Characterization of Intermediates in the Reaction of Ozone with Di-tert-butylacetylene. A Novel Pivaloylating System

Article abstract of DOI:10.1021/jo00333a012

Reaction of di-tert-butylacetylene (1a) with ozone in <-40 deg C aprotic solvents upon warming leads to pivalic anhydride, pivalil, and pivalic acid, with evolution of isobutane, isobutene, carbon dioxide, and carbon monoxide.Spectral and chemical evidence indicated the presence of at least two labile intermediates in the reaction.Ozonolysis of the alkyne in the presence of compounds containing a hydroxyl function led to their pivaloyl derivatives with incorporation of both tert-butyl groups, probably via fragmentation of an adduct of ROH to an intermediate carbonyl oxide.