REARRANGEMENT OF ORGANONITROGEN COMPOUNDS. IMIDE-ISOMIDE EQUILIBRIA
Abstract
The purpose of this investigation is to obtain basic information on rearrangements of organonitrogen compounds; specifically studied was the reaction of substituted formamides to yield isocyanides. Imide-isoimide equilibria were studied by an analysis of the thermal decomposition products of N-alkyl(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
- Aug 01, 1968
- Accession Number
- AD0677361
Entities
People
- Daniel J. Hoy
- Edward J. Poziomek