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The structure and mechanism of formation of C5H9O+ from ionized phytyl methyl ether |
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| Authors: | R D Bowen R T Gallagher S Meyerson |
| Institution: | 1. Chemistry and Chemical Technology, University of Bradford, BD7 1DP, Bradford, West Yorkshire, England 2. Department of Chemistry, University of Warwick, CV4 7AL, Coventry, England 3. 650 North Tippecanoe Street, 46403, Gary, Indiana, USA |
| Abstract: | The recent proposal that ionized phytyl methyl ether C16H33(CH3)C=CHCH2OCH 3 +· ] undergoes an allylic rearrangement to ionized isophytyl methyl ether CH2=CHC(C16H33)(CH3)OCH 3 +· ] before elimination of an alkyl radical is discussed. Both literature precedent and new results in which the structure of the M-C16H 33 · ]+ fragment ion is established by comparison of its collision-induced dissociation mass spectrum with the spectra of isomeric C5H9O+ ions of known structure are inconsistent with this proposal. The forma Hon of CH3CH=CHCH=O+CH3 by loss of a γ-alkyl substituent without skeletal isomerization rather than CH2=CHC(CH3)=O+CH3 after allylic rearrangement is explained in terms of a mechanism that involves two 1,2-H shifts, followed by σ-cleavage of the resultant ionized enol ether, C16H33(CH3)CH-CH=CHOCH 3 +· . |
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