Rearrangement of pinane derivatives. Part 8. Deamination of 2αH-pinan-3α-ylamine

Abstract

Solvolysis of 2αH-pinan-3α-yl toluene-p-sulphonate has been shown to proceed with concomitant 1,2-hydride shift to give the pinan-2-yl carbocation. Contrary to earlier reports, this species reacts normally to give, in good yield, pinan-2-yl substitution products. In contrast the pinan-3-ylamines react via a similar route, but give much smaller amounts of pinan-2-yl products. The usual reasons for differences between solvolysis and deamination (i.e. the intermediacy of diazonium ions and/or high-energy ions) can be discounted, and possible reasons for the differences in behaviour are discussed.