Direct conversion of terpenylalkanolamines to ethylidyne N-nitroso compounds

A series of mono- and diterpenylalkanolamines bearing isopropylidene functionality on the terpene group was reacted with sodium nitrite in aqueous acetic acid to yield ethylidyne N-nitroso analogues. The key feature of this direct conversion involved initial N-nitrosation followed by apparent elimination of a "CH₄" unit (not necessarily methane) from the isopropylidene double bond. The product distribution data for ethylidyne nitrosamines derived from tertiary terpenyl alkanolamines reflect the conformational outcome of the nitrosative dealkylation process. For β,γ-unsaturated allylic diterpenylethanolamines, electronic effects appeared to be important for controlling the product distribution of ethylidyne nitrosamines in light of the highly selective α-cleavage observed in the nitrosation reactions.