A computational study into the reactivity of epichlorohydrin and epibromohydrin under basic conditions in the gas phase and solution |
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Authors: | G. N. Merrill |
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Affiliation: | Department of Chemistry, University of Texas at San Antonio, San Antonio, Texas 78249, USADepartment of Chemistry, University of Texas at San Antonio, 6900 North Loop 1604 West, San Antonio, TX 78249, USA.=== |
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Abstract: | Ab initio molecular orbital calculations were carried out on epibromohydrin (EBH) and epichlorohydrin (ECH) in an attempt to elucidate their reactivity with respect to a hard nucleophile, hydroxide. These systems were modeled in both the gas phase and a polar solvent under basic conditions. In the gas phase, it was determined that a direct displacement mechanism (nucleophilic attack at the C1 position) was operative for EBH, while an indirect pathway (nucleophilic attack at the C3 position and subsequent intramolecular displacement) was followed for ECH. In an acetone solution, only the indirect displacement mechanism was found to occur. An electrostatic argument is advanced to account for this behavior in polar solution. Copyright © 2007 John Wiley & Sons, Ltd. |
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Keywords: | epibromohydrin epichlorohydrin hydroxide reaction mechanism gas phase solution ab initio modeling |
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