DEAMINATION OF PRIMARY AMINES WITH BENZYL NITRITE

Deamination of aniline on heating with benzyl nitrite without solvent or in cyclohexane leads to the formation of benzaldehyde, bibenzyl, st ilbene, phenol and 4-benzylphenol, while in tetrahydrofuran as a solve nt toluene is formed in addition to the above products. Similar deamin ation reactions have been carried out on 1-naphthylamine, 2-naphthylam ine and benzylamine. A free radical mechanism has been suggested invol ving the intermediacy of the corresponding arene benzyldiazotate which undergoes homolysis of either the benzyl-O or the N-O bond. The rates of deamination of some m- or p-substituted anilines have also been me asured which are found to increase with increasing-I effect of the sub stituent. Application of Hammett equation gives rho = 0.604.