5-(Chloromethyl)-1,3-benzodioxole [C8H7ClO2]

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14 reactions in Reaxys

2018-02-09 04h:27m:17s (EST)

O

1. Query O

Search as: As drawn

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O O

Cl

O O

O

Rx-ID: 23314185 View in Reaxys 1/14 Yield 80 %

Conditions & References With hydrogenchloride in water, T= 20 °C Zhang, Bingyu; Lv, Chao; Li, Weibo; Cui, Zhiming; Chen, Dongdong; Cao, Fangjun; Miao, Fang; Zhou, Le; Chemical and Pharmaceutical Bulletin; vol. 63; nb. 4; (2015); p. 255 - 262 View in Reaxys

69.8 %

3.1 : 1, Preparation of pepper base chlorine 100g of 1,2-methyleneoxy benzene, 40g paraformaldehyde into 500ml three reaction flask, at room temperature (20-25 ° C) was stirred and 275ml hydrochloric acid was added dropwise over about 55 minutes. Dripped at room temperature for 4 hours, Add dichloromethane extraction 2 times, Each 100ml, combined dichloromethane, Add 20g calcium chloride and dry overnight, filter, The dichloromethane was removed by rotary evaporation under reduced pressure at 40 ° C. Oil pump high vacuum distillation, product 74.2g, GC purity 93.1percent, the main peak after the impurity content of 0.44percent Yield 70.3percent. Recycling pepper ring 26.2g, purity 94.1percent, for the application. With hydrogenchloride in water, Time= 4.91667h, T= 20 - 25 °C , Concentration Patent; Taicang Hongshan Environmental Protection Technology Co., Ltd.; Liu Lu; (9 pag.); CN107216318; (2017); (A) Chinese View in Reaxys

64.8 %

3.1 : 1. Preparation of piperonyl chloride 100 g of 1,2-methylenedioxybenzene and 40 g of paraformaldehyde were charged into 500 ml of a three-necked reaction flask, and the mixture was stirred at room temperature (20 to 25 degrees), 266 ml of hydrochloric acid was added dropwise, and the mixture was added dropwise for about 50 minutes, stirring at room temperature for 2 hours, adding dichloromethane extraction, each 100ml, combined, adding 20g of calcium chloride drying overnight, filtration, 40 degrees under pressure steam distillation to remove methylene chloride, oil pump high vacuum distillation, 73.7 g of product, 92.6percent of GC purity, 0.45percent of impurity content after main peak. Yield 64.8percent. With hydrogenchloride, Time= 2.83333h, T= 20 - 25 °C Patent; Suzhou Hongsen Pharmaceutical Co., Ltd.; Di, Jinxing; Fan, Chao; Lu, Hongbin; (6 pag.); CN106432212; (2017); (A) Chinese View in Reaxys

50.9 %

a :(a) Synthesis of chloromethyl-benzodioxole The following are introduced into a 2 litre flask : 82.9 g p-CH20 (96percent) (2.6 moles) 300 g 1, 3- benzodioxole (99.4percent) (2.4 moles) 540 ml of toluene 784 g HCI (37percent) (7.9 moles). The mixture is allowed to react for 4 hours under a head of N2, maintaining the temperature at 20-25°C with an ice bath. After separating the phases, a crude product of 818.0 g is obtained with the following composition: 1, 3-benzodioxole 15.6percent w/w (127.6 g) (1.05 moles) 5-chloromethyl-1, 3-benzodioxole 25.94percent w/w (212.19 g) (1.24 moles) Conversion of 1, 3-benzodioxole : 57.2percent Selectivity of 5-chloromethyl-1, 3-benzodioxole : 89.0percent Yield of 5-chloromethyl-1, 3-benzodioxole : 50.9percent With hydrogenchloride in water, toluene, Time= 4h, T= 20 - 25 °C , Conversion of starting material Patent; ENDURA S.P.A.; WO2005/42512; (2005); (A1) English View in Reaxys 1 :Reference Example 1Preparation of a Toluene Solution of Piperonyl Chloride; In a glass reaction vessel equipped with a thermometer, a temperature regulator, a dropping apparatus, and a stirrer were placed 4.89 kg (40 mol) of 1,2methylenedioxybenzene, 3.9 kg (42 mol) of toluene, 1.41 kg (43.2 mol) of paraformaldehyde, and 9.10 kg (90.8 mol) of a 36percent aqueous solution of hydrochloric acid, and 9.90 kg of a toluene solution of piperonyl chloride as a desired product was obtained in accordance with the method described in Non-Patent Literature 2. With hydrogenchloride in water, toluene, Industry scale Patent; Doi, Takashi; Yoshida, Yoshihiro; Douyama, Daisuke; Katsura, Ryousuke; Fujitsu, Satoru; Yasuda, Shinji; Kimura, Keisuke; Oomori, Kiyoshi; US2012/323021; (2012); (A1) English

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View in Reaxys 2 : Example 2: Synthesis of piperonal: Example 2: Synthesis of piperonal:Paraformaldehyde (180 g), 30percent hydrochloric acid (730 g), toluene (1 kg) and methylenedioxybenzene (488g) were charged into a 3 litre glass reactor. Hydrogen chloride gas was passed rapidly at about -10°C through the reaction medium for 5 to 10 hours. The GC content of the chloromethyl derivative was ~ 90percent at this stage. The aqueous portion was drained off and the organic portion containing MDB-CI was digested with hexamine (670 g) at about 80°C till the content of the chloromethyl derivative was less than 0.5percent by GC analysis. 50percent aqueous acetic acid (1.3 kg) was added to the resulting hexamine complex and the reaction mass was digested at about 80°C for 6 to 8 hours. The aqueous portion was drained off. The solvent was recovered, and the crude product was distilled to separate a fraction containing unreacted methylenedioxybenzene (25 g) and piperonal of purity greater than 95percent by GC analysis (380 g). With hydrogenchloride in toluene, T= -10 °C Patent; ANTHEA AROMATICS PRIVATE LIMITED; MOHAPATRA, Manoj Kumar; BENDAPUDI, Ramamohanrao; MENACHERRY, Paul Vincent; PAUL, Vincent; (31 pag.); WO2016/103058; (2016); (A1) English View in Reaxys 2 :To the 500 mL flask was added solvent carbon tetrachloride 200 ml, pepper ring 61 g (0.5 mol), 46.3 g (0.63 mol) of formaldehyde solution at a concentration of 40percent, 0.5 g of catalyst trimethyl dodecylammonium bromide, After stirring evenly, add the concentration 60 g (0.7 mol) of 36percent hydrochloric acid was added and the dropping time was controlled at 150 minutes,The reaction was carried out at 60 °C for 12 hours, Static, separation of the lower oil,A solution of piperonyl chloride carbon tetrachloride; With hydrogenchloride, dodecyltrimethylammonium bromide in tetrachloromethane, water, Time= 12h, T= 60 °C , Solvent Patent; Li, Dongfeng; (11 pag.); CN103936709; (2017); (B) Chinese View in Reaxys

HO

O

Cl

O

O O

Rx-ID: 129623 View in Reaxys 2/14 Yield 100 %

Conditions & References With 1,3,5-trichloro-2,4,6-triazine, dimethyl sulfoxide, Time= 0.333333h, T= 20 °C , chemoselective reaction Sun, Lili; Peng, Guisheng; Niu, Hongmei; Wang, Qiang; Li, Chunbao; Synthesis; nb. 24; (2008); p. 3919 - 3924; Art.No: F17308SS View in Reaxys

100 %

3.1 :Piperonyl alcohol (10 g, 65.7 mmol) was dissolved in benzene. Triethylamine (11 mNo., 78.8 mmol) and thionyl chloride (11 mNo., 131.4 mmol) were added dropwise thereto and was stirred for 24 hours at 0 °C . The reaction mixture was extracted with sodium bicarbonate and ethyl acetate, the organic layer was separated, and dried over anhydrous magnesium sulfate to obtain 5- chloromethyl benzo[1,3]dioxol (11.2 g, yield 100 percent). 1H NMR (200MHz, CDCl3) : No. 6.88-6.75 (m, 3H), 5.97 (s, 2H), 4.53 (s, 2H). With thionyl chloride, triethylamine in benzene, Time= 24h, T= 0 °C Patent; KOREA RESEARCH INSTITUTE OF CHEMICAL TECHNOLOGY; JEIL PHARM. CO., LTD.; KOREA RESEARCH INSTITUTE OF BIOSCIENCE AND BIOTECHNOLOGY; CJ CORP.; WO2005/100303; (2005); (A1) English View in Reaxys

98 %

With thionyl chloride in benzene Vinogradova, V. I.; Yunusov, M. S.; Kuchin, A. V.; Tolstikov, G. A.; Sagandykov, R. T.; et al.; Chemistry of Natural Compounds; vol. 26; nb. 1; (1990); p. 54 - 59; Khimiya Prirodnykh Soedinenii; nb. 1; (1990); p. 67 - 74 View in Reaxys

98 %

With hydrogenchloride, Time= 0.333333h

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Bourry, Anne; Akue-Gedu, Rufine; Rigo, Benoit; Henichart, Jean-Pierre; Sanz, Gerard; Couturier, Daniel; Journal of Heterocyclic Chemistry; vol. 40; nb. 6; (2003); p. 989 - 993 View in Reaxys 98 %

With phosphorus trichloride in dichloromethane, Time= 2.5h, T= 20 °C Marguerit, Melanie; Little, Gill; Wang, Yi; He, Linli; Allwein, Shawn; Reif, James; Rossi, Jason; Roemmele, Renee; Bakale, Roger; European Journal of Organic Chemistry; vol. 2015; nb. 36; (2015); p. 8003 - 8010 View in Reaxys

97 %

173 : Synthesis of Compound 173.2. Example 173 Synthesis of ethyl 1-(2H-1,3-benzodioxol-4-ylmethyl)-3-(2-hydroxyethyl)-5-methyl-2,4-dioxo-1H,2H,3H,4H-thieno[2,3d]pyrimidine-6-carboxylate (I-40) Synthesis of Compound 173.2. Into a 50-mL round-bottom flask, purged and maintained with an inert atmosphere of nitrogen, was placed 173.1 (400 mg, 2.63 mmol, 1.00 equiv), thionyl chloride (626 mg, 5.26 mmol, 2.00 equiv) and dichloromethane (20 mL). The resulting solution was stirred for 1 h at room temperature. The resulting mixture was concentrated under vacuum. This resulted in 460 mg (97percent) of 173.2 as a yellow oil. With thionyl chloride in dichloromethane, Time= 1h, T= 20 °C Patent; Nimbus Apollo, Inc.; Harriman, Geraldine C.; Masse, Craig E.; Harwood, James; Bhat, Sathesh; Greenwood, Jeremy Robert; US2013/123231; (2013); (A1) English View in Reaxys

95 %

With hydrogenchloride in chloroform, toluene, T= -5 °C Pelter, Andrew; Ward, Robert S.; Pritchard, Martyn C.; Kay, I. Trevor; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); (1988); p. 1615 - 1624 View in Reaxys

94 %

9.1 : Preparation of 5- (chloromethyl) benzo [d] [1,3] dioxole Piperenyl alcohol (2.00 g, 13.15 mmol) was added under argon atmosphere,And triethylamine (1.94 mL, 13.93 mmol)Was dissolved in dichloromethane (44 mL), Cooled to 0 [deg.] C and DCM (18 mL)Thionyl chloride (1.44 mL, 19.72 mmol) was added dropwise. The reaction solution was stirred at room temperature for 2 hours, and the completion of the reaction was confirmed by TLC (hexane: ethyl acetate = 2: 1). The reaction solution was cooled to 0 ° C, washed with distilled water (65 mL), a 2N aqueous solution of chloride chloride (10 mL) and saturated sodium hydrogencarbonate solution (40 mL), and the organic solvent layer extracted with dichloromethane (15 mL x 3) After washing with saturated solution (25 mL), the organic solvent layer was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure to remove the solvent. The concentrate was separated and purified by column chromatography (hexane: ethyl acetate = 3: 1) to obtain the title compound (2.11 g, 94percent yield). With thionyl chloride, triethylamine in dichloromethane, Time= 2h, T= 0 - 20 °C , Inert atmosphere Patent; Korea Institute of Science and Technology; Kum, Kyo Chang; Kim, Eun Kyung; Sau, Sun Hee; Lee, Jae Wook; Lee, Joo Hyun; Sin, Sang Chul; (39 pag.); KR2016/59366; (2016); (A) Korean View in Reaxys

87 %

With thionyl chloride, Time= 2.5h, T= 0 - 30 °C Porcal, Williams; Merlino, Alicia; Boiani, Mariana; Gerpe, Alejandra; Gonzalez, Mercedes; Cerecetto, Hugo; Organic Process Research and Development; vol. 12; nb. 2; (2008); p. 156 - 162 View in Reaxys

86 %

1.1 :<Example 1> Preparation of 1, 3-benzodioxol-5-ylmetl mlthyl sulfone; Step (1) : Preparation of 5-(chlorolllethyl)-1, 3-benzodioxol; 20 g of 1, 3-benzodioxol-5-yl methanol was dissolved in 50 ml of thionyl chloride at 0°C and stirred for 30 minutes, then reacted at 30°C for 2 hours. The reaction mixture was dried under reduced pressure, and then fractionated by column chromatography using ethyl acetate: n-hexane (1: 3), to give 19 g of the title compound of the following chemical formula 3 (Rf : 0.55, Yield: 86percent). [Chemical Formula 3] The compound was dissolved in CDC13 and TMS and then characterized by'H NMR spectroscopy. The result is as follows; IHNMR S : 4.53 (s, 2H), 5.98 (s, 2H), 6.75-6. 88 (m, 3H). With thionyl chloride, Time= 2.5h, T= 0 - 30 °C

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Patent; HAN, Sang Min; LEE, Myung Hee; CHOI, Won Chul; WO2005/70915; (2005); (A1) English View in Reaxys 80 %

With dimethyl sulfoxide, N-phenyl-benzimidoyl chloride in chloroform, Time= 6h, T= 20 °C Wang, Qiang; Xu, Jian; Xu, Zhou-Qing; Yan, Ji-Dan; Research on Chemical Intermediates; vol. 39; nb. 5; (2013); p. 2071 - 2076 View in Reaxys With hydrogenchloride, benzene, T= 0 °C Decker; Koch; Chemische Berichte; vol. 38; (1905); p. 1741 View in Reaxys With hydrogenchloride Tiffeneau; Bulletin de la Societe Chimique de France; vol. <4> 9; (1911); p. 932 View in Reaxys With hydrogenchloride, benzene Spaeth; Schmidt; Monatshefte fuer Chemie; vol. 53/54; (1929); p. 469 View in Reaxys With thionyl chloride Mannich; Walther; Archiv der Pharmazie (Weinheim, Germany); (1927); p. 7 View in Reaxys With pyridine, thionyl chloride, chloroform Schoepf; Salzer; Justus Liebigs Annalen der Chemie; vol. 544; (1944); p. 1,15 View in Reaxys With thionyl chloride, benzene Schultz; Arnold; Journal of the American Chemical Society; vol. 71; (1949); p. 1911,1913 View in Reaxys With tetrachloromethane, triphenylphosphine Mandai, Tadakatsu; Moriyama, Tadashi; Tsujimoto, Koichiro; Kawada, Mikio; Otera, Junzo; Tetrahedron Letters; vol. 27; nb. 5; (1986); p. 603 - 606 View in Reaxys With phosphorus pentachloride, calcium carbonate in diethyl ether, Time= 0.166667h, T= 0 °C Jaegfeldt, Hans; Kuwanw, Theodore; Johansson, Gillis; Journal of the American Chemical Society; vol. 105; nb. 7; (1983); p. 1805 - 1814 View in Reaxys With thionyl chloride in toluene, Time= 6h, Heating Mouysset; Bellan; Payard; Tisne-Versailles; Farmaco, Edizione Pratica; vol. 42; nb. 11; (1987); p. 805 - 813 View in Reaxys With thionyl chloride, polymer-bound Huenig base in diethyl ether, T= 0 °C Capraro, Hans-Georg; Bold, Guido; Faessler, Alexander; Cozens, Robert; Klimkait, Thomas; Lazdins, Janis; Mestan, Juergen; Poncioni, Bernard; Roesel, Johannes L.; Stover, David; Lang, Marc; Archiv der Pharmazie; vol. 329; nb. 6; (1996); p. 273 - 278 View in Reaxys With thionyl chloride in 1,4-dioxane, T= 20 °C Lisowski, Vincent; Enguehard, Cecile; Lancelot, Jean-Charles; Caignard, Daniel-Henri; Lambel, Stephanie; Leonce, Stephane; Pierre, Alain; Atassi, Ghanem; Renard, Pierre; Rault, Sylvain; Bioorganic and Medicinal Chemistry Letters; vol. 11; nb. 16; (2001); p. 2205 - 2208

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View in Reaxys 7.a : 1st Stage 1st Stage Preparation of Piperonyl Chloride Piperonyl alcohol (1 g; 6.57 mM) was dissolved in diethyl ether (10 ml), and to this was slowly added concentrated hydrochloric acid (3.81 ml). This was left to stir for 30 minutes. The excess solvent was removed to yield a colourless oil which crystallized at 4° C., (99percent). 1 H NMR: d: 4.8 (s,2H,CH ); 6.2(s,2H,OCH O); 7.0(m,3H, aromatics) 2 2 With hydrogenchloride in diethyl ether Patent; Newcastle University Ventures Limited; US5756510; (1998); (A1) English View in Reaxys a : a. a. 3,4-Methylenedioxybenzyl chloride 153.9 g (1.29 mols) of thionyl chloride are poured onto 65.6 g (0.431 mol) of 3,4-methylenedioxybenzyl alcohol. The mixture is stirred for 90 minutes at ambient temperature (15°-25° C.) and the excess thionyl chloride is then evaporated. The residue is taken up in dimethylformainde (DMF) and the latter is then evaporated. Finally, the residue is taken up in 500 ml of DMF (it is not necessary to isolate the 3,4-methylenedioxybenzyl chloride thus obtained). With thionyl chloride in N,N-dimethyl-formamide Patent; Societe Anonyme Dite: Laboratoire L. Lafon; US4128656; (1978); (A1) English View in Reaxys 4 : 3,4-Methylenedioxybenzyl chloride (16) 3,4-Methylenedioxybenzyl chloride (16) A solution of 3,4-methylenedioxybenzyl alcohol (15) (50 g, 328.62 mmol) in CH2Cl2 (50 ml) was cooled to 0° C. and SOCl2 (250 ml) added dropwise. The reaction mixture was stirred at 0° C. for 1 hour, at room temperature for 4 hours, then evaporated to dryness. The residue was purified by distillation under vacuum to give 3,4-methylenedioxybenzyl chloride (16) (49 g, 87percent). Rf 0.75 (CHCl3/EtOAc 20:1) With thionyl chloride in dichloromethane Patent; Bornaghi, Laurent; Dekany, Gyula; Drinnan, Nicholas Barry; Papageorgiou, John; West, Michael Leo; US2004/58888; (2004); (A1) English View in Reaxys With hydrogenchloride, Time= 1.5h, T= 0 - 20 °C Wei, Meng-Xue; Wang, Cheng-Tao; Du, Ji-Yuan; Qu, Hu; Yin, Pei-Rong; Bao, Xu; Ma, Xiao-Yan; Zhao, XianHe; Zhang, Guo-Biao; Fan, Chun-An; Chemistry - An Asian Journal; vol. 8; nb. 9; (2013); p. 1966 - 1971 View in Reaxys With thionyl chloride, Inert atmosphere Miyake, Yoshihiro; Ota, Shin-Ichi; Shibata, Masashi; Nakajima, Kazunari; Nishibayashi, Yoshiaki; Organic and Biomolecular Chemistry; vol. 12; nb. 30; (2014); p. 5594 - 5596 View in Reaxys With thionyl chloride, N,N-dimethyl-formamide in dichloromethane, T= 0 - 20 °C , Schlenk technique, Inert atmosphere Sun, Yan-Yan; Yi, Jun; Lu, Xi; Zhang, Zhen-Qi; Xiao, Bin; Fu, Yao; Chemical Communications; vol. 50; nb. 75; (2014); p. 11060 - 11062 View in Reaxys

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4.1.4 1-(Chloromethyl)-4-methoxybenzene (2c) General procedure: 4-Methoxybenzaldehyde (27g, 0.2mol) was dissolved in methanol (80mL) and water (20mL). To this mixture was added KBH4 (5g, 0.1mol) in batches, then stirred at room temperature for 2h. The pH was adjusted to 3 with 10percent HCl to quench the reaction and then the pH was adjusted to 8 with saturated sodium hydrogen carbonate solution. Volatiles were removed under reduced pressure, and then the residue was taken up with toluene and washed with water and brine. The organic phase was dried with MgSO4 and evaporated under reduced pressure. The crude 11c was added to thionyl chloride (50mL) and heated to reflux for 3h. Volatiles were removed under reduced pressure to afford 2c (28.5g, 89percent) as colorless oil. With pyridine, thionyl chloride in dichloromethane, Time= 3h Cai, Jin; Liu, Ligang; Hong, Kwon Ho; Wang, Peng; Li, Lushen; Cao, Meng; Sun, Chunlong; Wu, Xiaoqing; Zong, Xi; Chen, Junqing; Ji, Min; Bioorganic and Medicinal Chemistry; vol. 23; nb. 4; (2015); p. 657 - 667 View in Reaxys

O

Cl

O

Rx-ID: 22377185 View in Reaxys 3/14 Yield

Conditions & References Reaction Steps: 2 1: alcoholic NaOH-solution 2: benzene; hydrogen chloride / 0 °C With hydrogenchloride, sodium hydroxide, benzene Decker; Koch; Chemische Berichte; vol. 38; (1905); p. 1741 View in Reaxys Reaction Steps: 2 1: sodium tetrahydroborate / methanol / 0.5 h / 0 - 20 °C 2: hydrogenchloride / 1.5 h / 0 - 20 °C With hydrogenchloride, sodium tetrahydroborate in methanol Wei, Meng-Xue; Wang, Cheng-Tao; Du, Ji-Yuan; Qu, Hu; Yin, Pei-Rong; Bao, Xu; Ma, Xiao-Yan; Zhao, XianHe; Zhang, Guo-Biao; Fan, Chun-An; Chemistry - An Asian Journal; vol. 8; nb. 9; (2013); p. 1966 - 1971 View in Reaxys Reaction Steps: 2 1: potassium borohydride / water; methanol / 2 h / 20 °C 2: thionyl chloride; pyridine / dichloromethane / 3 h With pyridine, thionyl chloride, potassium borohydride in methanol, dichloromethane, water Cai, Jin; Liu, Ligang; Hong, Kwon Ho; Wang, Peng; Li, Lushen; Cao, Meng; Sun, Chunlong; Wu, Xiaoqing; Zong, Xi; Chen, Junqing; Ji, Min; Bioorganic and Medicinal Chemistry; vol. 23; nb. 4; (2015); p. 657 - 667 View in Reaxys Reaction Steps: 2 1: sodium tetrahydroborate / dichloromethane; methanol / 0.5 h / 20 °C 2: thionyl chloride / dichloromethane / 0.5 h / 20 °C With sodium tetrahydroborate, thionyl chloride in methanol, dichloromethane Patent; Southeast University; Chi, Jin; Ji, min; (19 pag.); CN103539760; (2016); (B) Chinese View in Reaxys

O O

Cl

O O

Rx-ID: 43705451 View in Reaxys 4/14 Yield 75.5 %

Conditions & References 4.2 : 3) Synthesis of 5-chloromethyl-1,3-benzodioxane 7

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5mL of thionyl chloride was added dropwise to the methylene chloride solution of the product of the previous step with stirring at room temperature.The mixture was stirred for 0.5 hour and then poured into 100 mL of ice water. The pH was adjusted to neutral with NaHC03, and the aqueous layer was separated. The organic layer was washed twice with saturated brine and dried over anhydrous magnesium sulfate. Filtration and concentration of a yellow oil, 4.5 g, 75.5percent yield in two steps. With thionyl chloride in dichloromethane, Time= 0.5h, T= 20 °C Patent; Southeast University; Chi, Jin; Ji, min; (19 pag.); CN103539760; (2016); (B) Chinese View in Reaxys

Si

O

Cl

O

HO

O

Rx-ID: 10545231 View in Reaxys 5/14 Yield

Conditions & References With potassium fluoride, chloro-trimethyl-silane in acetonitrile, Time= 0.0166667h, T= 22 °C Peng, Yu; Li, Wei-Dong Z.; Synlett; nb. 8; (2006); p. 1165 - 1168 View in Reaxys

O

Cl

O

HO

O

Rx-ID: 23332531 View in Reaxys 6/14 Yield

Conditions & References c :(c) Synthesis of piperonyl alcohol by hydrolysing piperonyl acetate 1.92 g of tetrabutylammonium chloride hydrate (98percent) (0.00677 moles) and 76.9 g NaOH (97percent) (1.9 moles) are added to the crude piperonyl acetate synthesis product of the previous synthesis, at ambient temperature. While adding the NaOH the temperature rises to 45-50°C. The temperature is brought to 80-85°C under agitation and N2 flow. The mixture is allowed to react for 2 hours under these conditions. After cooling, the mixture is filtered. The phases are separated and a crude product weighing 777.9 g is obtained, with the following composition: piperonyl alcohol 23.74percent w/w (184.67 g) (1.2 moles) 1, 3-benzodioxole 16.12percent w/w (125.4 g) (1.03 moles) Conversion of 5-chloromethyl-1, 3-benzodioxole : 100percent Yield of piperonyl alcohol relative to 5-chloromethyl-1, 3-benzodioxole : 97.6percent With sodium hydroxide, tetrabutyl-ammonium chloride in water, Time= 2h, T= 20 - 85 °C , Product distribution / selectivity Patent; ENDURA S.P.A.; WO2005/42512; (2005); (A1) English View in Reaxys

HO

O O

Cl

diisopropylaminomethylpolystyrene

O O

Rx-ID: 24654871 View in Reaxys 7/14 Yield

Conditions & References 44.a : 44a 44a 3,4-Methylenedioxybenzyl chloride 15.04 ml of thionyl chloride are added dropwise, at 0° C., over the space of 25 min and under argon, to 10.82 g of 3,4-methylenedioxybenzyl alcohol (Fluka, Buchs, Switzerland) and 48 g of diisopropylaminomethylpolystyrene (polyhunig base: polystyrene crosslinked with 2percent divinylbenzene, diisopropylaminomethylated; Fluka, Buchs, Switzerland) in 200 ml of abs. ether. After having been stirred at 0° C. for a further 1.5 h, the mixture is filtered with suction and the filtrate is concentrated on a RE and then under HV. The residue is purified by chromatography on silica gel (eluent: C), and the title compound thus obtained. TLC Rf (hexane:ethyl acetate, 4:1)=0.47; 1 H-NMR (200 MHz, CDCl3): 6.95-6.7(m, 3H), 5.97(s, 2H), 4.53(s, 2H).

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With thionyl chloride Patent; Ciba-Geigy Corporation; US5663200; (1997); (A1) English View in Reaxys

O

Cl

O

Rx-ID: 5435331 View in Reaxys 8/14 Yield

Conditions & References Stewart,F.H.C.; Australian Journal of Chemistry; vol. 24; (1971); p. 2193 - 2197 View in Reaxys Matsumoto; Chemical and pharmaceutical bulletin; vol. 15; nb. 12; (1967); p. 1990 - 1995 View in Reaxys Dallacker,F. et al.; Chemische Berichte; vol. 104; (1971); p. 2526 - 2533 View in Reaxys Birch,A.J. et al.; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); (1974); p. 2190 - 2194 View in Reaxys Gensler,W.J. et al.; Journal of Organic Chemistry; vol. 40; (1975); p. 733 - 739 View in Reaxys Yamada et al.; Chemical and Pharmaceutical Bulletin; vol. 10; (1962); p. 680,684 View in Reaxys

O

Cl

O

Rx-ID: 80600 View in Reaxys 9/14 Yield

Conditions & References With formaldehyd, zinc(II) chloride, Petroleum ether, Reagens 4: Chlorwasserstoff Schorygin et al.; Zhurnal Obshchei Khimii; vol. 8; (1938); p. 975,978; Chem. Zentralbl.; vol. 110; nb. I; (1939); p. 2178 View in Reaxys

O

Cl

H

O

H N

O

NH 2

O

E

Cl

O

Rx-ID: 5526134 View in Reaxys 10/14 Yield

Conditions & References Schorygin et al.; Zhurnal Obshchei Khimii; vol. 8; (1938); p. 975,978; Chem. Zentralbl.; vol. 110; nb. I; (1939); p. 2178 View in Reaxys

O O

Cl

O

bis-<benzo<1,3>dioxol-5-yl>-methane O

O

Rx-ID: 5726714 View in Reaxys 11/14 Yield

Conditions & References With hydrogenchloride, water, zinc(II) chloride, Petroleum ether Schorygin et al.; Zhurnal Obshchei Khimii; vol. 8; (1938); p. 975,978; Chem. Zentralbl.; vol. 110; nb. I; (1939); p. 2178 View in Reaxys

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HO

O

Cl

1,2-bis<2-(-p-toluenesulfonyloxy)ethoxy>amine

O

HO

Rx-ID: 22404384 View in Reaxys 12/14 Yield

Conditions & References Reaction Steps: 2 1: aq.-ethanolic NaOH-solution / 110 °C 2: petroleum ether; zinc chloride; water; hydrochloric acid With hydrogenchloride, sodium hydroxide, water, zinc(II) chloride, Petroleum ether Schorygin et al.; Zhurnal Obshchei Khimii; vol. 8; (1938); p. 975,978; Chem. Zentralbl.; vol. 110; nb. I; (1939); p. 2178 View in Reaxys Reaction Steps: 2 1: aq.-ethanolic NaOH-solution / 110 °C 2: paraformaldehyde; zinc chloride; petroleum ether / Reagens 4: Chlorwasserstoff With sodium hydroxide, formaldehyd, zinc(II) chloride, Petroleum ether Schorygin et al.; Zhurnal Obshchei Khimii; vol. 8; (1938); p. 975,978; Chem. Zentralbl.; vol. 110; nb. I; (1939); p. 2178 View in Reaxys

Cl

H

O

HO

Cl

O

Rx-ID: 5586705 View in Reaxys 13/14 Yield

Conditions & References Carre; Libermann; Bulletin de la Societe Chimique de France; vol. <5> 2; (1935); p. 291,294 View in Reaxys

Cl

H

O

HO

O

Cl

O

Rx-ID: 5435332 View in Reaxys 14/14 Yield

Conditions & References T= 0 °C Decker; Koch; Chemische Berichte; vol. 38; (1905); p. 1741 View in Reaxys

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