methyl 2-(chloromethyl)benzoate

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: A solution of 196 g of methyl 2-chloromethylbenzoate and 83.7 g of thiourea in 500 ml of ethanol is refluxed for 4 hours. The reaction solution is concentrated under reduced pressure and to the resulting residue is added 300 ml of isopropylalcohol. The precipitated crystals are collected by filtration and dried to give 112.8 g of the title compound. The reaction solution is concentrated under reduced pressure and to the resulting residue is added 300 ml of isopropylalcohol The precipitated crystals are collected by filtration dried

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

実験手順: A mixture of water (50 ml) and 29.5 g of sodium thiosulfate pentahydrate was added to o-(chloromethyl)benzoic acid methyl ester 20 g, and stirred for 5 hours at 50˜55° C. 300 ml of acetic acid was added and then excess of chlorine gas for 3 hours was infused, while maintaining the internal temperature of reactor at 5˜10° C. The reaction mixture was further stirred for 1 hour at the same temperature. Excess of chlorine gas was removed via infusion of nitrogen gas and with the addition of ice water (300 ml), stirred for 30 minutes. A solid, so formed, was filtered with a cold water and dried to afford 22.4 g of desired compound (yield 83%) as a white solid. while maintaining the internal temperature of reactor at 5˜10° C The reaction mixture was further stirred for 1 hour at the same temperature Excess of chlorine gas was removed via infusion of nitrogen gas and with the addition of ice water (300 ml) stirred for 30 minutes A solid, so formed was filtered with a cold water dried

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

実験手順: 180 g of o-(chloromethyl)benzoyl chloride was placed in a double-neck 500 ml flask equipped with a thermometer, cooler and dropping funnel. While maintaining the internal temperature of a reactor at 40˜50° C., 50 ml of methanol was added dropwise. After all amounts of methanol were infused, the reacting mixture was stirred for 10 hours, while maintaining the internal temperature of a reactor at 40˜50° C. After a distillator was equipped, a fractional distillation under reduced pressure was made to afford 165 g of desired compound (yield 94%) as oil. equipped with a thermometer, cooler While maintaining the internal temperature of a reactor at 40˜50° C. while maintaining the internal temperature of a reactor at 40˜50° C After a distillator was equipped a fractional distillation under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: To a suitable vessel containing about 16.2 g of an approximate 50:50 mixture of methyl α-chloro-o-toluate and methyl α-bromo-o-toluate is added 100 ml of acetonitrile and 17.2 g (0.085 mol) of tributylphosphine and held at reflux under nitrogen for about 45 minutes. The solvent is removed under vacuum and the residue is dissolved in 370 ml of water. The aqueous solution is extracted twice with ether and added to a solution of 102 g (1.0 mol) of sodium bromide in 150 ml of water. This mixture is extracted with three 150 ml portions of chloroform. The chloroform extracts are combined, dried over calcium sulfate and concentrated under vacuum to 36.3 g of colorless oil. Two triturations of this oil with ether provides a white solid which upon recrystallization from ethyl acetate-ether yields approximately 24.6 g of o-methoxycarbonylbenzyltributylphosphonium bromide having a melting point of 65°-66°. To a suitable vessel containing at reflux under nitrogen for about 45 minutes The solvent is removed under vacuum the residue is dissolved in 370 ml of water The aqueous solution is extracted twice with ether This mixture is extracted with three 150 ml portions of chloroform dried over calcium sulfate concentrated under vacuum to 36.3 g of colorless oil Two triturations of this oil with ether provides a white solid which upon recrystallization from ethyl acetate-ether

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

実験手順: A solution of 196 g of methyl 2-chloromethylbenzoate and 83.7 g of thiourea in 500 ml of ethanol is refluxed for 4 hours. The reaction solution is concentrated under reduced pressure and to the resulting residue is added 300 ml of isopropylalcohol. The precipitated crystals are collected by filtration and dried to give 112.8 g of the title compound. The reaction solution is concentrated under reduced pressure and to the resulting residue is added 300 ml of isopropylalcohol The precipitated crystals are collected by filtration dried

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

実験手順: A solution of 196 g of methyl 2-chloromethylbenzoate and 83.7 g of thiourea in 500 ml of ethanol is refluxed for 4 hours. The reaction solution is concentrated under reduced pressure and to the resulting residue is added 300 ml of isopropylalcohol. The precipitated crystals are collected by filtration and dried to give 112.8 g of the title compound. The reaction solution is concentrated under reduced pressure and to the resulting residue is added 300 ml of isopropylalcohol The precipitated crystals are collected by filtration dried

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

実験手順: To a suitable vessel containing about 16.2 g of an approximate 50:50 mixture of methyl α-chloro-o-toluate and methyl α-bromo-o-toluate is added 100 ml of acetonitrile and 17.2 g (0.085 mol) of tributylphosphine and held at reflux under nitrogen for about 45 minutes. The solvent is removed under vacuum and the residue is dissolved in 370 ml of water. The aqueous solution is extracted twice with ether and added to a solution of 102 g (1.0 mol) of sodium bromide in 150 ml of water. This mixture is extracted with three 150 ml portions of chloroform. The chloroform extracts are combined, dried over calcium sulfate and concentrated under vacuum to 36.3 g of colorless oil. Two triturations of this oil with ether provides a white solid which upon recrystallization from ethyl acetate-ether yields approximately 24.6 g of o-methoxycarbonylbenzyltributylphosphonium bromide having a melting point of 65°-66°. To a suitable vessel containing at reflux under nitrogen for about 45 minutes The solvent is removed under vacuum the residue is dissolved in 370 ml of water The aqueous solution is extracted twice with ether This mixture is extracted with three 150 ml portions of chloroform dried over calcium sulfate concentrated under vacuum to 36.3 g of colorless oil Two triturations of this oil with ether provides a white solid which upon recrystallization from ethyl acetate-ether

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

実験手順: To a suitable vessel containing about 16.2 g of an approximate 50:50 mixture of methyl α-chloro-o-toluate and methyl α-bromo-o-toluate is added 100 ml of acetonitrile and 17.2 g (0.085 mol) of tributylphosphine and held at reflux under nitrogen for about 45 minutes. The solvent is removed under vacuum and the residue is dissolved in 370 ml of water. The aqueous solution is extracted twice with ether and added to a solution of 102 g (1.0 mol) of sodium bromide in 150 ml of water. This mixture is extracted with three 150 ml portions of chloroform. The chloroform extracts are combined, dried over calcium sulfate and concentrated under vacuum to 36.3 g of colorless oil. Two triturations of this oil with ether provides a white solid which upon recrystallization from ethyl acetate-ether yields approximately 24.6 g of o-methoxycarbonylbenzyltributylphosphonium bromide having a melting point of 65°-66°. To a suitable vessel containing at reflux under nitrogen for about 45 minutes The solvent is removed under vacuum the residue is dissolved in 370 ml of water The aqueous solution is extracted twice with ether This mixture is extracted with three 150 ml portions of chloroform dried over calcium sulfate concentrated under vacuum to 36.3 g of colorless oil Two triturations of this oil with ether provides a white solid which upon recrystallization from ethyl acetate-ether

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

実験手順: A solution of 196 g of methyl 2-chloromethylbenzoate and 83.7 g of thiourea in 500 ml of ethanol is refluxed for 4 hours. The reaction solution is concentrated under reduced pressure and to the resulting residue is added 300 ml of isopropylalcohol. The precipitated crystals are collected by filtration and dried to give 112.8 g of the title compound. The reaction solution is concentrated under reduced pressure and to the resulting residue is added 300 ml of isopropylalcohol The precipitated crystals are collected by filtration dried