Study of the Mechanism for the Hydrolysis of Alkoxy(aryl)(phenyl)-λ6-sulfanenitriles, ArPhS(OR)(N)

doi:10.1246/BCSJ.73.957

Paper

Study of the Mechanism for the Hydrolysis of Alkoxy(aryl)(phenyl)-λ6-sulfanenitriles, ArPhS(OR)(N)

Published Apr 15, 2000 · T. Yoshimura, T. Dong, T. Fujii

Bulletin of the Chemical Society of Japan

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Abstract

The hydrolysis of alkoxy(aryl)(phenyl)-λ6-sulfanenitriles in several buffer solutions was found to follow a good pseudo-first-order kinetic equation, giving the corresponding sulfoximides and alcohols (for the case of the hydrolysis of neopentyloxy-λ6-sulfanenitrile, giving a rearranged product, 2-methyl-2-butanol). The dependence of the rate of hydrolysis on the structure of the alkyl group showed the opposite trend to the usual SN2 character, i.e. Me < Pr < Bu ≈ Et < i–Pr, except for neopentyl. The pH-rate profiles indicated that the rate of hydrolysis is also first order in [H+] at pH more than 6.08, and trends to saturate at low pH. According to these kinetic results, a two-step reaction mechanism was proposed which involves a pre-equilibrium protonation on the nitrogen atom of the alkoxy-λ6-sulfanenitriles, followed by a rate-determining C-O bond cleavage via an SN2 or SN1 mechanism on the alkyl carbon atom depending on the structure of the alkyl group. From a double-reciprocal plot of 1/kobs vs. 1/[...

Study Snapshot

Hydrolysis of alkoxy(aryl)(phenyl)-6-sulfanenitriles follows a pseudo-first-order kinetic equation, with a two-step reaction mechanism involving pre-equilibrium protonation on the nitrogen atom and rate-determining C-O bond

PopulationOlder adults (50-71 years)

Sample size24

MethodsObservational

OutcomesBody Mass Index projections

ResultsSocial networks mitigate obesity in older groups.

Study of the Mechanism for the Hydrolysis of Alkoxy(aryl)(phenyl)-λ6-sulfanenitriles, ArPhS(OR)(N)

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