Issue 12, 1984

Linear free energy relationship in naphthalene system. Kinetics of oxidation of 4-substituted 1-naphthyl methyl sulphides with peroxoanions

Abstract

The kinetics of the oxidation of several 4-substituted 1-naphthyl methyl sulphides and methyl 2-naphthyl sulphide with potassium peroxodisulphate and potassium peroxodiphosphate have been studied in 70% acetic acid–30% water (v/v) mixture. The results are in accord with rate-limiting electrophilic attack of the oxidants on the sulphide. The applicability of the Hammett equation to the rate data employing naphthalene and benzene substituent constants has been critically examined. Excellent results emerge in the correlation of rate constants with σp+ constants in both oxidations. The diminution in the electron-withdrawing ability of the acetyl group present in the 4-position of the naphthyl ring has been attributed to the steric inhibition of resonance of the acetyl group by the proximate peri-hydrogen. The reactivity order of methyl phenyl, methyl 1-naphthyl, and methyl 2-naphthyl sulphides (2-C10H7SMe > C6H5SMe > 1-C10H7SMe) found in these oxidations has been explained on the basis of polar and steric effects.

Article information

Article type
Paper

J. Chem. Soc., Perkin Trans. 2, 1984, 2065-2068

Linear free energy relationship in naphthalene system. Kinetics of oxidation of 4-substituted 1-naphthyl methyl sulphides with peroxoanions

C. Srinivasan, S. Perumal and N. Arumugam, J. Chem. Soc., Perkin Trans. 2, 1984, 2065 DOI: 10.1039/P29840002065

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements