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Spectral and Mechanistic Investigation of Oxidative Decarboxylation of Phenylsulfinylacetic Acid by Cr(VI)
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 Title & Authors
Spectral and Mechanistic Investigation of Oxidative Decarboxylation of Phenylsulfinylacetic Acid by Cr(VI)
Subramaniam, Perumal; Selvi, Natesan Thamil; Devi, Soundarapandian Sugirtha;
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 Abstract
The oxidative decarboxylation of phenylsulfinylacetic acid (PSAA) by Cr(VI) in 20% acetonitrile -80% water (v/v) medium follows overall second order kinetics, first order each with respect to [PSAA] and [Cr(VI)] at constant [] and ionic strength. The reaction is acid catalysed, the order with respect to [] is unity and the active oxidizing species is found to be . The reaction mechanism involves the rate determining nucleophilic attack of sulfur atom of PSAA on chromium of forming a sulfonium ion intermediate. The intermediate then undergoes ,-cleavage leading to the liberation of . The product of the reaction is found to be methyl phenyl sulfone. The operation of substituent effect shows that PSAA containing electron-releasing groups in the meta- and para-positions accelerate the reaction rate while electron withdrawing groups retard the rate. An excellent correlation is found to exist between log and Hammett constants with a negative value of reaction constant. The value decreases with increase in temperature evidencing the high reactivity and low selectivity in the case of substituted PSAAs.
 Keywords
Phenylsulfinylacetic acid;Oxidative decarboxylation;Nucleophilic attack of sulfur;Substituent effect;
 Language
English
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