Kinetic evidence for the formation of monocationic N,N'-disubstituted phthalamide in tertiary amine-catalyzed hydrolysis of N-substituted phthalimides

J Org Chem. 2007 Oct 26;72(22):8452-8. doi: 10.1021/jo701295n. Epub 2007 Oct 6.

Abstract

A kinetic study on the aqueous cleavage of N-(2-methoxyphenyl)phthalimide (1) and N-(2-hydroxyphenyl)phthalimide (2), under the buffers of N-methylmorpholine, reveals the equilibrium presence of monocationic amide (Ctam) formed due to nucleophilic reactions of N-methylmorpholine with 1 and 2. Pseudo-first-order rate constants for the reactions of water and HO- with Ctam (formed through nucleophilic reaction of N-methylmorpholine with 1) are 4.60 x 10(-5) s-1 and 47.9 M-1 s-1, respectively. But the cleavage of Ctam, formed through nucleophilic reaction of N-methylmorpholine with 2, involves intramolecular general base (2'-O- group of Ctam)-assisted water attack at carbonyl carbon of cationic amide group of Ctam in or before the rate-determining step.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amines / chemistry*
  • Catalysis
  • Cations / chemical synthesis
  • Cations / chemistry
  • Hydrolysis
  • Kinetics
  • Molecular Structure
  • Phthalimides / chemical synthesis*
  • Phthalimides / chemistry
  • Water / chemistry

Substances

  • Amines
  • Cations
  • Phthalimides
  • Water