University of Illinois Urbana-Champaign

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

Autrey, Tom

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Description

Title
The Photochemistry of Beta-Naphthoyl Azide and 4-Acetylphenoxycarbonyl Azide: The Chemical and Physical Properties of Acylnitrenes
Author(s)
Autrey, Tom
Issue Date
1987
Doctoral Committee Chair(s)
Schuster, Gary B.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Language
eng
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.
Graduation Semester
1987
Type of Resource
text
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http://hdl.handle.net/2142/77258

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