Abstract
AbstractRate 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 at 310 K in benzene. Hexanethiol (k = 6.5 × 107M−1s−1) reacts considerably faster than alkyl sulfides and disulfides. For these compounds the reaction rate constants are slightly dependent on the α‐hydrogen type, changing (when it is expressed per hydrogen atom) only a factor 5 for sulfides and 3 for disulfides when the α‐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 ktert‐butoxy/kbenzophenone range from ca 10−3 (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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