Theoretical study on the alkaline and neutral hydrolysis of succinimide derivatives in deamidation reactions


Konuklar F. A. , Aviyente V., LOPEZ M.

JOURNAL OF PHYSICAL CHEMISTRY A, vol.106, no.46, pp.11205-11214, 2002 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 106 Issue: 46
  • Publication Date: 2002
  • Doi Number: 10.1021/jp0261531
  • Title of Journal : JOURNAL OF PHYSICAL CHEMISTRY A
  • Page Numbers: pp.11205-11214

Abstract

The hydrolysis of a succinimide derivative in alkali and neutral media has been studied at the B3LYP/6-31+G* level. Stepwise and concerted mechanisms have been considered in a vacuum. Both mechanisms have been also studied in solution by means of integral equation formalism-polarizable continuum model with a single point calculation. In basic medium, the stepwise mechanism consists of a bond cleavage and a subsequent rotation of the hydroxyl group that require 8.6 and 3.0 kcal/mol, respectively. For the concerted hydrolysis in the same medium, the barrier is 9.8 kcal/mol. In neutral medium, the hydrolysis is facilitated by the presence of a polar continuum, whereas in basic medium, the polar environment hinders hydrolysis of succinimide.