Methyleneketenes and methylenecarbenes. XVIII. A pyrolytic synthesis of aniline from trimethylsilyl (E,E)-2-Cyanohexa-2,4-dienoate

Abstract

Flash vacuum pyrolysis of trimethylsilyl (E,E)-2-cyanohexa-2,4-dienoate(α-cyanosorbate) (4) gives N-trimethylsilylaniline through O-to-N silyl transfer with decarboxylation, followed by rearrangement of intermediate N-silylketenimines (5) and (6). After hydrolysis, aniline is obtained in 53% yield from the α-cyano acid (3).