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Nucleophilic Reactions at Tertiary Carbon. Part 1. The 1,2-dimethyl-1-cyclohexyl cation

✍ Scribed by Konrad B. Becker; Cyril A. Grob

Publisher
John Wiley and Sons
Year
1973
Tongue
German
Weight
636 KB
Volume
56
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

Stereoisomeric ion pairs are implicated as intermediates in the solvolysis of cis and trans‐1‐chloro‐1,2‐dimethylcyclohexane, cis‐4 and trans‐4, respectively. This follows from the rates and products of these stereoisomeric tertiary chlorides in 80% ethanol and 50% acetone.

The composition of elimination and substitution products from cis‐4 and trans‐4 differs markedly and the differences are accentuated by silver ion. Furthermore, substitution products are formed with predominant inversion of configuration.

The equilibrium constant for isomerization of cis‐4 and trans‐4 shows the latter to be more stable by 0.7 kcal/mol. Since the solvolysis rates of the chlorides are equal, the transition state for trans‐4 is also more stable by 0.7 kcal. By inference the intermediates differ by a similar amount of energy which is ascribed to more efficient solvation of the trans ion pair 13.

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