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A computational study into the reactivity of epichlorohydrin and epibromohydrin under basic conditions in the gas phase and solution
Author(s) -
Merrill G. N.
Publication year - 2007
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1119
Subject(s) - chemistry , nucleophile , reactivity (psychology) , epichlorohydrin , computational chemistry , intramolecular force , gas phase , polar , solvent , ab initio , phase (matter) , hydroxide , displacement (psychology) , moiety , organic chemistry , medicine , psychology , physics , alternative medicine , pathology , astronomy , psychotherapist , catalysis
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.