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
- 1 January 1987
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Perkin Transactions 2
- No. 7,p. 913-920
- https://doi.org/10.1039/p29870000913
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 + 0.48λH 2/100 + 5.10π*+ 4.17α+ 0.73β where δH 2 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 δH 2 and α are smaller still, and the terms in δH 2 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.Keywords
This publication has 0 references indexed in Scilit: