Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of the Pyridinolysis of Benzyl Bromides in Dimethyl Sulfoxide

  • Published : 1999.10.20
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Abstract

Nucleophilic substitution reaction of Y-benzyl bromide with X-pyridines are investigated in DMSO at 45.0℃. Biphasic rate dependence is observed on varying the substituents in the substrate (Y) as well as in the nucleophile (X). The two well-defined straight lines in the Hammett (ρy) and Bronsted ( βx) plots are interpreted to indicate the changes in transition-state structure, a decrease in bond cleavage as the substituent on the substrate is changed from electron-donors ( ρy < 0) to electron-acceptors ( ρy > 0), and an increase in the extent of bond formation with the corresponding changes of the substituent on the pyridine. A Jencks' type analysis of separate polar (ρ) and resonance (ρr) effects can also be accounted for by the change of the transition-state structure, not by the variable combination of polar and resonance effects.

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