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Regiospecificity of intramolecular hydrogen transfer in cyclohexanol following chemical ionization
Author(s) -
Fenselau Catherine,
Green Mark M.,
Jardine Ian
Publication year - 1979
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.1210140608
Subject(s) - cyclohexanol , chemistry , deuterium , protonation , intramolecular force , kinetic isotope effect , reagent , ring (chemistry) , cyclohexanone , hydrogen , chemical ionization , photochemistry , selectivity , ion , ionization , stereochemistry , organic chemistry , catalysis , physics , quantum mechanics
Both H 2 O and HDO are eliminated from protonated d 11 ‐cyclohexanol under chemical ionization conditions using methane as the reagent gas. The elimination of H 2 O and HDO from the [M+H] + ions of cyclohexanol specifically labeled with deuterium in the 1; 2,6; 3,5; and 4 positions has been measured. It is found that there is considerable selectivity as to the position from which deuterium is lost in the elimination of HDO. That is, transfer from C‐4 is favored, some transfer from C‐3(5) occurs, little deuterium is lost from C‐2(6) and none is lost from C‐1. A mechanism involving ring protonation and ring opening followed by deuterium transfer to oxygen with subsequent loss of HDO is proposed to account for these observations.