Action of Alkylmagnesium and Alkyllithium Reagents on Some Quaternary Hydrazonium Salts

Article abstract of DOI:10.1021/jo00248a011

Benzophenone N-methyl-N,N-pentane-1,5-diylhydrazonium iodide (1a) and its p,p'-dichloro and p,p'-dimethoxy analogues undergo loss of CH3I in boiling ethyl ether or THF, but the fluoroborates are stable.The complexes formed from 1 and Grignard reagents do not undergo incorporation of deuterium when they are hydrolyzed with D2O.When 1 and analogues are treated with propyl- and decylmagnesium bromide, the corresponding alkane, alkene, and bialkyl are produced, facts imply formation of alkyl radicals by a single-electron-transfer process.With all alkyl Grignard reagents studied, the overwhelming reaction is reductive cleavage of the N,N bond to form imines unsubstituted on nitrogen; no N-alkyl imines were detected.Small amounts of 1,1-diarylalkylamines, formed about 2percent of benzhydrylamine in reaction with 1a.Sodium cyanide reacted with the tetrafluoroborate analogue of 1a to form acetonitrile by demethylation; neither addition nor reduction was detected.Sodium azide behaved analogously.