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KMID : 1059519970410010039
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Journal of the Korean Chemical Society
1997 Volume.41 No. 1 p.39 ~ p.45
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Acid and Nucleophile-Catalyzed Hydrolysis of Sulfinamides
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Lee Jong-Pal
Uhm Tae-Seop
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Abstract
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We have been kinetically studied on acid and nucleophile catalysis for hydrolysis of sulfinamides at 25℃ in aqueous solution at the ionic strength of 0.1 M with NaClO4 by spectrophotometrically. The substrates which the leaving group aniline has electron donating group were shown a breakdown of pH-rate profile at near pH 3 as well as the substrate having electron donating group at benzenesulfinyl group. The break is ascribed to a change in the rate determining step of the reaction involving a hypervalent intermediate. However, the substrates which have the leaving group with electron withdrawing group were not observed a breakdown of pH-rate profile at pH 3. Catalysis of halide ion was observed in the hydrolysis of sulfinamides. The nucleophile reactivity observed was in the order of Br- > Cl-, but also found to depend upon the acid concentration of solution. From the Hammett’s reaction constant ρ values which were obtained by effect of substituent of sulfinamides, we expect that the reaction mechanism may proceed via sulfonium cation.
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