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- Title
Extent of nucleophilic participation in the solvolyses of an aryl chloromethyl ether, α, p-dichloroanisole.
- Authors
Park, Byoung-Chun; Kevill, Dennis N.
- Abstract
The specific rates of solvolysis of α, p-dichloroanisole (chloromethyl p-chlorophenyl ether, 1) have been measured conductimetrically in a variety of hydroxylic solvents. In three typical solvents, at 25.0 °C, the rate is 20-45 times greater than for the corresponding sulfide. In a comparison with the solvolysis of a substrate with an alkyl group replacing the aryl group, chloromethyl ethyl ether (2), at -10.0 °C in four typical solvents, 1 reacted considerably more slowly than 2, by a little over four orders of magnitude. An extended Grunwald-Winstein equation treatment of the specific rates of solvolyses in 24 solvents at 25.0 °C leads to an l value of 0.68 ± 0.04 and an m value of 0.59 ± 0.03 (l/m = 1.15). Appreciable nucleophilic assistance in the progress to the transition state is indicated and either nucleophilic solvation to an ionisation process or a loose SN2 transition state with extensive bond-breaking accompanied by a smaller degree of bond-making lead to an appropriate transition state.
- Subjects
ETHYLENE dichloride; ARYL chlorides; ANISOLE; CHLOROMETHYL methyl ether; GRUNWALD-Winstein equation
- Publication
Journal of Chemical Research, 2013, Vol 37, Issue 8, p483
- ISSN
1747-5198
- Publication type
Article
- DOI
10.3184/174751913X13734534378121