Mechanism of the addition of alcohols to substituted phenylisothiocyanates : Electrical effects of the substituents on the reaction

Rao, CNR and Venkataraghavan, R (1962) Mechanism of the addition of alcohols to substituted phenylisothiocyanates : Electrical effects of the substituents on the reaction. In: Tetrahedron, 18 (5). pp. 531-537.

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Abstract

The addition reaction of alcohols to substituted phenylisothiocyanates is found to be a second-order reaction. The reaction is catalysed by triethylamine. First-order rate constants of the addition reaction have been determined in excess of ethanol, for a number of substituted phenylisothiocyanates and the rate data give a satisfactory linear correlation with Hammett σ constants of groups. While the energies of activation vary randomly with substitution, the entropies of activation bear a linear relationship to the energies of activation. Infra-red spectra indicate that the thiourethanes which are the products of the addition reaction exist in the thioamide form. The most prominent resonance form which can satisfactorily explain both the kinetic and infrared data, has been suggested.

Item Type:	Journal Article
Publication:	Tetrahedron
Publisher:	Elsevier Science
Additional Information:	Copyright of this article belongs to Elsevier Science.
Department/Centre:	Division of Chemical Sciences > Organic Chemistry Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	02 Jun 2010 04:45
Last Modified:	19 Sep 2010 06:08
URI:	http://eprints.iisc.ac.in/id/eprint/28240

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