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 added dropwise to a solution of phosgene (5.5 g.) in benzene (50 ml.) over 1 hour at 3° to 5° C. The mixture was stirred for 3.5 hours at the same temperature and allowed to stand overnight. A solution of tert-butyl alcohol (7.4 g.) and pyridine (5.0 ml.) in benzene (20 ml.) was added dropwise for 1 hour under ice-cooling to the resultant solution containing 2-chlorocarbonyloxyimino2-phenylacetonitrile. The resultant mixture was stirred for 4 hours at the same temperature, and pyridine (3.0 ml.) was added dropwise thereto. The mixture was then 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 then 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 obtain 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