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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
dc.contributor.advisor | Givens, Richard S. | |
dc.contributor.author | Senadheera, Sanjeewa N. | |
dc.date.accessioned | 2010-07-30T11:02:09Z | |
dc.date.available | 2010-07-30T11:02:09Z | |
dc.date.issued | 2010-01-28 | |
dc.date.submitted | 2010 | |
dc.identifier.other | http://dissertations.umi.com/ku:10731 | |
dc.identifier.uri | http://hdl.handle.net/1808/6469 | |
dc.description.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. | |
dc.format.extent | 263 pages | |
dc.language.iso | EN | |
dc.publisher | University of Kansas | |
dc.rights | This item is protected by copyright and unless otherwise specified the copyright of this thesis/dissertation is held by the author. | |
dc.subject | Organic chemistry | |
dc.subject | Analytical chemistry | |
dc.subject | Chemistry | |
dc.subject | Biochemistry | |
dc.subject | Alpha-diazoketones | |
dc.subject | Photo-favorskii rearrangement | |
dc.subject | Photo-wolff rearrangement | |
dc.subject | Quenching with molecular oxygen | |
dc.subject | Time-resolved ir spectroscopy | |
dc.subject | Triplet sensitization | |
dc.title | 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 | |
dc.type | Dissertation | |
dc.contributor.cmtemember | Carlson, Robert G. | |
dc.contributor.cmtemember | Hanson, Paul R. | |
dc.contributor.cmtemember | Aldrich, Jane V. | |
dc.contributor.cmtemember | Johnson, Michael | |
dc.thesis.degreeDiscipline | Chemistry | |
dc.thesis.degreeLevel | Ph.D. | |
kusw.oastatus | na | |
kusw.oapolicy | This item does not meet KU Open Access policy criteria. | |
kusw.bibid | 8085514 | |
dc.rights.accessrights | openAccess |
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Dissertations [4889]