Author:
Anderson RJ,Ang P,England BD,McCann VH,McLennan DJ
Abstract
The rates of E2 elimination
from DDT and SN2 substitution on allyl bromide by alkoxide and
hydroxide ions have been measured using aqueous-alcoholic solvent mixtures. The
results are anomalous in terms of previous theories. The E2 hydrogen nucleophilicity
order of OEt- > OMe-
> OH- towards 2-phenethyl bromide in dioxan has been obtained by
extrapolating rates of reaction in alkaline dioxan-alcohol or dioxan-water
mixtures to 100% dioxan. The nucleophilicity order contrasts with the basicity
order: OEt- > OH- > OMe-
but is the same as the carbon nucleophilicity order. The validity is questioned
of using similar carbon- nucleophilicity and elimination-reactivity orders as
positive evidence for the E2C mechanism of eliminations promoted by weak bases
which are also strong carbon nucleophiles.
Cited by
13 articles.
订阅此论文施引文献
订阅此论文施引文献，注册后可以免费订阅5篇论文的施引文献，订阅后可以查看论文全部施引文献
1. Modeling the formation of 2,3,7,8-tetrachlorodibenzo-p-dioxin in the historical manufacture of 2,4,5-trichlorophenol;Environmental Forensics;2017-10-02
2. The effect of alkyl substitution on the thermodynamic stability and kinetic reactivity of α-anions of metal—carbene complexes;Journal of Organometallic Chemistry;1976-10
3. A case for the concerted SN2 mechanism of nucleophilic aliphatic substitution;Accounts of Chemical Research;1976-08-01
4. A revised transition state spectrum for concerted bimolecular β-eliminations;Tetrahedron;1975-01
5. Eliminations promoted by weak bases. Part VI. Isotope, basicity, and substituent effects on the dehydrochlorination of 1,1-diaryl-2,2,2-trichloroethanes in dimethylformamide;Journal of the Chemical Society, Perkin Transactions 2;1974