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Steric Effects on Reaction Rates. VI. Application of a New MM2 Force-Field for Carbenium Ions to Solvolysis Rates of Secondary p-Toluenesulfonates

✍ Scribed by Paul Müller; Jiri Mareda

Publisher: John Wiley and Sons
Year: 1985
Tongue: German
Weight: 408 KB
Volume: 68
Category: Article
ISSN: 0018-019X
DOI: 10.1002/hlca.19850680115

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✦ Synopsis

Abstract

An empirical force‐field for carbenium ions has been incorporated in Allinger's MM2 programme. Structural parameters of secondary carbenium ions calculated by this method are compared with those obtained with Schleyer's BIGSTRN calculations. The strain changes occurring upon solvolysis of secondary p‐toluenesulfonates are evaluated by means of this force‐field and correlated with the rate constants for solvolysis. The equation for correlation of acetolysis, relative to cyclohexyl p‐toluenesulfonate, of 28 k~c~ substrates is Δ__G__ = 0.67 Δ__E__~st~ ‐ 0.20 (r = 0.958).

📜 SIMILAR VOLUMES

Steric Effects on Reaction Rates. IV. Ev

Steric Effects on Reaction Rates. IV. Evaluation of the Ketone Model for the Solvolysis Transition State of Secondary p-Toluenesulfonates

✍ Paul Müller; Jacky Blanc; Jean-Claude Pcrlberger 📂 Article 📅 1982 🏛 John Wiley and Sons 🌐 German ⚖ 430 KB

## Abstract The rates of solvolysis of secondary __p__‐toluenesulfonates in acetic acid or 97% trifluoroethanol are interpreted in terms of strain changes between substrate and the corresponding ketone. Such strain changes are obtained from force‐field calculations (Δ__E__~st~) and from equilibrati