Issue 0, 1968

Elimination reactions. Part II. Pyrolytic and base-promoted decompositions of thujyl compounds

Abstract

Dehydrations of (–)-thujol, (–)-neothujol, (+)-isothujol, and (+)-neoisothujol by pyridine–phosphorus oxychloride, and also pyrolyses of the derived dimethylamine oxides and S-methyl xanthates, gave, singly or in mixture, (–)-α-thujene, (+)-β-thujene, and the hitherto uncharactised (+)-β-isothujene. In view of the known stereospecificity of these reactions, the results confirm recently assigned configurations for the alcohols. Hofmann degradation of the four thujyltrimethylammonium hydroxides gave products attributable to concurrent anti- and syn-eliminations, and tracer studies showed that part of the latter process from the isothujyl ‘onium compound involved the α′-β mechanism. Pyrolysis of thujyl acetates and borates, or treatment of the alcohols with iodine or zinc chloride, resulted exclusively in ring-opened products. A brief study of additions to (+)-sabinene and (–)-α-thujene suggests that generation of the 4-thujyl carbonium ion is favoured over that of the 3-thujyl ion, despite the potentialities of the latter for formation of a non-classical species.

Article information

Article type
Paper

J. Chem. Soc. B, 1968, 1339-1346

Elimination reactions. Part II. Pyrolytic and base-promoted decompositions of thujyl compounds

D. V. Banthorpe and H. ff. S. Davies, J. Chem. Soc. B, 1968, 1339 DOI: 10.1039/J29680001339

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements