Abstract
The possibility of the Me 3 Si - species to be a nucleofuge of a compound containing the NSiMe 3 group was investigated. Treatment of hydrazines with 1.1 equiv of Me 3 SiCl, Me 3 SiSiMe 3 , or Ph 2 MeSiSiMePh 2 in the presence of 1.0 equiv of potassium hydride gave the corresponding 2-tetrazenes (R 1 R 2 NN=NNR 1 R 2 ) in fair to good yields. The hydrazines included 1-methyl-1-phenylhydrazine (9), 1-aminopiperidine (10), 1-amino-2,6-dimethylpiperidine (11), 4-aminomorpholine (12), and 1-aminohomopiperidine (13). In these reactions, Me 3 SiCl, Me 3 SiSiMe 3 , and Ph 2 MeSiSiMePh 2 acted as oxidizing agents. Results from control experiments supported the proposed mechanism: silylation of hydrazines gave monosilylhydrazines, decomposition of monosilylhydrazines generated aminonitrenes, and dimerization of aminonitrenes afforded 2-tetrazenes. In the decomposition of monosilylhydrazines, Me 3 Si - behaved as a leaving group from the NSiMe 3 moiety. © 1989 American Chemical Society.