ISSN:
0030-493X
Keywords:
Chemistry
;
Analytical Chemistry and Spectroscopy
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
New experimental data on the rearrangement reaction of various phenoxyethyl halides to give [C6H6O]+· are presented and compared with previous studies so that a coherent picture of this process can be developed. By examining the metastable kinetic energy release for low energy decomposing molecular ions of the phenoxyethyl halides, it has been concluded that formation of [C6H6O] occurs by competitive 1,2 and 1,3 hydrogen shifts from the alkyl carbons to oxygen followed by a rate determining C—O bond cleavage. This is substantiated by the absence of a primary hydrogen isotope effect. For more highly activated molecular ions, a new mechanism comes into play as evidenced by the appearance of a small hydrogen isotope effect. It is postulated that this third mechanism involves transfer of the alkyl hydrogen to the ortho position of the ring by a rate determining 1,5 shift, followed by a 1,3 hydrogen shift from the ortho methylene group to oxygen and rapid C—O bond cleavage. This 1,3 hydrogen shift to oxygen appears to be ‘catalysed’ by the halogen atoms yielding phenol ions. No indications have been found for the formation of tautomeric 2,4-cyclohexadienone ions. Furthermore, highly activated molecular ions produce [C6H6O]+· which can undergo metastable decomposition to lose carbon monoxide. Kinetic energy release measurements for the latter reaction show that the majority of these [C6H6O]+·ions have been formed as phenol ions as well. These arguments are supported by energetic measurements and by comparisons with previous ion cyclotron resonance and collisional activation studies.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/oms.1210140904
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