O-ethyl benzenecarbothioate

反応条件: temp:78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 21 parts of cyanamide and 83 parts of ethyl thiobenzoate are successively introduced into a solution of 12.5 parts of sodium in 260 parts of ethanol, and the mixture is refluxed for one hour at 78° C. It is then left to stand for 12 hours, 40 parts of chloroacetonitrile are added, and the reaction mixture is refluxed for one hour at 78° C. The product is precipitated by means of 300 parts of water, and filtered off. 78 parts of 2-phenyl-4-amino-5-cyano-thiazole (78% of theory) of melting point 178°-179° C. are obtained. It is then left the reaction mixture is refluxed for one hour at 78° C The product is precipitated by means of 300 parts of water filtered off

反応条件: temp:78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 21 parts of cyanamide and 83 parts of ethyl thiobenzoate are successively introduced into a solution of 12.5 parts of sodium in 260 parts of ethanol, and the mixture is refluxed for one hour at 78° C. It is then left to stand for 12 hours, 40 parts of chloroacetonitrile are added, and the reaction mixture is refluxed for one hour at 78° C. The product is precipitated by means of 300 parts of water, and filtered off. 78 parts of 2-phenyl-4-amino-5-cyano-thiazole (78% of theory) of melting point 178°-179° C. are obtained. It is then left the reaction mixture is refluxed for one hour at 78° C The product is precipitated by means of 300 parts of water filtered off

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 70 ml (0.487 mol) of ethyl benzoate were heated to reflux for 12 hours with 100 g (0.247 mol) of Lawesson reagent in 350 ml of xylene. After cooling to 20° the reaction mixture was diluted with 500 ml of hexane and filtered. The filtrate was flash-chromatographed on 1 kg of silica gel. Elution was carried out with hexane. The fractions which were pure according to the thin-layer chromatogram (eluent: toluene) were combined and evaporated under reduced pressure. There were obtained 72 g (89%) of O-ethyl thiobenzoate as a dark yellow evil-smelling oil which was used without further purification. After cooling to 20° the reaction mixture filtered The filtrate was flash-chromatographed on 1 kg of silica gel Elution evaporated under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 70 ml (0.487 mol) of ethyl benzoate were heated to reflux for 12 hours with 100 g (0.247 mol) of Lawesson reagent in 350 ml of xylene. After cooling to 20° the reaction mixture was diluted with 500 ml of hexane and filtered. The filtrate was flash-chromatographed on 1 kg of silica gel. Elution was carried out with hexane. The fractions which were pure according to the thin-layer chromatogram (eluent: toluene) were combined and evaporated under reduced pressure. There were obtained 72 g (89%) of O-ethyl thiobenzoate as a dark yellow evil-smelling oil which was used without further purification. After cooling to 20° the reaction mixture filtered The filtrate was flash-chromatographed on 1 kg of silica gel Elution evaporated under reduced pressure

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Prepare a suspension of NaCN (0.25 g, 5.2 mmol) in ethanol (50 mL). Add dropwise ethyl isocyanoacetate (5 mL, 45.6 mmol) and thiobenzoic acid O-ethyl ester (6.9 g, 41.5 mmol) in ethanol (25 mL). Stir the reaction mixture at 50° C. for 96 hours and then concentrate in vacuo to an oil. Chromatograph (silica gel, 3:7 hexane/ethyl acetate) to afford 5-phenylthiazole-4-carboxylic acid ethyl ester (6.0 g). MS: m/e=234 (MH+). Prepare concentrate in vacuo to an oil

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Prepare a solution of ethyl benzoate (10 g, 66.5 mmol) in xylene (100 mL). Add Lawesson's reagent (14.5 g, 36 mmol). Reflux the reaction for 5 hours, then concentrate in vacuo to an oil. Chromatograph (silica gel, 100% Hexane) to afford thiobenzoic acid O-ethyl ester (6.9 g). 1H NMR (CDCl3) δ 8.20 (d, J=8 Hz, 2H), 7.52 (t, J=7 Hz, 1H), 7.39 (t, J=7 Hz, 2H), 4.69-4.78 (m, 2H), 1.55 (t, J=7 Hz, 3H). Reflux the reaction for 5 hours concentrate in vacuo to an oil

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Prepare a solution of ethyl benzoate (10 g, 66.5 mmol) in xylene (100 mL). Add Lawesson's reagent (14.5 g, 36 mmol). Reflux the reaction for 5 hours, then concentrate in vacuo to an oil. Chromatograph (silica gel, 100% Hexane) to afford thiobenzoic acid O-ethyl ester (6.9 g). 1H NMR (CDCl3) δ 8.20 (d, J=8 Hz, 2H), 7.52 (t, J=7 Hz, 1H), 7.39 (t, J=7 Hz, 2H), 4.69-4.78 (m, 2H), 1.55 (t, J=7 Hz, 3H). Reflux the reaction for 5 hours concentrate in vacuo to an oil

反応条件: temp:78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 21 parts of cyanamide and 83 parts of ethyl thiobenzoate are successively introduced into a solution of 12.5 parts of sodium in 260 parts of ethanol, and the mixture is refluxed for one hour at 78° C. It is then left to stand for 12 hours, 40 parts of chloroacetonitrile are added, and the reaction mixture is refluxed for one hour at 78° C. The product is precipitated by means of 300 parts of water, and filtered off. 78 parts of 2-phenyl-4-amino-5-cyano-thiazole (78% of theory) of melting point 178°-179° C. are obtained. It is then left the reaction mixture is refluxed for one hour at 78° C The product is precipitated by means of 300 parts of water filtered off

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 70 ml (0.487 mol) of ethyl benzoate were heated to reflux for 12 hours with 100 g (0.247 mol) of Lawesson reagent in 350 ml of xylene. After cooling to 20° the reaction mixture was diluted with 500 ml of hexane and filtered. The filtrate was flash-chromatographed on 1 kg of silica gel. Elution was carried out with hexane. The fractions which were pure according to the thin-layer chromatogram (eluent: toluene) were combined and evaporated under reduced pressure. There were obtained 72 g (89%) of O-ethyl thiobenzoate as a dark yellow evil-smelling oil which was used without further purification. After cooling to 20° the reaction mixture filtered The filtrate was flash-chromatographed on 1 kg of silica gel Elution evaporated under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 70 ml (0.487 mol) of ethyl benzoate were heated to reflux for 12 hours with 100 g (0.247 mol) of Lawesson reagent in 350 ml of xylene. After cooling to 20° the reaction mixture was diluted with 500 ml of hexane and filtered. The filtrate was flash-chromatographed on 1 kg of silica gel. Elution was carried out with hexane. The fractions which were pure according to the thin-layer chromatogram (eluent: toluene) were combined and evaporated under reduced pressure. There were obtained 72 g (89%) of O-ethyl thiobenzoate as a dark yellow evil-smelling oil which was used without further purification. After cooling to 20° the reaction mixture filtered The filtrate was flash-chromatographed on 1 kg of silica gel Elution evaporated under reduced pressure

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Prepare a suspension of NaCN (0.25 g, 5.2 mmol) in ethanol (50 mL). Add dropwise ethyl isocyanoacetate (5 mL, 45.6 mmol) and thiobenzoic acid O-ethyl ester (6.9 g, 41.5 mmol) in ethanol (25 mL). Stir the reaction mixture at 50° C. for 96 hours and then concentrate in vacuo to an oil. Chromatograph (silica gel, 3:7 hexane/ethyl acetate) to afford 5-phenylthiazole-4-carboxylic acid ethyl ester (6.0 g). MS: m/e=234 (MH+). Prepare concentrate in vacuo to an oil

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Prepare a solution of ethyl benzoate (10 g, 66.5 mmol) in xylene (100 mL). Add Lawesson's reagent (14.5 g, 36 mmol). Reflux the reaction for 5 hours, then concentrate in vacuo to an oil. Chromatograph (silica gel, 100% Hexane) to afford thiobenzoic acid O-ethyl ester (6.9 g). 1H NMR (CDCl3) δ 8.20 (d, J=8 Hz, 2H), 7.52 (t, J=7 Hz, 1H), 7.39 (t, J=7 Hz, 2H), 4.69-4.78 (m, 2H), 1.55 (t, J=7 Hz, 3H). Reflux the reaction for 5 hours concentrate in vacuo to an oil