The Photochemistry of Beta-Naphthoyl Azide and 4-Acetylphenoxycarbonyl Azide: The Chemical and Physical Properties of Acylnitrenes

117 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1987.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.U of I OnlyRestricted to the U of I community idenfinitely during batch ingest of legacy ETD