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

Venugopalan, Paloth; Venkatesan, K.; Klausen, Jörg; Novotny-Bregger, Elisabeth; Leumann, Christian; Eschenmoser, Albert; Dunitz, Jack D. (1991). On the Methyl-Transfer Reaction in Crystalline Methyl 2-(Methylthio)benzenesulfonate: a Thermally Induced Non-Topochemical Solid-State Reaction. Helvetica chimica acta, 74(3), pp. 662-669. Verlag Helvetica Chimica Acta 10.1002/hlca.19910740323

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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 (Original Article)

Division/Institute:

08 Faculty of Science > Departement of Chemistry and Biochemistry

UniBE Contributor:

Leumann, Christian

Subjects:

500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry

ISSN:

0018-019X

Publisher:

Verlag Helvetica Chimica Acta

Language:

English

Submitter:

Christian Leumann

Date Deposited:

21 May 2015 09:26

Last Modified:

21 May 2015 09:26

Publisher DOI:

10.1002/hlca.19910740323

URI:

https://boris.unibe.ch/id/eprint/68878

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