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Decompositions of metastable [C 6 H 12 O] + ions with the oxygen on the third carbon: Ring‐size preferences in [C n H 2 n O] + ˙ ions
Author(s) -
Griffin Lawrence L.,
Holden Katherine,
Hudson Charles E.,
McAdoo David J.
Publication year - 1986
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210210403
Subject(s) - ring (chemistry) , chemistry , ion , metastability , hydrogen , deuterium , ring size , carbon fibers , enol , oxygen , isomerization , photochemistry , catalysis , organic chemistry , materials science , atomic physics , physics , composite number , composite material
The isomerizations preceding the metastable decompositions in the mass spectrometer of a number of [C 6 H 12 O] + ˙ ions with the oxygen on the third carbon are characterized utilizing deuterium labeling. Hydrogens are transferred in these ions by three‐, five‐ and six‐membered ring rearrangements, with propensities determined by features of the individual reactions. Three‐membered ring hydrogen transfers between α and β‐carbons are preferred to all five‐membered ring hydrogen transfers. However, six‐membered ring hydrogen transfers take place to the apparent exclusion of three‐membered ring hydrogen transfers to enol carbons when the products are of comparable stability. The low‐energy [C 6 H 12 O] + ˙ isomerizations characterized are predictable from the behavior of their lower homologs. It is concluded that the determinants of these reactions are the same as those of other highly reactive organic intermediates.