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 $190\sp\circ$C thermolysis of 20 yielded a mixture of products from C-C and C-N homolysis, with a $\Delta\rm G\ddagger$ of 34.8 kcal $\rm mol\sp{-1}.\ \Delta G\ddagger\sb{C-C}$-$\rm\Delta G\ddagger\sb{C-N}$ 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 $190\sp\circ$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.
| Identifer | oai:union.ndltd.org:RICE/oai:scholarship.rice.edu:1911/14043 |
| Date | January 1996 |
| Creators | Irby, Timothy Andrew |
| Contributors | Engel, Paul S. |
| Source Sets | Rice University |
| Language | English |
| Detected Language | English |
| Type | Thesis, Text |
| Format | 62 p., application/pdf |
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