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|Title:||The Photochemistry of Beta-Naphthoyl Azide and 4-Acetylphenoxycarbonyl Azide: The Chemical and Physical Properties of Acylnitrenes|
|Doctoral Committee Chair(s):||Schuster, Gary B.|
|Department / Program:||Chemistry|
|Degree Granting Institution:||University of Illinois at Urbana-Champaign|
|Abstract:||We have examined the chemical and physical properties of two acylnitrenes, 4-acetylphenoxycarbonylnitrene (APN) and $\beta$-naphthoylnitrene (BNN) generated by the photolysis of 4-acetylphenoxycarbonyl azide and $\beta$-naphthoyl azide (BNA) respectively. These nitrenes were investigated using low-temperature optical, electron spin resonance, and transient absorption spectroscopy as well as by traditional chemical trapping techniques.
APN is a ground state triplet nitrene which appears to be no more than 5 kcal/mol below the lowest energy singlet nitrene. The properties of APN are dominated by those typically associated with triplet nitrenes: nonstereospecific addition to olefins and a readily detectable electron spin resonance spectrum.
BNN is the first bona fide example of an acylnitrene with a singlet ground state. The properties of BNN are those typically associated with singlet nitrenes: direct or triplet sensitized irradiation of BNA gives products derived exclusively from the singlet nitrene.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1987.
|Date Available in IDEALS:||2015-05-13|