Bis(dimethoxymethyl) peroxide and bis(1,1-dimethoxyethyl) peroxide

Abstract

The title compounds 1 and 2, the first examples of peroxides polysubstituted at the α and α′ positions by alkoxy groups, are formed by benzophenone sensitized photooxygenation of trimethoxymethane and 1,1,1-trimethoxyethane, respectively. No peroxide was formed from tetramethoxymethane. Allowing 98% hydrogen peroxide and trimethoxymethane to stand results in an 80% yield of 1, so that 1 and 2 are probably formed by such a disproportionation reaction during photooxygenation. Compound 1 is converted quantitatively to methanol, methyl formate, and dimethyl carbonate in pyridine solution at 60 °C. In acidic methanol both 1 and 2 undergo solvolysis rapidly with exclusive cleavage of the carbon – peroxy oxygen bond. Signals for the ether and peroxy oxygens of 1 appear at 34 and 263 ppm and those of 2 appear at 40 and 264 ppm in the 17O nuclear magnetic resonance spectrum. Luminescence results when 1 and 2 are heated to 150 °C.