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[摘要]：Experimental and computational evidence suggests that the cleavage of n-butyl and tert-butyl 3-bromodiazirine-3-carboxylates by sodium n-butoxide in DMF, affording high yields of dibutyl carbonates, may proceed by nucleophilic acyl displacement of the bromodiazirinyl anion, a weakly bound complex of a cyclic carbene c-CN(2) (diazirinylidene) and a bromide ion. We explain the formation of substantial amounts of di-n-butoxymethane in the presence of n-butanol by a sequence of O-H insertion and denitrogenation reactions of the putative c-CN(2) carbene. This ground-state singlet species is the last undescribed member of the CN(2) family of reactive intermediates. It differs from classical N-heterocyclic carbenes by its high ionization potential and electron affinity. |
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