HYDROCARBON FORMING PATHWAYS FROM AMINE DIAZOTIZATIONS

Diazotization of several deuterium-labeled isobutyl- and sec-butylamines in protic and aprotic solvents gave hydrocarbon mixtures containing methylcyclopropane. The deuterium contents of the methylcyclopropanes suggest that a minor amount (∼2%) of the methylcyclopropane arises via a partially equilibrating protonated methylcyclopropane. From the deuterium content of isobutylene it is possible to calculate the extent of hydride shift to t- butyl cation in its formation. Rearrangement (1,2-hydride shift) of sec-butyl cation obtained from isobutylamine via a 1,2-methyl shift was found to be solvent dependent. Possible explanations for this phenomenon are considered. © 1969, American Chemical Society. All rights reserved.