Ozonolysis of vinyl chloride in methanol: a convenient entry to methoxymethylhydroperoxide and its chemistry

Abstract
Ozonolysis of vinyl chloride (7) in methanol at −78 °C afforded methoxymethylhydroperoxide (10) in high yield along with only trace amounts of methyl formate (14). The former (10) was converted into a mixture of methyl formate (14) as the major and dimethylformal (18) as the minor product by HCl-catalysis in methanol. Reduction of 10 with dimethylsulfide and subsequent treatment with HCl–methanol gave dimethylformal (18). Partial reduction of 10 with a deficient amount of triphenylphosphine gave formaldehyde hemiacetal (19) and methoxymethylhydroxymethylperoxide (20).

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