Interaction of α-pinene with carboxylic acids

Valkanas, GN

dc.contributor.author	Valkanas, GN	en
dc.date.accessioned	2014-03-01T01:37:49Z
dc.date.available	2014-03-01T01:37:49Z
dc.date.issued	1976	en
dc.identifier.issn	00223263	en
dc.identifier.uri	https://dspace.lib.ntua.gr/xmlui/handle/123456789/21757
dc.relation.uri	http://www.scopus.com/inward/record.url?eid=2-s2.0-0011494283&partnerID=40&md5=b9f2e9cd0b3ffe7e73851e3d6ee0c466	en
dc.title	Interaction of α-pinene with carboxylic acids	en
heal.type	journalArticle	en
heal.publicationDate	1976	en
heal.abstract	The interaction of α-d-pinene with a series of organic acids from acetic to octanoic, under a wide range of olefin to acid ratios, yields esteric and rearrangement products after ring opening to the p-menthane system and ring rearrangement to the camphane system. Evidence is presented that the esterification proceeds through two distinct mechanisms one of which is highly dependent on the ionizing power and the nucleophilicity of the solution. This reaction leads to α-terpinyl esters while the esterification to bornyl and α-fenchyl esters is a reaction of zero order in the organic acid that constitutes 23.6 ± 1.5% of total product under all conditions. Furthermore, the bicyclic esters bornyl and α-fenchyl are produced in a constant ratio (bornyl/α-fenchyl = 1.6 ± 0.2). The esterification to give the terpinyl esters is explained as proceeding through solvolysis of a carbonium ion after a ring bond rupture. The esterification to give bornyl and α-fenchyl esters is considered to be the result of the filling of the vacant orbital created after a skeletal rearrangement with strain release from the pinane to the camphane skeletal system. The isomerization reaction is also suggested as following two reaction paths, one through carbonium ion intermediates producing limonene and terpinolene and the other through nonclassical intermediates with distributed charge to produce camphene and α- and β-fenchenes. For all these reactions consistent mechanistic explanations of the results are given.	en
heal.journalName	Journal of Organic Chemistry	en
dc.identifier.volume	41	en
dc.identifier.issue	7	en
dc.identifier.spage	1179	en
dc.identifier.epage	1183	en