The products of flash vacuum pyrolysis of N-acetyl, N-methyl, N-benzyl and N-heteroaryl- substituted benzotriazole, 2, 1-benzoxazol-3-one and 2, 1-benzothiazol-3-one have been compared. The pyrolysis of benzotriazoles and benzisoxazolones appears to involve an iminocarbene intermediate, although the N-benzyl analogues react by radical pathways. Benzisothiazolones appear to form iminoketene intermediates.