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Title: | Acetate-Catalyzed Bromination and Deuterium Exchange of 2-Butanone (I). The Mechanism for the Bimolecular Displacement Reactions of α-Haloketones (II) |
Authors: | Thorpe, James William |
Advisor: | Warkentin, John |
Department: | Chemistry |
Keywords: | acetate, catalyzed, bromination, deuterium, bimolecular displacement, reactions |
Publication Date: | Oct-1971 |
Abstract: | <p> The regioselectivities of bromination and deuterium exchange of 2-butanone are shown to be the same, under identical conditions. This work firmly establishes that enolization is the rate-determining step for the former reaction, contrary to some recent reports in the literature.</p> <p> The steric effects and activation parameters in the bimolecular nucleophilic displacement reactions of a series of α-haloketones and alkyl halides are shown to be inconsistent with either a bridging or conjugation mechanism for the observed rate enhancements of haloketone over alkyl halide.</p> <p> The stereoelectronic requirements of this mechanism are tested in a system where the stereochemistry is known (cis- and trans-chlorocyclohexanones). The activation parameters suggest that only in the case where the geometry is correct for maximum conjugation (trans-chlorocyclohexanone) is there an appreciable difference in mechanism (stereoelectronically) from displacement at ordinary saturated carbon.</p> |
URI: | http://hdl.handle.net/11375/20856 |
Appears in Collections: | Digitized Open Access Dissertations and Theses |
Files in This Item:
File | Description | Size | Format | |
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Thorpe_James_W._1971Oct_Ph.D..pdf | 6.48 MB | Adobe PDF | View/Open |
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