2-Phenylpropan-2-ol to Prop-1-en-2-ylbenzene (alpha-Methylstyrene) by Asch

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41 reactions in Reaxys

2016-05-12 15h:50m:56s (EST)

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Search as: As drawn, No salts, No mixtures

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Rx-ID: 278983 View in Reaxys 1/41 Yield 97 %

Conditions & References 1 :A cumene solution (containing 0 ppm by weight of propylene oxide) containing 25percent by weight of cumyl alcohol and hydrogen were passed through a fixed bed flow reactor in which activated alumina was packed, at a rate of 1.6g/minute and 105 Ncc/minute, respectively. In addition, LHSV(Liquid Hourly Space Velocity) was 9 h-1, the pressure was 1.0 MPaG, and the temperature was 200°C. The dehydration conversion of cumyl alcohol in the obtained reaction mixture was 97percent. With aluminum oxide in isopropyl-benzene, T= 200 °C , p= 7500.75Torr , Product distribution / selectivity Patent; Sumitomo Chemical Company, Limited; EP1674439; (2006); (A1) English View in Reaxys

83 %

With copper(II) sulfate in neat (no solvent), Time= 1h, T= 95 °C , p= 25Torr Hoffman, Robert V.; Bishop, Richard D.; Fitch, Patricia M.; Hardenstein, Richard; Journal of Organic Chemistry; vol. 45; nb. 5; (1980); p. 917 - 919 View in Reaxys

80 %

With chloro-trimethyl-silane, acetic anhydride in acetonitrile, Time= 3h Kumareswaran; Gupta, Anuradha; Vankar, Yashwant D.; Synthetic Communications; vol. 27; nb. 2; (1997); p. 277 - 282 View in Reaxys

78 %

With tetrachlorosilane in chloroform, Time= 5h, Heating Firouzabadi, Habib; Iranpoor, Naser; Hazarkhani, Hassan; Karimi, Babak; Synthetic Communications; vol. 33; nb. 21; (2003); p. 3653 - 3660 View in Reaxys

75 %

With sulfuric acid, Heating Amelichev, V. A.; Nosovskii, M. V.; Saidov, G. V.; J. Gen. Chem. USSR (Engl. Transl.); vol. 51; nb. 8; (1981); p. 1879 - 1885,1613 - 1619 View in Reaxys

68 - 97 %

2; 3; 1 :It was carried out in the same manner as in Example 1 except that a cumene solution (containing 110 ppm by weight of propylene oxide) containing 25percent by weight of cumyl alcohol was used. The dehydration conversion of cumyl alcohol in the obtained reaction mixture was 97percent.; It was carried out in the same manner as in Example 1 except that a cumene solution (containing 1200 ppm by weight of propylene oxide) containing 25percent by weight of cumyl alcohol was used. The dehydration conversion of cumyl alcohol in the obtained reaction mixture was 96percent.; It was carried out in the same manner as in Example 1 except that a cumene solution (containing 12500 ppm by weight of propylene oxide) containing 25percent by weight of cumyl alcohol was used. The dehydration conversion of cumyl alcohol in the obtained reaction mixture was 68percent. With methyloxirane, aluminum oxide in isopropyl-benzene, T= 200 °C , p= 7500.75Torr , Product distribution / selectivity Patent; Sumitomo Chemical Company, Limited; EP1674439; (2006); (A1) English View in Reaxys

46 %

With methyltrioxorhenium (VII) in benzene, Time= 72h Zhu, Zuolin; Espenson, James H.; Journal of Organic Chemistry; vol. 61; nb. 1; (1996); p. 324 - 328 View in Reaxys With 1,2-benzenedicarboxylic acid, phenol Patent; Soc. Usines Chim. Rhone-Poulenc; US2866832; (1956) View in Reaxys

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With kieselguhr Sabetay; Bulletin de la Societe Chimique de France; vol. <4> 47; (1930); p. 614,617 View in Reaxys With iodine Woronkow; Broun; Karpenko; Zhurnal Obshchei Khimii; vol. 19; (1949); p. 1927,1939; ; (1950); p. 1955 View in Reaxys With organic acids, phenol Patent; Soc. Usines Chim. Rhone-Poulenc; US2866832; (1956) View in Reaxys Tissier; Grignard; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 132; (1901); p. 685 View in Reaxys With potassium peroxodisulfate Matsubara; Perkin; Journal of the Chemical Society; vol. 87; (1905); p. 671 View in Reaxys T= 250 °C , durch Ueberleiten ueber Kupfer Tiffeneau; Annales de Chimie (Cachan, France); vol. <8>10; (1907); p. 190; Annales de Chimie (Cachan, France); vol. <8>11; (1907); p. 144 View in Reaxys With acetic anhydride Danilow; Venus-Danilowa; Chemische Berichte; vol. 60; (1927); p. 1062; Zhurnal Russkago Fiziko-Khimicheskago Obshchestva; vol. 59; (1927); p. 204 View in Reaxys Tiffeneau; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 134; (1902); p. 846; Annales de Chimie (Cachan, France); vol. <8> 10; (1907); p. 166 View in Reaxys Staudinger; Breusch; Chemische Berichte; vol. 62; (1929); p. 455 View in Reaxys Hurd; Webb; Journal of the American Chemical Society; vol. 49; (1927); p. 557 View in Reaxys With oxalic acid Tiffeneau; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 134; (1902); p. 846; Annales de Chimie (Cachan, France); vol. <8> 10; (1907); p. 166 View in Reaxys With oxalic acid Danilow; Venus-Danilowa; Chemische Berichte; vol. 60; (1927); p. 1062; Zhurnal Russkago Fiziko-Khimicheskago Obshchestva; vol. 59; (1927); p. 204 View in Reaxys Staudinger; Breusch; Chemische Berichte; vol. 62; (1929); p. 455 View in Reaxys Hurd; Webb; Journal of the American Chemical Society; vol. 49; (1927); p. 557 View in Reaxys With hydrogenchloride, T= 120 °C , Behandeln mit Pyridin im Einschlussrohr Harries; Justus Liebigs Annalen der Chemie; vol. 390; (1912); p. 264 View in Reaxys With 3-chloro-benzenecarboperoxoic acid in dichloromethane, 1.) -60 deg C, 3.5 h, 2.) room temperature, 20 h

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Hino, Tohru; Yamaguchi, Hitoshi; Matsuki, Kenji; Nakano, Kumiko; Sodeoka, Mikiko; Nakagawa, Masako; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 1; (1983); p. 141 - 146 View in Reaxys With sulfuric acid in water, T= 25 °C Moodie, Roy B.; Richards, Stuart N.; Thorne, Melanie P.; Journal of the Chemical Society, Chemical Communications; (1987); p. 870 - 871 View in Reaxys With 2,6-Di-tert-butyl-4-methylphenyl-2-hydroxyphenyl-phosphatphosphol in chlorobenzene, Rate constant Schwertlick, K.; Rueger, C.; Noack, R.; Journal fuer Praktische Chemie (Leipzig); vol. 324; nb. 5; (1982); p. 697 705 View in Reaxys With sulfuric acid in water, T= 25 °C , Equilibrium constant, Rate constant Moodie, Roy B.; Richards, Stuart N.; Thorne, Melanie P.; Journal of the Chemical Society, Chemical Communications; (1987); p. 870 - 871 View in Reaxys With sulfuric acid in various solvent(s), T= 80 °C , Kinetics, Further Variations: Temperatures Gagarin; Mamedov; Kharlampidi; Petroleum Chemistry; vol. 42; nb. 3; (2002); p. 187 - 191 View in Reaxys With isopropyl-benzene, sulfuric acid, T= 110 °C , Kinetics, Further Variations: Reagents, Temperatures Mamedov; Gagarin; Kharlampidi; Russian Journal of Applied Chemistry; vol. 75; nb. 4; (2002); p. 585 - 588 View in Reaxys With toluene-4-sulfonic acid in benzene Peppe, Clovis; Lang, Ernesto Schulz; De Andrade, Fabiano Molinos; De Castro, Lierson Borges; Synlett; nb. 10; (2004); p. 1723 - 1726 View in Reaxys With hydrogenchloride, T= 325.2 - 386.2 °C , Kinetics, Further Variations: HCl pressure; initial pressure of title comp. Rasse, Rafael J.; Dominguez, Rosa M.; Herize, Armando; Tosta, Maria; Brusco, Doris; Chuchani, Gabriel; Journal of Physical Organic Chemistry; vol. 20; nb. 1; (2007); p. 44 - 48 View in Reaxys 43.9 % Chromat.

With hydrogenchloride, Time= 0.266667h, T= 340.5 °C Rasse, Rafael J.; Dominguez, Rosa M.; Herize, Armando; Tosta, Maria; Brusco, Doris; Chuchani, Gabriel; Journal of Physical Organic Chemistry; vol. 20; nb. 1; (2007); p. 44 - 48 View in Reaxys Reaction Steps: 2 1: HCl gas 2: pyridine / acetonitrile / 55 °C With pyridine, hydrogenchloride in acetonitrile Balachandran; Santhosh Kumar; Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry; vol. 44; nb. 8; (2005); p. 1731 - 1734 View in Reaxys Reaction Steps: 2 1: 1.) KH / 1.) ether, mineral oil, 15 min, 2.) ether, up to r.t. 2: 15 percent / BF3*Et2O / pentane / 1.) -5 deg C, 15 min, 2.) up to r.t. With boron trifluoride diethyl etherate, potassium hydride in pentane Bourgeois; Montaudon; Maillard; Tetrahedron; vol. 49; nb. 12; (1993); p. 2477 - 2484 View in Reaxys

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Reaction Steps: 2 1: HCl / Eingiessen des Reaktionsproduktes in Eiswasser 2: pyridine With pyridine, hydrogenchloride Klages; Chemische Berichte; vol. 35; (1902); p. 2649; Chemische Berichte; vol. 39; (1906); p. 2591 View in Reaxys 0.1 - 11.8 %

1; 2; 3 : Example 1 40 Grams of a mixed solution composed of 5percent by weight of cumyl alcohol and 95 percent by weight of cumene as a raw material were charged in an autoclave, then stirred and heated at 136°C for 60 minutes. α-Methyl styrene was produced by dehydration of cumyl alcohol. The result is shown in Table 1.Example 2 It was carried out in the same manner as in Example 1 except that the temperature is 155°C. The result is shown in Table 1.Example 3 It was carried out in the same manner as in Example 1 except that the temperature is 184°C. The result is shown in Table 1.Comparative Example 1 It was carried out in the same manner as in Example 1 except that the temperature is 194°C. The result is shown in Table 1. [Table 1] Example 1Example 2Example 3Comparative Example 1Temperature heated (°C)136155184194α-MS yield(percent) *10.11.33.511.8* 1: α-Methyl styrene yield (percent) = [Amount of α-methyl styrene produced(mol)/amount of cumyl alcohol in raw material(mol)] x 100 The above Examples and Comparative Example were carried out by using the raw material described above as a bottom liquid, respectively, and it is found that when the temperature heated became 190°C orhigher, production of α -methyl styrene, in other words, production of water was remarkable. in isopropyl-benzene, Time= 1h, T= 136 - 194 °C Patent; Sumitomo Chemical Company, Limited; EP1484326; (2004); (A1) English View in Reaxys 1; 2; 3; 4 :A cumene solution (containing 200 ppm of formic acid) containing 25percent by weight of cumyl alcohol and hydrogen were passed through a fixed bed flow reactor in which an activated alumina was packed, at a rate of 1.6g/minute and 105 Ncc/minute, respectively. At this time, LHSV(Liquid Hourly Space Velocity) was 9/hour, the pressure was 1.0 MPaG, and the temperature was 200°C. The dehydration conversion of cumyl alcohol in the obtained reaction mixture was 97percent.; Example 2; It was carried out in the same manner as in Example 1 except that a cumene solution (containing 130 ppm of formic acid) containing 25percent by weight of cumyl alcohol was used. The dehydration conversion of cumyl alcohol in the obtained reaction mixture was 93percent.; Example 3; It was carried out in the same manner as in Example 1 except that a cumene solution (containing 60 ppm of formic acid) containing 25percent by weight of cumyl alcohol was used. The dehydration conversion of cumyl alcohol in the obtained reaction mixture was 85percent.; Example 4; It was carried out in the same manner as in Example 1 except that a cumene solution (containing 30 ppm of formic acid) containing 25percent by weight of cumyl alcohol was used. The dehydration conversion of cumyl alcohol in the obtained reaction mixture was 74percent.; Comparative Example 1; It was carried out in the same manner as in Example 1 except that a cumene solution (containing 5 ppm of formic acid) containing 25percent by weight of cumyl alcohol was used. The dehydration conversion of cumyl alcohol in the obtained reaction mixture was 46percent. With aluminum oxide, formic acid in isopropyl-benzene, T= 200 °C , Conversion of starting material Patent; Sumitomo Chemical Company, Limited; EP1621527; (2006); (A1) English View in Reaxys 9 : EXAMPLE 9 EXAMPLE 9 A cumene solution containing 40.2percent w/w cumene hydroperoxide, 0.65percent w/w acetophenone and 2.44percent w/w phenyldimethyl carbinol was fed at 400 ml/h to the reactor illustrated in FIG. 1 packed with 3 mm stainless steel gauze rings, the reactor being maintained at a pressure of 500 mm absolute. A solution of 1.0percent w/w sulphuric acid in acetophenone was fed as a separate stream through a common inlet with the cumene solution at such a rate that the sulphuric acid concentration in the total feed was 365 ppm. The products distilled at 140° C. and the distillate accounted for 96.7percent of the total weight fed. The phenol and acetone yields were 86.4 mole percent and 90.7 mole percent respectively and the yield of alphamethylstyrene was 3.8 mole percent. A tar containing acid was drained from the bottom of the reactor. With sulfuric acid, isopropylbenzene hydroperoxide in acetophenone Patent; BP Chemicals Limited; US4246203; (1981); (A1) English

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View in Reaxys 1 :Example 1; According to the method described in the specification, an oxidization reaction solution (1) containing 31percent by weight of cumene hydroperoxide was obtained by oxidizing cumene with an oxygen-containing gas (air) in an oxidation step. An epoxidation reaction solution (2) containing mainly propylene oxide, cumyl alcohol, unreacted propylene, and cumene was obtained by passing the oxidization reaction solution and propylene through a reactor filled with a titanium-containing silicon oxide catalyst in an epoxidation step. The unreacted propylene (3) was separated and removed from the resulting reaction solution (2) to obtain a reaction solution (4) after recovering propylene. The reaction solution (4) after recovering propylene was used in the following Example 3 and Comparative Example 1.First, the reaction solution (4) after recovering propylene was separated into a fraction of a solution (5) containing mainly cumyl alcohol and cumene and a fraction containing mainly propylene oxide in a propylene oxide purification step, and then the fraction containing mainly <n="27"/>propylene oxide was distilled with a plurality of distillation columns including extraction and distillation so as to satisfy product quality to obtain a propylene oxide product. Regarding the fraction of the solution (5) containing mainly cumyl alcohol and cumene, cumyl alcohol was subjected to a dehydration reaction and a hydrogenation reaction in a hydrogenation step to obtain cumene, which was recycled to the oxidization step.Fig. 1 is a schematic flow chart described in the specification. , Dehydration Patent; SUMITOMO CHEMICAL COMPANY, LIMITED; WO2008/123384; (2008); (A1) English View in Reaxys With phosphorous pentoxide, vacuum distillation Prusek, Ondrej; Bures, Filip; Pytela, Oldrich; Collection of Czechoslovak Chemical Communications; vol. 74; nb. 1; (2009); p. 85 - 99 View in Reaxys 1 :Example 1 Using the apparatus as shown in FIG. 1, Example 1 was carried out. A liquid (2) (a cumene solution containing about 25percent by weight of cumyl alcohol) and a gas (3) (hydrogen) were fed through the bottom of the column (1), and the resulting mixed fluid of the gas and the liquid was flowed upward through the column. Within the column, there was provided the gas-liquid dispersing device according to the present invention comprising the plate (4) which was arranged perpendicular to the flow direction of the fluid and blocked the flow of the fluid. The plate had holes (5) for gas-liquid mixed fluid, the holes were connected to the conduits (6) extending downward from the plate, and three passages (7) for the gas per one conduit were provided through the side surface of the conduit. As was described above, in order that the positional relationship in the levels of the passages for the gas through the conduit flexibly accommodates the change in the height of the space of the gas in accordance with the change of the operation conditions and the throughput, the first passage for the gas was provided at the level of 75 mm downward from the plate, the second one was at the level of additionally 40 mm downward from the first passage and the third one was at the level of further additionally 40 mm downward from the second passage. The ratio of H/L was about 12.7, wherein height of the column (1) was H and length of conduits (6) was L.The structure of the end (8) of the lower part of the conduit had a structure which was closed by a cap. And, two small holes as the passages for the liquid per one conduit were provided through the conduit at the same level of 45 mm upward from the lower end of the conduit.The diameter of the hole of the plate was generally the same as that of the conduit.The ratio of N/S was 15/m2 wherein N is the number of the holes of the plate and S is an area [m2] of the lower surface of the plate.The linear velocity (v) of the gas-liquid mixed fluid flowing through the hole of the plate was about 2 m/s which is based on the volume of the fluid of the entrance (lower) side of the hole for the gas-liquid mixed fluid.The velocity (g) of the gas flowing through the passage for the gas provided through the side surface of the conduit was about 54 m/s which is based on the volume of the gas of the entrance side of the passage for the gas.The velocity (h) of the liquid flowing through the passage for the liquid provided through the conduit was about 6 m/s.Thus, it was confirmed that a space (with a thickness of 380 mm) containing the gas was formed by flowing the liquid and the gas at a predetermined ratio through the conduit from the down side to the upper side of the plate. The value of dPG-dPL was 8.7 kPa at this point.Above the gas-liquid dispersion device, there was provided a bed (10) of packing comprising spherical alumina catalysts (partially supporting a noble metal). Under the conditions of a catalyst bed temperature of about 200° C. to 230° C. and a column top pressure of about 1.5 MPaG to 2 MPaG, cumyl alcohol was intra-molecularly dehydrated to α-methylstylene, and α-methylstylene was successively converted to cumene by reacting with hydrogen. When the state of the gas-liquid dispersion is insufficient, there would be caused channeling in the reactor, and thereby an insufficient hydrogenation zone and an excessive hydrogenation zone would be partially formed. The formation of such zones is one of factors which worsen the loss of cumene in the hydrogenation step. Then, the state of the dispersion was evaluated by the following index. The index for the insufficient hydrogenation was a concentration of αmethylstylene at the outlet of the column (referred to as a leak-concentration of α-methylstylene). As a result, the obtained reaction product had the leak-concentration of α-methylstylene (the index for the insufficient hydrogenation) was 323 ppm by weight. In Table 1, the results of Example 1 are shown with "with dispersion plate".

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With spherical alumina catalysts (partially supporting a noble metal) in isopropyl-benzene, T= 200 - 230 °C , the gas-liquid dispersion device, Industry scale, Product distribution / selectivity Patent; Sumitomo Chemical Company, Limited; US2011/4009; (2011); (A1) English View in Reaxys Reaction Steps: 3 1: copper(l) chloride / 20 °C 2: dichloromethane / -30 °C 3: toluene / 1 h / 110 °C With copper(l) chloride in dichloromethane, toluene, 3: Chugaev type reaction Schur, Christine; Becker, Nina; Bergstraesser, Uwe; Gottwald, Thomas; Hartung, Jens; Tetrahedron; vol. 67; nb. 12; (2011); p. 2338 - 2347 View in Reaxys With C30H29N7ORu(2+)*2F6P(1-) in acetonitrile, T= 20 °C , Inert atmosphere, Irradiation Kojima, Takahiko; Nakayama, Kazuya; Sakaguchi, Miyuki; Ogura, Takashi; Ohkubo, Kei; Fukuzumi, Shunichi; Journal of the American Chemical Society; vol. 133; nb. 44; (2011); p. 17901 - 17911 View in Reaxys With dichloro bis(acetonitrile) palladium(II), p-benozquinone in hexadeuterioacetone, Time= 72h, T= 20 °C Dong, Jia Jia; Harvey, Emma C.; Faans-Mastral, Martn; Browne, Wesley R.; Feringa, Ben L.; Journal of the American Chemical Society; vol. 136; nb. 49; (2014); p. 17302 - 17307 View in Reaxys

Rx-ID: 23426135 View in Reaxys 2/41 Yield

Conditions & References II.IIB :20.0 cc of the above Cu/Zn/Zr catalyst from IIA was crushed and sized into 6-20 mesh particles. The catalyst was mixed with 45 grams of 80 mesh silicon carbide and centered inside a 69 cm long stainless steel reactor tube between beds of 20 mesh SiC and glass wool. The reactor tube had an internal diameter of 1. 5cm. The catalyst was slowly reduced by heating the catalyst particles at a rate of 3°C per minute from 20°C to 180°C while flowing 0.05 wt. percent hydrogen in nitrogen at a rate of 10 L/Hr. The catalyst was allowed to reduce at 180°C for 2 hours and then the hydrogen content in the nitrogen was doubled every 2 hours until the gas was 3.2 wt. percent hydrogen in nitrogen. The catalyst was reduced for a final two-hour period after which the gas was switched to 99.999percent hydrogen and the reactor was pressurized with hydrogen to a gauge pressure of 290 psig (20 bar) while the catalyst bed was maintained at 180OC. The hydrogen flow rate was adjusted to 2 L/Hr. A mixture containing about 25.5 wt. percent of 2-phenyl-2-propanol (obtained from AVOCADO CHEMICAL) AND 74.5 WTpercent OF CUMENE (OBTAINED FROM ALDRICH CHEMICAL CO. ) WAS fed the reactor at a feed rate of 33.5 g/hr. while maintaining the hydrogen flow rate and a bed temperature of 180°C. After a week of operation, a sample of the reactor product was collected, dried of water and analyzed by gas chromatography. The product contained 8.1 wt. percent 2-phenyl-2propanol, 91.2 wt. percent OF CUMENE, 0.1 wt. percent alpha-methyl styrene, 0.1 wt. percent of i-propylcyclohexane and 0.5 wt. percent of cumene dimers. Stage 1: With α6H-SiC, hydrogen, Cu/Zn/Zr catalyst, T= 20 - 180 °C Stage 2: With hydrogen, T= 180 °C , p= 15001.5Torr Patent; SHELL OIL COMPANY; WO2005/5350; (2005); (A2) English View in Reaxys II.IIE :A feedstock containing about 25 wt. percent cumyl alcohol* (>98percent purity, obtained from Avocado Chemical) in 75 wt. percent cumene (>99percent purity obtained from Aldrich Chemical) was made by blending. The hydrogenolysis reaction was conducted under the conditions provided in the Table 4 below. Two hydrogen flowrates were used during the testing, 2L/Hr or 4/Hr. The results of the testing are shown in Table 5 and Table 6. As demonstrated, this fixed bed process produces a cumene product stream of about 91 wt. percent purity having 7.9 wt. percent of unconverted cumyl alcohol, 0.6 wt. percent of cumene dimers and 0.1 wt. percent OF ISOPROPYLCYCLOHEXANE as side products.

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With hydrogen, reduced copper chromite catalyst (G-22/2), Time= 600 - 800h, T= 180 °C , p= 15001.5Torr Patent; SHELL OIL COMPANY; WO2005/5350; (2005); (A2) English View in Reaxys II.IIC :The experiment of IIB was repeated using the copper on silica catalyst described in Example 1B (T-366) obtained from Sud Chemie. 20 cc of the catalyst was used. Due to the higher activity of the reduced T-366 catalyst, the testing was conducted at a temperature of 150°C. After 200 hours of operation, the dried product contained 9.7 wt. percent 2-phenyl-2- propanol, 88.4 WT. percent of cumene, 0.1 wt. percent alpha-methyl styrene, 0.1 wt. percent of iPROPYLCYCLOHEXANE and 1.7 wt. percent of cumene dimers. When operated at 180°C, the product contained less than 5 wt. percent 2-phenyl-2-propanol. With hydrogen, reduced copper on silica (T-366) catalyst, T= 150 °C , p= 15001.5Torr Patent; SHELL OIL COMPANY; WO2005/5350; (2005); (A2) English View in Reaxys

Rx-ID: 2011786 View in Reaxys 3/41 Yield

Conditions & References

31 %, 57 %

With phosphorus tribromide in chloroform, Time= 2h, T= 40 °C , Title compound not separated from byproducts Kamer, Paul C. J.; Nolte, Roeland J. M.; Drenth, Wiendelt; Journal of the American Chemical Society; vol. 110; nb. 20; (1988); p. 6818 - 6825 View in Reaxys

67 % Spectr., 30 % Spectr.

With triphenylphosphine in dichloromethane, Time= 0.25h, T= 20 °C Tongkate, Pratoomrat; Pluempanupat, Wanchai; Chavasiri, Warinthorn; Tetrahedron Letters; vol. 49; nb. 7; (2008); p. 1146 - 1148 View in Reaxys

13C

Rx-ID: 3473262 View in Reaxys 4/41 Yield

Conditions & References With (carboxysulfamoyl)triethylammonium hydroxide, inner salt, tert-butyl-pyrocatechol, Methyl jasmonate in benzene, T= 50 °C Johnston, Linda J.; Ingold, K. U.; Journal of the American Chemical Society; vol. 108; nb. 9; (1986); p. 2343 2348 View in Reaxys

Rx-ID: 25930492 View in Reaxys 5/41 Yield 53 %

Conditions & References With 4-(N,N-dimethlyamino)pyridine, Time= 24h, T= 100 °C Sakakura, Akira; Kawajiri, Kimio; Ohkubo, Takuro; Kosugi, Yuji; Ishihara, Kazuaki; Journal of the American Chemical Society; vol. 129; nb. 47; (2007); p. 14775 - 14779 View in Reaxys

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Rx-ID: 23148853 View in Reaxys 6/41 Yield

Conditions & References

0.01 - 0.40 %

4; 5; 6; 2 : Example 4 40 Grams of a cumene mixed solution containing 3percent by weight of propylene oxide and 24percent by weight of cumyl alcohol were charged in an autoclave, then stirred and heated at 136°C for 60 minutes. α-Methyl styrene was produced by dehydration of cumyl alcohol. Further, propylene glycol was produced through a reaction of water with propylene oxide. The result is shown in Table 2.Example 5 It was carried out in the same manner as in Example 4 except that the temperature is 155°C. The result is shown in Table 2.Example 6 It was carried out in the same manner as in Example 4 except that the temperature is 174°C. The result is shown in Table 2.Comparative Example 2 It was carried out in the same manner as in Example 4 except that the temperature is 194°C. The result is shown in Table 2. [Table 2] Example 4Example 5Example 6Comparative Example 2Temperature heated (°C)136155174194αMS yield(percent)0.010.020.070.40PG concentration (ppm by weight) *218354277*2: Concentration of propylene glycol in mixture after heating In each of the above Examples 4-6 and Comparative Example 2, a liquid in which a small amount of propylene oxide was added to cumyl alcohol and cumene, was used, and it is found that when the temperature heated became 190°C or higher, production of α-methyl styrene remarkably increases, and propylene glycol also increases together with the increases of α-methyl styrene. in isopropyl-benzene, Time= 1h, T= 136 - 194 °C Patent; Sumitomo Chemical Company, Limited; EP1484326; (2004); (A1) English View in Reaxys

2H 2H

Rx-ID: 2295661 View in Reaxys 7/41 Yield

Conditions & References

60 %

With Burgess reagent in benzene, Heating Somich, Cathleen; Mazzocchi, Paul H.; Ammon, Herman L.; Journal of Organic Chemistry; vol. 52; nb. 16; (1987); p. 3614 - 3619 View in Reaxys With toluene-4-sulfonic acid in benzene, Heating Choi, Jongwook; Tang, Lihao; Norton, Jack R.; Journal of the American Chemical Society; vol. 129; nb. 1; (2007); p. 234 - 240 View in Reaxys

Rx-ID: 9068953 View in Reaxys 8/41 Yield

Conditions & References

54 % Chromat., 29 % Chromat., 13 % Chromat.

With copper(l) iodide, chloro-trimethyl-silane, iodine, lanthanum in acetonitrile, Time= 1h, T= 82 °C

54 % Chromat., 13 %

With lanthanum, chloro-trimethyl-silane, iodine, copper(l) iodide in acetonitrile, Time= 1h, T= 82 °C

Nishino, Toshiki; Nishiyama, Yutaka; Sonoda, Noboru; Tetrahedron Letters; vol. 43; nb. 20; (2002); p. 3689 3691 View in Reaxys

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Chromat., 29 % Chromat.

Nishino, Toshiki; Nishiyama, Yutaka; Sonoda, Noboru; Bulletin of the Chemical Society of Japan; vol. 76; nb. 3; (2003); p. 635 - 641 View in Reaxys

36 % Chromat., 6 % Chromat., 29 % Chromat.

With lanthanum, chloro-trimethyl-silane, iodine, CoI2 in acetonitrile, Time= 1h, T= 82 °C Nishino, Toshiki; Nishiyama, Yutaka; Sonoda, Noboru; Bulletin of the Chemical Society of Japan; vol. 76; nb. 3; (2003); p. 635 - 641 View in Reaxys

Rx-ID: 23755686 View in Reaxys 9/41 Yield

Conditions & References 1; 1 :The catalyst A of 3 m-thick as a first layer and the catalyst B of 1.2 m-thick as a second layer were packed in a reactor having an inner diameter of 4 mm. The first layer and second layer were heated to 230 °C and 190°C, respectively, and 0.1 liter/minute of hydrogen and 1.6 g/minute of a cumene solution having a cumyl alcohol concentration of 23 percent by weight under a pressure of 4 MPa-G, were simultaneously fed to the reactor, continuously. After the reaction of 106 hours, a cumyl alcohol conversion was 99.8percent and a selectivity of a cumene dimer (hydrogenated product of an α-methyl styrene dimer) was 0.9percent. Further, a concentration of α-methyl styrene in cumene obtained was less than 0.01 percent by weight.; The catalyst B of 0.1 m-thick as a first layer, the catalyst A of 0.2 m-thick as a second layer, the catalyst B of 0.4 m-thick as a third layer, the catalyst A of 0.4 m-thick as a fourth layer, the catalyst B of 0.4 m-thick as a fifth layer, the catalyst A of 2.4 m-thick as a sixth layer and the catalyst B of 0.4 m-thick as a seventh layer (catalyst A: 3 m-thick in total, catalyst B: 1. 3 m-thick in total) were packed in a reactor having an inner diameter of 4 mm OE. The first and second layers, the third to fifth layers, and the sixth and sevens layers were heated to 180°C, 200°C and 230°C, respectively, and 0.1 normal liter/minute of hydrogen and 1.6 g/ minute of a cumene solution having a cumyl alcohol concentration of 23 percent by weight under a pressure of 4 MPa-G, were simultaneously fed to the reactor, continuously. After the reaction of 88 hours, a cumyl alcohol conversion was 99.9percent and a selectivity of a cumene dimer (hydrogenated product of an α-methyl styrene dimer) was 0.2percent. Further, a concentration of α-methyl styrene in cumene obtained was less than 0.01 percent by weight. With hydrogen, aluminum oxide, 0.05 palladium/alumina, Time= 88 - 106h, T= 180 - 230 °C , p= 30003Torr , Product distribution / selectivity Patent; Sumitomo Chemical Company, Limited; EP1666442; (2006); (A1) English View in Reaxys

Rx-ID: 24794773 View in Reaxys 10/41 Yield 85.5 %

Conditions & References DETAILED DESCRIPTION OF THE DRAWINGSA cumene oxidation product mixture is introduced into the process via line 1 into decomposing vessel 2. A circulating stream comprising cumene hydroperoxide, an acid catalyst, phenol and acetone is introduced into decomposing vessel 2 via line 8. The two hereinabove described streams which are introduced into decomposing vessel 2 pass through decomposing vessel 2 while contacting indirect heat exchange surfaces 3. A resulting admixed and cooled inventory in decomposing vessel 2 is removed therefrom via line 4. A coolant is introduced into chamber 16 via line 15 and flows into indirect heat exchange surfaces 3. A resulting coolant which has been heated by the flowing contents of decomposing vessel 2 is passed from indirect heat exchange surfaces 3 into chamber 17. A resulting heated coolant is removed from chamber 17 via line 18 and recovered. The heated coolant may be cooled and recycled to indirect heat exchange surfaces 3. The reacted flowing stream which was removed from decomposing vessel 2 via line 4 is carried via lines 5 and 19 and introduced into pump 6. The resulting pressurized stream is carried from pump 6 via line 7 and a portion is further carried via line 8 and introduced into decomposing vessel 2 as described hereinabove. Another portion of the pressurized circulating stream from pump 6 and carried via line 7 is carried via line 10 and is admixed with an acid catalyst which is intro-

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duced via line 11. The resulting mixture containing the acid catalyst is carried via line 12 and introduced into calorimeter 13 which is used to monitor and control the operating conditions for the decomposition of the CHP. A resulting stream is removed from calorimeter 13 via lines 14, 5 and 19 and is passed into pump 6 as hereinabove described. Another portion of the pressurized stream from pump 6 is carried via lines 7 and 9 and introduced into heat exchanger 20 to be heated. A resulting heated stream is removed from heat exchanger 20 via line 21 and introduced into flash drum 22. A vapor stream comprising acetone is removed from flash drum 22 via line 24 and introduced into heat exchanger 25 for cooling. A resulting cooled and condensed stream comprising acetone is removed from heat exchanger 25 via line 26 and is introduced into pump 6 via lines 26 and 19. A resulting stream comprising acetone and phenol is removed from flash drum 22 via line 23 and recovered.; ILLUSTRATIVE EMBODIMENTA cumene oxidation product mixture containing an 88.5 weight percent cumene hydroperoxide (CHP) in an amount of 26 m3/hr is introduced into a decomposer vessel containing heat exchange surfaces sufficient to maintain a desired temperature during the exothermic decomposition of CHP to produce phenol and acetone. The contents of the decomposer include CHP, an acid catalyst, phenol and acetone and are circulated in an external flowing loop and re-introduced into the decomposer. The external flowing loop is circulated at a flow rate of about 26 m3/hr and contains a sulfuric acid level of about 6 wppm and maintained at a temperature of about 75° C. (167° F.). The residence time of the cumene oxidation product mixture in the decomposer and the external flowing loop is about 15 minutes. A decomposer product stream containing a CHP concentration of about 3 weight percent is removed from the external flowing loop and is passed through a dehydrator operated at a temperature of 135° C. (275° F.). The resulting AMS yield is 85.5 mol percent and the feed cumene/phenol yield weight ratio is 1.290. Thus, the weight yield ratio is now very close to the theoretical limit for this type of chemistry of 1.277. The feed cumene/phenol yield mol ratio is 0.989. Stage 1: With sulfuric acid, Time= 0.25h, T= 75 °C Stage 2:, T= 135 °C , in dehydrator Patent; UOP LLC; US7141700; (2006); (B1) English View in Reaxys 72.7 - 85.5 %

DETAILED DESCRIPTION OF THE DRAWINGSIn FIG. 1, a cumene oxidation product stream containing CHP is introduced into the process via line 1 and enters metering vessel 2. A resulting stream containing cumene oxidation product is removed from metering vessel 2 via line 3 and a portion thereof is transported via line 4 and joins a flowing circulating loop carried in line 33 and the resulting admixture is transported via line 6 and introduced into vertical heat exchanger 7. A cooling medium is provided via line 8 and is introduced into vertical heat exchanger 7 and a resulting heated medium is removed via line 9 and recovered. The cooling medium may be recirculated after cooling, if desired. A cooled process stream is removed from vertical heat exchanger 7 via line 10 and is admixed with another portion of the cumene oxidation product stream provided via lines 3 and 5, and a make-up acetone stream provided via line 11. The resulting mixture is transported via line 12 and is admixed with an acetone recycle stream provided via line 29 and the resulting admixture is carried via line 14 and introduced into pump 15. A resulting stream is transported from pump 15 via lines 16 and 17. At least a portion of the flowing stream in line 17 is carried via line 21 and introduced into vertical heat exchanger 30. A cooling medium is provided via line 31 and introduced into vertical heat exchanger 30 and a resulting heated medium is removed from vertical heat exchanger 30 via line 32. A cooled flowing stream is removed from vertical heat exchanger 30 via line 33 and is admixed with cumene oxidation product as hereinabove described. A portion of the flowing stream in line 15 is transported via line 18 and introduced into calorimeter 20 which is used to monitor and control the operating conditions for the decomposition of the CHP. A sulfuric acid stream is carried via line 19 and introduced into calorimeter 20. The resulting admixture from calorimeter 20 is introduced into line 14 via line 13. Another portion of the flowing stream in line 17 is carried via line 22 and introduced into heat exchanger 23 to be heated. A resulting heated stream is removed from heat exchanger 23 via line 24 and introduced into flash drum 25. A stream rich in acetone is removed from flash drum 25 via line 27 and introduced into heat exchanger 28. A resulting cooled stream is removed from heat exchanger 28 via line 29 and introduced into line 14. A stream containing acetone and phenol is removed from flash drum 25 via line 26 and recovered.In FIG. 2, three data points, (A, B and C) from the Illustrative Embodiment are plotted in a graph showing alphamethylstyrene (AMS) yield as a function of a decomposer residence time.; Illustrative EmbodimentA cumene oxidation product mixture containing 79 weight percent cumene hydroperoxide at a rate of 41.8 m3/hr is passed through a metering vessel maintained at a temperature of about 60° C. (140° F.) and at a liquid hourly space velocity of 30 hr-1 with an average residence time of 26 minutes. The resulting effluent in an amount of 41.8 m3/hr from the metering vessel is introduced into a circulating decomposer loop having a volume of 18.1 m3. The circulating decomposer loop is operated at a residence time of 26 minutes, a sulfuric acid level of 54 wppm and temperature of 60° C. to produce a decomposer product containing a CHP concentration of 0.63 weight percent. The resulting decomposer effluent is passed through a dehydrator operated at a temperature of 120° C. The resulting AMS yield is 72.7 mol percent and the cumene/phenol yield ratio is 1.322. This run is in accordance with the present invention. The results are summarized and presented in Table 1 as Run A. The AMS yield result is plotted in FIG. 2 and is identified as point "A".; A cumene oxidation product mixture containing an 83 weight percent cumene hydroperoxide at a rate of 39.8 m3/hr is passed through a metering vessel maintained at a temperature of about 60° C. (140° F.) and at a liquid

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hourly space velocity of 30 hr-1 with an average residence time of 20 minutes. The resulting effluent in an amount of 39.8 m3/hr from the vessel is introduced into circulating decomposer loop having a volume of 13.3 m3. This lower volume in the circulating decomposer loop is made possible by the use of two vertically oriented heat exchangers. The circulating decomposer loop is operated at a residence time of 20 minutes, a sulfuric acid level of 40 wppm and a temperature of 60° C. to produce a decomposer product containing a CHP concentration of 1.5 weight percent. The resulting decomposer effluent is passed through a dehydrator operated at a temperature of 135° C. The resulting AMS yield is 80.6 mol percent and the cumene/phenol yield ratio is 1.311. This run is in accordance with the present invention. The results are summarized and presented in Table 1 as Run A. The AMS yield result is plotted in FIG. 2 and is identified as point "B".; A cumene oxidation product mixture containing an 88.5 weight percent cumene hydroperoxide at a rate of 26 m3/hr is passed through a metering vessel maintained at temperature of about 75° C. (167° F.) and at a liquid hourly space velocity of 30 hr-1 with an average residence time of 15 minutes. The resulting effluent at a rate of 26 m3/hr from the vessel is introduced into a circulating decomposer loop having a volume of 12.5 m3. Two vertically oriented heat exchangers are used in this run along with an acetone recycle in an amount of 8.6 m3/hr. the circulating decomposer loop is operated at a residence time of 15 minutes, a sulfuric acid level of 6 wppm and a temperature of 75° C. to produce a decomposer product containing a CHP concentration of 3.0 weight percent. The resulting decomposer effluent is passed through a dehydrator operated at a temperature of 135° C. The resulting AMS yield is 85.5 mol percent and the cumene/phenol yield ratio is 1.290. Thus the yield ratio has improved using the process of this invention to a level where it is now very close to the theoretical limit for this type of chemistry of 1.277. This run is in accordance with the present invention. The results are summarized and presented in Table 1 as Run C. The AMS yield result is plotted in FIG. 2 and is identified as point "C". TABLE 1 Operation Summary RUN A B C CLIP Concentration, wt percent 79 83 88.5 Predecomposer vessel, LHSV 30 30 30Decomposer feed rate, m3/hr. 41.8 39.8 2.6Decomposer volume, m3 18.1 13.3 12.5 Decomposer residence time, min. 26 20 15 Decomposer acid level, wppm 54 40 6 Decomposer temperature, ° C. 60 60 75 Decomposer product CLIP level, wt percent 0.63 1.5 3.0 Dehydrator temperature, ° C. 120 135 135 Cumene Feed/phenol yield ratio, wt/wt 1.322 1.311 1.290 AMS Yield, mol percent 72.7 80.6 85.5 Cumene feed/phenol yield ratio, mol/mol 0.966 0.974 0.989 Stage 1: With sulfuric acid, Time= 0.25 - 0.433333h, T= 60 - 75 °C Stage 2:, T= 120 - 135 °C , in dehydrator, Product distribution / selectivity Patent; UOP LLC; US7141701; (2006); (B1) English View in Reaxys

Rx-ID: 4522627 View in Reaxys 11/41 Yield

Conditions & References

95 %

With scandium tris(trifluoromethanesulfonate), Time= 1.3h, T= -40 °C , Yields of byproduct given Ishihara, Kazuaki; Kubota, Manabu; Kurihara, Hideki; Yamamoto, Hisashi; Journal of Organic Chemistry; vol. 61; nb. 14; (1996); p. 4560 - 4567 View in Reaxys

O O

Rx-ID: 2011780 View in Reaxys 12/41 Yield 35 %, 10 %, 40 %

Conditions & References With acetic anhydride, cobalt(II) chloride in acetonitrile, Time= 8h, T= 25 °C Iqbal, Javed; Srivastava, Rajiv Ranjan; Journal of Organic Chemistry; vol. 57; nb. 7; (1992); p. 2001 - 2007 View in Reaxys

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Rx-ID: 23573045 View in Reaxys 13/41 Yield 45.73 51.50 %

Conditions & References 1; 2; 3 :In these Examples, the analysis of hydroxyacetone was carried out on an Agilent 6890 Gas chromatograph (GC). GC separation was carried out on glass column with a length 24 inches 1/4 inch outer diameter, configured for on column injection, packed with chromsorb 102 80/100 mesh, with helium as carrier gas at 30 milliliters per minute (ml/min). The injector temperature was maintained at 160° C. and the detector temperature was maintained at 250° C. The initial column temperature was kept at 110° C. for 3 minutes hold time, this was followed by a temperature increase at 7° C. per minute to reach 150° C., held for 2 minutes, at 150° C., followed by a temperature increase at 10° C. per minute to reach 200° C. and held at 200° C. for 15 minutes. The column was calibrated with standard hydroxyacetone (obtained from Aldrich Chemical Company, 97percent pure) at a concentration ranging from 5 parts per million (ppm) to 244 ppm made in a 50:50 mixture of cumene and phenol. Hydroxyacetone in the reaction mixture was analyzed by neutralizing a test sample with anhydrous sodium carbonate (around 1.5 g of sodium carbonate is utilized to neutralize 10 g of sample reaction mixture). The sample reaction mixture was directly injected into the GC without dilution to obtain maximum intensity of the HA peak in the sample. The analysis of cumene, AMS, acetophenone, DMBA, and DCP was carried out on an Agilent 6890 column Gas chromatograph. GC separation was carried out on SBP-1 liquid phase, 30 meter length, 0.53 millimeter inner diameter and a film thickness of 3.0 micrometer. The GC was initially calibrated using standard Aldrich samples of cumene, AMS, acetophenone, DMBA, and DCP diluted in 50:50 acetone and phenol mixture. The diluted standard samples were injected into GC with an on-column injector. About 10 grams of sample reaction mixture was neutralized with anhydrous sodium carbonate (1.5 grams) to avoid degradation and further reaction of cleavage products. The stabilized reaction mixture was then weighed accurately and diluted with an equal weight of acetone. The solution was than injected into an on-column GC. Samples at specific time intervals were analyzed and compared to the GC chromatogram of a standard to determine the cleavage of CHP to corresponding products. The analysis of phenol was carried out on a Shimadzu GC. The GC separation was carried out on HP-50 column, 30 meter length, 0.25 millimeter inner diameter and 0.25 micrometer film thickness. The injector and detector temperature were kept at 290° C., split ratio of 1:100 was used to avoid saturation of column. The initial column temperature was kept at 50° C., which was followed by a temperature increase of 8° C. per minute to 240° C. and then held at 240° C. for 10 minutes. The GC was initially calibrated with phenol obtained from Aldrich. The phenol standard was prepared by diluting phenol in acetonitrile to obtain various concentration levels of phenol. The diluted standard samples were then injected into the GC. Samples were analyzed by weighing about 100 milligrams of reaction mixture and diluting the reaction mixture with acetonitrile to a homogeneous mixture of 10 milliliters, and injecting into a GC with HP-50 Column. Samples at specific time intervals during reaction were analyzed and compared to the GC chromatogram of the standard sample to determine percentage of phenol formed by cleavage of CHP. Comparative Examples 1, 2, and 3 In these comparative examples, CHP was decomposed in a prior art two-step continuous process to obtain a phenol product, wherein the molar ratio of the phenol to acetone was maintained at 0.77:1 as in Comparative Example 1 or 1:1 as in Comparative Examples 2 and 3. The process generally included adding CHP to an agitated mixture of phenol, acetone, and sulfuric acid. The composition of the feed stream entering the reactor is illustrated in Table 1. In the first step of the continuous process, a typical synthetic feed stream comprising phenol, acetone, and CHP was fed to a glass reactor fitted with a condenser having a capacity of about 150 milliliters through the respective inlets for the feed stream and acid catalyst. The reactor was also fitted with a temperature probe to monitor the temperature and external heating/cooling jacket to maintain the temperature. The contents of the reactor were continuously stirred with a magnetic stirrer. The composition of the feed stream and amount of catalyst added is illustrated in Table I below. The reactor in the first step was maintained at 50° C. The residence time of the feed stream was monitored and maintained at 1 minute in the first step of the process. Sulfuric acid (98percent) was added separately and simultaneously with the feed stream to the reactor. The resultant effluent was analyzed for residual CHP, DMBA, hydroxyacetone, DCP and phenol. Results of the analysis are included in Table 2 below. The resulting effluent was then neutralized using 1percent aqueous ammonia solution, to result in a mixture containing 100 ppm acid catalyst, in a neutralizer. This neutralized effluent was then fed to the second step reactor. The reactor used in the second step was a stainless steel chamber having a capacity of 300 ml and is fitted with criss-cross baffles to ensure efficient mixing of the reactor contents. The second step reactor is maintained at 130° C. and under a pressure of 90 psig. The residence time maintained in the second step was 17 minutes. The resulting mixture from second step was analyzed using gas chromatographic

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techniques. The results of the analysis are included in Table 2 below. In these examples, CHP was decomposed in a continuous 2-STEP process to obtain a phenol product, wherein the molar ratio of phenol to acetone was greater than or equal to 1.2:1, and the effluent produced from the first step contained at least 1percent residual CHP. Table 3 illustrates the composition of the feed stream. The process generally included adding CHP to an agitated mixture of phenol, acetone, and sulfuric acid. In the first step of the continuous process, a typical synthetic feed composition having phenol, acetone, and CHP was fed to a glass reactor fitted with a condenser having a capacity of about 150 milliliters through the respective inlets for the feed stream and acid catalyst. The reactor was also fitted with a temperature probe to monitor the temperature and external heating/cooling jacket to maintain the temperature. The contents of the reactor were continuously stirred with a magnetic stirrer. The composition of the feed stream and amount of catalyst added is illustrated in Table II below. The reactor in the first step was maintained at 50° C. The residence time of the feed stream was monitored and maintained at 1 minute in the first step of the process. Sulfuric acid (98percent) of concentration was added separately and simultaneously with the feed stream to the reactor. The resultant effluent was analyzed for residual CHP, DMBA, hydroxyacetone, DCP and phenol. Results of the analysis are included in Table 4 below. The resulting mixture was the neutralized using 1percent aqueous ammonia solution to result in a mixture containing 100 ppm acid catalyst, in a neutralizer. This neutralized effluent was then fed to the second step reactor. The reactor used in the second step was a stainless steel chamber having a capacity of 300 ml and is fitted with criss-cross baffles to ensure efficient mixing of the reactor contents. The second step reactor is maintained at 130° C. and under a pressure of 90 psig. The residence time maintained in the second step was 17 minutes. The resulting mixture from second step was analyzed using gas chromatographic techniques. The results of the analysis are included in Table 4 below. With sulfuric acid in water, T= 50 - 200 °C , Product distribution / selectivity Patent; Tatake, Prashant Anil; Kumbhar, Pramod Shankar; Singh, Bharat; Fulmer, John William; Mandal, Sabyasachi; Kumar, Arun N.; Pawar, Rupesh; US2005/222466; (2005); (A1) English View in Reaxys

HO O

Rx-ID: 27897451 View in Reaxys 14/41 Yield

Conditions & References 2 :Example 2; CHP decomposition was carried out in the same equipment as in Example 1, but the reactor for synthesis of the catalytic system had a volume of 20 μL, and a mixture having the composition shown in Table 3 was used as feedstock.The feedstock was fed to the reactor at a rate of 10 mL/h, concentrated (96percent) sulfuric acid was fed at a rate of 1.1 μL/h, which corresponded to a concentration of 0.02 wt. percent, and phenol for mixing with sulfuric acid was fed at a rate of 0.9 μL/h, which corresponded to a sulfuric acid/phenol ratio of 2:1. The mixture of phenol and sulfuric acid was held for 600 minutes at a temperature of 20° C. The circulation rate of the reaction mixture was 200 mL/h, and the temperature in the reactor was 70° C. As used herein, concentrated sulfuric acid means "commercially available usual sulfuric acid", which generally means about 93 to 96percent sulfuric acid (H2SO4). With sulfuric acid, phenol in water, T= 70 °C , Product distribution / selectivity Patent; Nelson, Mark; Sederel, Willem Lodewyk; Dyckman, Arkady Samuilovich; Grebenshchikov, Ilya Nikolaevich; Pinson, Viktor Vladimirovich; Zinenkov, Andrey Vladimirovich; US2008/214872; (2008); (A1) English View in Reaxys 6 :Example 6 (Comparative Example)The CHP cleavage reaction was carried out using the same equipment as in Example 1, but the feed of composition presented in Table 7 was used. CHP feed was pumped at rate of 26 ml/hr, and the sulfuric acid rate was 4 μL/h. Circulation rate and temperature regime used were the same as presented in Example 1.Reaction product discharged form the first stage reactor was passed to the second stage reactor together with a 5percent ammonia solution in water fed at rate of 8 μL/h. The composition of reaction mixture produced is presented in Table 8. Stage 1: With sulfuric acid in water, T= 40 - 125 °C

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Stage 2: With ammonia in water, T= 125 °C , Product distribution / selectivity Patent; Nelson, Mark; Sederel, Willem Lodewyk; Dyckman, Arkady Samuilovich; Grebenshchikov, Ilya Nikolaevich; Pinson, Viktor Vladimirovich; Zinenkov, Andrey Vladimirovich; US2008/214873; (2008); (A1) English View in Reaxys

OH O

Rx-ID: 29443976 View in Reaxys 15/41 Yield

Conditions & References

72 %, 23 %

With pentafluorophenyldihydroxyborane in toluene, Time= 16h, Reflux, Molecular sieve, Friedel-Crafts arylation McCubbin, J. Adam; Krokhin, Oleg V.; Tetrahedron Letters; vol. 51; nb. 18; (2010); p. 2447 - 2449 View in Reaxys

Rx-ID: 2011787 View in Reaxys 16/41 Yield

Conditions & References

60 %, 23 %

With phosphoric acid, acetic anhydride, Time= 48h, Ambient temperature Gurudutt, K. N.; Rao, L. Jagan Mohan; Rao, Sanjay; Srinivas, P.; Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry; vol. 32; nb. 4; (1993); p. 468 - 470 View in Reaxys

31 %, 45 %

With 1,3,2-benzodithiazole 1,1,3,3-tetraoxide, acetic anhydride, T= 20 °C Barbero, Margherita; Cadamuro, Silvano; Dughera, Stefano; Venturello, Paolo; Synthesis; nb. 22; (2008); p. 3625 - 3632 View in Reaxys

Rx-ID: 23426134 View in Reaxys 17/41 Yield

Conditions & References II.B.i :The 6-20 mesh particles of reduced T-366 catalyst, prepared by the procedure of Illustrative Embodiment II (A) (i), were loaded into the reflux zone of a thick walled 31 cm long Vigreux column with an internal diameter of 1.5 cm while inside a nitrogen filled glove box. A small, piece of glass wool was used to support the catalyst particles. The column was attached to a thick walled 250 ml round bottom flask which served as the bottom segment of the reactor for catalytic distillation. Hydrogen gas was added via a regulator to the apparatus to maintain a pressure between 1 and 10 bar. The flow rate was adjusted to maintain twice the amount of hydrogen required for the reaction stoichiometry. 50 grams of 2-phenyl-2-propanol (cumyl alcohol) from Avacado Chemical was added to the 250 mL flask which contained a magnetic stir bar at the bottom of the round bottom flask. The flask containing the cumyl alcohol was lowered into a heater and then the temperature was raised until the liquid refluxed in the Vigreux column containing the catalyst. Lower boiling cumene and water were distilled out from the top of the column. Additional cumyl alcohol was continually added with a slight molar excess of hydrogen to replace the amount of cumyl alcohol that was converted to cumene and distilled off. The cumene product easily separated from the denser water phase. It was optionally dried further with 3A molecular sieves. The results are provided in TABLE 2 below. As shown, the top product stream produced, (after removal of the water), had a purity of cumene of >99.5 wt. percent. No measurable cumyl

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alcohol (<0. 1 wt. percent) was found in the cumene product. When desired, the bottoms can be removed, optionally diluted with cumene and sent to a fixed bed hydrogenation reactor to make additional cumene. With hydrogen, hydrogenated copper on silica (T-366), p= 750.075 - 7500.75Torr , Product distribution / selectivity Patent; SHELL OIL COMPANY; WO2005/5402; (2005); (A2) English View in Reaxys

Rx-ID: 2011788 View in Reaxys 18/41 Yield

Conditions & References

39 %

With Lawesson's reagent in toluene, Time= 3h, Heating Nishio, Takehiko; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 10; (1993); p. 1113 - 1118 View in Reaxys

39 %

With Lawesson's reagent in toluene, Time= 3h, Heating Nishio, Takehiko; Journal of the Chemical Society, Chemical Communications; nb. 4; (1989); p. 205 - 206 View in Reaxys

Rx-ID: 10289693 View in Reaxys 19/41 Yield

Conditions & References With .alpha.,.alpha.,.alpha.-trichloroacetamide, triphenylphosphine in dichloromethane, Time= 0.25h, T= 30 °C Pluempanupat, Wanchai; Chavasiri, Warinthorn; Tetrahedron Letters; vol. 47; nb. 38; (2006); p. 6821 - 6823 View in Reaxys

Rx-ID: 2011785 View in Reaxys 20/41 Yield 28 %, 57 %

Conditions & References With triphenyl phosphite, tetraethylammonium bromide in acetonitrile, constant current electrolysis, 25 mA Maeda, Hatsuo; Maki, Toshihide; Eguchi, Kaoru; Koide, Takashi; Ohmori, Hidenobu; Tetrahedron Letters; vol. 35; nb. 24; (1994); p. 4129 - 4132 View in Reaxys

Rx-ID: 27897449 View in Reaxys 21/41

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Yield

Conditions & References 3 :Example 1; Decomposition of cumene hydroperoxide was carried out on a pilot unit in the form of a reactor with a volume of 12 mL, equipped with a circulation loop to mix the reaction mass and a water jacket to maintain the assigned temperature. To prepare the catalyst, a reactor with a volume of 10 μL was used, and sulfuric acid and phenol were fed by pumps to the reactor. Catalyst and feedstock were fed to the stream of reaction mass at the input to the reactor. The composition of the feedstock is shown in Table 1. Sulfuric acid was also fed to the catalyst synthesis reactor at a rate of 3 μL/h, phenol was fed at a rate of 6 μL/h, which corresponds to a concentration in the reaction medium of 0.02 wt. percent, and the holding time in the reactor was 70 minutes at a temperature of 45° C. The rate at which the feedstock was fed to the CHP decomposition reactor was 27 mL/h. The rate of circulation of the reaction mass was 500 mL/h. The temperature in the reactor was maintained at 75° C. by supplying a heat transfer agent of the corresponding temperature to the jacket of the reactor.The stream emerging from the CHP decomposition reactor was cooled to room temperature and analyzed by GC. The composition of the reaction mass of CHP decomposition is shown in Table 2.; Example 2; CHP decomposition was carried out in the same equipment as in Example 1, but the reactor for synthesis of the catalytic system had a volume of 20 μL, and a mixture having the composition shown in Table 3 was used as feedstock.The feedstock was fed to the reactor at a rate of 10 mL/h, concentrated (96percent) sulfuric acid was fed at a rate of 1.1 μL/h, which corresponded to a concentration of 0.02 wt. percent, and phenol for mixing with sulfuric acid was fed at a rate of 0.9 μL/h, which corresponded to a sulfuric acid/phenol ratio of 2:1. The mixture of phenol and sulfuric acid was held for 600 minutes at a temperature of 20° C. The circulation rate of the reaction mixture was 200 mL/h, and the temperature in the reactor was 70° C. As used herein, concentrated sulfuric acid means "commercially available usual sulfuric acid", which generally means about 93 to 96percent sulfuric acid (H2SO4). With sulfuric acid, sulfur trioxide, phenol, T= 70 - 75 °C , Product distribution / selectivity Patent; Nelson, Mark; Sederel, Willem Lodewyk; Dyckman, Arkady Samuilovich; Grebenshchikov, Ilya Nikolaevich; Pinson, Viktor Vladimirovich; Zinenkov, Andrey Vladimirovich; US2008/214872; (2008); (A1) English View in Reaxys 2; 5 :Example 2; Decomposition of CHP was carried out in the same equipment as in Example 1, and a mixture having the composition shown in Table 3 was used as feedstock.The feedstock was supplied to the reactor at a rate of 10 mL/h, and concentrated (96percent) sulfuric acid was fed at a rate of 0.55 μL/h, which corresponded to a concentration of 0.009 wt. percent, and phenol for mixing with sulfuric was supplied at a rate of 0.45 μL/h, which corresponded to a sulfuric acid/phenol ratio of 2:1. The mixture of phenol and sulfuric acid was held for 600 minutes at a temperature of 20° C. The circulation rate of the reaction mass was 200 mL/h. The reaction mass emerging from the first stage reactor was mixed with acetone supplied at a rate of 3 mL/h, and was fed to the second stage reactor. The temperature was 50° C. in the first stage reactor, and 140° C. in the second stage reactor. Table 4 shows the composition of the reaction mass resulting from the CHP decomposition.; Example 5; Decomposition of CHP was carried out in the same equipment as in Example 1, except that a mixture having the composition shown in Table 5 was used as feedstock.The feedstock was fed to the reactor at a rate of 25 mL/h, concentrated (96percent) sulfuric acid was fed at a rate of 1.3 μL/h, which corresponded to a concentration of 0.009 wt. percent, and phenol for mixing with sulfuric acid was fed at a rate of 3.4 μL/h, (which corresponded to a sulfuric acid/phenol ratio of 1:1.5). The mixture of phenol and sulfuric acid were held for 140 minutes at a temperature of 42° C. The circulation rate of the reaction mass was 200 mL/h. The reaction mass emerging from the first stage reactor was mixed with acetone fed at a rate of 11 mL/h, and water fed at a rate of 0.2 mL/h. The obtained mixture was fed to the second stage reactor. The temperature was 40° C. in the first stage reactor, and 90° C. in the second stage reactor. The composition of the reaction mass resulting from the CHP decomposition is shown in Table 6. With sulfuric acid, phenol in water, T= 40 - 140 °C , Product distribution / selectivity Patent; Nelson, Mark; Sederel, Willem Lodewyk; Dyckman, Arkady Samuilovich; Grebenshchikov, Ilya Nikolaevich; Pinson, Viktor Vladimirovich; Zinenkov, Andrey Vladimirovich; US2008/214873; (2008); (A1) English View in Reaxys 3 :Example 3; Decomposition of CHP was carried out in the same equipment and under the same conditions as in Example 2, except that 0.3 μL/h of 30percent fuming sulfuric acid (oleum) was fed to the reactor, and phenol was fed at a rate of 600 μL/h (the ratio in terms of sulfuric acid to phenol in this Example was 1:1000) to prepare the catalyst. The residence time of the mixture in the reactor was 1 minute at a temperature of 80° C. Table 4 shows the composition of the reaction mass resulting from the CHP decomposition. With sulfuric acid, sulfur trioxide, phenol, T= 50 - 140 °C , Product distribution / selectivity Patent; Nelson, Mark; Sederel, Willem Lodewyk; Dyckman, Arkady Samuilovich; Grebenshchikov, Ilya Nikolaevich; Pinson, Viktor Vladimirovich; Zinenkov, Andrey Vladimirovich; US2008/214873; (2008); (A1) English

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View in Reaxys 2 2H

2 2H

2H 2

OH2 2H H 2H

2 2H

Rx-ID: 35351230 View in Reaxys 22/41 Yield

Conditions & References With Burgess Reagent in toluene, T= 50 °C , Inert atmosphere, Schlenk technique Vyas, Devendra J.; Larionov, Evgeny; Besnard, Celine; Guenee, Laure; Mazet, Clement; Journal of the American Chemical Society; vol. 135; nb. 16; (2013); p. 6177 - 6183 View in Reaxys

Rx-ID: 31323241 View in Reaxys 23/41 Yield

Conditions & References With dihydrogen peroxide in water, acetonitrile, Time= 24h, T= 80 °C Estrada, Ana C.; Simoes, Mario M. Q.; Santos, Isabel C. M. S.; Neves, M. Graca P. M. S.; Cavaleiro, Jose A. S.; Cavaleiro, Ana M. V.; Monatshefte fur Chemie; vol. 141; nb. 11; (2010); p. 1223 - 1235 View in Reaxys

Rx-ID: 32799224 View in Reaxys 24/41 Yield 62 %Spectr.

Conditions & References Stage 1: With triethylamine tris(hydrogen fluoride), triethylamine in ethyl acetate, Time= 0.0833333h, T= 5 - 23 °C Stage 2: With TFFH in ethyl acetate, Time= 2h, T= 60 °C Bellavance, Gabriel; Dube, Pascal; Nguyen, Bao; Synlett; nb. 4; (2012); p. 569 - 572 View in Reaxys

HO O

Rx-ID: 27897450 View in Reaxys 25/41 Yield

Conditions & References 1 :Example 1; Decomposition of cumene hydroperoxide was carried out on a pilot unit in the form of a reactor with a volume of 12 mL, equipped with a circulation loop to mix the reaction mass and a water jacket to maintain the assigned temperature. To prepare the catalyst, a reactor with a volume of 10 μL was used, and sulfuric acid and phenol were fed by pumps to the reactor. Catalyst and feedstock were fed to the stream of reaction mass at the input to the reactor. The composition of the feedstock is shown in Table 1. Sulfuric acid was also fed to the catalyst synthesis reactor at a rate of 3 μL/h, phenol was fed at a rate of 6 μL/h, which corresponds to a concentration in the reaction medium of 0.02 wt. percent, and the holding time in the reactor was 70 minutes at a temperature of 45° C. The rate at which the feedstock was fed to the CHP decomposition reactor was 27 mL/h. The rate of circulation of the reaction

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mass was 500 mL/h. The temperature in the reactor was maintained at 75° C. by supplying a heat transfer agent of the corresponding temperature to the jacket of the reactor.The stream emerging from the CHP decomposition reactor was cooled to room temperature and analyzed by GC. The composition of the reaction mass of CHP decomposition is shown in Table 2. With sulfuric acid, phenol in water, T= 75 °C , Product distribution / selectivity Patent; Nelson, Mark; Sederel, Willem Lodewyk; Dyckman, Arkady Samuilovich; Grebenshchikov, Ilya Nikolaevich; Pinson, Viktor Vladimirovich; Zinenkov, Andrey Vladimirovich; US2008/214872; (2008); (A1) English View in Reaxys 5 :Example 5 (Comparative Example); The CHP cleavage reaction was carried out essentially the same as in Example 1, but in this case the feed of composition used was as presented in Table 5. Concentrated sulfuric acid catalyst was fed at a rate of 5 μL/h directly to the cleavage reactor. The produced reaction mixture was analyzed and the final composition is presented in Table 6. With sulfuric acid in water, T= 75 °C , Product distribution / selectivity Patent; Nelson, Mark; Sederel, Willem Lodewyk; Dyckman, Arkady Samuilovich; Grebenshchikov, Ilya Nikolaevich; Pinson, Viktor Vladimirovich; Zinenkov, Andrey Vladimirovich; US2008/214872; (2008); (A1) English View in Reaxys

Rx-ID: 27897453 View in Reaxys 26/41 Yield

Conditions & References 4 :Example 4; Decomposition of CHP was carried out in the same equipment and under the same conditions as in Example 1, but 75percent sulfuric acid was supplied to the reactor at a rate of 2 μL/h, and phenol was supplied at a rate of 5 μL/h (the ratio in terms of sulfuric acid to phenol was 1:2). The residence time of the mixture in the reactor was about 80 minutes at a temperature of 60° C. The composition of the reaction mass is shown in Table 4. With sulfuric acid, phenol in water, T= 40 - 125 °C , Product distribution / selectivity Patent; Nelson, Mark; Sederel, Willem Lodewyk; Dyckman, Arkady Samuilovich; Grebenshchikov, Ilya Nikolaevich; Pinson, Viktor Vladimirovich; Zinenkov, Andrey Vladimirovich; US2008/214873; (2008); (A1) English View in Reaxys

O O

Rx-ID: 2346793 View in Reaxys 27/41 Yield 35 %, 40 %, 10 %

Conditions & References With cobalt(II) chloride in acetonitrile, Time= 8h, T= 25 °C , other tertiary alcohols, other time, temperature, Product distribution, Mechanism Iqbal, Javed; Srivastava, Rajiv Ranjan; Journal of Organic Chemistry; vol. 57; nb. 7; (1992); p. 2001 - 2007 View in Reaxys

40 %, 10 %, 35 %

With cobalt(II) chloride in acetonitrile, Time= 8h, T= 25 °C Iqbal, Javed; Srivastava, Rajiv Ranjan; Journal of Organic Chemistry; vol. 57; nb. 7; (1992); p. 2001 - 2007 View in Reaxys

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35 %, 40 %, 10 %

With cobalt(II) chloride in acetonitrile, Time= 8h, T= 25 °C Iqbal, Javed; Srivastava, Rajiv Ranjan; Journal of Organic Chemistry; vol. 57; nb. 7; (1992); p. 2001 - 2007 View in Reaxys

Rx-ID: 27897452 View in Reaxys 28/41 Yield

Conditions & References 4 :Example 1; Decomposition of cumene hydroperoxide was carried out on a pilot unit in the form of a reactor with a volume of 12 mL, equipped with a circulation loop to mix the reaction mass and a water jacket to maintain the assigned temperature. To prepare the catalyst, a reactor with a volume of 10 μL was used, and sulfuric acid and phenol were fed by pumps to the reactor. Catalyst and feedstock were fed to the stream of reaction mass at the input to the reactor. The composition of the feedstock is shown in Table 1. Sulfuric acid was also fed to the catalyst synthesis reactor at a rate of 3 μL/h, phenol was fed at a rate of 6 μL/h, which corresponds to a concentration in the reaction medium of 0.02 wt. percent, and the holding time in the reactor was 70 minutes at a temperature of 45° C. The rate at which the feedstock was fed to the CHP decomposition reactor was 27 mL/h. The rate of circulation of the reaction mass was 500 mL/h. The temperature in the reactor was maintained at 75° C. by supplying a heat transfer agent of the corresponding temperature to the jacket of the reactor.The stream emerging from the CHP decomposition reactor was cooled to room temperature and analyzed by GC. The composition of the reaction mass of CHP decomposition is shown in Table 2.; Example 2; CHP decomposition was carried out in the same equipment as in Example 1, but the reactor for synthesis of the catalytic system had a volume of 20 μL, and a mixture having the composition shown in Table 3 was used as feedstock.The feedstock was fed to the reactor at a rate of 10 mL/h, concentrated (96percent) sulfuric acid was fed at a rate of 1.1 μL/h, which corresponded to a concentration of 0.02 wt. percent, and phenol for mixing with sulfuric acid was fed at a rate of 0.9 μL/h, which corresponded to a sulfuric acid/phenol ratio of 2:1. The mixture of phenol and sulfuric acid was held for 600 minutes at a temperature of 20° C. The circulation rate of the reaction mixture was 200 mL/h, and the temperature in the reactor was 70° C. As used herein, concentrated sulfuric acid means "commercially available usual sulfuric acid", which generally means about 93 to 96percent sulfuric acid (H2SO4). With sulfuric acid, phenol in water, T= 85 °C , Product distribution / selectivity Patent; Nelson, Mark; Sederel, Willem Lodewyk; Dyckman, Arkady Samuilovich; Grebenshchikov, Ilya Nikolaevich; Pinson, Viktor Vladimirovich; Zinenkov, Andrey Vladimirovich; US2008/214872; (2008); (A1) English View in Reaxys

HO O

Rx-ID: 27897454 View in Reaxys 29/41 Yield

Conditions & References 1 :Example 1; Decomposition of cumene hydroperoxide was carried out on a pilot unit consisting of two reactors: the first stage was a CHP decomposition reactor that had a volume of 12 mL and was equipped with a circulation loop, and the second stage reactor was a displacement reactor that had a volume of 7 mL. The reaction mass from the first stage reactor was partially fed to the second reactor and partially returned to the input of the first reactor, thus

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accomplishing its circulation. Catalyst and feedstock, the composition of which is shown in Table 1, were fed to the stream of reaction mass at the input to the first stage reactor. The catalyst was prepared by mixing concentrated sulfuric acid with phenol, which were fed by two pumps into a constant-temperature reactor with a capacity of 10 μL, from which the mixture was directed to the CHP decomposition reactor. The feedstock having the composition shown in Table 1, as well as a catalyst obtained directly by mixing concentrated sulfuric acid at a rate of 1 μL/h and phenol at a rate of 9 μL/h (ratio 1:5), were fed to the CHP decomposition reactor, and the mixture was kept for 60 minutes at a temperature of 50° C. As used herein, concentrated sulfuric acid means "commercially available usual sulfuric acid", which generally means about 93 to 96percent sulfuric acid (H2SO4). This feed corresponds to a sulfuric acid concentration of 0.007 wt. percent in the reaction medium. The rate of circulation of the reaction mass was 500 mL/h. The temperature in the reactor was kept at a level of 40° C. by supplying a heat transfer agent of the corresponding temperature to the jacket of the reactor.The stream emerging from the first stage reactor was diluted with acetone supplied at a rate of 8 mL/h, and was fed to the second stage reactor heated to a temperature of 125° C. The stream emerging from the second stage reactor was cooled and analyzed by GC. The composition of the reaction mass of CHP decomposition is shown in Table 2. With sulfuric acid, phenol in water, T= 40 - 125 °C , Product distribution / selectivity Patent; Nelson, Mark; Sederel, Willem Lodewyk; Dyckman, Arkady Samuilovich; Grebenshchikov, Ilya Nikolaevich; Pinson, Viktor Vladimirovich; Zinenkov, Andrey Vladimirovich; US2008/214873; (2008); (A1) English View in Reaxys

Cl OH

Cl Cl

O HN

N H

O O

Rx-ID: 39191784 View in Reaxys 30/41 Yield

Conditions & References With dichloro bis(acetonitrile) palladium(II), p-benozquinone in acetone, Time= 18h, T= 20 °C , Solvent Dong, Jia Jia; Harvey, Emma C.; Faans-Mastral, Martn; Browne, Wesley R.; Feringa, Ben L.; Journal of the American Chemical Society; vol. 136; nb. 49; (2014); p. 17302 - 17307 View in Reaxys

Rx-ID: 33242722 View in Reaxys 31/41 Yield

Conditions & References 1 :[Examples 1 and 2] Alpha methyl styrene was prepared according to the process flow diagram ofFig. 2. First, oxidation of cumene was progressed with an oxidizer under the following conditions using 3 oxidation reactors in a phenol process to prepare a stream including cumene hydroperoxide (CHP) of concentration of 25 wtpercent. (1) Condition of introducing first oxidizer supply (CHP 0.4percent + cumene 99.6percent) 1 ml/min, 02: 100 ml/min, pressure: 3bar, reaction temperature: 100 °C (2) Condition of introducing second oxidizer supply (CHP 8.42percent + cumene 91.58percent) 1 ml/min, 02: 100 ml/min, pressure:3bar, reaction temperature: 96 °C (3) Condition of introducing third oxidizer supply (CHP 16.27percent + cumene 83.73percent) 1 ml/min, 02: 100 ml/min, pressure: 3bar, reaction temperature: 94 °C The concentration of CHP stream was changed from 8.4 to 24 wtpercent while passing through 3 oxidation reactors as shown in the following Table 1. Then, 25 wtpercent of the stream of low concentration was separated and transferred to a receiver (20), and then, supplied to a catalytic hydrogenation reactor (30). The hydrogenation reactor was filled with a catalyst Pd/C, hydrogen was introduced and the reaction was progressed while maintaining internal temperature. And, the reactant of cumene hydroperoxide stream of 25 wtpercent concentration was introduced top-down of the reactor using a pressurization pump. The hydrogenation reaction was progressed under conditions of 150 g of cumene hydroperoxide (CHP) of 25 wtpercent concentration, 1 g of 1 wtpercent Pd/C, and hydrogen flow rate of 150 cc/min. And, the mole ratio of the cumene hydroperoxide stream and the introduced hydrogen was maintained 1 :8. The hydrogen reaction was progressed respectively for 7 hours and 3 hours in Examples 1 and 2. As the result, final product with cumene hydroperoxide (CHP) conversion rate of 99.97percent, CA increase rate of 960.5percent, and CA concentration of 25percent was obtained. After the reaction was completed, conversion rate of cumene hydroperoxied into cumyl alcohol was analyzed with liquid chromatography, and the result was

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shown in Table 2. After the hydrogenation reaction is completed, prepared cumyl alcohol is supplied to the receiver (20), and transferred to the stripper (40). Thereby, the stripper (40) is filled with a mixture of cumyl alcohol obtained by the hydrogenation reaction, and a stream including cumyl alcohol and cumene hydroperoxide which are not used in the hydrogen reaction. Then, the mixture is concentrated in the stripper (40), passed through a receiver (50) and transferred to a cleavage reactor (60), and the remainder is directly transferred to the cleavage reactor. And then, an acid catalyst is introduced in the cleavage reactor (60), and the mixture is continuously dehydrated so that the acid catalyst decomposes cumene hydroperoxide into phenol and acetone, and dehydrates cumyl alcohol into AMS. Into the cleavage reactor, 100 g of feedstock (CHP 72 wtpercent, CA 8 wtpercent, cumene 20 wtpercent) and 1 g of H2S04 were introduced to progress the reaction. And, the reaction temperature was maintained 65 °C , and raised to 1 10°C after conversion until the concentration of CHP became less than 1percent, so as to convert CA into AMS. The mixture of phenol, acetone and AMS produced in the cleavage reactor (60) was transferred to a neutralizer reactor (70), and a neutralization agent was introduced to progress a neutralization reaction. After neutralization, the product was transferred to a distillation reactor (80), and separated into phenol, AMS and acetone through distillation. By the above reaction, yield for conversion from CHP into phenol was 99.36percent, yield for conversion from CHP into aceton was 98.30percent, and yield for conversion from CA into AMS was 82.45percent. [Table 1 ]The above Table 1 shows that most of CHP was decomposed into phenol and acetone and the concentration decreased from 82 wtpercent to 1 wtpercent in the 1st cleavage reactor, and 1 wtpercent of CHP decreased to 1 wtpercent or less in the 2nd cleavage reactor. With sulfuric acid, T= 65 - 100 °C , Product distribution / selectivity Patent; LG CHEM, LTD.; HA, Seung-Back; YOO, Suk-Joon; CHO, Dong-Hyun; WO2012/74194; (2012); (A2) English View in Reaxys

OH O

Rx-ID: 2011782 View in Reaxys 32/41 Yield

Conditions & References With tris(triphenylphosphine)ruthenium(II) chloride in various solvent(s), Time= 3h, T= 180 °C , Product distribution Pri-Bar, Ilan; Buchman, Ouri; Schumann, Hebert; Kroth, Heinz J.; Blum, Jochanan; Journal of Organic Chemistry; vol. 45; nb. 22; (1980); p. 4418 - 4428 View in Reaxys With 9,10-anthracenedicarbonitrile, benzyl-phenylsulphide in acetonitrile-D3, T= 40 °C , Irradiation, photoinduced oxidation of benzyl phenyl sulfides promoted by 9,10-dicyanoanthracene; stability of photoproducts or possible primary photoproducts, Product distribution Baciocchi, Enrico; Crescenzi, Cristina; Lanzalunga, Osvaldo; Tetrahedron; vol. 53; nb. 12; (1997); p. 4469 4478 View in Reaxys

Rx-ID: 31323243 View in Reaxys 33/41 Yield

Conditions & References Reaction Steps: 2 1: dihydrogen peroxide / water; acetonitrile / 24 h / 80 °C 2: dihydrogen peroxide / water; acetonitrile / 24 h / 80 °C With dihydrogen peroxide in water, acetonitrile Estrada, Ana C.; Simoes, Mario M. Q.; Santos, Isabel C. M. S.; Neves, M. Graca P. M. S.; Cavaleiro, Jose A. S.; Cavaleiro, Ana M. V.; Monatshefte fur Chemie; vol. 141; nb. 11; (2010); p. 1223 - 1235 View in Reaxys

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Rx-ID: 10199107 View in Reaxys 34/41 Yield

Conditions & References With (CO)4(palladium)4(acetate)4, Time= 2h, T= 60 °C , Title compound not separated from byproducts Stolarov; Dobrokhotova; Kryukova; Kozitsyna; Gekhman; Vargaftik; Moiseev; Russian Chemical Bulletin; vol. 54; nb. 3; (2005); p. 803 - 806 View in Reaxys

O O

N N

O O

Rx-ID: 1867208 View in Reaxys 35/41 Yield

Conditions & References in dichloromethane, Time= 4h, Yield given Maslak, Przemyslaw; Chapman, William H.; Journal of Organic Chemistry; vol. 55; nb. 26; (1990); p. 6334 - 6347 View in Reaxys

infusorial earht

Rx-ID: 7449778 View in Reaxys 36/41 Yield

Conditions & References T= 300 - 400 °C , bei der Destillation Ramart; Amagat; Annales de Chimie (Cachan, France); vol. <10> 8; (1927); p. 295; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 182; (1926); p. 1343 View in Reaxys

copper

H20 Rx-ID: 7454258 View in Reaxys 37/41

Yield

Conditions & References T= 250 °C Tiffeneau; Annales de Chimie (Cachan, France); vol. <8>10; (1907); p. 190; Annales de Chimie (Cachan, France); vol. <8>11; (1907); p. 144 View in Reaxys

H20 Rx-ID: 7454254 View in Reaxys 38/41

Yield

Conditions & References T= 100 °C Klages; Chemische Berichte; vol. 35; (1902); p. 2649; Chemische Berichte; vol. 39; (1906); p. 2591

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View in Reaxys

H20

acidic sulfate potassium

Rx-ID: 7454257 View in Reaxys 39/41 Yield

Conditions & References Matsubara; Perkin; Journal of the Chemical Society; vol. 87; (1905); p. 671 View in Reaxys

OH O

H20

Rx-ID: 7454255 View in Reaxys 40/41 Yield

Conditions & References Tiffeneau; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 134; (1902); p. 846; Annales de Chimie (Cachan, France); vol. <8> 10; (1907); p. 166 View in Reaxys

H20 Rx-ID: 7454256 View in Reaxys 41/41

Yield

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