N,N-Dimethylaniline → 2-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrile

Participants

Reaction Steps

A solution of 2-hydroxyimino-2-phenylacetonitrile (14.6 g) and dimethylaniline (13.2 g.) in a mixture of benzene (80 ml.) and dioxane (8 ml.) was dropwise added to a solution of trichloromethyl chloroformate (phosgene dimer) (11 g.) in benzene (50 ml.) under ice-cooling, and the mixture was stirred for 3 hours at the same temperature and allowed to stand overnight. To the mixture containing 2-chlorocarbonyloxyimino-2-phenylacetonitrile was dropwise added a solution of tert-butyl alcohol (14.8 g.) and pyridine (16.0 ml.) in benzene (20 ml.) under ice-cooling. The reaction mixture was stirred for 6 hours together with gradual elevation of the reaction temperature to room temperature and allowed to stand overnight. Water was added to the reaction mixture, and the organic layer was separated. The organic layer was in turn washed with 1N hydrochloric acid, a sodium chloride aqueous solution, a sodium bicarbonate aqueous solution and water and then dried. The solvent was distilled off, and methanol was added to the residue. The mixture was cooled by ice-water, and the precipitates were collected by filtration and washed with a small amount of cooled methanol to give 2-tert-butoxycarbonyloxyimino-2-phenylacetonitrile (9.5 g.). From the mother liquor the object compound (9.4 g.) was further obtained. Both of the object compounds obtained above were combined and recrystallized from methanol to give the pure compound (14.6 g.), mp 84° to 86° C.

Provenance & Evidence