C. G. Moore, M. Porter
1960
Citations
0
Influential Citations
10
Citations
Journal
Tetrahedron
Abstract
Abstract 2,4-Dinitrobenzenesulphenyl chloride (I) reacts with dialkyl, diaralkyl, and alkyl aralkyl monosulphides at ca. 20° in dry acetic acid to give alkyl or aralkyl 2,4-dinitrophenyl disulphides together with alkyl or aralkyl chlorides as major products. The reactivity order with respect to the constitution of the sulphide is: tertiary alkyl > benzyl > secondary alkyl > primary alkyl. With unsymmetrical sulphides, the more branched alkyl group is displaced by the 2,4-dinitrophenylthio group. Monosulphides containing allylically-unsaturated groups react with I both by its addition to the double bond and by fission of a CS bond in the derived adduct. Based on the response of both the course and rate of reaction to the constitution of the monosulphide and to the nature of the solvent a polar mechanism is proposed, involving an initial electrophilic attack of the sulphenylchloride on the sulphide sulphur to give a “sulphonium ion” type intermediate which then undergoes cleavage of a preferred CS bond (dependent on the structures of the alkyl and aralkyl groups) to give the observed products.