KETENIMINE NITRILE REARRANGEMENTS OF N-ALKOXYKETENIMINES UNDER THEIR GENERATION CONDITIONS

Citation
Gv. Shustov et al., KETENIMINE NITRILE REARRANGEMENTS OF N-ALKOXYKETENIMINES UNDER THEIR GENERATION CONDITIONS, Bulletin of the Russian Academy of Sciences, Division of Chemical Sciences, 41(11), 1992, pp. 2039-2045
Citations number
11
Categorie Soggetti
Chemistry
ISSN journal
10635211
Volume
41
Issue
11
Year of publication
1992
Part
2
Pages
2039 - 2045
Database
ISI
SICI code
1063-5211(1992)41:11<2039:KNRONU>2.0.ZU;2-B
Abstract
C,C-Substituted N-ethoxyketenimines are extremely unstable even under their generation conditions (dehydrochlorination of N-ethoxyimidoyl ch lorides, dehalogenation of alpha-bromo-N-ethoxyimidoyl halides, the re action of methylmethoxycarbonylketene with N-ethoxytriphenylphosphinim ine) undergo two types of rearrangements: synchronous ring decompositi on down to acetaldehyde and the corresponding CH-nitrile and 1,3-migra tion of the EtO group with formation of alpha-ethoxynitriles. We sugge st that the instability of N-alkoxyketenimines is mainly due to weaken ing of the NO bond as a result of pi(CC)-sigma(NO) hyperconjugation.