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https://hdl.handle.net/2440/4715
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Type: | Journal article |
Title: | Competitive charge-remote and anion-induced fragmentations of thenon-8-enoate anion. A charge-remote reaction which co-occurs withhydrogen scrambling |
Author: | Dua, S. Bowie, J. Cerda, B. Wesdemiotis, C. Raftery, M. Kelly, J. Taylor, M. Blanksby, S. Buntine, M. |
Citation: | Journal of the Chemical Society, Perkin Transactions 2, 1997; 4(4):695-702 |
Publisher: | Royal Society of Chemistry |
Issue Date: | 1997 |
ISSN: | 1472-779X 1364-5471 |
Statement of Responsibility: | Suresh Dua, John H. Bowie, Blas A. Cerda, Chrys Wesdemiotis, Mark. J. Raftery, Julian F. Kelly, Mark S. Taylor, Stephen J. Blanksby and Mark A. Buntine |
Abstract: | The non-8-enoate anion undergoes losses of the elements of C₃H₆, C₄H₈ and C₆H₁₂ on collisional activation. The mechanisms of these processes have been elucidated by a combination of product ion and labelling (²H and ¹³C) studies, together with a neutralisation reionisation mass spectrometric study. These studies allow the following conclusions to be made. (i) The loss of C3H6 involves cyclisation of the enolate anion of non-8-enoic acid to yield the cyclopentyl carboxylate anion and propene. (ii) The loss of ‘C₄H₈’ is a charge-remote process (one which proceeds remote from the charged centre) which yields the pent-4-enoate anion, butadiene and dihydrogen. This process co-occurs and competes with complex H scrambling. (iii) The major loss of ‘C₆H₁₂’ occurs primarily by a charge-remote process yielding the acrylate anion, hexa-1,5-diene and dihydrogen, but in this case no H scrambling accompanies the process. (iv) It is argued that the major reason why the two charge-remote processes occur in preference to anion-induced losses of but-1-ene and hex-1-ene from the respective 4- and 2-anions is that although these anions are formed, they have alternative and lower energy fragmentation pathways than those involving the losses of but-1-ene and hex-1-ene; viz. the transient 4-anion undergoes facile proton transfer to yield a more stable anion, whereas the 2-(enolate) anion undergoes preferential cyclisation followed by elimination of propene [see (i) above]. |
Rights: | © Royal Society of Chemistry 2008 |
DOI: | 10.1039/a607437e |
Published version: | http://dx.doi.org/10.1039/a607437e |
Appears in Collections: | Aurora harvest 6 Chemistry publications |
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