STUDIES IN THE PYROLYSIS OF N-FORMYLACETAMIDES. THE IMIDE-ISOIMIDE REARRANGEMENT
Abstract
The purpose of this investigation is to obtain basic information on the reaction of substituted formamides giving isocyanides. Imide-isoimide equilibria were studied by an analysis of the thermal decomposition products of N-alkyl-(or-aryl-)N-formylacetamides. Relative yields in decarbonylation (arising from imide) vs. isocyanide formation (arising from isoimide) in the pyrolysis of N-phenyl-, N-n-butyl-, N-sec-butyl-, and N-cyclohexyl-N- formylacetamides were found to be >99:<1, 86:14, 57:43, and 51:49, respectively. Nitriles rather than isocyanides were isolated because of the isomerization which occurs at high temperatures. It is concluded that the quantities of amide and nitrile isolated may be the net result of a number of reactions: imide- isoimide reversible rearrangement, isoimide alpha elimination (possibly reversible), imide decarbonylation (irreversible), isocyanide-nitrile isomerization (irreversible), and imide regeneration from isocyanide and acid through formamide and acetic anhydride. Among the imides studied both an electronic and a steric effect appear to be operating.
Document Details
- Document Type
- Technical Report
- Publication Date
- Apr 15, 1968
- Accession Number
- AD0694282
Entities
People
- Daniel J. Hoy
- Edward J. Poziomek