ISSN:
0030-493X
Keywords:
Chemistry
;
Analytical Chemistry and Spectroscopy
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Nearly all [C5H10O]+· isomers with the oxygen on the second carbon are shown to interconvert with each other and lose methyl and ethylene at the threshold for dissociation. The methyls contain the carbons from the 1- and 5-positions with about equal frequency, and C(3) or perhaps C(4) about half as often as either terminal carbon. CH3 CH2 CH2 CO+ is formed by loss of the C(1) methyl and by loss of the C(5) methyl. Hydorgen transfer between C(5) and the oxygen and between the oxygen and C(4) are facile, and 1,2-hydrogen transfers between C(3) and C(4) occur with high frequency. Extensive skeletal rearrangements also take placae by 1,2-shifts between C(2), C(3) and C(4). We attribute the occurrence of teh three-center shifts between C(2), C(3) and C(4) to the presence of considerable charge density on C(2) and C(3) in many of the [C5H10O]+· isomers. The isomerizations of [C5H10O]+· can be considered a mixture of free radical and carbocation reactions. Strong similarities exist between the isomerizations of metastable [C5H10O]+· ions with the oxygen on the second carbon and those of isomers of ionized butanoic acid, methyl butanoate and n-butanal.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/oms.1210190802
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