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    A Crossover Mechanistic Investigation of the Wolff vs. photo-Favorskii Rearrangement of Diazo-p-Hydroxyacetophenone: Methoxy Substituent Effects on p-Hydroxyphenacyl Cage; Exploratory Studies of Hydroxyquinoline-Based Phototriggers

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    Issue Date
    2010-01-28
    Author
    Senadheera, Sanjeewa N.
    Publisher
    University of Kansas
    Format
    263 pages
    Type
    Dissertation
    Degree Level
    Ph.D.
    Discipline
    Chemistry
    Rights
    This item is protected by copyright and unless otherwise specified the copyright of this thesis/dissertation is held by the author.
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    Abstract
    A series of substituted p-hydroxyphenacyl (pHP) and 8-hydroxyquinoline photoremovable protecting groups were designed, synthesized and their photochemistry explored. The light-induced release of phosphates, carboxylates, phenyl ethers and molecular nitrogen (N2) was studied. It was found that photorelease of diethyl phosphate from o-methoxy substituted pHP derivatives were 50% more efficient than the m-methoxy derivatives. In addition, convenient, high yield, one-pot syntheses of several p-HP chromophores were made from their corresponding benzoic acids via the α-diazo-p-hydroxyacetophenones. Photochemical and photophysical studies of the diazo pHP derivatives provided insight into the mechanism of N2 release. Time-resolved IR spectroscopic measurements, sensitization and quenching studies and product analyses support a mechanism for nitrogen release that proceeds via a photochemical Wolff rearrangement pathway. A preliminary study on the photochemistry of 1,5-substituted 8-hydroxyquinolines showed a strong dependence on the leaving group and the presence or absence of oxygen for this heterocyclic pHP analog.
    URI
    http://hdl.handle.net/1808/6469
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    • Dissertations [4473]
    • Chemistry Dissertations and Theses [336]

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    Contact KU ScholarWorks
    785-864-8983
    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    785-864-8983

    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    Image Credits
     

     

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