Ultrafast time-resolved infrared spectroscopy study of the photochemistry of N,N-diethyldiazoacetamide: rearrangement in the excited state

J Am Chem Soc. 2009 Jul 22;131(28):9646-7. doi: 10.1021/ja904009x.

Abstract

Ultrafast infrared spectroscopy shows that in chloroform, beta-lactam is formed immediately after the laser pulse but gamma-lactam is formed from both slow and fast processes. It is concluded that beta-lactam is formed from the diazoamide excited state via the rearrangement in the excited state (RIES) mechanism and that gamma-lactam is formed from both RIES and carbene. In methanol, both carbene decay and the rise of amide ether product are observed directly. Predictions from density functional theory calculations are consistent with these observations.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acetamides / chemistry*
  • Diazonium Compounds / chemistry*
  • Lactams / chemistry
  • Photolysis*
  • Spectroscopy, Fourier Transform Infrared
  • Time Factors

Substances

  • Acetamides
  • Diazonium Compounds
  • Lactams
  • N,N-diethyldiazoacetamide