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Issue 7, 1987
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Linear solvation energy relationships. Part 37. An analysis of contributions of dipolarity–polarisability, nucleophilic assistance, electrophilic assistance, and cavity terms to solvent effects on t-butyl halide solvolysis rates

Abstract

Solvolysis/dehydrohalogenation rates of t-butyl chloride in 21 hydrogen bond donor (HBD) and non-HBD solvents are well correlated (r= 0.9973, s.d. = 0.24) by the equation: log k=–14.60 + 0.48λH2/100 + 5.10π*+ 4.17α+ 0.73β where δH2 is the solvent cohesive energy density, and π*, α, and β are the solvatochromic parameters that scale solvent diplority–polarizability, HBD acidity (electrophilicity), and hydrogen-bond acceptor basicity (nucleophilicity). In the corresponding equation over the same solvent set for t-butyl bromide, the terms in δH2 and α are smaller still, and the terms in δH2 and β are not statistically significant. It is shown that a trifluoroethanol (TFE)–ethanol plot, wherein ButCl and 1-adamantyl chloride (1-AdCl) solvolysis rates are compared, can be interpreted as evidence for electrophilic assistance of 1-AdCl in TFE rather than the more usual interpretation of nucleophilic assistance to ButCl in EtOH–H2O.

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Article type: Paper
DOI: 10.1039/P29870000913
J. Chem. Soc., Perkin Trans. 2, 1987, 913-920

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    Linear solvation energy relationships. Part 37. An analysis of contributions of dipolarity–polarisability, nucleophilic assistance, electrophilic assistance, and cavity terms to solvent effects on t-butyl halide solvolysis rates

    M. H. Abraham, R. M. Doherty, M. J. Kamlet, J. M. Harris and R. W. Taft, J. Chem. Soc., Perkin Trans. 2, 1987, 913
    DOI: 10.1039/P29870000913

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