[1.3] -Hydroxylwanderung bei Radikalkationen von Allen-und Acetylenalkoholen/[1,3]-Hydroxyl Migration in Cation Radicals of Allene and Acetylene Alcohols
Open Access
- 1 September 1979
- journal article
- Published by Walter de Gruyter GmbH in Zeitschrift für Naturforschung B
- Vol. 34 (9) , 1307-1319
- https://doi.org/10.1515/znb-1979-0930
Abstract
Contrary to previous conclusions it is shown that the molecular ions of 1, 2, and 3 do not interconvert prior to dissociation. Investigation of labelled compounds establishes a new typ of intramolecular [1,3]-hydroxyl migration to allenic and acetylenic carbons. It is shown that both 1 and 2 undergo irreversible rearrangement to an a,β-unsaturated ketone 4. Methyl loss from the intermediate 4, which accounts for 90% of the total methyl elimination, is preceded by partial hydrogen exchange processes between the three methyl groups of 4. The actual dissociation can be described as an a-cleavage to the carbonyl function. The unusual formation of CH3CO+ " is shown to occur exclusively from 1. However, it is demonstrated that prior to CH3CO+ formation 1 rearranges to m. The mechanistic details of this as well as alternative processes are discussed.Keywords
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