Premium
The thermal isomerization of 1‐(α‐aroyloxybenzylideneamino)‐4,5‐di‐methyl‐1,2,3‐triazoles (isoimides) to the corresponding imides
Author(s) -
Maroulis A. J.,
HadjiantoniouMaroulis C. P.
Publication year - 1984
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570210616
Subject(s) - chemistry , lone pair , nucleophile , moiety , isomerization , nitrogen , medicinal chemistry , sigmatropic reaction , photochemistry , stereochemistry , organic chemistry , catalysis , molecule
The title isoimides rearrange upon heating to the corresponding imides through a [1,3] O⇀N aroyl transfer. The reaction is slightly accelarated by electron withdrawing substituents in the migrating moiety and retarded by electron donating as it is suggested by the positive (+0.5) Hammett ϱ value. The mechanism operating is either a rate determining nucleophilic attack by the nitrogen lone pair on the carbonyl carbon or a sigmatropic [π2s + σ2a] process which does not involve the lone pair of electrons on nitrogen and π or‐bitals of the carbonyl group.