PHOTOLYSIS OF NITRATE ESTERS: PART I. PHOTONITRATION OF DIPHENYLAMINE

Abstract

The photolysis of nitrate esters dissolved in benzene or ethanol or absorbed on filter paper occurred readily under illumination in the 265 mμ to 334 mμ spectral region. Equimolar amounts of 1,4;3,6-dianhydro-D-glucitol-2,5-dinitrate and diphenylamine dissolved in absolute ethanol or benzene did not react in the dark at 25°. Irradiation of the nitrogen-purged solutions for 2 hours at 15° with a mercury arc followed by chromatographic separation yielded 2-nitro-, 4-nitro-, N-nitroso-, and 4-nitroso-diphenylamine together with about 4% unreacted diphenylamine and an unidentified mixture of more polar compounds. In a partial fractionation of the aromatic photoproducts approximately 80% of the original diphenylamine was recovered in the form of the monosubstituted derivatives which contained about 37% of the original ester nitrogen as C-nitro groups and 2 to 3% as C- and N-nitroso groups.Possible mechanisms of the photonitration are discussed.