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Inductive charge dispersal in the solvolysis of 3-substituted bicyclo[1.1.1] pentyl bromides

✍ Scribed by Cyril A. Grob; Cheng Xi Yang; Ernest W. Della; Dennis K. Taylor

Publisher: Elsevier Science
Year: 1991
Tongue: French
Weight: 212 KB
Volume: 32
Category: Article
ISSN: 0040-4039
DOI: 10.1016/s0040-4039(00)79433-0

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✦ Synopsis

Solvolysis rates and products of 3-substituted bxyclo[l.l.l1pentyl branldes indicate extremely strong inductive charge dispersal in the ionization to bxyclo[l .l.l lpentyl-l-cations, the precursors of 3-methylenecyclobutls. Recent studies have shown that the solvolys~s rates (log k) of several bl-and trlcyclic halides and sulfonates correlate linearly with the inductive constants d: of neighql boring substltuents according to the equation log k = pI d, . The reaction constant PI, the so-called lnductlvlty, gauges the sensitlvlty of the rate to the inductive effect of substltuents at various posltlons and 1s a measure of charge dispersal in the resulting carbenium ion. Since 6: values were derived from the pKa of 4-substituted qulnuclldlnium 2 perchlorates 1 , in which sterlc, cotqugatlve and hypercoqugatlve effects are negli- gible or absent, these correlatrons indicate that relative lonlzation rates are controlled only by the inductive effect of substituents.

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