Aerobic oxidation of cycloalkanes, alcohols and ethylbenzene catalyzed by the novel carbon radical chain promoter NHS (N-hydroxy saccharin)

Replacementof Ishii's N-hydroxyphthalimide (NHPI) with the novel carbon radical chain promoter N-hydroxysaccharin (NHS) affords, in combination with metal salts, notably Co, or other additives, selective catalytic autoxidation of hydrocarbons, alcohols and alkylbenzenes under mild conditions (25 ± 100 °C, O2 1 atm). The effects of solvent, temperature and the nature of the additives were investigated to give an optimised oxidation protocol for the various systems. The NHS/Co combination was more reactive than NHPI/Co in the autoxidation of cycloalkanes. In contrast, the opposite order of reactivity was observed in the autoxidation of ethylbenzene and alcohols. It is suggested, on the basis of bond dissociation energy (BDE) considerations, that this is a result of a change in the rate-limiting step with the more reactive ethylbenzene and alcohol substrates. In the autoxidation of the model cycloalkane, cyclododecane, the best results (90% selectivity to a 4 : 1 mixture of alcohol and ketone at 24% conversion) were obtained with NHS/Co(acac)3 in PhCF3 at 80 °C. Competitionexperiments revealed that, in contrast to what is commonly believed, formation of the dicarboxylic acid by ring opening is nota resultof further oxidation of the ketone product. It is suggested that ring opened products are a result of beta-scission of the cycloalkoxy radical formed via (metal-catalysed) decomposition of the hydroperoxide. This is suppressed in the presence of NHS (or NHPI) which efficiently scavenge the alkoxy radicals.