Nitrosation and Nitration of Olefins using Nitrogen Monoxide

Nitrosation of various α, β-unsaturated carbonyl compounds with nitrogen monoxide or butyl nitrite was achieved in the presence of silane and a catalytic amount of N,N'-bis(2-ethoxycarbonyl-3-oxobutylidene)ethylenediaminatocobalt(n) complex catalyst. In the presence of a catalytic amount of tris (1,3-diketonato) iron (III) complex, various terminal and 1,2-disubstituted olefins were converted into the corresponding nitroso alkane dimers in fairly good yields on treatment with phenylsilane and butyl nitrite. Nitration of various terminal olefins into corresponding nitro olefins were performed on treatment with nitrogen monoxide. Nitroalcohols, minor coproducts, were dehydrated to yield nitro olefins by the subsequent treatment with acidic activated aluminum. By GC analysis, evolution of an equimolar amount of nitrogen gas was observed during the present nitration. A possible reaction pathway including the formation of nitro nitroso compounds, key intermediates, was proposed.