The Photochemistry of 3- and 4-Nitro Phenyl Azides

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.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Liang, Tsuei-Yun

• Chemistry, Organic

Identifier

(UMI)AAI8721692

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70372