Protonated cyclopropanes. X. Studies on the deamination of n-butylamine-1-14C and the decomposition of 3-(n-butyl-1-14C)-1-phenyltriazene

Abstract

The HNO2 deamination of n-butylamine-1-14C (1-NH2-1-14C) in aqueous HClO4 gave a n-butyl-14C alcohol (1-OH-14C) with about 0.7% scrambling of the label from C-1 to C-2, and a sec-butyl-14C alcohol (2-OH-14C) which showed extensive scrambling between C-1 and C-4, as well as small amounts of rearrangement of the label into C-2 and C-3. Analysis of the data suggested that about 2.5% of the 2-OH-14C product could be derived from equilibrating protonated methylcyclopropane intermediates. The HClO4 catalyzed decomposition of 3-(n-butyl-1-14C)-1-phenyltriazene (1-NNNHPh-1-14C) gave the unrearranged 1-OH-1-14C and a 2-OH-14C which showed only about 17–18% scrambling from C-1 toC-4. It is suggested that the different results observed in the deamination and the triazene decomposition may be due to a more ready initial formation of an ion pair in the triazene decomposition.