反应详情

A solution of 2-hydroxyimino-2-phenylacetonitrile (2.2 g.) and dimethylaniline (1.80 g.) in a mixture of benzene (25 ml.) and dioxane (3 ml.) was added dropwise to a solution of trichloromethyl chloroformate (phosgene dimer) (1.5 g.) in benzene (20 ml.) under ice-cooling. The mixture was stirred for 3 hours at the same temperature and allowed to stand overnight. A solution of 1-cyclopropylethanol (1.4 g.) and pyridine (1.2 ml.) in benzene (10 ml.) was added dropwise, under ice-cooling, to the resultant mixture containing 2-chlorocarbonyloxyimino-2-phenylacetonitrile. The mixture was stirred for 2 hours at the same temperature, for 4 hours at room temperature and allowed to stand overnight. The reaction mixture was then washed with 1N hydrochloric acid, water, a sodium bicarbonate aqueous solution and water, and dried over magnesium sulfate. The solvent was distilled off and a small amount of methanol to the oily residue was added a small amount of methanol. The mixture was allowed to stand in a refrigerator and the precipitated crystals were collected by filtration and recrystallized from methanol to give 2-(1-cyclopropylethoxycarbonyloxyimino)-2-phenylacetonitrile (0.7 g.), mp 65° to 67° C.

1. temperaturecooling
2. waitto stand overnight
3. stirringThe mixture was stirred for 2 hours at the same temperature, for 4 hours at room temperature
4. waitto stand overnight
5. washThe reaction mixture was then washed with 1N hydrochloric acid, water
6. dry with materiala sodium bicarbonate aqueous solution and water, and dried over magnesium sulfate
7. distillationThe solvent was distilled off
8. additiona small amount of methanol to the oily residue was added a small amount of methanol
9. filtrationthe precipitated crystals were collected by filtration
10. customrecrystallized from methanol