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|Title:||The Photochemistry of 3- and 4-Nitro Phenyl Azides|
|Department / Program:||Chemistry|
|Degree Granting Institution:||University of Illinois at Urbana-Champaign|
|Abstract:||The photochemistry of 4-nitro and 3-nitrophenyl azides in inert and reactive solvents was examined. Photolysis of nitrophenyl azides in solution at room temperature or in a frozen glass at 77 K gives triplet nitrenes. The products of the reaction of triplet nitrenes depend on the power of the light source. Triplet 4-nitrophenyl nitrene dimerizes to form azobenzene at a diffusion controlled rate and reacts with the tertiary amine by single-electron transfer. The rate constant of the reaction of triplet nitrenes with O$\sb2$ is ca. 10,000 fold slower than the dimerization. The precursors of the triplet nitrenes can be trapped by secondary amines. The mechanisms of these reactions are discussed.|
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1987.
|Date Available in IDEALS:||2014-12-15|