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On the Methyl-Transfer Reaction in Crystalline Methyl 2-(Methylthio)benzenesulfonate: a Thermally Induced Non-Topochemical Solid-State Reaction

Venugopalan, K and Venkatesan, P and Klausen, Jorg and Bregger, Elisabeth N and Leumann, Christian and Eschenmoser, Albert and Dunitz, Jack D (1991) On the Methyl-Transfer Reaction in Crystalline Methyl 2-(Methylthio)benzenesulfonate: a Thermally Induced Non-Topochemical Solid-State Reaction. In: Helvetica Chimica Acta, 74 (3). pp. 662-669.

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Abstract

The rearrangement of methyl 2-(methylthio)benzenesulfonate (1) to the zwitterionic 2-(dimethyl-sulfonium)benzenesulfonate (2) is known to proceed in solution by intermolecular Me transfers. The same rearrangement has been observed to occur in crystalline 1, but the crystal structure shows that the molecular packing is not conducive to intermolecular Me transfer. The reaction has been carried out with mixed crystals composed of 1 and deuteriomethylated (D6)-l. By fast-atom-bombardment mass spectroscopy, it has been shown that the product consists of a 1:2:1 mixture of the non-, tri-, and hexadeuterated species, the mixture expected, if the solid-state reaction proceeds by intermolecular Me transfers. From this result, together with the slower rates of conversion in the single crystal compared with the melt, it can be concluded that the reaction must occur not topochemically but rather at defects such as microcavities, surfaces, and other irregularities in the ordered crystal arrangement.

Item Type: Journal Article
Additional Information: The copyright belongs to Verlag GmbH & Co. KGaA, Weinheim.
Department/Centre: Division of Chemical Sciences > Organic Chemistry
Date Deposited: 21 Oct 2005
Last Modified: 27 Aug 2008 11:31
URI: http://eprints.iisc.ernet.in/id/eprint/3868

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