Rearrangement of Cyclic Ethynylcarbinols. III. A Few Supplementary Reaction with Monocyclic and Bicyclic Terpenoids.

抄録

1) Although 3-ethynylmenthol and 2-ethynylcarbomenthol, among monocyclic compounds of camphor system, have been reported as undergoing Meyer-Schuster rearrangement in the main, the present series of experiments have clarified that the Rupe reaction also progresses in these compounds, same as in 1-ethynylcyclohexanol. 2) 2-Ethynyl-1, 3, 3-trimethyl-2-norborneol undergoes Meyer-Schuster rearrangement by treatment with hydrochloric acid and formic acid, but only the Rupe reaction takes place, accompanied by the Wagner rearrangement, by treatment with sulfuric acid. 3) 1-Methyl-2-ethynylnorborneol undergoes both Meyer-Schuster rearrangement and Rupe reaction, irrespective of the catalyst used. This compound is similar to monocyclic compounds in that it undergoes endocyclic dehydration during the Rupe reaction. 4) 2-Ethynylnorborneol dose not undergo the Meyer-Schuster rearrangement and only the Rupe reaction takes place, similar to monocyclic compounds in general.