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Kinetics and mechanism of the reaction of substituted benzyl chlorides with copper in dimethylformamide
Author(s) -
Egorov Anatoly M.,
Matyukhova Svetlana A.,
Anisimov Alexander V.
Publication year - 2005
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.964
Subject(s) - chemistry , copper , dimethylformamide , hammett equation , substituent , kinetics , reaction rate constant , inorganic chemistry , reaction mechanism , dissolution , medicinal chemistry , photochemistry , organic chemistry , catalysis , solvent , physics , quantum mechanics
The reaction of copper metal with various substituted benzyl chlorides in dimethylformamide was studied. The kinetic and thermodynamic parameters of the reaction was clarified. Hammett plots of log( k / k 0 ) vs the substituent constant σ gave a good correlation (ρ = 0.43, S ρ = 0.05, r = 0.960). The structure of the organic group has little effect on the rate of reaction of substituted benzyl chlorides with copper. In the absence of atmospheric oxygen, the oxidative dissolution of copper proceeded via a single‐electron transfer mechanism with formation of 1,2‐diphenylethanes and copper(I) complexes. The stereochemistry and intermediate compound were also studied. The reaction mechanism is discussed. Copyright © 2005 John Wiley & Sons, Ltd.