SOME ASPECTS OF VINYL AZIDE CHEMISTRY . THERMALLY INDUCED REACTIONS

A comparison of the chemistry of terminal and internal vinyl azides is presented. On decomposition, internal vinyl azides formed azirines while terminal vinyl azides did not. The nature of the products from the latter azides depended upon the substituents on the carbon β to the azido group. In solvents other than ethanol, 9-(azidomethylenejfluorene gave 9-(N,N-fluorenylideneaminomethylene)fluorene, while 2-azido-1, 1-diphenylethylene and 1-azido-2-phenylpropene formed indole derivatives. The latter two compounds when decomposed in ethanol produced dihydropyrazines at the expense of indole formation. Possible mechanisms for these reactions are considered. In addition, the geminal vinyl diazide, 9-diazidomethylenefluorene, was found to form 9-azido-9-fluorenecarbonitrile while the vicinal diazide, 2,3-diazido (N-phenyl)maleimide, gave N,N-bis-(cyanocarbonyl)aniline. © 1968, American Chemical Society. All rights reserved.