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|Title:||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)|
|Author(s):||Schrock, Alan Keith|
|Department / Program:||Chemistry|
|Degree Granting Institution:||University of Illinois at Urbana-Champaign|
|Abstract:||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.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1984.
|Date Available in IDEALS:||2014-12-15|