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- Title
Extent of nucleophilic participation in the solvolyses of alkyl chloromethyl ethers and sulfides.
- Authors
Park, Byoung-Chun; Kevill, Dennis N.
- Abstract
The specific rates of solvolysis have been determined for chloromethyl ethyl ether (3) and chloromethyl octyl ether (4) at -10.0 °C and for chloromethyl methyl sulfide (5) at 25.0 °C in a variety of pure and binary solvents. These values were used for a correlation analysis treatment using the extended Grunwald-Winstein equation incorporating literature values for solvent nucleophilicity (NT) and solvent ionising power (YCl). Appreciable values were found for the sensitivities towards changes in both NT and YCl values. Using a literature specific rate of hydrolysis at 25.0 °C for fluoromethyl methyl ether (2), the required value for chloromethyl methyl ether (1) was obtained from use of NT and YCl values and the sensitivities for 3 to changes in their values, to adjust an experimental specific rate value for 1 in 100% ethanol to the corresponding value in 100% water. In this way, an estimated kCl/kF of 1.2 x 105 was obtained, essentially identical to values for the solvolyses of tert-butyl halides. A unimolecular mechanism for the solvolyses, with appreciable nucleophilic solvation of the developing carbocation, is proposed. Electronic supplementary information provides, for several solvents, specific rates of solvolysis for 3, 4, and 5 at additional temperatures and the calculated activation parameters.
- Subjects
CHLOROMETHYL methyl ether; SULFIDES; SOLVOLYSIS; ALCOHOL; LINEAR free energy relationship; METHYL ether
- Publication
Journal of Chemical Research, 2012, Vol 36, Issue 11, p652
- ISSN
1747-5198
- Publication type
Article
- DOI
10.3184/174751912X13469242440149