Substituent Effects. XVI. Acetolysis of 2-Phenylethyl Tosylates
- 1 March 1987
- journal article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 60 (3) , 1091-1095
- https://doi.org/10.1246/bcsj.60.1091
Abstract
The acetolysis rates of 2-arylethyl tosylates were determined for a series of aryl substituents. The non-linear substituent effect was reasonably accounted for on the basis of two linear LArSR relationships; one for the aryl-assisted (FkΔ) and one for the unassisted (ks) processes, respectively. A precise dissection of the apparent substituent effect into individual effects for both processes was achieved in this manner. The substituent effect on the ks process can be described as a linear function of σ° with a small ρs of −0.19, and that on the FkΔ process in terms of the LArSR Eq., with ρΔ=−3.87 and an rΔ=0.631. The use of σ+ for the FkΔ process failed to give any reasonable dissection. The r value for this FkΔ process is essentially identical to that for the neophyl solvolysis. The unique r value of 0.6 is concluded to be characteristic of β-arylassisted ionization processes in general.This publication has 20 references indexed in Scilit:
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