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Schrock, Alan Keith 2014-12-15T23:18:11Z 2014-12-15T23:18:11Z 10000-01-01 1984 1984 One. The photochemistry of phenyl azide, 1-naphthyl azide, 2-naphthyl azide, 1-anthryl azide, 2-anthryl azide, 1-pyrene azide, and 2-pyrene azide was examined by laser flash photolysis inert and reactive solvents. The products of direct photolysis of the aryl azides can depend dramatically on the concentration of the azide and on the power of the light source. Direct irradiation gives the triplet aryl nitrenes, with relatively long-lived singlet-state precursors. The structures of these intermediates and their rates of reaction with secondary amines are discussed. Two. Thermolysis of 1,4-diphenyl-1,4-dioxa-2,3-benzopyrone in p-xylene solution generates chemiluminescence and three products. The major product is 1,4-diphenyl-2,3-benzodioxin (o-xylylene peroxide). This peroxide eventually becomes o-dibenzoylbenzene which is isolated from the reaction in 85% yield. Two other products, 1,3-diphenylisobenzofuran and phenyl-o-benzoyl benzoate, are isolated in yields of ca. 2% and 5%, respectively. The lifetime and reactions of the o-oxylylene peroxide are discussed. The observed chemiluminescence results from interaction of the o-xylylene peroxide with the minor product 1,3-diphenylisobenzofuran according to the chemically initiated electron-exchange luminescence (CIEEL) mechanism. Made available in DSpace on 2014-12-15T23:18:11Z (GMT). No. of bitstreams: 1 8422148.pdf: 7431213 bytes, checksum: 49a1b267f8902358c404f1d88a660ca5 (MD5) Previous issue date: 1984 Embargo set by: Seth Robbins for item 70423 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 269 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1984. http://hdl.handle.net/2142/70257 (UMI)AAI8422148 Chemistry, Organic Part One: Photochemistry of Aryl Azides. Chemical Properties of the Transient Intermediates. Part Two: Thermolysis of an Endoperoxide. Generation of an O-Xylylene Peroxide (Nitrene) text Dissertation Ph.D. Chemistry Chemistry University of Illinois at Urbana-Champaign