ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The second ionization of the 4-chloro-3-methylbutanoyl ion forms a primary alkyl acyl dication, as a tight ion pair. Methyl and hydrogen shifts occur to comparable extents indicating that the relative stability of the product (sec- or tert-carbocation) does not influence the energy barrier for the shift. The product of methyl shift (1,3-sec-alkyl acyl dication) loses the proton closest to the counterion in the tight ion pair and forms the pent-3-enoyl cation. Protonation-deprotonation of the latter, followed by internal acylation, gives the protonated cyclopent-2-enone. The dication resulting from hydrogen shift loses a proton from C-2 and gives the 3-methylbut-2-enoyl cation.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610031004
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