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

Participants

Reaction Steps

A solution of 2-hydroxyimino-2-phenylacetonitrile (7.3 g.) and dimethylaniline (6.0 g) in a mixture of benzene (50 ml) and dioxane (5 ml.) was dropwise added to a solution of phosgene (5.5 g.) in benzene (50 ml.) over 1 hour at 3° to 5° C, and the mixture was stirred for 3.5 hours at the same temperature and allowed to stand overnight. To the resultant solution containing 2-chlorocarbonyloxyimino-2-phenylacetonitrile was dropwise added, over 1 hour under ice-cooling, a solution of tert-butyl alcohol (7.4 g.) and pyridine (5.0 ml.) in benzene (20 ml.). The resultant mixture was stirred for 4 hours at the same temperature, and pyridine (3.0 ml.) was dropwise added thereto, after which the mixture was stirred for 1 hour at room temperature and allowed to stand overnight. Water was added thereto and the organic layer was separated. The organic layer was in turn washed with 1N hydrochloric acid (3 times), a sodium chloride aqueous solution, a sodium bicarbonate aqueous solution (twice) and a sodium chloride aqueous solution (twice) and concentrated. The residue was allowed to stand to give crystals. The crystals were triturated in aqueous methanol, collected by filtration, washed with n-hexane and dried to give 2-tert-butoxycarbonyloxyimino-2-phenylacetonitrile (7.0 g.), mp 84° to 86° C.

Provenance & Evidence