwasserstoff vermischt, wieder in den Verdampfer eintritt. Der kondensierte fluessige Reaktionsaustrag, das Abgas und das Kreisgas werden gaschromatographisch quantitativ analysiert. Bei einer Reaktortemperatur von 255 °C, einem Druck von 5 bar und Katalysatorbelastung von 0.27 [KG/LKATH] bei einem Wasserstoff : MSA-Molverhaeltnis von 85 : 1 einen Reaktionsaustrag der Zusammensetzung : 91 percent GBL, 5 percent THF, 1 percent BDO, 1 percent BSA With hydrogen, T= 255 °C , p= 3750.38Torr Patent; BASF AKTIENGESELLSCHAFT; WO2003/104176; (2003); (A1) German View in Reaxys 1.c : 1 c) Hydrierapparatur Die zur Hydrierung verwendete Druckapparatur besteht aus einem Verdampfer, einem Reaktor, einem Kuehler mit Quenchzulauf, einer Wasserstoffzufuhr, einer Abgasleitung und einem Kreisgasgeblaese. Der Druck in der Apparatur wird konstant gehalten. Das aufgeschmolzene MSA wird von oben auf den vorgeheizten [(245°C)] Verdampfer gepumpt und verdampft. Auf den Verdampfer gelangt ebenfalls von oben eine Mischung aus frischem Wasserstoff und Kreisgas. Wasserstoff und MSA gelangen so von unten in den temperierten Reaktor. Der Reaktorinhalt besteht aus einem Gemisch aus Glasringen und Katalysator. Nach der Hydrierung verlaesst das entstandene GBL zusammen mit Wasser, anderen Reaktionsprodukten und Wasserstoff den Reaktor und wird im Kuehler durch Quenchen niedergeschlagen. Ein Teil des Kreisgases wird ausgeschleust, bevor der Rest, mit Frischwasserstoff vermischt, wieder in den Verdampfer eintritt. Der kondensierte fluessige Reaktionsaustrag, das Abgas und das Kreisgas werden gaschromatographisch quantitativ analysiert. Bei einer Reaktortemperatur von 255 °C, einem Druck von 5 bar und Katalysatorbelastung von 0.27 [KG/LKATH] bei einem Wasserstoff : MSA-Molverhaeltnis von 85 : 1 einen Reaktionsaustrag der Zusammensetzung : 91 percent GBL, 5 percent THF, 1 percent BDO, 1 percent BSA With hydrogen, T= 255 °C , p= 3750.38Torr Patent; BASF AKTIENGESELLSCHAFT; WO2003/104214; (2003); (A2) German View in Reaxys 1.c : 1 c) Hydrierapparatur Die zur Hydrierung verwendete Druckapparatur besteht aus einem Verdampfer, einem Reaktor, einem Kuehler mit Quenchzulauf, einer Wasserstoffzufuhr, einer Abgasleitung und einem Kreisgasgeblaese. Der Druck in der Apparatur wird konstant gehalten. Das aufgeschmolzene MSA wird von oben auf den vorgeheizten [(245°C)] Verdampfer gepumpt und verdampft. Auf den Verdampfer gelangt ebenfalls von oben eine Mischung aus frischem Wasserstoff und Kreisgas. Wasserstoff und MSA gelangen so von unten in den temperierten Reaktor. Der Reaktorinhalt besteht aus einem Gemisch aus Glasringen und Katalysator. Nach der Hydrierung verlaesst das entstandene GBL zusammen mit Wasser, anderen Reaktionsprodukten und Wasserstoff den Reaktor und wird im Kuehler durch Quenchen niedergeschlagen. Ein Teil des Kreisgases wird ausgeschleust, bevor der Rest, mit Frischwasserstoff vermischt, wieder in den Verdampfer eintritt. Der kondensierte fluessige Reaktionsaustrag, das Abgas und das Kreisgas werden gaschromatographisch quantitativ analysiert. Bei einer Reaktortemperatur von [255 °C,] einem Druck von 5 bar und Katalysatorbelastung von 0.27 [KG/LKATH] bei einem Wasserstoff : MSA-Molverhaeltnis von 85 : 1 einen Reaktionsaustrag der Zusammensetzung : 91 percent GBL, 5 percent THF, [1] percent BDO, [1] percent BSA

98/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

With hydrogen, T= 255 °C , p= 3750.38Torr Patent; BASF AKTIENGESELLSCHAFT; WO2003/104175; (2003); (A1) German View in Reaxys O O

OH HO

Rx-ID: 22891353 View in Reaxys 164/281 Yield

Conditions & References 2.c : 2 c) Hydrierapparatur Der in Beispiel 2a beschriebene Katalysator wird nach der Aktivierung in einer 300 mL- Autoklaven gefuellt und mit dem Reaktionsaustrag der MSA-Hydrierung in Beispiel 1 versetzt. Nach einer Reaktionsdauer von 48 h bei 180 °C und 80 bar konnten im Austrag 89 percent BDO, 2 percent GBL, 6 percent THF nachweisen. With hydrogen, Time= 48h, T= 180 °C , p= 60006Torr Patent; BASF AKTIENGESELLSCHAFT; WO2003/104176; (2003); (A1) German View in Reaxys 2.c : 2 c) Hydrierapparatur Der Reaktor der in Beispiel Ic beschriebenen Hydrierapparatur wird mit 220 ml des nach Beispiel 2 a hergestellten Katalysators und 130 ml Glasringen gefuellt. Die Aktivierung erfolgte wie in Beispiel 1 b beschrieben. Als Edukt wird der Reaktionsaustrag der MSA-Hydrierung aus Beispiel 1 eingesetzt, aus dem mehr als 50 percent des BSA-Gehaltes durch partielle Kondensation entfernt wurden. Bei einer Reaktortemperatur von [180 °C,] einem Druck von 60 bar und Katalysatorbelastung von 0.15 kg/ LKath (Wasserstoff : [GBL-MOLVERHaeLTNIS] 200 : 1) erhaelt man einen Reaktionsaustrag der Zusammensetzung : 87 percent BDO, 7 percent GBL, 5 percent THF. With hydrogen, T= 180 °C , p= 45004.5Torr Patent; BASF AKTIENGESELLSCHAFT; WO2003/104214; (2003); (A2) German View in Reaxys 2.c : 2 c) Hydrierapparatur Der Reaktor der in Beispiel Ic beschriebenen Hydrierapparatur wird mit 220 ml des nach Beispiel 2 a hergestellten Katalysators und 130 ml Glasringen gefuellt. Die Aktivierung erfolgte wie in Beispiel 1 b beschrieben. Als Edukt wird der Reaktionsaustrag der MSA-Hydrierung aus Beispiel 1 eingesetzt, aus dem mehr als 50 percent des BSA-Gehaltes durch partielle Kondensation entfernt wurden. Bei einer Reaktortemperatur von [180 °C,] einem Druck von 60 bar und Katalysatorbelastung von 0.15 kg/ LKath (Wasserstoff : [GBL-MOLVERHaeLTNIS] 200 : 1) erhaelt man einen Reaktionsaustrag der Zusammensetzung : 87 percent BDO, 7 percent GBL, 5 percent THF. With hydrogen, T= 180 °C , p= 45004.5Torr Patent; BASF AKTIENGESELLSCHAFT; WO2003/104175; (2003); (A1) German View in Reaxys O

O O

Rx-ID: 23051251 View in Reaxys 165/281 Yield

Conditions & References 5 : Example 5 The catalyst of the example was prepared by impregnating aqueous Re2O5 and SnCl4 on 1percent platinum/carbon precursor obtained from Aldrich (cat. No.20,592-3). Then 6.5 grams on dry basis of a catalyst composition of 1percent platinum, 6percent rhenium, 0.8percent tin was loaded in a continuous bubble column reactor to measure activity and selectivity. The comparative examples were prepared similarly, except for the composition. [00039] The continuous bubble column reactor consisted of a vertical Hastelloy C pipe, 3/4 inch I.D. by 41.5 inches long (2 cm I.D. by 105 cm long) with multiple ports for loading catalyst and reactants and removing products. The reactor was heated continuously and held at 250 degrees C and maintained at a pressure of 2,000 psi (1.38.x.107 Pa) with a constant hydrogen flow. The feed solution was aqueous 30percent maleic acid and was

99/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

fed at about 22 to 25 cm3/hr. Hydrogen was bubbled through the reactor at 1100 sccm (standard cubic centimeters per minute) to provide the agitation to slurry the catalyst and to sweep THF, by-products and water from the reactor in the vapor phase. [00040] Table 2 shows data on the inventive platinum-rhenium-tin catalyst opposite Comparative Example catalysts run in the reactor under similar conditions. [00041] Peak THF STY and THF STY at 200 hours were measured as grams THF/kg catalyst/hr. Useful Selectivity at 200 hours was measured as the quantity (carbon in THF, GBL, BDO and SAC in product) divided by the quantity (all carbon collected in product). Deactivation Rate was measured over hours 100 to 200 in terms of THF STY/day.[TABLEUS-00002] TABLE 2 Peak Useful Catalyst (percentTHFTHF STY atSelectivityDeactivationExampleon carbon)STY200 hrsat 200 hrsRate 51percent Pt,6percent74060094percent16 Re,0.8percent SnG1percent Ru, 6percent41520089percent24 ReH2percent Ru, 6percent76040091percent31 Re, 0.9percent Sn [00042] The platinum-rhenium-tin catalyst clearly showed a selectivity advantage of several percent over the ruthenium-rhenium and the ruthenium-rhenium-tin catalysts. Also, the platinum-rheniumtin catalyst had initial activity comparable to the ruthenium-rhenium-tin catalyst, but it retained more of that activity as the run continued as indicated by the lower deactivation rate and the higher THF STY at the 200 hour mark. With hydrogen, 1% Pt,6% Re,0.8% Sn on C in water, Time= 200h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; E. I. du Pont de Nemours and Company; US6670490; (2003); (B1) English View in Reaxys H : Example 5 The catalyst of the example was prepared by impregnating aqueous Re2O5 and SnCl4 on 1percent platinum/carbon precursor obtained from Aldrich (cat. No.20,592-3). Then 6.5 grams on dry basis of a catalyst composition of 1percent platinum, 6percent rhenium, 0.8percent tin was loaded in a continuous bubble column reactor to measure activity and selectivity. The comparative examples were prepared similarly, except for the composition. [00039] The continuous bubble column reactor consisted of a vertical Hastelloy C pipe, 3/4 inch I.D. by 41.5 inches long (2 cm I.D. by 105 cm long) with multiple ports for loading catalyst and reactants and removing products. The reactor was heated continuously and held at 250 degrees C and maintained at a pressure of 2,000 psi (1.38.x.107 Pa) with a constant hydrogen flow. The feed solution was aqueous 30percent maleic acid and was fed at about 22 to 25 cm3/hr. Hydrogen was bubbled through the reactor at 1100 sccm (standard cubic centimeters per minute) to provide the agitation to slurry the catalyst and to sweep THF, by-products and water from the reactor in the vapor phase. [00040] Table 2 shows data on the inventive platinum-rhenium-tin catalyst opposite Comparative Example catalysts run in the reactor under similar conditions. [00041] Peak THF STY and THF STY at 200 hours were measured as grams THF/kg catalyst/hr. Useful Selectivity at 200 hours was measured as the quantity (carbon in THF, GBL, BDO and SAC in product) divided by the quantity (all carbon collected in product). Deactivation Rate was measured over hours 100 to 200 in terms of THF STY/day.[TABLEUS-00002] TABLE 2 Peak Useful Catalyst (percentTHFTHF STY atSelectivityDeactivationExampleon carbon)STY200 hrsat 200 hrsRate 51percent Pt,6percent74060094percent16 Re,0.8percent SnG1percent Ru, 6percent41520089percent24 ReH2percent Ru, 6percent76040091percent31 Re, 0.9percent Sn [00042] The platinum-rhenium-tin catalyst clearly showed a selectivity advantage of several percent over the ruthenium-rhenium and the ruthenium-rhenium-tin catalysts. Also, the platinum-rheniumtin catalyst had initial activity comparable to the ruthenium-rhenium-tin catalyst, but it retained more of that activity as the run continued as indicated by the lower deactivation rate and the higher THF STY at the 200 hour mark. With hydrogen, 2% Ru,6% Re,0.9% Sn on C in water, Time= 200h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; E. I. du Pont de Nemours and Company; US6670490; (2003); (B1) English View in Reaxys G : Example 5 The catalyst of the example was prepared by impregnating aqueous Re2O5 and SnCl4 on 1percent platinum/carbon precursor obtained from Aldrich (cat. No.20,592-3). Then 6.5 grams on dry basis of a catalyst composition of 1percent platinum, 6percent rhenium, 0.8percent tin was loaded in a continuous bubble column reactor to measure activity and selectivity. The comparative examples were prepared similarly, except for the composition. [00039] The continuous bubble column reactor consisted of a vertical Hastelloy C pipe, 3/4 inch I.D. by 41.5 inches long (2 cm I.D. by 105 cm long) with multiple ports for loading catalyst and reactants and removing products. The reactor was heated continuously and held at 250 degrees C and maintained at a pressure of 2,000 psi (1.38.x.107 Pa) with a constant hydrogen flow. The feed solution was aqueous 30percent maleic acid and was fed at about 22 to 25 cm3/hr. Hydrogen was bubbled through the reactor at 1100 sccm (standard cubic centimeters per minute) to provide the agitation to slurry the catalyst and to sweep THF, by-products and water from the reactor in the vapor phase. [00040] Table 2 shows data on the inventive platinum-rhenium-tin catalyst opposite Comparative Example catalysts run in the reactor under similar conditions. [00041] Peak THF STY and THF STY at 200 hours were measured as grams THF/kg catalyst/hr. Useful Selectivity at 200 hours was measured as the quantity (carbon in THF, GBL, BDO and SAC in product) divided by the quantity (all carbon collected in product). Deactivation Rate was measured over hours 100 to 200 in terms of THF STY/day.[TABLEUS-00002] TABLE 2 Peak Useful Catalyst (percentTHFTHF STY atSelectivityDeactivationExampleon carbon)STY200 hrsat 200 hrsRate 51percent Pt,6percent74060094percent16 Re,0.8percent SnG1percent Ru, 6percent41520089percent24 ReH2percent Ru, 6percent76040091percent31 Re, 0.9percent Sn [00042] The platinum-rhenium-tin catalyst clearly showed a selectivity

100/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

advantage of several percent over the ruthenium-rhenium and the ruthenium-rhenium-tin catalysts. Also, the platinum-rheniumtin catalyst had initial activity comparable to the ruthenium-rhenium-tin catalyst, but it retained more of that activity as the run continued as indicated by the lower deactivation rate and the higher THF STY at the 200 hour mark. With hydrogen, 1% Ru,6% Re on C in water, Time= 200h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; E. I. du Pont de Nemours and Company; US6670490; (2003); (B1) English View in Reaxys O O

HO HO

Rx-ID: 23052161 View in Reaxys 166/281 Yield

Conditions & References A : Examples 1-4 The catalysts were prepared in-situ and tested simultaneously by adding to a 300-cc autoclave 0.4 g 1percent platinum/carbon precursor obtained from Aldrich (cat. No.20,592-3) and given amounts of Re2O5 and SnCl4 (as applicable) to give the catalyst compositions given in Table 1. Also, 125 g of 20percent aqueous GBL was added to the autoclave as the test solution. The autoclave was heated to 250° C. and then pressurized to 2000 psig (14.x.106 Pa gage) with H2, while stirring. The conditions were maintained for 45 min, after which it was rapidly cooled down and the products were analyzed by GC (gas chromatography) to determine the net molar production rate (STY), and molar selectivity. The results are shown in Table 1. [00033] The STY and Selectivity are defined as follows: [00034] STY=mol/Kg of catalyst-hr [00035] Molar Selectivity=(THF+BDO)STY/[(THF +BDO)STY+By-products STY] [00036] By-products=propanol+butanol+propionic acid+butyric acid[TABLE-US-00001] TABLE 1 Molar SelectivityEx.Catalyst percent on CTHF+BDO STYTHF+BDO A1percent Pt11.20.65B1percent Pt,1percent Re23.90.79C1percent Pt,3percent Re41.20.84D1percent Pt,4percent Re45.10.85E1percent Pt,5percent Re55.70.8711percent Pt,3percent Re,0.2percent Sn33.00.9021percent Pt,3percent Re,04percent Sn40.70.9031percent Pt,3percent Re,0.6percent Sn26.90.9141percent Pt,3percent Re,0.8percent Sn40.00.91F1percent Pt,0.8percent Sn28.80.92 [00037] It can be observed from Table 1 that although adding rhenium to a platinum-carbon catalyst increases the catalytic activity and selectivity, the selectivity is further increased by the addition of tin. With hydrogen, 1 % platinum on carbon in water, Time= 0.75h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; E. I. du Pont de Nemours and Company; US6670490; (2003); (B1) English View in Reaxys 1 : Examples 1-4 The catalysts were prepared in-situ and tested simultaneously by adding to a 300-cc autoclave 0.4 g 1percent platinum/carbon precursor obtained from Aldrich (cat. No.20,592-3) and given amounts of Re2O5 and SnCl4 (as applicable) to give the catalyst compositions given in Table 1. Also, 125 g of 20percent aqueous GBL was added to the autoclave as the test solution. The autoclave was heated to 250° C. and then pressurized to 2000 psig (14.x.106 Pa gage) with H2, while stirring. The conditions were maintained for 45 min, after which it was rapidly cooled down and the products were analyzed by GC (gas chromatography) to determine the net molar production rate (STY), and molar selectivity. The results are shown in Table 1. [00033] The STY and Selectivity are defined as follows: [00034] STY=mol/Kg of catalyst-hr [00035] Molar Selectivity=(THF+BDO)STY/[(THF +BDO)STY+By-products STY] [00036] By-products=propanol+butanol+propionic acid+butyric acid[TABLE-US-00001] TABLE 1 Molar SelectivityEx.Catalyst percent on CTHF+BDO STYTHF+BDO A1percent Pt11.20.65B1percent Pt,1percent Re23.90.79C1percent Pt,3percent Re41.20.84D1percent Pt,4percent Re45.10.85E1percent Pt,5percent Re55.70.8711percent Pt,3percent Re,0.2percent Sn33.00.9021percent Pt,3percent Re,04percent Sn40.70.9031percent Pt,3percent Re,0.6percent Sn26.90.9141percent Pt,3percent Re,0.8percent Sn40.00.91F1percent Pt,0.8percent Sn28.80.92 [00037] It can be observed from Table 1 that although adding rhenium to a platinum-carbon catalyst increases the catalytic activity and selectivity, the selectivity is further increased by the addition of tin. With hydrogen, 1% Pt,3% Re,0.2% Sn on C in water, Time= 0.75h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; E. I. du Pont de Nemours and Company; US6670490; (2003); (B1) English View in Reaxys

101/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

2 : Examples 1-4 The catalysts were prepared in-situ and tested simultaneously by adding to a 300-cc autoclave 0.4 g 1percent platinum/carbon precursor obtained from Aldrich (cat. No.20,592-3) and given amounts of Re2O5 and SnCl4 (as applicable) to give the catalyst compositions given in Table 1. Also, 125 g of 20percent aqueous GBL was added to the autoclave as the test solution. The autoclave was heated to 250° C. and then pressurized to 2000 psig (14.x.106 Pa gage) with H2, while stirring. The conditions were maintained for 45 min, after which it was rapidly cooled down and the products were analyzed by GC (gas chromatography) to determine the net molar production rate (STY), and molar selectivity. The results are shown in Table 1. [00033] The STY and Selectivity are defined as follows: [00034] STY=mol/Kg of catalyst-hr [00035] Molar Selectivity=(THF+BDO)STY/[(THF +BDO)STY+By-products STY] [00036] By-products=propanol+butanol+propionic acid+butyric acid[TABLE-US-00001] TABLE 1 Molar SelectivityEx.Catalyst percent on CTHF+BDO STYTHF+BDO A1percent Pt11.20.65B1percent Pt,1percent Re23.90.79C1percent Pt,3percent Re41.20.84D1percent Pt,4percent Re45.10.85E1percent Pt,5percent Re55.70.8711percent Pt,3percent Re,0.2percent Sn33.00.9021percent Pt,3percent Re,04percent Sn40.70.9031percent Pt,3percent Re,0.6percent Sn26.90.9141percent Pt,3percent Re,0.8percent Sn40.00.91F1percent Pt,0.8percent Sn28.80.92 [00037] It can be observed from Table 1 that although adding rhenium to a platinum-carbon catalyst increases the catalytic activity and selectivity, the selectivity is further increased by the addition of tin. With hydrogen, 1% Pt,3% Re,0.4% Sn on C in water, Time= 0.75h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; E. I. du Pont de Nemours and Company; US6670490; (2003); (B1) English View in Reaxys 3 : Examples 1-4 The catalysts were prepared in-situ and tested simultaneously by adding to a 300-cc autoclave 0.4 g 1percent platinum/carbon precursor obtained from Aldrich (cat. No.20,592-3) and given amounts of Re2O5 and SnCl4 (as applicable) to give the catalyst compositions given in Table 1. Also, 125 g of 20percent aqueous GBL was added to the autoclave as the test solution. The autoclave was heated to 250° C. and then pressurized to 2000 psig (14.x.106 Pa gage) with H2, while stirring. The conditions were maintained for 45 min, after which it was rapidly cooled down and the products were analyzed by GC (gas chromatography) to determine the net molar production rate (STY), and molar selectivity. The results are shown in Table 1. [00033] The STY and Selectivity are defined as follows: [00034] STY=mol/Kg of catalyst-hr [00035] Molar Selectivity=(THF+BDO)STY/[(THF +BDO)STY+By-products STY] [00036] By-products=propanol+butanol+propionic acid+butyric acid[TABLE-US-00001] TABLE 1 Molar SelectivityEx.Catalyst percent on CTHF+BDO STYTHF+BDO A1percent Pt11.20.65B1percent Pt,1percent Re23.90.79C1percent Pt,3percent Re41.20.84D1percent Pt,4percent Re45.10.85E1percent Pt,5percent Re55.70.8711percent Pt,3percent Re,0.2percent Sn33.00.9021percent Pt,3percent Re,04percent Sn40.70.9031percent Pt,3percent Re,0.6percent Sn26.90.9141percent Pt,3percent Re,0.8percent Sn40.00.91F1percent Pt,0.8percent Sn28.80.92 [00037] It can be observed from Table 1 that although adding rhenium to a platinum-carbon catalyst increases the catalytic activity and selectivity, the selectivity is further increased by the addition of tin. With hydrogen, 1% Pt,3% Re,0.6% Sn on C in water, Time= 0.75h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; E. I. du Pont de Nemours and Company; US6670490; (2003); (B1) English View in Reaxys 4 : Examples 1-4 The catalysts were prepared in-situ and tested simultaneously by adding to a 300-cc autoclave 0.4 g 1percent platinum/carbon precursor obtained from Aldrich (cat. No.20,592-3) and given amounts of Re2O5 and SnCl4 (as applicable) to give the catalyst compositions given in Table 1. Also, 125 g of 20percent aqueous GBL was added to the autoclave as the test solution. The autoclave was heated to 250° C. and then pressurized to 2000 psig (14.x.106 Pa gage) with H2, while stirring. The conditions were maintained for 45 min, after which it was rapidly cooled down and the products were analyzed by GC (gas chromatography) to determine the net molar production rate (STY), and molar selectivity. The results are shown in Table 1. [00033] The STY and Selectivity are defined as follows: [00034] STY=mol/Kg of catalyst-hr [00035] Molar Selectivity=(THF+BDO)STY/[(THF +BDO)STY+By-products STY] [00036] By-products=propanol+butanol+propionic acid+butyric acid[TABLE-US-00001] TABLE 1 Molar SelectivityEx.Catalyst percent on CTHF+BDO STYTHF+BDO A1percent Pt11.20.65B1percent Pt,1percent Re23.90.79C1percent Pt,3percent Re41.20.84D1percent Pt,4percent Re45.10.85E1percent Pt,5percent Re55.70.8711percent Pt,3percent Re,0.2percent Sn33.00.9021percent Pt,3percent Re,04percent Sn40.70.9031percent Pt,3percent Re,0.6percent Sn26.90.9141percent Pt,3percent Re,0.8percent Sn40.00.91F1percent Pt,0.8percent Sn28.80.92 [00037] It can be observed from Table 1 that although adding rhenium to a platinum-carbon catalyst increases the catalytic activity and selectivity, the selectivity is further increased by the addition of tin. With hydrogen, 1% Pt,3% Re,0.8% Sn on C in water, Time= 0.75h, T= 250 °C , p= 103432Torr , Conversion of starting material

102/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Patent; E. I. du Pont de Nemours and Company; US6670490; (2003); (B1) English View in Reaxys F : Examples 1-4 The catalysts were prepared in-situ and tested simultaneously by adding to a 300-cc autoclave 0.4 g 1percent platinum/carbon precursor obtained from Aldrich (cat. No.20,592-3) and given amounts of Re2O5 and SnCl4 (as applicable) to give the catalyst compositions given in Table 1. Also, 125 g of 20percent aqueous GBL was added to the autoclave as the test solution. The autoclave was heated to 250° C. and then pressurized to 2000 psig (14.x.106 Pa gage) with H2, while stirring. The conditions were maintained for 45 min, after which it was rapidly cooled down and the products were analyzed by GC (gas chromatography) to determine the net molar production rate (STY), and molar selectivity. The results are shown in Table 1. [00033] The STY and Selectivity are defined as follows: [00034] STY=mol/Kg of catalyst-hr [00035] Molar Selectivity=(THF+BDO)STY/[(THF +BDO)STY+By-products STY] [00036] By-products=propanol+butanol+propionic acid+butyric acid[TABLE-US-00001] TABLE 1 Molar SelectivityEx.Catalyst percent on CTHF+BDO STYTHF+BDO A1percent Pt11.20.65B1percent Pt,1percent Re23.90.79C1percent Pt,3percent Re41.20.84D1percent Pt,4percent Re45.10.85E1percent Pt,5percent Re55.70.8711percent Pt,3percent Re,0.2percent Sn33.00.9021percent Pt,3percent Re,04percent Sn40.70.9031percent Pt,3percent Re,0.6percent Sn26.90.9141percent Pt,3percent Re,0.8percent Sn40.00.91F1percent Pt,0.8percent Sn28.80.92 [00037] It can be observed from Table 1 that although adding rhenium to a platinum-carbon catalyst increases the catalytic activity and selectivity, the selectivity is further increased by the addition of tin. With hydrogen, 1% Pt,0.8% Sn on C in water, Time= 0.75h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; E. I. du Pont de Nemours and Company; US6670490; (2003); (B1) English View in Reaxys C : Examples 1-4 The catalysts were prepared in-situ and tested simultaneously by adding to a 300-cc autoclave 0.4 g 1percent platinum/carbon precursor obtained from Aldrich (cat. No.20,592-3) and given amounts of Re2O5 and SnCl4 (as applicable) to give the catalyst compositions given in Table 1. Also, 125 g of 20percent aqueous GBL was added to the autoclave as the test solution. The autoclave was heated to 250° C. and then pressurized to 2000 psig (14.x.106 Pa gage) with H2, while stirring. The conditions were maintained for 45 min, after which it was rapidly cooled down and the products were analyzed by GC (gas chromatography) to determine the net molar production rate (STY), and molar selectivity. The results are shown in Table 1. [00033] The STY and Selectivity are defined as follows: [00034] STY=mol/Kg of catalyst-hr [00035] Molar Selectivity=(THF+BDO)STY/[(THF +BDO)STY+By-products STY] [00036] By-products=propanol+butanol+propionic acid+butyric acid[TABLE-US-00001] TABLE 1 Molar SelectivityEx.Catalyst percent on CTHF+BDO STYTHF+BDO A1percent Pt11.20.65B1percent Pt,1percent Re23.90.79C1percent Pt,3percent Re41.20.84D1percent Pt,4percent Re45.10.85E1percent Pt,5percent Re55.70.8711percent Pt,3percent Re,0.2percent Sn33.00.9021percent Pt,3percent Re,04percent Sn40.70.9031percent Pt,3percent Re,0.6percent Sn26.90.9141percent Pt,3percent Re,0.8percent Sn40.00.91F1percent Pt,0.8percent Sn28.80.92 [00037] It can be observed from Table 1 that although adding rhenium to a platinum-carbon catalyst increases the catalytic activity and selectivity, the selectivity is further increased by the addition of tin. With hydrogen, 1% Pt,3% Re on C in water, Time= 0.75h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; E. I. du Pont de Nemours and Company; US6670490; (2003); (B1) English View in Reaxys D : Examples 1-4 The catalysts were prepared in-situ and tested simultaneously by adding to a 300-cc autoclave 0.4 g 1percent platinum/carbon precursor obtained from Aldrich (cat. No.20,592-3) and given amounts of Re2O5 and SnCl4 (as applicable) to give the catalyst compositions given in Table 1. Also, 125 g of 20percent aqueous GBL was added to the autoclave as the test solution. The autoclave was heated to 250° C. and then pressurized to 2000 psig (14.x.106 Pa gage) with H2, while stirring. The conditions were maintained for 45 min, after which it was rapidly cooled down and the products were analyzed by GC (gas chromatography) to determine the net molar production rate (STY), and molar selectivity. The results are shown in Table 1. [00033] The STY and Selectivity are defined as follows: [00034] STY=mol/Kg of catalyst-hr [00035] Molar Selectivity=(THF+BDO)STY/[(THF +BDO)STY+By-products STY] [00036] By-products=propanol+butanol+propionic acid+butyric acid[TABLE-US-00001] TABLE 1 Molar SelectivityEx.Catalyst percent on CTHF+BDO STYTHF+BDO A1percent Pt11.20.65B1percent Pt,1percent Re23.90.79C1percent Pt,3percent Re41.20.84D1percent Pt,4percent Re45.10.85E1percent Pt,5percent Re55.70.8711percent Pt,3percent Re,0.2percent Sn33.00.9021percent Pt,3percent Re,04percent Sn40.70.9031percent Pt,3percent Re,0.6percent Sn26.90.9141percent Pt,3percent Re,0.8percent Sn40.00.91F1percent Pt,0.8percent Sn28.80.92 [00037] It can be observed from Table 1 that although adding rhenium to a platinum-carbon catalyst increases the catalytic activity and selectivity, the selectivity is further increased by the addition of tin. With hydrogen, 1% Pt,4% Re on C in water, Time= 0.75h, T= 250 °C , p= 103432Torr , Conversion of starting material

103/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Patent; E. I. du Pont de Nemours and Company; US6670490; (2003); (B1) English View in Reaxys E : Examples 1-4 The catalysts were prepared in-situ and tested simultaneously by adding to a 300-cc autoclave 0.4 g 1percent platinum/carbon precursor obtained from Aldrich (cat. No.20,592-3) and given amounts of Re2O5 and SnCl4 (as applicable) to give the catalyst compositions given in Table 1. Also, 125 g of 20percent aqueous GBL was added to the autoclave as the test solution. The autoclave was heated to 250° C. and then pressurized to 2000 psig (14.x.106 Pa gage) with H2, while stirring. The conditions were maintained for 45 min, after which it was rapidly cooled down and the products were analyzed by GC (gas chromatography) to determine the net molar production rate (STY), and molar selectivity. The results are shown in Table 1. [00033] The STY and Selectivity are defined as follows: [00034] STY=mol/Kg of catalyst-hr [00035] Molar Selectivity=(THF+BDO)STY/[(THF +BDO)STY+By-products STY] [00036] By-products=propanol+butanol+propionic acid+butyric acid[TABLE-US-00001] TABLE 1 Molar SelectivityEx.Catalyst percent on CTHF+BDO STYTHF+BDO A1percent Pt11.20.65B1percent Pt,1percent Re23.90.79C1percent Pt,3percent Re41.20.84D1percent Pt,4percent Re45.10.85E1percent Pt,5percent Re55.70.8711percent Pt,3percent Re,0.2percent Sn33.00.9021percent Pt,3percent Re,04percent Sn40.70.9031percent Pt,3percent Re,0.6percent Sn26.90.9141percent Pt,3percent Re,0.8percent Sn40.00.91F1percent Pt,0.8percent Sn28.80.92 [00037] It can be observed from Table 1 that although adding rhenium to a platinum-carbon catalyst increases the catalytic activity and selectivity, the selectivity is further increased by the addition of tin. With hydrogen, 1% Pt,5% Re on C in water, Time= 0.75h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; E. I. du Pont de Nemours and Company; US6670490; (2003); (B1) English View in Reaxys B : Examples 1-4 The catalysts were prepared in-situ and tested simultaneously by adding to a 300-cc autoclave 0.4 g 1percent platinum/carbon precursor obtained from Aldrich (cat. No.20,592-3) and given amounts of Re2O5 and SnCl4 (as applicable) to give the catalyst compositions given in Table 1. Also, 125 g of 20percent aqueous GBL was added to the autoclave as the test solution. The autoclave was heated to 250° C. and then pressurized to 2000 psig (14.x.106 Pa gage) with H2, while stirring. The conditions were maintained for 45 min, after which it was rapidly cooled down and the products were analyzed by GC (gas chromatography) to determine the net molar production rate (STY), and molar selectivity. The results are shown in Table 1. [00033] The STY and Selectivity are defined as follows: [00034] STY=mol/Kg of catalyst-hr [00035] Molar Selectivity=(THF+BDO)STY/[(THF +BDO)STY+By-products STY] [00036] By-products=propanol+butanol+propionic acid+butyric acid[TABLE-US-00001] TABLE 1 Molar SelectivityEx.Catalyst percent on CTHF+BDO STYTHF+BDO A1percent Pt11.20.65B1percent Pt,1percent Re23.90.79C1percent Pt,3percent Re41.20.84D1percent Pt,4percent Re45.10.85E1percent Pt,5percent Re55.70.8711percent Pt,3percent Re,0.2percent Sn33.00.9021percent Pt,3percent Re,04percent Sn40.70.9031percent Pt,3percent Re,0.6percent Sn26.90.9141percent Pt,3percent Re,0.8percent Sn40.00.91F1percent Pt,0.8percent Sn28.80.92 [00037] It can be observed from Table 1 that although adding rhenium to a platinum-carbon catalyst increases the catalytic activity and selectivity, the selectivity is further increased by the addition of tin. With hydrogen, 1% Pt,1% Re on C in water, Time= 0.75h, T= 250 °C , p= 103432Torr , Conversion of starting material Patent; E. I. du Pont de Nemours and Company; US6670490; (2003); (B1) English View in Reaxys O HO OH O

O O

HO HO

OH HO

Rx-ID: 23746425 View in Reaxys 167/281 Yield 6.00 %Chromat., 2.19 %Chromat., 0.13 %Chromat.,

Conditions & References 6 :The method of Example 1 was repeated except that the maleic acid was replaced with fumaric acid (20.3g, 98percent). After 12 hours at temperature, the reactor was cooled to room temperature The liquid product was recovered from the autoclave (90. 1g) and analysed (wtpercent), water (82.74), propanol (0.13), propionic acid (0.04), tetrahydrofuran (6.00), y-butylractone (2.19), butanediol (8.35) ; giving an overall molar selectivity to tetrahydrofuran of 40.0percent, y-butyrolactone of 12.2percent, and to butanediol of 44.53percent. Titration against 0. 01M sodium hydroxide gave >98percent conversion of the fumaric acid

104/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

8.35 With water, hydrogen, η(+)-tris(pentane-2,5-dionato)ruthenium, [2-((diphenylphospino)methyl)-2-methyl-1,3-propanediyl]bis[di%Chromat., phenylphosphine], Time= 12h, T= 241 °C , p= 36961.4 - 52476.2Torr , Product distribution / selectivity 0.04 %Chromat. Patent; DAVY PROCESS TECHNOLOGY LIMITED; WO2003/93208; (2003); (A1) English View in Reaxys O

O O

Rx-ID: 23753679 View in Reaxys 168/281 Yield

Conditions & References

27.43 %Chromat., 0.333 %Chromat., 15.37 %Chromat., 12.29 %Chromat., 0.01 %Chromat.

2; 3 :In Example 2, Example 1 was repeated using 48.64g of water and 23.26g of dimethyl maleate as feed. The reaction was conducted at 191°C. After 53 hours the liquid and gaseous products were cooled and the liquid product analysed by gas chromatography and found to be off gas (molpercent) hydrogen (98.9), carbon monoxide (0.08), methane (0.01) and carbon dioxide (0.113) liquid (wtpercent) methanol (15.37) water (67.11) tetrahydrofuran (27.43), y-butyrolactone (0.333) and butanediol (12.29) giving a molar conversion of 99. 5molpercent and a selected activity to desired products of (molpercent) tetrahydrofuran (27.43) y-butylractone (1.88) butanediol of (66.24). In Example 3, Example 1 was again repeated using 48.4g of water and 20. 1 g of methyl propionate as feed. The reaction was conducted at 192°C. After 15 hours the reactor was cooled and the liquid product analysed by gas chromatography and found to be methanol (10.25) water (70.75) propanol (18.27) methyl propionate (<0. 1) propionic acid (<0. 1) propyl propionate (<0. 1), giving a molar selectivity and conversion of >99. 5percent With water, hydrogen, η(+)-tris(pentane-2,5-dionato)ruthenium, [2-((diphenylphospino)methyl)-2-methyl-1,3-propanediyl]bis[diphenylphosphine], Time= 53h, T= 191 °C , p= 36961.4 - 52476.2Torr , Product distribution / selectivity Patent; DAVY PROCESS TECHNOLOGY LIMITED; WO2003/93208; (2003); (A1) English View in Reaxys

O OH

Rx-ID: 9058431 View in Reaxys 169/281 Yield

Conditions & References

57 %, 10 %

With hydrogen, (acetylacetonato)dicarbonylrhodium (l), molybdenum hexacarbonyl in 1,4-dioxane, Time= 3h, T= 150 °C , p= 75007.5Torr Behr, Arno; Brehme, Volker A.; Advanced Synthesis and Catalysis; vol. 344; nb. 5; (2002); p. 525 - 532 View in Reaxys Rx-ID: 23058585 View in Reaxys 170/281

Yield

Conditions & References

5.3 %, 10.4 %, 79.1 %

With hydrogen, T= 190 °C , p= 46504.7Torr , Gas phase Patent; BASF Aktiengesellschaft; US6350924; (2002); (B1) English View in Reaxys

O O

Rx-ID: 23058586 View in Reaxys 171/281

105/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Yield

Conditions & References

1 %, 0.4 %, With hydrogen, copper catalyst, T 4489, Sud-Chemie AG, Munich, T= 150 - 280 °C , p= 187519Torr , Neat liquid(s) and 98 %, 0.5 % gas(es)/vapour(s) Patent; BASF Aktiengesellschaft; US6350924; (2002); (B1) English View in Reaxys

OH HO

Rx-ID: 24213864 View in Reaxys 172/281 Yield

Conditions & References 2 : Performance of 1percent Pt/CaCO3 Catalyst (10 gms)in the Hydrogenation of 1,4 Butynediol to 1,4 Butenediol and 1,4 Butanediol EXAMPLE 2 Performance of 1percent Pt/CaCO3 Catalyst (10 gms)in the Hydrogenation of 1,4 Butynediol to 1,4 Butenediol and 1,4 Butanediol This example illustrates the performance of 1percent Pt/CaCO3 catalyst (10 gms) in the hydrogenation of 1,4 butynediol to 1,4 butenediol and 1,4 butanediol The reaction was carried out in a fixed bed reactor in the presence of the catalyst according to the procedure described hereinabove. With calcium carbonate Patent; Council of Scientific and Industrial Research; US6469221; (2002); (B1) English View in Reaxys OH

HO HO

Rx-ID: 1546703 View in Reaxys 173/281 Yield

Conditions & References

99 %

With hydrogen, copper-palladium, silica gel in ethanol, T= 25 °C , p= 760Torr , Kinetics Spee; Boersma; Meijer; Slagt; Van Koten; Geus; Journal of Organic Chemistry; vol. 66; nb. 5; (2001); p. 1647 - 1656 View in Reaxys

10 %, 67 %

With LaNi5 hydride in tetrahydrofuran, methanol, Time= 6h, T= 0 °C Imamoto, Tsuneo; Mita, Takeshi; Yokoyama, Masataka; Journal of Organic Chemistry; vol. 52; nb. 26; (1987); p. 5695 5699 View in Reaxys

poly(tetramethylene succinate-co-tetramethylene adipate)

HO OH

OH O

Rx-ID: 8796099 View in Reaxys 174/281 Yield

Conditions & References With Chromobacterium viscosum extracellular lipase in water, Time= 20h, T= 35 °C , pH= 7.5, Enzymatic reaction, Title compound not separated from byproducts Kitakuni; Yoshikawa; Nakano; Sasuga; Nobiki; Naoi; Yokota; Ishioka; Yakabe; Environmental Toxicology and Chemistry; vol. 20; nb. 5; (2001); p. 941 - 946 View in Reaxys

106/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

O O

OH HO

Rx-ID: 8965706 View in Reaxys 175/281 Yield

Conditions & References

55 % Chromat., 15 % Chromat.

With 1,3-propanedithiol, cerium(III) chloride, sodium iodide in nitromethane, Time= 30h, Heating Bartoli; Cupone; Dalpozzo; De Nino; Maiuolo; Marcantoni; Procopio; Synlett; nb. 12; (2001); p. 1897 - 1900 View in Reaxys

O OH

OH HO

Rx-ID: 5189260 View in Reaxys 176/281 Yield

Conditions & References

89 %

With ammonium nitrate, Montmorillonite-K10, Time= 0.0416667h, microwave irradiation, deprotection Meshram; Sumithra; Reddy; Ganesh; Yadav; Synthetic Communications; vol. 29; nb. 16; (1999); p. 2807 - 2815 View in Reaxys

80 %

With lithium bromide in methanol, Time= 6h, Heating, Substitution Reddy; Bhanumathi; Rao; Synthetic Communications; vol. 30; nb. 23; (2000); p. 4323 - 4328 View in Reaxys

Si O

OH Si

Rx-ID: 5103636 View in Reaxys 177/281 Yield

Conditions & References

92 %

With H-Y zeolite in methanol, Time= 4h, Ambient temperature Itoh, Akichika; Kodama, Tomohiro; Masaki, Yukio; Synlett; nb. 3; (1999); p. 357 - 359 View in Reaxys

HO O

Rx-ID: 5264390 View in Reaxys 178/281 Yield

Conditions & References With phosphate buffer, carboxylesterase from Brevibacterium linens IFO 12171 in water, T= 30 Â°C , pH= 7.0, Enzymatic reaction, Hydrolysis, Enzyme kinetics Sakai, Yasuyoshi; Ishikawa, Junko; Fukasaka, Shunji; Yurimoto, Hiroya; Mitsui, Ryoji; Yanase, Hideshi; Kato, Nobuo; Bioscience, Biotechnology and Biochemistry; vol. 63; nb. 4; (1999); p. 688 - 697 View in Reaxys O

OH HO

Rx-ID: 24362739 View in Reaxys 179/281 Yield

Conditions & References 3 : EXAMPLE 3

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

107/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

EXAMPLE 3 The hydrogenation of 2.5 g of 1,3-butadiene diepoxide and 22.5 g of tetrahydrofuran with 0.5 g of catalyst B was carried out as described in Example 1. Catalyst B was activated beforehand in a stream of hydrogen for 1 hour at 250° C. and used in the form of 4 mm extrudates. At a conversion of 100percent, 77 mol percent of 1,4-butanediol and 8 mol percent of n-butanol were obtained. in tetrahydrofuran, hydrogen Patent; Basf Aktiengesellschaft; US5977417; (1999); (A) English View in Reaxys

Cl OH

Rx-ID: 815304 View in Reaxys 180/281 Yield

Conditions & References With phosphate buffer, potassium chloride, Ambient temperature, 3,3 Hz UV irradiation mercury electrode, different pH, Mechanism Krivenko; Tomilov; Smirnov; Kotkin; Kurmaz; Russian Journal of General Chemistry; vol. 68; nb. 2; (1998); p. 266 - 273 View in Reaxys With copper, methylamine Patent; Celanese Corp.; US2389347; (1941) View in Reaxys

O Si

Rx-ID: 5110813 View in Reaxys 181/281 Yield

Conditions & References With hydrogen, palladium dihydroxide in methanol, Time= 10h, Ambient temperature, Yield given Itoh, Akichika; Kodama, Tomohiro; Maeda, Shiro; Masaki, Yukio; Tetrahedron Letters; vol. 39; nb. 51; (1998); p. 9461 9464 View in Reaxys

O Si

Si O

Rx-ID: 5110814 View in Reaxys 182/281 Yield 13 %, 83 %

Conditions & References With Ti-HMS, hydrogen, 5% Pd on active carbon in methanol, Time= 3h, p= 760Torr , Ambient temperature Itoh, Akichika; Kodama, Tomohiro; Maeda, Shiro; Masaki, Yukio; Tetrahedron Letters; vol. 39; nb. 51; (1998); p. 9461 9464 View in Reaxys

O O

OH HO

Rx-ID: 5142308 View in Reaxys 183/281 Yield 51 %

Conditions & References With diisobutylaluminium hydride, 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) in diethyl ether, toluene, Time= 2h, T= 0 - 20 °C

108/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Taniguchi, Takahiko; Ogasawara, Kunio; Angewandte Chemie - International Edition; vol. 37; nb. 8; (1998); p. 1136 - 1137 View in Reaxys

Si O

Rx-ID: 4770207 View in Reaxys 184/281 Yield

Conditions & References

10 %, 70 %

With lithium aluminium tetrahydride in diethyl ether, Time= 2h, T= 0 °C Saravanan, Parthasarathy; Gupta, Suparna; DattaGupta, Arpita; Gupta, Sonia; Singh, Vinod K.; Synthetic Communications; vol. 27; nb. 15; (1997); p. 2695 - 2699 View in Reaxys

Si O

OH Si

Rx-ID: 4478915 View in Reaxys 185/281 Yield

Conditions & References

32 %, 56 %

With dichloro bis(acetonitrile) palladium(II) in water, acetone, Time= 6h, T= 75 °C Wilson, Noel S.; Keay, Brian A.; Journal of Organic Chemistry; vol. 61; nb. 9; (1996); p. 2918 - 2919 View in Reaxys

OH O

Rx-ID: 4488396 View in Reaxys 186/281 Yield

Conditions & References

5 % Chromat., 78 % Chromat.

O O

O OH

Rx-ID: 4488904 View in Reaxys 187/281 Yield 6 % Chromat., 65 % Chromat.

Conditions & References With dichloro bis(acetonitrile) palladium(II) in water, N,N-dimethyl-formamide, acetone, Time= 9h, T= 120 °C , Title compound not separated from byproducts Wilson, Noel S.; Keay, Brian A.; Journal of Organic Chemistry; vol. 61; nb. 9; (1996); p. 2918 - 2919 View in Reaxys

109/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Rx-ID: 4563035 View in Reaxys 188/281 Yield

Conditions & References With dirhodium tetraacetate, hydrogen, triethylphosphine in ethanol, Time= 4h, T= 120 °C , p= 30400Torr , hydrocarbonylation, Product distribution Simpson, Michael C.; Currie, Alan W. S.; Andersen, Jo-Ann M.; Cole-Hamilton, David J.; Green, Michael J.; Journal of the Chemical Society - Dalton Transactions; nb. 9; (1996); p. 1793 - 1800 View in Reaxys

Rx-ID: 4578321 View in Reaxys 189/281 Yield

Conditions & References With dirhodium tetraacetate, hydrogen, triethylphosphine in ethanol, Time= 4h, T= 120 °C , p= 30400Torr , hydrocarbonylation, effect of time, CO:H2 ratio, PEt3:Rh ratio, temperature, and pressure, Product distribution Simpson, Michael C.; Currie, Alan W. S.; Andersen, Jo-Ann M.; Cole-Hamilton, David J.; Green, Michael J.; Journal of the Chemical Society - Dalton Transactions; nb. 9; (1996); p. 1793 - 1800 View in Reaxys

Rx-ID: 4578322 View in Reaxys 190/281 Yield

Conditions & References With dirhodium tetraacetate, hydrogen, triethylphosphine in toluene, Time= 4h, T= 120 °C , p= 30400Torr , hydrocarbonylation, Product distribution Simpson, Michael C.; Currie, Alan W. S.; Andersen, Jo-Ann M.; Cole-Hamilton, David J.; Green, Michael J.; Journal of the Chemical Society - Dalton Transactions; nb. 9; (1996); p. 1793 - 1800 View in Reaxys OH

OH HO HO

Rx-ID: 4154970 View in Reaxys 191/281 Yield

Conditions & References With hydrogen, ruthenium palladium in propan-1-ol, T= 89.9 °C , Rate constant Karavanov, A. N.; Gryaznov, V. M.; Batyrev, I. G.; Olenina, E. G.; Russian Journal of Physical Chemistry; vol. 69; nb. 5; (1995); p. 739 - 743; Zhurnal Fizicheskoi Khimii; vol. 69; nb. 5; (1995); p. 816 - 821 View in Reaxys

110/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

HO O O

O HO

HO OH

OH HO

HO O

OH OH

HO HO

O OH

HO OH

O O

OH O

H H

HO O OH H

OH HO

OH H

OH OH

O HO

OH OH

HO O O

H O

H OH

Rx-ID: 4375081 View in Reaxys 192/281 Yield

Conditions & References in water, T= 25 °C , Equilibrium constant Spencer, J. N.; DeGarmo, Jarusha; Paul, I. M.; He, Qing; Ke, Xiaoming; et al.; Journal of Solution Chemistry; vol. 24; nb. 6; (1995); p. 601 - 610 View in Reaxys

O O

Rx-ID: 24513399 View in Reaxys 193/281 Yield

Conditions & References Examples 8 to 12 Examples 8 to 12 The general procedure of Examples 1 to 7 is repeated using dimethyl maleate, diethyl maleate, diethyl succinate, dimethyl fumarate, or gamma-butyrolactone in place of dimethyl 1,4-cyclohexane-dicarboxylate, resulting in each case in production of butane-1,4-diol.

111/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

A similar improvement in catalyst activity is observed following the reactivation procedure. Patent; Eastman Chemical Company; US5387753; (1995); (A) English View in Reaxys

Rx-ID: 3988560 View in Reaxys 194/281 Yield

Conditions & References With hydrogen, dirhodium tetraacetate, triethylphosphine in ethanol, Time= 4h, T= 120 °C , studies (D2, EtOD) quantification of isotopomers, Product distribution MacDougall, Joanna K.; Simpson, Michael C.; Cole-Hamilton, David J.; Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999); nb. 20; (1994); p. 3061 - 3066 View in Reaxys

Rx-ID: 3989151 View in Reaxys 195/281 Yield

OH HO H

Rx-ID: 25414530 View in Reaxys 196/281 Yield

Conditions & References 9 : Synthesis of (R)-3HB/(R)-3-Hydroxy-valeric Acid/1,4-Butanediol Oligomer EXAMPLE 9 Synthesis of (R)-3HB/(R)-3-Hydroxy-valeric Acid/1,4-Butanediol Oligomer In a reactor were charged 104.89 g (0.889 mol) of (R)-3HB, 29.3 g (0.222 mol) of (R)-3-hydroxyvaleric acid (hereinafter abbreviated as (R)-3HV), 5.0 g (0.0556 mol) of 1,4-butanediol, and 0.55 g (2.22 mmol) of dibutyltin oxide, and the mixture was allowed to react in the same manner as in Example 1 to obtain 101.9 g (percent yield: 98.3percent) of the titled oligomer. 1H-NMR (400 MHz, CDC ) η (ppm): 3 (R)-3HB Segment: 1.22-1.33 (48H, m), 2.35-2.70 (32H, m), 4.16 (m), 5.20-5.35 (m) (R)-3HV Segment: 0.85-1.00 (12H, m), 1.63 (8H, m), 2.35-2.70 (8H, m), 4.16 (m), 5.17 (m) 1,4-Butanediol Segment: 1.70 (4H, m), 4.10 (4H, m) IR (liquid film, cmmin 1): 3500, 2980, 1740, 1385, 1305, 1190 Mw: 1,320 Mn: 910 Tm: 77.0°C Patent; Takasago International Corporation; EP552896; (1993); (A1) English View in Reaxys

112/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

O O

Rx-ID: 1546714 View in Reaxys 197/281 Yield

Conditions & References With hydrogen, nickel in water, T= 70 °C , p= 11250.9Torr , influence of dispersity on the activity, selectivity, and stability of Raney-nickel catalyst, Product distribution Rusina, S. V.; Litvin, E. F.; Kheifets, V. I.; Sharf, V. Z.; J. Appl. Chem. USSR (Engl. Transl.); vol. 65; nb. 1; (1992); p. 151 155,125 - 128 View in Reaxys

O O O

OH HO O

OH HO

HO OH

Rx-ID: 3104474 View in Reaxys 198/281 Yield

Conditions & References With disodium hydrogenphosphate, sodium dihydrogenphosphate, water, T= 75 °C , ΔE(excit.), Thermodynamic data, Rate constant Maniar; Kalonia; Simonelli; Journal of Pharmaceutical Sciences; vol. 81; nb. 7; (1992); p. 705 - 709 View in Reaxys

O O O

OH OH HO

O HO

OH HO

O OH

Rx-ID: 3105740 View in Reaxys 199/281 Yield

113/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

O O O

O O

OH HO

Rx-ID: 3106291 View in Reaxys 200/281 Yield

OH HO

Rx-ID: 1546700 View in Reaxys 201/281 Yield

Conditions & References With hydrogen, Montmorillonite-Ph2PPd(II) in tetrahydrofuran, Time= 2h, T= 25 °C , p= 760Torr , other catalysts (5percent PdC, Lindlar catalyst), other solvents (ethyl acetate), Product distribution Chickos, James S.; Uang, Jack Y.-J.; Keiderling, Tim A.; Journal of Organic Chemistry; vol. 56; nb. 7; (1991); p. 2594 - 2596 View in Reaxys OH

OH HO

Rx-ID: 1839826 View in Reaxys 202/281 Yield

Conditions & References With hydrogen, Montmorillonite-Ph2PPd(II) in tetrahydrofuran, Time= 2h, T= 25 °C , p= 760Torr , other catalysts (Lindlar catalyst); no solvent; at 50 deg C, Product distribution Chickos, James S.; Uang, Jack Y.-J.; Keiderling, Tim A.; Journal of Organic Chemistry; vol. 56; nb. 7; (1991); p. 2594 - 2596 View in Reaxys HO

H OH

Rx-ID: 1878325 View in Reaxys 203/281

114/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Yield

Conditions & References With dihydrogen peroxide, Ambient temperature, Irradiation, selectivity; effect of H2O2 feeding rate, Product distribution, Quantum yield Shimizu, Yuichi; Sugimoto, Shun'ichi; Kawanishi, Shunichi; Suzuki, Nobutake; Chemistry Letters; nb. 1; (1991); p. 35 - 36 View in Reaxys HO

H OH

OH HO

Rx-ID: 1878354 View in Reaxys 204/281 Yield

Conditions & References With dihydrogen peroxide, Ambient temperature, Irradiation, var. H2O2 feeding rate, Quantum yield Shimizu, Yuichi; Sugimoto, Shun'ichi; Kawanishi, Shunichi; Suzuki, Nobutake; Bulletin of the Chemical Society of Japan; vol. 64; nb. 12; (1991); p. 3607 - 3612 View in Reaxys

H HO OH

acetaldehyde

Rx-ID: 7068119 View in Reaxys 205/281 Yield

Conditions & References With dihydrogen peroxide, Ambient temperature, Irradiation, var. H2O2 feeding rate and CH3OH content, Quantum yield Shimizu, Yuichi; Sugimoto, Shun'ichi; Kawanishi, Shunichi; Suzuki, Nobutake; Bulletin of the Chemical Society of Japan; vol. 64; nb. 12; (1991); p. 3607 - 3612 View in Reaxys

OH O

Rx-ID: 24822711 View in Reaxys 206/281 Yield

Conditions & References 1.c : (c) (c) Hydrogenation 120 g of a mixture of the acetals of the formulae IIa (85percent) and IIb (15percent) obtained as per section (a) were hydrogenated at 175Â° C. and 200 bar in the presence of 14 g of a hydrogen-activated copper catalyst (55.6percent of CuO, 43.6percent of Al2 O3) for 10 hours. The reacted mixture was distilled to yield 66.5 g of tetrahydrofuran, 46.5 g of 1,4-butanediol and 2.5 g of 4,4'-dihydroxydibutyl ether. Patent; BASF Aktiengesellschaft; US5008408; (1991); (A) English View in Reaxys

Rx-ID: 24903685 View in Reaxys 207/281 Yield

Conditions & References 2 : EXAMPLE 2 EXAMPLE 2

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

115/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

The operation was conducted in the same manner as in Example 1 except that 0.625 mmol of hypophosphorous acid was used instead of phosphoric acid used in Example 1, whereby the conversion of η-butyrolactone was 36.6percent and the amount of 1,4butanediol formed was 123.6 mmol. The yield of 1,4-butanediol was 31.5percent, and the selectivity was 86.1percent. Further, the amounts of tetrahydrofuran and n-butanol formed as byproducts were 1.1 mmol and 3.0 mmol, respectively. Patent; Mitsubishi Kasei Corporation; US5077442; (1991); (A) English View in Reaxys 4 : EXAMPLE 4 EXAMPLE 4 The operation was conducted in the same manner as in Example 1 except that 0.625 mmol of phosphorous acid instead of phosphoric acid used in Example 1, whereby the conversion of η-butyrolactone was 42.4percent, and the amount of 1,4-butanediol formed was 125.7 mmol. The yeild of 1,4-butanediol was 32.0percent, and the selectivity was 75.5percent. Further, the amounts of tetrahydrofuran and n-butanol formed as byproducts were 1.0 mmol and 0.8 mmol, respectively. Patent; Mitsubishi Kasei Corporation; US5077442; (1991); (A) English View in Reaxys 5 : EXAMPLE 5 EXAMPLE 5 The operation was conducted in the same manner as in Example 1 except that 0.625 mmol of phenyl phosphonic acid was used instead of phosphoric acid used in Example 1, whereby the conversion of η-butyrolactone was 53.3percent, and the amount of 1,4-butanediol formed was 159.9 mmol. The yeild of 1,4-butanediol was 40.7percent, and the selectivity was 76.4percent. Further, the amounts of tetrahydrofuran and n-butanol formed as byproducts were 2.0 mmol and 0.6 mmol, respectively. Patent; Mitsubishi Kasei Corporation; US5077442; (1991); (A) English View in Reaxys C.2 : COMPARATIVE EXAMPLE 2 COMPARATIVE EXAMPLE 2 The operation was conducted in the same manner as in Example 1 except that 0.625 mmol of ammonium hexafluorophosphate was used instead of phosphoric acid used in Example 1, whereby the conversion of η-butyrolactone was 30.7percent, and the amount of 1,4-butanediol formed was 96.9 mmol. The yeild of 1,4-butanediol was 24.7percent, and the selectivity was 80.5percent. Further, the amounts of tetrahydrofuran and n-butanol formed as byproducts were 3.0 mmol and 1.9 mmol, respectively. Patent; Mitsubishi Kasei Corporation; US5077442; (1991); (A) English View in Reaxys

Rx-ID: 2146914 View in Reaxys 208/281 Yield

Conditions & References With sodium hydroxide, dihydrogen peroxide, dibromoborane, 1.) CH2Cl2, 0,5 h, -78 to 25 deg C, 2.) THF, 0,5 h, reflux, Yield given. Multistep reaction Ryu, Ilhyong; Hirai, Akira; Suzuki, Haruhisa; Sonoda, Noboru; Murai, Shinji; Journal of Organic Chemistry; vol. 55; nb. 5; (1990); p. 1409 - 1410 View in Reaxys Cl O

O S

OH Cl

Rx-ID: 24880228 View in Reaxys 209/281 Yield

Conditions & References XII : Preparation of Tetramethylene 1,1-Ethanedisulfonate

116/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

EXAMPLE XII Preparation of Tetramethylene 1,1-Ethanedisulfonate 1,4-Butanediol, obtained from Aldrich Chemical Co. (3.6 g, 0.04 mole) was dissolved in 75 ml of glyme in a 1 liter round bottom flask. A solution of 1,1-ethanedisulfonyl chloride (9.1 g, 0.04 mole) dissolved in 25 ml of glyme wa added to the flask through a dropping funnel. The reaction mixture was kept below -20° C. with a dowanol-dry ice bath. Triethylamine (8.08 g, 0.08 mole) dissolved in 100 ml of glyme was added to the mixture through a 125 ml dropping funnel over a period of 1 hour. Care was taken to maintain anhydrous conditions by covering the dropping funnels with drying tubes containing CaCl2. The reaction mixture was brought to 25° C. in a cold water bath. With triethylamine Patent; Cronyn; Marshall W.; US4950768; (1990); (A) English View in Reaxys

OH HO

H 3O3Yb

Rx-ID: 26381792 View in Reaxys 210/281 Yield

Conditions & References

83 %, 100 %, 75 %

With hydrogen cation in tetrahydrofuran, shaken for 10 min at room temp.; centrifuged, decanted, soln. contains naphthalene, pptn. hydrolysed in THF: butanediol detd. by GLC in the organic layer and a pptn. (Yb(OH)3) Bochkarev, M. N.; Trifonov, A. A.; Fedorova, E. A.; Emelyanova, N. S.; Basalgina, T. A.; et al.; Journal of Organometallic Chemistry; vol. 372; (1989); p. 217 - 224 ; (from Gmelin) View in Reaxys

O HO HO

HO HO

Rx-ID: 2343346 View in Reaxys 211/281 Yield

Conditions & References With lithium aluminium tetrahydride, oxygen, cobalt(II) acetate, sodium bromide, multistep reaction Druliner, J. D.; Wasserman, E.; Journal of the American Chemical Society; vol. 110; nb. 16; (1988); p. 5270 - 5275 View in Reaxys

O Si

OH HO

HO O

Rx-ID: 3914197 View in Reaxys 212/281 Yield 75 % Chromat.

Conditions & References in 1,4-dioxane, T= 20 °C Nedogrel, E. P.; Musavirov, R. S.; Zhurkina, I. P.; Kantor, E. A.; Rakhmankulov, D. L.; J. Appl. Chem. USSR (Engl. Transl.); vol. 61; nb. 4; (1988); p. 937 - 940,856 - 859

117/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

View in Reaxys O– O

OH HO

O O–

Rx-ID: 1986980 View in Reaxys 213/281 Yield

Conditions & References With carbon monoxide, Paraquat in water, T= 40 °C , pH: 5.5; Clostridium thermoaceticum Simon, Helmut; White, Hiltrud; Lebertz, Herbert; Thanos, Iordanes; Angewandte Chemie; vol. 99; nb. 8; (1987); p. 785 787 View in Reaxys

O O

Rx-ID: 2113841 View in Reaxys 214/281 Yield

Conditions & References With Cumene hydroperoxide, T= 120 °C , further hydroperoxide; transformations initiated by hydroperoxides Nurberdiev, R.; Khekimov, Yu. K.; Rol'nik, L. Z.; Zlotskii, S. S.; Rakhmankulov, D. L.; et al.; Doklady Chemistry; vol. 296; nb. 9; (1987); p. 418 - 419; Dokl. Akad. Nauk SSSR Ser. Khim.; vol. 296; nb. 3; (1987); p. 609 - 611 View in Reaxys

Br Br O O O

Rx-ID: 2401884 View in Reaxys 215/281 Yield

Conditions & References

30 %

With tetraethylammonium perchlorate in N,N-dimethyl-formamide, electrolysis Ojima, Fumihiro; Matsue, Tomokazu; Osa, Tetsuo; Chemistry Letters; (1987); p. 2235 - 2238 View in Reaxys

Br Br

Rx-ID: 3797326 View in Reaxys 216/281 Yield 67 %

Conditions & References With tetraethylammonium perchlorate in N,N-dimethyl-formamide, electrolysis Ojima, Fumihiro; Matsue, Tomokazu; Osa, Tetsuo; Chemistry Letters; (1987); p. 2235 - 2238 View in Reaxys

118/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Br Br

O O

Rx-ID: 3801386 View in Reaxys 217/281 Yield

Conditions & References

74 %

With tetraethylammonium perchlorate in N,N-dimethyl-formamide, electrolysis; var. esters and dihaloalkanes, Mechanism Ojima, Fumihiro; Matsue, Tomokazu; Osa, Tetsuo; Chemistry Letters; (1987); p. 2235 - 2238 View in Reaxys

74 %

With tetraethylammonium perchlorate in N,N-dimethyl-formamide, electrolysis Ojima, Fumihiro; Matsue, Tomokazu; Osa, Tetsuo; Chemistry Letters; (1987); p. 2235 - 2238 View in Reaxys

O OH

Rx-ID: 1860792 View in Reaxys 218/281 Yield

Conditions & References With potassium hydroxide, T= 180 °C , Product distribution Trofimov, B. A.; Oparina, L. A.; Parshina, L. N.; Lavrov, V. I.; Grigorenko, V. I.; Zhumabekov, M. K.; Journal of Organic Chemistry USSR (English Translation); vol. 22; nb. 8; (1986); p. 1424 - 1428; Zhurnal Organicheskoi Khimii; vol. 22; nb. 8; (1986); p. 1583 - 1587 View in Reaxys O H

Rx-ID: 1501990 View in Reaxys 219/281 Yield

Conditions & References With sodium hydroxide, dimethylsulfide borane complex, dihydrogen peroxide in tetrahydrofuran, Time= 2h, T= 0 °C , other heterocyclic olefins, other hydroborating agents; var. reaction conditions, Product distribution, Mechanism Brown, Herbert C.; Prasad, J. V. N. Vara; Zee, Sheng-Hsu; Journal of Organic Chemistry; vol. 50; nb. 10; (1985); p. 1582 1589 View in Reaxys

OH HO

Rx-ID: 1456986 View in Reaxys 220/281 Yield 0.2 mmol, 20.5 mmol, 1.2 mmol

Conditions & References With zinc sulfide in water, Time= 24h, Irradiation, Product distribution, Quantum yield Yanagida, Shozo; Azuma, Takayuki; Kawakami, Horishi; Kizumoto, Hirotoshi; Sakurai, Hiroshi; Journal of the Chemical Society, Chemical Communications; nb. 1; (1984); p. 21 - 22 View in Reaxys

119/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Rx-ID: 1934556 View in Reaxys 221/281 Yield

Conditions & References With lithium aluminium tetrahydride, oxygen, 1) 140 deg C, 2) THF, Product distribution Pritzkow, Wilhelm; Voerckel, Volkmar; Journal fuer Praktische Chemie (Leipzig); vol. 326; nb. 4; (1984); p. 572 - 578 View in Reaxys

HO OH

OH HO

OH OH

Rx-ID: 1938782 View in Reaxys 222/281 Yield

Yield

HO OH

OH HO

OH OH

Rx-ID: 3790152 View in Reaxys 225/281 Yield

HO HO

120/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

HO OH

Rx-ID: 3923550 View in Reaxys 226/281 Yield

Rx-ID: 3323188 View in Reaxys 227/281 Yield

Conditions & References

8 %, 19 %, 72 %, 1 %

With 2-ethoxy-ethanol, N,N,N'N'-tetramethyl-1,3-propanediamine, hexarhodium hexadecacarbonyl in water, Time= 5h, T= 60 °C , p= 7600Torr , further amine additives, variation of reaction conditions, Product distribution Kaneda, Kiyotomi; Imanaka, Toshinobu; Teranishi, Shiichiro; Chemistry Letters; (1983); p. 1465 - 1466 View in Reaxys

8 %, 19 %, 72 %, 1 %

With 2-ethoxy-ethanol, N,N,N'N'-tetramethyl-1,3-propanediamine, hexarhodium hexadecacarbonyl in water, Time= 5h, T= 60 °C , p= 7600Torr Kaneda, Kiyotomi; Imanaka, Toshinobu; Teranishi, Shiichiro; Chemistry Letters; (1983); p. 1465 - 1466 View in Reaxys

O HO

OH HO

Rx-ID: 25113141 View in Reaxys 228/281 Yield

Conditions & References 2 : EXAMPLE 2 The butane-1,4-diol obtained contains tetrahydrofuran in an amount of 5percent by weight, based on butanediol formed from maleic anhydride. The purity of the butane-1,4-diol purified by distillation is 99.5percent (gas chromatographic analysis). For re-use for absorption, only some, if any, of the crude butanediol produced in the hydrogenation requires to be worked up by distillation. Patent; BASF Aktiengesellschaft; US4361710; (1982); (A) English View in Reaxys

Cl Cl

Rx-ID: 25121116 View in Reaxys 229/281 Yield

Conditions & References 5 : EXAMPLE 5 EXAMPLE 5 A mixture of 11.9 g 1,4-dichlorobutane (82percent purity), 30 g of water and 1 ml of concentrated sulfuric acid as catalyst was heated in a shaking Hastelloy reactor (2.5 cm inside diameter*13.8 cm deep) at 170° C. for 2 hours. Upon cooling, the reaction mixture was found to contain 1,4-butanediol (by chromatography). With sulfuric acid in water Patent; National Distillers and Chemical Corp.; US4338290; (1982); (A) English

121/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

View in Reaxys

Rx-ID: 1513679 View in Reaxys 230/281 Yield

Conditions & References With 2-propyl-[1,3]dioxane, lithium aluminium tetrahydride, boron trichloride, 1.) CH2Cl2, 0.2 h, 2.) Et2O, 30 min, Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Bonner, Trevor G.; Lewis, David; Rutter, Keith; Journal of the Chemical Society, Perkin Transactions 1: Organic and BioOrganic Chemistry (1972-1999); (1981); p. 1807 - 1810 View in Reaxys

HO HO

Rx-ID: 1522653 View in Reaxys 231/281 Yield

Conditions & References

82.3 %, 1.0 %, 4.8 %, 1.2 %, 1.0 %

With hydrogen, 5% platinum on alumina, T= 250 °C , p= 152000Torr , var. catalysts, Product distribution Timofeev, A. F.; Shevchenko, V. S.; Tereshchenko, F. G.; J. Appl. Chem. USSR (Engl. Transl.); vol. 54; nb. 2; (1981); p. 335 338,225 - 228 View in Reaxys

O O O

O O

Rx-ID: 1567494 View in Reaxys 232/281 Yield

Conditions & References

78 % Chromat., 6 % Chromat., 3 % Chromat., 13 % Chromat.

With hydrogen, rhenium, Time= 18h, T= 199.9 °C , p= 172514Torr , further catalyst: Tc "black", Title compound not separated from byproducts

21 % Chromat., 66 % Chromat., 5 % Chromat., 8 % Chromat.

With hydrogen, Tc "black", Time= 24h, T= 199.9 °C , p= 172514Torr , further catalyst: Re "black", Title compound not separated from byproducts

21 % Chromat., 66 % Chromat., 5 % Chromat., 8 % Chromat.

With hydrogen, Tc "black", Time= 24h, T= 199.9 °C , p= 172514Torr , Product distribution

Bayerl, Bernd; Wahren, Manfred; Zeitschrift fuer Chemie (Stuttgart, Germany); vol. 21; nb. 4; (1981); p. 149 View in Reaxys

122/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

78 % Chromat., 6 % Chromat., 3 % Chromat., 13 % Chromat.

With hydrogen, rhenium, Time= 18h, T= 199.9 Â°C , p= 172514Torr , Product distribution Bayerl, Bernd; Wahren, Manfred; Zeitschrift fuer Chemie (Stuttgart, Germany); vol. 21; nb. 4; (1981); p. 149 View in Reaxys

Rx-ID: 1831367 View in Reaxys 233/281 Yield

Conditions & References With sodium hydroxide, sodium tetrahydroborate, mercury(II) diacetate in water, 1) 30 min, 2) ca. 0.5 h, Product distribution, Mechanism Brown, Herbert C.; Lynch, Gary J.; Journal of Organic Chemistry; vol. 46; nb. 3; (1981); p. 531 - 538 View in Reaxys H OH

Rx-ID: 1831373 View in Reaxys 234/281 Yield

Conditions & References With sodium hydroxide, sodium tetrahydroborate, mercury(II) diacetate in tetrahydrofuran, water, 1) 30 min, 2) ca. 0.5 h, Product distribution, Mechanism Brown, Herbert C.; Lynch, Gary J.; Journal of Organic Chemistry; vol. 46; nb. 3; (1981); p. 531 - 538 View in Reaxys

Rx-ID: 1936878 View in Reaxys 235/281 Yield

Conditions & References

28 % Chromat.

With sodium hydroxide, sodium tetrahydroborate, mercury(II) diacetate in tetrahydrofuran, water, 1) 30 min room temp., 2) 0.5-1 h reflux; investigation of other reduction conditions, Product distribution, Mechanism Brown, Herbert C.; Lynch, Gary J.; Journal of Organic Chemistry; vol. 46; nb. 3; (1981); p. 531 - 538 View in Reaxys

Rx-ID: 1941457 View in Reaxys 236/281 Yield

Conditions & References

18 % Chromat., 80 % Chromat.

O O

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

123/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

HO OH

resinous polyester

Rx-ID: 5744641 View in Reaxys 237/281 Yield

Conditions & References

56.8 %, 0.4 %, 3.7 %, 0.9 %, 1.4 %

With hydrogen, 5% platinum on alumina in various solvent(s), T= 250 °C , p= 152000Torr , var. catalysts, Product distribution Timofeev, A. F.; Shevchenko, V. S.; Tereshchenko, F. G.; J. Appl. Chem. USSR (Engl. Transl.); vol. 54; nb. 2; (1981); p. 335 338,225 - 228 View in Reaxys

OH HO

HO OH

Rx-ID: 1895929 View in Reaxys 238/281 Yield

Conditions & References With dinitrogen monoxide in water, Time= 1h, Ambient temperature, Irradiation, pulse radiolysis, Rate constant, Mechanism Soeylemez, Turan; Sonntag, Clemens von; Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999); (1980); p. 391 - 394 View in Reaxys

OH HO HO

Rx-ID: 25349135 View in Reaxys 239/281 Yield

Conditions & References 4 : EXAMPLE 4 EXAMPLE 4 According to the general procedure of Example 1, 279.5 g. of a 2-butoxy-1,4-butanediol-containing mixture was placed in a stirred autoclave along with 15.0 g. of copper chromite catalyst. The autoclave was then heated to 250° C. under 3,000 psig of hydrogen pressure and maintained under these conditions for 1 hour. Thereafter, the autoclave contents were recovered and analyzed for conversion of the 2-butoxy-1,4-butanediol to 1,4-butanediol and n-butanol. With hydrogen, copper chromite Patent; Denka Chemical Corporation; US4172961; (1979); (A) English View in Reaxys O

OH OH

Rx-ID: 25343933 View in Reaxys 240/281 Yield

Conditions & References 5 : EXAMPLE 5 The resulting yields of 1,4-butanediol, η-butyrolactone and tetrahydrofuran, based on 2-hydroperoxy tetrahydrofuran, were 83.7percent, 7.2percent and 4.1percent, respectively. The operation was repeated 60 times without a decrease in the yield of 1,4-butanediol. Patent; Toyo Soda Manufacturing Co., Ltd.; US4123616; (1978); (A) English View in Reaxys

124/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

H OH HO

Rx-ID: 25212314 View in Reaxys 241/281 Yield

Conditions & References II : Hydroformylation Of 2-Vinyl-4-methyl-1,3-dioxane To 3-(4'-methyl-1',3'-dioxane)propionaldehyde A portion of the aldehyde fraction (20 grams), water (30 grams) and Raney nickel (0.5 gram) were charged into the autoclave and heated to 198° C under 400-435 psig of hydrogen. Total reaction time was 120 minutes. The product mixture was cooled and analyzed by gas chromatography. The aldehyde starting material had converted completely into a mixture of 1,3-butanediol and 1,4-butanediol. Patent; Celanese Corporation; US4003918; (1977); (A) English View in Reaxys

(v2)

(v4)

B (v4)

H (v2)

Rx-ID: 26836877 View in Reaxys 242/281 Yield

Conditions & References With dihydrogen peroxide, slow react. with alkaline H2O2 at elevated temp.; Young; Shore; Journal of the American Chemical Society; vol. 91; (1969); p. 3497 ; (from Gmelin) View in Reaxys With H2O2, slow react. with alkaline H2O2 at elevated temp.; vol. B: B-Verb.14; 5.6, page 212 - 224 ; (from Gmelin) View in Reaxys Cl

B B

Rx-ID: 26642904 View in Reaxys 243/281 Yield

Conditions & References With sodium hydroxide, dihydrogen peroxide Zakharkin, L. I.; Kovredov, A. I.; Journal of General Chemistry USSR (English Translation); vol. 32; (1962); p. 1408 - 1410 ; (from Gmelin) View in Reaxys Mikhailov, B. M.; Kozminskaya, T. K.; Bezmenov, A. Ya.; Bull. Acad. Sci. USSR Div. Chem. Sci.; vol. 1965; (1965); p. 332 334 View in Reaxys vol. B: B-Verb.9; 5.2.8.2, page 220 - 226 ; (from Gmelin) View in Reaxys

(v2)

B (v4)

B H (v2)

(v4)

Rx-ID: 26842369 View in Reaxys 244/281 Yield

Conditions & References Weiss,H.G. et al.; Journal of the American Chemical Society; vol. 84; (1962); p. 3840 - 3843 ; (from Gmelin) View in Reaxys vol. B: B-Verb.14; 5, page 201 - 212 ; (from Gmelin) View in Reaxys

125/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

O HO

thenium

Rx-ID: 6868534 View in Reaxys 245/281 Yield

Conditions & References T= 205 °C , p= 132391Torr , Hydrogenation Broadbent et al.; Journal of Organic Chemistry; vol. 24; (1959); p. 1847,1852 View in Reaxys O O

rhenium

Rx-ID: 7066652 View in Reaxys 246/281 Yield

Conditions & References T= 210 °C , p= 183877 - 198587Torr , unverduennter Bernsteinsaeure.Hydrogenation Broadbent et al.; Journal of Organic Chemistry; vol. 24; (1959); p. 1847,1852 View in Reaxys O

rhenium

OH O O

Rx-ID: 7066653 View in Reaxys 247/281 Yield

Conditions & References T= 210 °C , p= 183877 - 198587Torr , geloester Bernsteinsaeure.Hydrogenation Broadbent et al.; Journal of Organic Chemistry; vol. 24; (1959); p. 1847,1852 View in Reaxys

OH O

Rx-ID: 243935 View in Reaxys 248/281 Yield

Conditions & References With hydrogenchloride, methanol, ethanol Moschkin; Vopr. Ispol'z. Pentozansoderzh. Syr'ya, Tr. Vses. Soveshch.; (1955); p. 225,247; Chem. Zentralbl.; vol. 130; (1959); p. 15048 View in Reaxys

H O

OH HO

Rx-ID: 6671855 View in Reaxys 249/281 Yield

Conditions & References T= 40 - 60 °C , p= 147102Torr , Hydrogenation Reppe et al.; Justus Liebigs Annalen der Chemie; vol. 596; (1955); p. 65 View in Reaxys

126/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

O HO

ruthenium

Rx-ID: 6868531 View in Reaxys 250/281 Yield

Conditions & References T= 152 - 190 °C , p= 529566 - 698732Torr , Hydrogenation Carnahan et al.; Journal of the American Chemical Society; vol. 77; (1955); p. 3766 View in Reaxys O

OH HO

Rx-ID: 18429 View in Reaxys 251/281 Yield

Conditions & References With iron pentacarbonyl, carbon monoxide, water, T= 85 - 120 °C , Reagens 4: Trimethylamin Reppe; Vetter; Justus Liebigs Annalen der Chemie; vol. 582; (1953); p. 135,148 View in Reaxys O O

Rx-ID: 36866 View in Reaxys 252/281 Yield

Conditions & References With nickel molybdenum oxide chromium oxide, T= 225 - 275 °C , p= 617827Torr , Hydrogenation.Nebenprodukt 2: 4-Hydroxy-buttersaeure-lacton Patent; Du Pont de Nemours and Co.; US2772293; (1953) View in Reaxys Patent; Du Pont de Nemours and Co.; US2772291; (1953) View in Reaxys O

OH HO

Rx-ID: 36877 View in Reaxys 253/281 Yield

Conditions & References With nickel-nickel molybdate-nickel chromate-catalyst, T= 250 °C , p= 617827Torr , Hydrogenation Patent; Du Pont de Nemours and Co.; US2772291; (1953) View in Reaxys

nickel-copper-chromium

Rx-ID: 6671856 View in Reaxys 254/281 Yield

Conditions & References T= 70 - 140 °C , p= 300 - 147102Torr , Hydrogenation Patent; I.G.Farbenind.; DE734881; (1939); View in Reaxys Schneiders; ; vol. 4; (1953); p. 755

127/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

View in Reaxys Patent; General Aniline and Film Corp.; US2319707; (1939) View in Reaxys Reppe,W.; View in Reaxys Reppe,W.; View in Reaxys Reppe; Experientia; vol. 5; (1949); p. 93,108; Justus Liebigs Annalen der Chemie; vol. 582; (1953); p. 1,16, 35 View in Reaxys OH

Raney nickel

OH O

HO HO

Rx-ID: 6672507 View in Reaxys 255/281 Yield

Conditions & References Produkt5: But-2η-en-1-ol.Hydrogenation Romanet; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 236; (1953); p. 1044 View in Reaxys

OH HO

Rx-ID: 682076 View in Reaxys 256/281 Yield

Conditions & References With cobalt linolenate, oxygen, dibenzoyl peroxide, T= 80 °C , p= 36775.4Torr , Hydrierung des Reaktionsprodukts an Palladium/Kohle in Dioxan bei 20-50grad/35-50at und anschliessend an Kupferoxid-Chromoxid bei 150-180grad/50at Patent; Phillips Petr. Co.; US2879306; (1952) View in Reaxys

Rx-ID: 682142 View in Reaxys 257/281 Yield

Conditions & References With cobalt linoleate, air, dibenzoyl peroxide, T= 71 °C , p= 41188.4Torr , bei Hydrieren des erhaltenen Peroxids an Palladium/ Kohle in Dioxan Patent; Phillips Petr. Co.; US2879306; (1952) View in Reaxys O O

copper-chromium oxide

O O

O HO

HO O

Rx-ID: 6188415 View in Reaxys 258/281 Yield

Conditions & References T= 250 °C , p= 220652Torr , Produkt 5: Tetrahydrofuran(?).Hydrogenation Adkins; Folkers; Journal of the American Chemical Society; vol. 53; (1931); p. 1096

128/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

View in Reaxys Patent; Roehm and Haas; US2091800; (1931) View in Reaxys Adkins; Billica; Journal of the American Chemical Society; vol. 70; (1948); p. 3121 View in Reaxys Wojcik; Adkins; Journal of the American Chemical Society; vol. 55; (1933); p. 4943 View in Reaxys

amalgam. aluminium

Rx-ID: 6868526 View in Reaxys 259/281 Yield

Conditions & References Paul; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 215; (1942); p. 304 View in Reaxys Paul; Tchelitcheff; Bulletin de la Societe Chimique de France; (1948); p. 197,202 View in Reaxys

copper chromite O O

(+-)-butanetriol-(1.2.4)

Rx-ID: 6868533 View in Reaxys 260/281 Yield

Conditions & References T= 150 °C , p= 257428Torr , Hydrogenation Adkins; Billica; Journal of the American Chemical Society; vol. 70; (1948); p. 3121 View in Reaxys

Raney nickel O O

(+-)-butanetriol-(1.2.4)

3.4-dihydroxy-butyric acid ethyl ester Rx-ID: 7050975 View in Reaxys 261/281

Yield

Conditions & References T= 100 °C , p= 257428Torr , Hydrogenation Adkins; Billica; Journal of the American Chemical Society; vol. 70; (1948); p. 3121 View in Reaxys

Raney nickel

Rx-ID: 6671858 View in Reaxys 262/281 Yield

Conditions & References T= 25 °C , p= 1105470Torr , Hydrogenation Johnson; Journal of the Chemical Society; (1946); p. 1013 View in Reaxys

129/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

copper-chromite

Rx-ID: 6868527 View in Reaxys 263/281 Yield

Conditions & References T= 230 °C , p= 514855Torr , Hydrogenation Patent; Du Pont de Nemours and Co.; US2437600; (1945) View in Reaxys O

alkaline KNO3

potassium succinate

OH O

nitrate/s of ethylene glycol

Rx-ID: 7082332 View in Reaxys 264/281 Yield

Conditions & References an einer Platinanode.Electrolysis Fichter; Bloch; Helvetica Chimica Acta; vol. 22; (1939); p. 1534 View in Reaxys O O

iron

Rx-ID: 6868530 View in Reaxys 265/281 Yield

Conditions & References Fichter; Siegrist; Helvetica Chimica Acta; vol. 18; (1935); p. 20,23 View in Reaxys

OH HO

Rx-ID: 549770 View in Reaxys 266/281 Yield

Conditions & References With 1,4-dioxane, copper oxide-chromium oxide, T= 250 °C , p= 147102 - 220652Torr , Hydrogenation Wojcik; Adkins; Journal of the American Chemical Society; vol. 56; (1934); p. 2419,2422 View in Reaxys O O

OH HO

O O

Rx-ID: 251400 View in Reaxys 267/281

130/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Yield

Conditions & References With copper oxide-chromium oxide, T= 255 °C , p= 154457Torr , Hydrogenation Patent; Du Pont de Nemours and Co.; US2040944; (1933) View in Reaxys O

O O

Rx-ID: 251401 View in Reaxys 268/281 Yield

Conditions & References With copper chromite, T= 255 °C , p= 220652Torr , Hydrogenation Patent; du Pont de Nemours and Co.; US2040944; (1933) View in Reaxys

OH O

copper chromite

Rx-ID: 6949645 View in Reaxys 269/281 Yield

Conditions & References T= 250 °C , Hoher Druck.Hydrogenation Wojcik; Adkins; Journal of the American Chemical Society; vol. 55; (1933); p. 4943 View in Reaxys O O

OH HO

O O

Rx-ID: 828195 View in Reaxys 270/281 Yield

Conditions & References With zinc chromite, copper, cadmium, T= 367 °C , p= 128714Torr , Hydrogenation Patent; du Pont de Nemours and Co.; US2079414; (1932) View in Reaxys

HO O

OH HO

Rx-ID: 289846 View in Reaxys 271/281 Yield

Conditions & References With hydrogen bromide Kirner; Richter; Journal of the American Chemical Society; vol. 51; (1929); p. 2505 View in Reaxys O

Br Br

Rx-ID: 638740 View in Reaxys 272/281

131/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Yield

Conditions & References With potassium acetate, und Verseifen des entstandenen Tetramethylenglykol-diacetats mit Calciumhydroxyd Bennett; Heathcoat; Journal of the Chemical Society; (1929); p. 271 View in Reaxys

HO O Br

Rx-ID: 7155573 View in Reaxys 273/281 Yield

Conditions & References Kirner; Richter; Journal of the American Chemical Society; vol. 51; (1929); p. 2505 View in Reaxys

Rx-ID: 38508 View in Reaxys 274/281 Yield

Conditions & References With ethanol, potassium acetate, und Verseifen des entstandenen Tetramethylenglykol-diacetats mit Kaliumhydroxyd Hill; Hibbert; Journal of the American Chemical Society; vol. 45; (1923); p. 3130 View in Reaxys

hydrogen

platinum

Rx-ID: 6671857 View in Reaxys 275/281 Yield

Conditions & References Lespieau; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 150; (1910); p. 1761; Annales de Chimie (Cachan, France); vol. <8>27; (1912); p. 176 View in Reaxys

Rx-ID: 219331 View in Reaxys 276/281 Yield

Conditions & References With diethyl ether, aluminium amalgam Harries; Chemische Berichte; vol. 35; (1902); p. 1179,1181; Justus Liebigs Annalen der Chemie; vol. 330; (1904); p. 218 Anm. View in Reaxys

O O

sodium amalgam

Rx-ID: 6868532 View in Reaxys 277/281 Yield

Conditions & References Harries; Chemische Berichte; vol. 35; (1902); p. 1179,1181; Justus Liebigs Annalen der Chemie; vol. 330; (1904); p. 218 Anm. View in Reaxys

diacetate of/the/ butanediol-(1.4)

Rx-ID: 6868528 View in Reaxys 278/281 Yield

Conditions & References With methyllithium, calcium carbonate

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

132/133

2018-07-13 16:28:42

1,4-Butanediol (1,4-BDO); Butane-1,4-diol; 1,4-Butylene glycol

Hamonet; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 132; (1901); p. 632; Bulletin de la Societe Chimique de France; vol. <3>33; (1905); p. 523 View in Reaxys

hydrochloride of tetramethylenediamine

Rx-ID: 6868529 View in Reaxys 279/281 Yield

Conditions & References With silver(I) nitrite Demjanow; Zhurnal Russkago Fiziko-Khimicheskago Obshchestva; vol. 24; (1892); p. 354 View in Reaxys O H N

N H

OH O

Rx-ID: 251142 View in Reaxys 280/281 Yield

Conditions & References With sulfuric acid Dekkers; Recueil des Travaux Chimiques des Pays-Bas; vol. 9; (1890); p. 101 View in Reaxys O H N

N H

OH HO

S OO

N2O

tetramethylene oxide (?) Rx-ID: 7087904 View in Reaxys 281/281

Yield

Conditions & References Dekkers; Recueil des Travaux Chimiques des Pays-Bas; vol. 9; (1890); p. 101 View in Reaxys

Copyright ÂŠ 2018 Elsevier Life Sciences IP Limited except certain content provided by third parties. Reaxys is a trademark of Elsevier Life Sciences IP Limited.

133/133

2018-07-13 16:28:42