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Abstract:

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    The title compounds 1 and 2, the first examples of peroxides polysubstituted at the a and a, position 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 60ºC. In acidic methanol both 1 and 2 undergo solvolysis rapidly with exclusive cleavage of the carbon-peroxy oxygen bond. Signal for the ether and peroxy oxigens 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 150ºC.

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