Using combinatorial kinetic isotope effects to determine reaction mechanisms /
Experimental kinetic isotope elects and experimental transition states for several reactions along with some newly developed techniques for mechanism elucidation are discussed. The reactions studied include electrophillic additions (bromination, expoxidation, dichlorcarbene) to pentane, Diels-Alder...
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| Format: | Thesis Book |
| Language: | English |
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[Place of publication not identified] :
[publisher not identified] ;
1999.
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| Subjects: | |
| Online Access: | http://proxy.library.tamu.edu/login?url=http://proquest.umi.com/pqdweb?did=731681741&sid=1&Fmt=2&clientId=2945&RQT=309&VName=PQD |
| Summary: | Experimental kinetic isotope elects and experimental transition states for several reactions along with some newly developed techniques for mechanism elucidation are discussed. The reactions studied include electrophillic additions (bromination, expoxidation, dichlorcarbene) to pentane, Diels-Alder (retro, Lewis acid catalyzed inverse electron demand) reactions, hydrogen atom abstraction (TBHP), and decarboxylation of 1,3-dimethylorotic acid. Experimental transition states were suggested when there was good agreement between experiment and theory. The experimental transition state obtained for the elucidation of pentane settled a 40 year old debate on the synchronicity of C-O bond formation. Dichlocarbene addition to pentane was the first experimental evidence for a non least-motion approach. The experimental transition state for the decarboxylation of 1,3-dimethylorotic acid may aid in explaining the difference between the uncatalyzed and enzymatic realigns. New techniques for mechanism elucidation are discussed. They include the separation of primary and secondary isotope elects from starting material reactivities, the determination of 170 and 180 isotope elects, and stereochemical labeling. |
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| Item Description: | Vita. "Major Subject: Chemistry". |
| Physical Description: | xv, 142 leaves : illustrations ; 28 cm. Issued also on microfiche from University Microfilm Inc. |
| Bibliography: | Includes bibliographical references (leaves 128-139). |