methyl 2-(chlorosulfonylmethyl)benzoate

Bedingungen: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Verfahren: 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

Bedingungen: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Verfahren: Liquified dimethylamine (73 ml) was added slowly with cooling to a 15% (w/w) solution of methyl 2-[(chlorosulfonyl)methyl]benzoate (42.0 g) in chlorobenzene. When addition was complete, the suspension was stirred 0.5 hour at room temperature, then filtered. The filtrate was concentrated to approximately 250 ml and added dropwise to a mixture of 150 ml of ethanol, 50 ml of water and 40 ml of 50% sodium hydroxide. The resulting suspension was stirred overnight at room temperature. The reaction solution was concentrated to dryness and the residue partitioned between 1000 ml water and 1000 ml of methylene chloride for 1.5 hour. The aqueous phase was separated, washed with 400 ml of methylene chloride, then acidified with concentrated hydrochloric acid. The precipitated solid was collected and dried overnight in vacuo to give 34.9 of 2-[(dimethylamino)sulfonylmethyl]benzoic acid, m.p. 112°-129°. When addition filtered The filtrate was concentrated to approximately 250 ml added dropwise to a mixture of 150 ml of ethanol, 50 ml of water and 40 ml of 50% sodium hydroxide The resulting suspension was stirred overnight at room temperature The reaction solution was concentrated to dryness the residue partitioned between 1000 ml water and 1000 ml of methylene chloride for 1.5 hour The aqueous phase was separated washed with 400 ml of methylene chloride The precipitated solid was collected dried overnight in vacuo

Bedingungen: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Verfahren: Liquified dimethylamine (73 ml) was added slowly with cooling to a 15% (w/w) solution of methyl 2-[(chlorosulfonyl)methyl]benzoate (42.0 g) in chlorobenzene. When addition was complete, the suspension was stirred 0.5 hour at room temperature, then filtered. The filtrate was concentrated to approximately 250 ml and added dropwise to a mixture of 150 ml of ethanol, 50 ml of water and 40 ml of 50% sodium hydroxide. The resulting suspension was stirred overnight at room temperature. The reaction solution was concentrated to dryness and the residue partitioned between 1000 ml water and 1000 ml of methylene chloride for 1.5 hour. The aqueous phase was separated, washed with 400 ml of methylene chloride, then acidified with concentrated hydrochloric acid. The precipitated solid was collected and dried overnight in vacuo to give 34.9 of 2-[(dimethylamino)sulfonylmethyl]benzoic acid, m.p. 112°-119°. When addition filtered The filtrate was concentrated to approximately 250 ml added dropwise to a mixture of 150 ml of ethanol, 50 ml of water and 40 ml of 50% sodium hydroxide The resulting suspension was stirred overnight at room temperature The reaction solution was concentrated to dryness the residue partitioned between 1000 ml water and 1000 ml of methylene chloride for 1.5 hour The aqueous phase was separated washed with 400 ml of methylene chloride The precipitated solid was collected dried overnight in vacuo

Bedingungen: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Verfahren: Liquified dimethylamine (73 ml) was added slowly with cooling to a 15% (w/w) solution of methyl 2-[(chlorosulfonyl)methyl]benzoate (42.0 g) in chlorobenzene. When addition was complete, the suspension was stirred 0.5 hour at room temperature, then filtered. The filtrate was concentrated to approximately 250 ml and added dropwise to a mixture of 150 ml of ethanol, 50 ml of water and 40 ml of 50% sodium hydroxide. The resulting suspension was stirred overnight at room temperature. The reaction solution was concentrated to dryness and the residue partitioned between 1000 ml water and 1000 ml of methylene chloride for 1.5 hour. The aqueous phase was separated, washed with 400 ml of methylene chloride, then acidified with concentrated hydrochloric acid. The precipitated solid was collected and dried overnight in vacuo to give 34.9 of 2-[(dimethylamino)sulfonylmethyl]benzoic acid, m.p. 112°-129°. When addition filtered The filtrate was concentrated to approximately 250 ml added dropwise to a mixture of 150 ml of ethanol, 50 ml of water and 40 ml of 50% sodium hydroxide The resulting suspension was stirred overnight at room temperature The reaction solution was concentrated to dryness the residue partitioned between 1000 ml water and 1000 ml of methylene chloride for 1.5 hour The aqueous phase was separated washed with 400 ml of methylene chloride The precipitated solid was collected dried overnight in vacuo

Bedingungen: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Verfahren: 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