Amine-Catalyzed Decarboxylation of Acetoacetic Acid. the Rate Constant for Decarboxylation of a β-Imino Acid

J. Peter Guthrie, Frank Jordan

Research output: Contribution to journalArticlepeer-review

54 Scopus citations

Abstract

Aminoacetonitrile (AAN) is the most powerful catalyst for the decarboxylation of acetoacetic acid out of a series of primary amines of widely varying pKa. The rate constants for AAN-catalyzed decarboxylation are closely similar to those for imine formation from AAN and ethyl acetoacetate. Spectrophotometric study of AAN-catalyzed decarboxylation revealed three successive kinetic processes characterized by three pseudo-first-order rate constants. The imine from AAN and acetoacetate could be trapped by cyanoborohydride. Analysis of the kinetics led to rate constants for imine formation and hydrolysis and for interconversion of imine and enamine, as well as for the decarboxylation of the imine. This latter rate constant, 10 sec-1, is 300,000 times faster than that for the decarboxylation of acetoacetic acid itself.

Original languageEnglish (US)
Pages (from-to)9136-9141
Number of pages6
JournalJournal of the American Chemical Society
Volume94
Issue number26
DOIs
StatePublished - Dec 1 1972
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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