Mechanistic insight into self-propagation of organo-mediated Beckmann rearrangement: a combined experimental and computational study.
J Org Chem
; 78(9): 4297-302, 2013 May 03.
Article
em En
| MEDLINE
| ID: mdl-23534968
ABSTRACT
Organo-mediated Beckmann rearrangement in the liquid phase, which has the advantage of high efficiency and straightforward experimental procedures, plays an important role in the synthesis of amides from oximes. However, the catalytic mechanisms of these organic-based promoters are still not well understood. In this work, we report a combined experimental and computational study on the mechanism of Beckmann rearrangement mediated by organic-based promoters, using TsCl as an example. A novel self-propagating cycle is proposed, and key intermediates of this self-propagating cycle are confirmed by both experiments and DFT calculations. In addition, the reason why cyclohexanone oxime is not a good substrate of the organo-mediated Beckmann rearrangement is discussed, and a strategy for improving the yield is proposed.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Oximas
/
Compostos de Tosil
/
Amidas
/
Modelos Químicos
Idioma:
En
Ano de publicação:
2013
Tipo de documento:
Article