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Polar Substituent Effects in the Solvolysis of Primary and Tertiary Alkyl Halides. Polar Effect IX

✍ Scribed by Cyril A. Grob; Adrian Waldner

Publisher: John Wiley and Sons
Year: 1980
Tongue: German
Weight: 352 KB
Volume: 63
Category: Article
ISSN: 0018-019X
DOI: 10.1002/hlca.19800630804

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✦ Synopsis

Abstract

When the Hammett‐Taft equation log (k/k~o~)=ρ^q^ · σ is applied to the solvolysis of the 3‐substituted propyl bromides 6a‐6i in ethanol/water 4:1 (v/v) log k correlates linearly with σ except in cases where R exerts an anchimeric effect. The reaction constant ρ^q^ for 6 is − 0.12 and is typical for a nucleophilic solvent‐assisted k~s~ process at a primary C‐atom. The tertiary halides 1 and 3, however, which react with little or no nucleophilic solvent assistance, i.e. by k~c~ processes, lead to larger ρ^q^ values of −0.71 and −1.14, respectively. The reaction constant p^q^ is therefore a sensitive gauge for charge development in the transition state for solvolysis of saturated compounds.

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