Ab initio and DFT conformational studies of propanal, 2-butanone, and analogous imines and enamines

Haizhen Zhong, Eugene L. Stewart, Maria Kontoyianni, J. Phillip Bowen

Research output: Contribution to journalArticle

18 Scopus citations

Abstract

The potential energy surfaces (PES) of 2-butanone, 2-butanimine, 1-butenamine, propanal, and propanimine have been explored with ab initio and DFT calculations at the RHF/6-311G**, MP2/6-311G **, and B3LYP/6-311G** levels of theory. In agreement with previous experimental and computational results, the PES provides two minima for each of the above molecules with the exception of 2-butanone, which clearly shows three distinct minima. Factors influencing the conformational preferences are also elaborated. Our calculations suggest that for 2-butanone and propanal, the steric and the bond dipole interactions are primarily responsible for the conformational preferences of these compounds. Additional charge-charge interactions might also play an important role in determining the imine conformations. For enamines, however, steric interactions play a critical role, with bond dipole interactions exerting some influence. Our results also suggest that for imine formation from butanone and/or propanal, the imine is the predominant product, not the enamine, which is consistent with experimental observations. Therefore, these calculations should provide a better understanding of the ketone/aldehyde to imine and enamine transformations. This transformation may introduce an important imine moiety for the analogues of trans-N-methyl-4-(1-naphthylvinyl)pyridine (NVP), a choline acetyltransferase (ChAT) inhibitor.

Original languageEnglish (US)
Pages (from-to)230-238
Number of pages9
JournalJournal of Chemical Theory and Computation
Volume1
Issue number2
DOIs
StatePublished - 2005

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

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