Alkali Metal Adducts of Aromatic Nitro Compounds Reactions and Use in Polymerization of Vinyl Monomers

The reaction of alkali metals with nitrobenzene and -nitro-toluene in THF at various molar ratios was found to lead to the formation of radical ions, dianions, and alkali metal adducts of reduction derivatives of the nitro compounds such as azo- and azoxybenzene. The anionic polymerization of styrene, methyl methacrylate, methacrylonitrile, and acrylonitrile by these anions was investigated. All the initiators did not polymerize styrene while the least reactive radical-anion was found to polymerize acrylonitrile completely, methacrylonitrile to a small extent, but not methyl methacrylate. The order of reactivity of those adducts toward organic halides was similar to that found in polymerization. Metallation of polynitrostyrene by lithium biphenyl solution led only to partial conversion of the nitro groups to radical-anions which were not reactive.