Direct Conversion of Terpenylalkanolamines to Ethylidyne N-Nitroso Compounds

Article abstract of DOI:10.1021/jo00364a013

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.