ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Kinetics of oxidation of twenty six S-arylmercaptoacetic acids (SAMA) (I) by sodium perborate (PB) have been studied in acid medium. The product of oxidation is the corresponding thiophenol. The rate data of meta-and para-substituted acids have been correlated with DSP equations. While the para-compounds correlate well with σI and σR° values, the meta-compounds correlate well with σI and σR- values. The reaction constants are negative and of smaller magnitudes. Further, the ortho-substituted acids show a good correlation with a triparametric equation involving Taft's σI and R° and Charton's steric parameter ν. There is a considerable steric contribution to the total ortho-substituent effect. Based on these observations, mechanism involving the formation of protonated arylsulfinylacetic acid intermediate, followed by an intramolecular rearrangement leading to the product thiophenol has been proposed. © 1995 John Wiley & Sons, Inc.
Additional Material:
9 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550270504
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