钠;3-甲氧基-3-氧代丙烷-1-磺酸盐

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 3-Methyl-4-nitrobenzyl bromide (60 g, 261 mmol) was added portionwise to a suspension of sodium 3-methoxy-3-oxopropane-1-sulfonate 13 (50 g, 1.1 equiv) in DMSO (400 ml) at r.t. (with occasional ice bath cooling to keep the temperature below 28 C) and this mixture was stirred at r.t. for 3 h (TLC (EtOAc/hexane 50%) indicated complete consumption of the starting material to cleanly form a new spot). MeOH (400 ml) was then added and the mixture was cooled down to −10 C. MeONa (62 ml of a 25% solution in MeOH) was added dropwise at −9 C and the reaction was warmed slowly to 0 C (where complete disappearance of the intermediate was seen by TLC). Finally, this mixture was poured portionwise into an aqueous solution containing hydroxylamine-O-sulfonic acid (118 g, 4 equiv) and NaOAc (107 g, 5 equiv) at 0 C (very exothermic reaction). The reaction was warmed very slowly to r.t. and was stirred at that temperature o.n. More water (1 L) and EtOAc (1 L) were added to dissolve the precipitate. The product was extracted into EtOAc, washed with brine and dried over Na2SO4. Evaporation of solvents gave a gummy solid, which was triturated in toluene (300 ml) for an hour to yield 49.35 g (82%) of pure 14 as a white solid. cooling consumption of the starting material to cleanly form a new spot) MeOH (400 ml) was then added the mixture was cooled down to −10 C MeONa (62 ml of a 25% solution in MeOH) was added dropwise at −9 C the reaction was warmed slowly to 0 C (where complete disappearance of the intermediate Finally, this mixture was poured portionwise into an aqueous solution very exothermic reaction) to dissolve the precipitate The product was extracted into EtOAc washed with brine dried over Na2SO4 Evaporation of solvents gave a gummy solid, which was triturated in toluene (300 ml) for an hour

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a suspension of 12 (141 g, 636 mmol) in THF (1.2 L) and MeOH (700 ml) in an ice bath was added slowly sodium methoxide (144 ml of a 25% solution in MeOH, 1.05 equiv). At the end of the addition, the bath was removed and the mixture stirred at r.t. for 1 h. The solvents were than evaporated and the remaining solid was triturated in ether containing a small amount of EtOAc. The slightly hygroscopic white solid was filtered and dried under high vacuum o.n. to yield 108.7 g (98%) of 13. At the end of the addition the bath was removed than evaporated the remaining solid was triturated in ether containing a small amount of EtOAc The slightly hygroscopic white solid was filtered dried under high vacuum o.n

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a suspension of 12 (141 g, 636 mmol) in THF (1.2 L) and MeOH (700 ml) in an ice bath was added slowly sodium methoxide (144 ml of a 25% solution in MeOH, 1.05 equiv). At the end of the addition, the bath was removed and the mixture stirred at r.t. for 1 h. The solvents were than evaporated and the remaining solid was triturated in ether containing a small amount of EtOAc. The slightly hygroscopic white solid was filtered and dried under high vacuum o.n. to yield 108.7 g (98%) of 13. At the end of the addition the bath was removed than evaporated the remaining solid was triturated in ether containing a small amount of EtOAc The slightly hygroscopic white solid was filtered dried under high vacuum o.n

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 3-Methyl-4-nitrobenzyl bromide (60 g, 261 mmol) was added portionwise to a suspension of sodium 3-methoxy-3-oxopropane-1-sulfonate 13 (50 g, 1.1 equiv) in DMSO (400 ml) at r.t. (with occasional ice bath cooling to keep the temperature below 28 C) and this mixture was stirred at r.t. for 3 h (TLC (EtOAc/hexane 50%) indicated complete consumption of the starting material to cleanly form a new spot). MeOH (400 ml) was then added and the mixture was cooled down to −10 C. MeONa (62 ml of a 25% solution in MeOH) was added dropwise at −9 C and the reaction was warmed slowly to 0 C (where complete disappearance of the intermediate was seen by TLC). Finally, this mixture was poured portionwise into an aqueous solution containing hydroxylamine-O-sulfonic acid (118 g, 4 equiv) and NaOAc (107 g, 5 equiv) at 0 C (very exothermic reaction). The reaction was warmed very slowly to r.t. and was stirred at that temperature o.n. More water (1 L) and EtOAc (1 L) were added to dissolve the precipitate. The product was extracted into EtOAc, washed with brine and dried over Na2SO4. Evaporation of solvents gave a gummy solid, which was triturated in toluene (300 ml) for an hour to yield 49.35 g (82%) of pure 14 as a white solid. cooling consumption of the starting material to cleanly form a new spot) MeOH (400 ml) was then added the mixture was cooled down to −10 C MeONa (62 ml of a 25% solution in MeOH) was added dropwise at −9 C the reaction was warmed slowly to 0 C (where complete disappearance of the intermediate Finally, this mixture was poured portionwise into an aqueous solution very exothermic reaction) to dissolve the precipitate The product was extracted into EtOAc washed with brine dried over Na2SO4 Evaporation of solvents gave a gummy solid, which was triturated in toluene (300 ml) for an hour

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a suspension of 12 (141 g, 636 mmol) in THF (1.2 L) and MeOH (700 ml) in an ice bath was added slowly sodium methoxide (144 ml of a 25% solution in MeOH, 1.05 equiv). At the end of the addition, the bath was removed and the mixture stirred at r.t. for 1 h. The solvents were than evaporated and the remaining solid was triturated in ether containing a small amount of EtOAc. The slightly hygroscopic white solid was filtered and dried under high vacuum o.n. to yield 108.7 g (98%) of 13. At the end of the addition the bath was removed than evaporated the remaining solid was triturated in ether containing a small amount of EtOAc The slightly hygroscopic white solid was filtered dried under high vacuum o.n