PHOTOCHEMICAL STUDIES OF SECONDARY NITRAMINES. 1. ABSORPTION SPECTRA OF NITRAMINES AND PHOTOLYSIS OF DIMETHYLNITRAMINE IN SOLUTION
PICATINNY ARSENAL DOVER NJ
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The report reviews the absorption spectra of several nitramines and gives new spectra for dimethylnitramine, RDX, and HMX. It also deals with the photolysis of dimethylnitramine in alcohol solution. Solvent shifts in the absorption spectra support the conclusion that dimethylnitramine undergoes a pi- pi electronic transition caused by intense absorption in the near UV 240 nm and exhibits weak absorption in n-hexane up to 318 nm, probably due to excitation of nonbonding electrons in the nitramino groups. Although the solvent chosen for the study was ethyl alcohol, some data are presented from photolysis in acetonitrile and n-hexane, as well as from irradiation in the solid form. G. C., NMR, IR, and UV techniques were used for product analysis. The major photolysis product of dimethylnitramine under the experimental conditions used appears to be N-nitrosodimethylamine, as in gas-phase thermal decomposition. In alcohol solution, its rate of formation increases considerably and later levels off with increasing initial concentration of dimethylnitramine. The overall photodecomposition is compared with previous thermal decomposition and electron- impact fragmentation data in terms of bond-breaking steps.
- Organic Chemistry
- Radiation and Nuclear Chemistry