Bis(dimethoxymethy1) peroxide and bis(1,l-dimethoxyethyl) peroxide1

KARL R. KOPECKY and JosB MOLINA. Can. J. Chem. 65 , 2350 (1987) The title compounds 1 and 2, the first examples of peroxides polysubstituted at the a and a' 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 170 nuclear magnetic resonance spectrum. Luminescence results when 1 and 2 are heated to 150°C.