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Reactivity of tert-butoxy radicals towards thiols, alkyl sulfides, and alkyl disulfides

✍ Scribed by M. V. Encinas; E. A. Lissi; C. Majmud; A. F. Olea

Publisher
John Wiley and Sons
Year
1989
Tongue
English
Weight
326 KB
Volume
21
Category
Article
ISSN
0538-8066

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✦ Synopsis

Rate constants for the reactions of tert-butoxy radicals (generated by the thermal decomposition of di-tert-butylperoxyoxalate) with several sulfur containing compounds have been measured a t 310 K in benzene. Hexanethiol ( k = 6.5 x lO'M-'s-') reacts considerably faster than alkyl sulfides and disulfides. For these compounds the reaction rate constants are slightly dependent on the a-hydrogen type, changing (when it is expressed per hydrogen atom) only a factor 5 for sulfides and 3 for disulfides when the a-hydrogen is changed from primary (methyl) to tertiary (isopropyl). The data obtained are compared to those found for the deactivation of the benzophenone triplet. Values of k,,, ~utoxy/kbenzophenone range from ca (di-tert-butyl disulfide) to 7.5 (hexanethiol). The results obtained are rationalized in terms of bond strength, steric hindrance, and charge transfer contributions to the critical configuration energies.

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