摘要：

The potent skin sensitizers hex-1-ene- and hexane-1,3-sultone have been synthesized isotopically labeled with 13C at reactive sites. The reactivity of 2-[13C]- and 3-[13C]hex-1-ene-1,3-sultones and of 3-[13C]hexane-1,3-sultone toward a series of model nucleophiles for protein amino acid residues, i.e., butylamine, diethylamine, imidazole, propanethiol, and phenol, was followed by 13C NMR spectroscopy. The reactivity in water of hex-1-ene-1,3-sultone toward model nucleophiles follows the hard and soft acid and base theory with the hard nucleophiles (primary and secondary amine and phenate) mainly reacting at position 3 by SN substitution, and the soft nucleophiles (thiolate and imidazole) mainly reacting at position 2 by a Michael addition reaction. Hexane-1,3-sultone reacts with model nucleophiles at position 3 by SN substitution. Both saturated and unsaturated sultones are sensitive to hydrolysis when reacted in water.

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