(4-methylphenyl)sulfonyl acetate

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 solution of 7 (10 g, 40 mmol, 1 equiv) and pyridine (22.6 mL, 280 mmol, 7 equiv) in dichloromethane (200 mL) was added p-toluenesulfonyl chloride (11.4 g, 60 mmol, 1.5 equiv). The mixture stirred at room temperature overnight. Pyridine (22.6 mL, 280 mmol, 7 equiv) and acetic anhydride (21.9 mL, 232 mmol, 5.8 equiv) were added at room temperature and the mixture was stirred overnight. The reaction was cooled to 5° C. and quenched with 2 N aq NaOH to pH 7. The aqueous layer was separated and extracted with dichloromethane (2×50 mL). The combined organics were dried over sodium sulfate, filtered, and concentrated. The resulting semi-solid was dissolved in isopropyl acetate (100 mL) and concentrated to dryness. This was repeated 2 more times. The resulting semi-solid was triturated in methyl tert-butyl ether (250 mL), filtered and dried under vacuum to afford 8.1 g of 8 (45%) as a pale yellow solid. the mixture was stirred overnight The reaction was cooled to 5° C. quenched with 2 N aq NaOH to pH 7 The aqueous layer was separated extracted with dichloromethane (2×50 mL) The combined organics were dried over sodium sulfate filtered concentrated The resulting semi-solid was dissolved in isopropyl acetate (100 mL) concentrated to dryness The resulting semi-solid was triturated in methyl tert-butyl ether (250 mL) filtered dried under vacuum

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

実験手順: To a solution of 7 (10 g, 40 mmol, 1 equiv) and pyridine (22.6 mL, 280 mmol, 7 equiv) in dichloromethane (200 mL) was added p-toluenesulfonyl chloride (11.4 g, 60 mmol, 1.5 equiv). The mixture stirred at room temperature overnight. Pyridine (22.6 mL, 280 mmol, 7 equiv) and acetic anhydride (21.9 mL, 232 mmol, 5.8 equiv) were added at room temperature and the mixture was stirred overnight. The reaction was cooled to 5° C. and quenched with 2 N aq NaOH to pH 7. The aqueous layer was separated and extracted with dichloromethane (2×50 mL). The combined organics were dried over sodium sulfate, filtered, and concentrated. The resulting semi-solid was dissolved in isopropyl acetate (100 mL) and concentrated to dryness. This was repeated 2 more times. The resulting semi-solid was triturated in methyl tert-butyl ether (250 mL), filtered and dried under vacuum to afford 8.1 g of 8 (45%) as a pale yellow solid. the mixture was stirred overnight The reaction was cooled to 5° C. quenched with 2 N aq NaOH to pH 7 The aqueous layer was separated extracted with dichloromethane (2×50 mL) The combined organics were dried over sodium sulfate filtered concentrated The resulting semi-solid was dissolved in isopropyl acetate (100 mL) concentrated to dryness The resulting semi-solid was triturated in methyl tert-butyl ether (250 mL) filtered dried under vacuum

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

実験手順: To a solution of 7 (10 g, 40 mmol, 1 equiv) and pyridine (22.6 mL, 280 mmol, 7 equiv) in dichloromethane (200 mL) was added p-toluenesulfonyl chloride (11.4 g, 60 mmol, 1.5 equiv). The mixture stirred at room temperature overnight. Pyridine (22.6 mL, 280 mmol, 7 equiv) and acetic anhydride (21.9 mL, 232 mmol, 5.8 equiv) were added at room temperature and the mixture was stirred overnight. The reaction was cooled to 5° C. and quenched with 2 N aq NaOH to pH 7. The aqueous layer was separated and extracted with dichloromethane (2×50 mL). The combined organics were dried over sodium sulfate, filtered, and concentrated. The resulting semi-solid was dissolved in isopropyl acetate (100 mL) and concentrated to dryness. This was repeated 2 more times. The resulting semi-solid was triturated in methyl tert-butyl ether (250 mL), filtered and dried under vacuum to afford 8.1 g of 8 (45%) as a pale yellow solid. the mixture was stirred overnight The reaction was cooled to 5° C. quenched with 2 N aq NaOH to pH 7 The aqueous layer was separated extracted with dichloromethane (2×50 mL) The combined organics were dried over sodium sulfate filtered concentrated The resulting semi-solid was dissolved in isopropyl acetate (100 mL) concentrated to dryness The resulting semi-solid was triturated in methyl tert-butyl ether (250 mL) filtered dried under vacuum

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

実験手順: To the acetic p-toluenesulfonic anhydride obtained above was then added at room temperature 100 ml. (1.13 mole) of dimethoxymethane. The temperature of the reaction rose to 38° C. within about 5 minutes. The reaction mixture was stirred for one hour. NMR analysis indicated the title product was obtained in 90% purity after removal of excess dimethoxymethane by stripping at room temperature. was then added at room temperature 100 ml

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Acetyl chloride (100 ml.; density=1.104 g./ml.) was charged into a suitable reaction flask containing 30 g. (0.158 mole) p-toluenesulfonic acid monohydrate. Vigorous evolution of HCl gas occurred immediately. An efficient HCl trap was attached to the reaction system. The reaction mixture was then heated to mild reflux (~55° C.) and was held to this temperature for 25 minutes. Heating was stopped and the reaction mixture allowed to drop to room temperature over 10-20 minutes with stirring. Vacuum (~20-50 mm) was applied cautiously to remove acetyl chloride without carryover. At the same time the mixture was heated gradually to 60° C. Distillation of acetyl chloride was complete in ~30 minutes with collection in an ice cold flask for reuse. The oil obtained was then subjected to vacuum (~5-10 mm) to remove the last traces of acetyl chloride and acetic acid at 37° C. A snow white solid then crystallized in about 30 minutes as the title product. containing 30 g An efficient HCl trap was attached to the reaction system The reaction mixture was then heated to mild reflux (~55° C.) Heating to drop to room temperature over 10-20 minutes to remove acetyl chloride without carryover Distillation of acetyl chloride was complete in ~30 minutes with collection in an ice cold flask for reuse The oil obtained to remove the last traces of acetyl chloride and acetic acid at 37° C A snow white solid then crystallized in about 30 minutes as the title product

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

実験手順: To the acetic p-toluenesulfonic anhydride obtained above was then added at room temperature 100 ml. (1.13 mole) of dimethoxymethane. The temperature of the reaction rose to 38° C. within about 5 minutes. The reaction mixture was stirred for one hour. NMR analysis indicated the title product was obtained in 90% purity after removal of excess dimethoxymethane by stripping at room temperature. was then added at room temperature 100 ml

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Acetyl chloride (100 ml.; density=1.104 g./ml.) was charged into a suitable reaction flask containing 30 g. (0.158 mole) p-toluenesulfonic acid monohydrate. Vigorous evolution of HCl gas occurred immediately. An efficient HCl trap was attached to the reaction system. The reaction mixture was then heated to mild reflux (~55° C.) and was held to this temperature for 25 minutes. Heating was stopped and the reaction mixture allowed to drop to room temperature over 10-20 minutes with stirring. Vacuum (~20-50 mm) was applied cautiously to remove acetyl chloride without carryover. At the same time the mixture was heated gradually to 60° C. Distillation of acetyl chloride was complete in ~30 minutes with collection in an ice cold flask for reuse. The oil obtained was then subjected to vacuum (~5-10 mm) to remove the last traces of acetyl chloride and acetic acid at 37° C. A snow white solid then crystallized in about 30 minutes as the title product. containing 30 g An efficient HCl trap was attached to the reaction system The reaction mixture was then heated to mild reflux (~55° C.) Heating to drop to room temperature over 10-20 minutes to remove acetyl chloride without carryover Distillation of acetyl chloride was complete in ~30 minutes with collection in an ice cold flask for reuse The oil obtained to remove the last traces of acetyl chloride and acetic acid at 37° C A snow white solid then crystallized in about 30 minutes as the title product

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

実験手順: To a solution of 7 (10 g, 40 mmol, 1 equiv) and pyridine (22.6 mL, 280 mmol, 7 equiv) in dichloromethane (200 mL) was added p-toluenesulfonyl chloride (11.4 g, 60 mmol, 1.5 equiv). The mixture stirred at room temperature overnight. Pyridine (22.6 mL, 280 mmol, 7 equiv) and acetic anhydride (21.9 mL, 232 mmol, 5.8 equiv) were added at room temperature and the mixture was stirred overnight. The reaction was cooled to 5° C. and quenched with 2 N aq NaOH to pH 7. The aqueous layer was separated and extracted with dichloromethane (2×50 mL). The combined organics were dried over sodium sulfate, filtered, and concentrated. The resulting semi-solid was dissolved in isopropyl acetate (100 mL) and concentrated to dryness. This was repeated 2 more times. The resulting semi-solid was triturated in methyl tert-butyl ether (250 mL), filtered and dried under vacuum to afford 8.1 g of 8 (45%) as a pale yellow solid. the mixture was stirred overnight The reaction was cooled to 5° C. quenched with 2 N aq NaOH to pH 7 The aqueous layer was separated extracted with dichloromethane (2×50 mL) The combined organics were dried over sodium sulfate filtered concentrated The resulting semi-solid was dissolved in isopropyl acetate (100 mL) concentrated to dryness The resulting semi-solid was triturated in methyl tert-butyl ether (250 mL) filtered dried under vacuum