N-(4-羟基-2-甲基苯)甲烷磺胺

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a mixture of 24.00 g (0.089 mol) of N-(2-methyl-4-hydroxyphenyl)methanesulfonamide, 9.00 g (0.089 mol) of triethylamine, and 150 ml of methylene chloride cooled to approximately 0° C. was added a solution of 9.32 g (0.089 mol) of methacryloyl chloride in 150 ml of methylene chloride and 50 ml of methylene chloride wash over approximately 20 minutes. The reaction mixture was then stirred for another 4 hours at reduced temperature, after which it was washed with 2 percent hydrochloric acid and twice with water. The organic phase was dried over magnesium sulfate, treated with decolorizing carbon, filtered and concentrated to an oil, which crystallized on cooling. The solid was recrystallized from 1:1 dichloroethane:hexane to give 14.7 g (61.3 percent of theory) of N-(2-methyl-4-methacryloyloxyphenyl)methanesulfonamide, m.p.=95° to 97° C. wash over approximately 20 minutes after which it was washed with 2 percent hydrochloric acid and twice with water The organic phase was dried over magnesium sulfate treated with decolorizing carbon filtered concentrated to an oil, which crystallized on cooling The solid was recrystallized from 1:1 dichloroethane

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a mixture of 24.00 g (0.089 mol) of N-(2-methyl-4-hydroxyphenyl)methanesulfonamide, 9.00 g (0.089 mol) of triethylamine, and 150 ml of methylene chloride cooled to approximately 0° C. was added a solution of 9.32 g (0.089 mol) of methacryloyl chloride in 150 ml of methylene chloride and 50 ml of methylene chloride wash over approximately 20 minutes. The reaction mixture was then stirred for another 4 hours at reduced temperature, after which it was washed with 2 percent hydrochloric acid and twice with water. The organic phase was dried over magnesium sulfate, treated with decolorizing carbon, filtered and concentrated to an oil, which crystallized on cooling. The solid was recrystallized from 1:1 dichloroethane:hexane to give 14.7 g (61.3 percent of theory) of N-(2-methyl-4-methacryloyloxyphenyl)methanesulfonamide, m.p.=95° to 97° C. wash over approximately 20 minutes after which it was washed with 2 percent hydrochloric acid and twice with water The organic phase was dried over magnesium sulfate treated with decolorizing carbon filtered concentrated to an oil, which crystallized on cooling The solid was recrystallized from 1:1 dichloroethane

反应条件: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of 4-(4-chloro-pyrazolo[3,4-d]pyrimidin-1-yl)-piperidine-1-carboxylic acid tert-butyl ester (Intermediate 19; 25 mg, 0.075 mmol), N-(4-hydroxy-2-methyl-phenyl)methanesulfonamide (ChemBridge Corporation, San Diego, Calif., USA; 15 mg, 0.075 mmol), and potassium carbonate (27 mg, 0.2 mmol) in dimethylformamide was heated in the microwave oven at 160° C. for 10 min. Saturated sodium carbonate solution was added to the reaction mixture and the precipitate was filtered through a silica plug, washing with methanol. The solvent was removed and the residue was purified by HPLC to afford 4-[4-(4-methanesulfonylamino-3-methyl-phenoxy)pyrazolo[3,4-d]pyrimidin-1-yl]-piperidine-1-carboxylic acid tert-butyl ester (12 mg, 33%) as an off white solid. Mass Spec MH+=503. the precipitate was filtered through a silica plug washing with methanol The solvent was removed the residue was purified by HPLC

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a mixture of 24.00 g (0.089 mol) of N-(2-methyl-4-hydroxyphenyl)methanesulfonamide, 9.00 g (0.089 mol) of triethylamine, and 150 ml of methylene chloride cooled to approximately 0° C. was added a solution of 9.32 g (0.089 mol) of methacryloyl chloride in 150 ml of methylene chloride and 50 ml of methylene chloride wash over approximately 20 minutes. The reaction mixture was then stirred for another 4 hours at reduced temperature, after which it was washed with 2 percent hydrochloric acid and twice with water. The organic phase was dried over magnesium sulfate, treated with decolorizing carbon, filtered and concentrated to an oil, which crystallized on cooling. The solid was recrystallized from 1:1 dichloroethane:hexane to give 14.7 g (61.3 percent of theory) of N-(2-methyl-4-methacryloyloxyphenyl)methanesulfonamide, m.p.=95° to 97° C. wash over approximately 20 minutes after which it was washed with 2 percent hydrochloric acid and twice with water The organic phase was dried over magnesium sulfate treated with decolorizing carbon filtered concentrated to an oil, which crystallized on cooling The solid was recrystallized from 1:1 dichloroethane