Thermal and photochemical decomposition of azo and azoxyalkanes

[摘要] The photolysis of vicinal azoazoxy compound 20 gave azo-side extrusion of N$sb2$ and formation of azoxy products resulting from radical disproportionation and recombination. Photolysis of vicinal bisazoxy compound 21 resulted in deoxygenation to 20 and vicinal bisazo compound 9B. The $190spcirc$C thermolysis of 20 yielded a mixture of products from C-C and C-N homolysis, with a $Deltam Gddagger$ of 34.8 kcal $m molsp{-1}. Delta Gddaggersb{C-C}$-$mDelta Gddaggersb{C-N}$ is calculated to be approximately 2.4 kcal mol$sp{-1}$ and 1.0 kcal mol$sp{-1}$ with and without 9,10-dihydroanthracene, respectively. Thermolysis of 21 and azoxy-tert-butane at $190spcirc$C resulted in decomposition at the azoxy functionality by a non-radical process similar to the Cope amine oxide pyrolysis. No products of C-C homolysis were seen in the thermolysis of 21.

[发布机构] Rice University

[效力级别] chemistry