PSEUDOHALOGEN CHEMISTRY. PART IV. HETEROLYTIC ADDITION OF THIOCYANOGEN TO ALKENES |
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Authors: | Richard Bonnett Robert G. Guy David Lanigan |
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Affiliation: | Department of Chemical Sciences , The Hatfield Polytechnic , P.O. Box 109, Hatfield, Hertfordshire, AL10 9AB, England |
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Abstract: | Abstract Thiocyanogen reacts slowly with alkenes, in the presence of a radical inhibitor in benzene or acetic acid in the dark at 25°, to yield α,β-dithiocyanates, α-isothiocyanates-β-thiocyanates and, in acetic acid, α-acetoxy-β-thiocyanates in varying proportions. The additions to alkyl alkenes are trans-stereospecific, and, in the case of the α-isothiocyanato-β-thiocyanates, non-regiospecific. The additions to aryl alkenes are trans-stereoselective and regiospecific, yielding the Markownikov-orientated α-isothiocyanato-β-thiocyanates. A heterolytic mechanism involving a two-step, kinetically controlled addition, with the formation of a cyano-sulfonium ion intermediate, e.g., 35, in the case of alkyl alkenes and an open carbonium ion, e.g., 36, in the case of aryl alkenes, is suggested. The diothiocyanate: isothiocyanato-thiocyanate ratios are discussed in terms of kinetic and steric control of reaction. |
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Keywords: | Phosphine selenides dipole moments conformational analysis quantum chemical calculations |
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