REARRANGEMENT OF ORGANONITROGEN COMPOUNDS. IMIDE-ISOMIDE EQUILIBRIA
Technical rept. Mar 1964-Mar 1968
EDGEWOOD ARSENAL ABERDEEN PROVING GROUND MD
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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-alkylaryl-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 991, 8614, 5743 and 5149, 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.
- Organic Chemistry