Perfluoroalkylation of the 2-Nitropropyl Anion. Evidence for an SRN1 Process

Article abstract of DOI:10.1021/jo00151a014

The reaction of primary perfluoroalkyl iodides (R_fI, R_f = n-C6F13, n-C8F17) and diiodides I(CF2)_nI (n=4,6) with the 2-nitropropyl anion gives 2-(perfluoroalkyl)-2-nitropropanes.The anion was employed as the tetrabutylammonium salt in benzene or in organic solvent /water mixtures or as the lithium salt in dimethylformamide or dimethyl sulfoxide with and without UV irradiation.Evidence is presented for an S_RN1 process by trapping of radical intermediates with benzene, styrene, methyl methacrylate, and vinyl acetate and by competition experiments with p-dinitrobenzene.Substitution of the nitro group in the 2-(perfluoroalkyl)-2-nitropropanes occurs under S_RN1 conditions with 2-nitropropyl anion, benzenethiolate, and hydride.