Kinetic Studies of Solvolysis. X. Transition from a van’t Hoff to an Arrhenius Intermediate Caused by Steric Hindrance at the Product-Formation Step of SN1 Reactions
- 1 November 1965
- journal article
- research article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 38 (11) , 1844-1852
- https://doi.org/10.1246/bcsj.38.1844
Abstract
1. The SN1 reactions of benzhydryl halides and hindered nucleophiles, i. e., potassium 2,6-di-t-butyl-4-methylphenoxide (I), tri-n-butylammonium 2,6-di-t-butyl-4-methylphenoxide (III), tri-n-butylamine and tri-n-butylammonium phenoxide (II), proceed through an Arrhenius intermediate and obey good second-order kinetics in acetonitrile at 110–140°C, whereas in the same solvent the reaction with potassium phenoxide is a typical SN1 reaction with a van’t Hoff intermediate at 70–120°C. This transition of the characteristics of the intermediates from a van’t Hoff to an Arrhenius type has been explained as being due to steric hindrance at the product-formation step of the SN1 reactions.Keywords
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