Studies in azide chemistry. Part VII. Synthesis and reactions of perfluoro-(2-azido-4-isopropylpyridine) and 2-azido-3,5,6-trifluoro-4-methoxypyridine

Abstract

Treatment of perfluoro-(4-isopropylpyridine) with sodium azide gave perfluoro-(2-azido-4-isopropylpyridine) and perfluoro-(2,6-diazido-4-isopropylpyridine). The former product reacted with sodium methoxide to give 2-azido-3,5-difluoro-4-(heptafluoroisopropyl)-6-methoxypyridine, with triphenylphosphine, diphenylacetylene, or acrylonitrile to give the corresponding iminophosphorane, 1,2,3-triazole, and aziridine, respectively, and with 1,1-diphenylethylene to give, after work-up, benzophenone and perfluoro-(2-amino-4-isopropylpyridine). Pyrolysis of perfluoro-(2-azido-4-isopropylpyridine) gave nitrogen and intractable material; attempts to intercept a nitrene intermediate failed.

2-Azido-3,5,6-trifluoro-4-methoxypyridine, prepared via nitrosation of 3,5,6-trifluoro-2-hydrazino-4-methoxypyridine or treatment of 2,3,5,6-tetrafluoro-4-methoxypyridine with sodium azide, reacted with hot acrylonitrile to give the corresponding aziridine and nitrogen.