Internal pressure's role in the selectivity of the bromine radical
The results of our studies demonstrate a link between selectivity in free radical brominations and the internal pressure of solvent. The study encompassed l8 solvents and/or mixtures over which the rate constant ratio for SH2 ring opening of cyclopropylbenzene (kC) vs hydrogen abstraction from tolue...
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ndltd-VTETD-oai-vtechworks.lib.vt.edu-10919-429802021-05-15T05:26:42Z Internal pressure's role in the selectivity of the bromine radical Hulvey, Glenn A. Chemistry Tanko, James M. Merola, Joseph S. Marand, Hervé L. LD5655.V855 1993.H848 Bromine Cyclopropylbenzene Free radicals (Chemistry) Toluene The results of our studies demonstrate a link between selectivity in free radical brominations and the internal pressure of solvent. The study encompassed l8 solvents and/or mixtures over which the rate constant ratio for SH2 ring opening of cyclopropylbenzene (kC) vs hydrogen abstraction from toluene (kH) by bromine atom was found to vary by nearly a factor of twenty as a function of solvent. The observed rate constant ratios correlate with the cohesive energy density of the solvent, which is approximately equal to the internal pressure (kC/kH is found to increase with increasing solvent pressure) for the solvents used in this study. A similar competition pitting cyclopropylbenzene against p-chlorotoluene shows the same solvent effect. It is suggested that the observed variation in selectivity "with solvent pressure occurs because the volume of activation with kC is more negative than for kH by about 20 cm3/mol. Master of Science 2014-03-14T21:37:23Z 2014-03-14T21:37:23Z 1993-01-05 2009-06-10 2009-06-10 2009-06-10 Thesis Text etd-06102009-063106 http://hdl.handle.net/10919/42980 http://scholar.lib.vt.edu/theses/available/etd-06102009-063106/ en OCLC# 29151924 LD5655.V855_1993.H848.pdf In Copyright http://rightsstatements.org/vocab/InC/1.0/ ix, 54 leaves BTD application/pdf application/pdf Virginia Tech |
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LD5655.V855 1993.H848 Bromine Cyclopropylbenzene Free radicals (Chemistry) Toluene |
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LD5655.V855 1993.H848 Bromine Cyclopropylbenzene Free radicals (Chemistry) Toluene Hulvey, Glenn A. Internal pressure's role in the selectivity of the bromine radical |
description |
The results of our studies demonstrate a link between selectivity in free radical brominations and the internal pressure of solvent. The study encompassed l8 solvents and/or mixtures over which the rate constant ratio for SH2 ring opening of cyclopropylbenzene (kC) vs hydrogen abstraction from toluene (kH) by bromine atom was found to vary by nearly a factor of twenty as a function of solvent. The observed rate constant ratios correlate with the cohesive energy density of the solvent, which is approximately equal to the internal pressure (kC/kH is found to increase with increasing solvent pressure) for the solvents used in this study. A similar competition pitting cyclopropylbenzene against p-chlorotoluene shows the same solvent effect. It is suggested that the observed variation in selectivity "with solvent pressure occurs because the volume of activation with kC is more negative than for kH by about 20 cm3/mol. === Master of Science |
author2 |
Chemistry |
author_facet |
Chemistry Hulvey, Glenn A. |
author |
Hulvey, Glenn A. |
author_sort |
Hulvey, Glenn A. |
title |
Internal pressure's role in the selectivity of the bromine radical |
title_short |
Internal pressure's role in the selectivity of the bromine radical |
title_full |
Internal pressure's role in the selectivity of the bromine radical |
title_fullStr |
Internal pressure's role in the selectivity of the bromine radical |
title_full_unstemmed |
Internal pressure's role in the selectivity of the bromine radical |
title_sort |
internal pressure's role in the selectivity of the bromine radical |
publisher |
Virginia Tech |
publishDate |
2014 |
url |
http://hdl.handle.net/10919/42980 http://scholar.lib.vt.edu/theses/available/etd-06102009-063106/ |
work_keys_str_mv |
AT hulveyglenna internalpressuresroleintheselectivityofthebromineradical |
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