Issue 0, 1971
From the journal:

Journal of the Chemical Society B: Physical Organic

The kinetics and mechanism of the reaction of cyclopentadienylidenetriarylphosphoranes with cyano-olefins. Part III. Elimination of hydrogen cyanide from 2-(1-phenyl-1,2,2-tricyanoethyl)cyclopentadienylidenetriphenylphosphorane; an E1CB reaction via an ion-pair

E. Lord,   M. P. Naan  and  C. D. Hall  

Abstract

Kinetic data on the base-catalysed elimination of hydrogen cyanide from 2-(1-phenyl-1,2,2-tricyanoethyl)-cyclopentadienylidenetriphenylphosphorane in benzene, benzene–acetonitrile, or acetonitrile solvent are reported. The elimination is of the first order in substrate and base (tertiary amine) and the second-order rate constants (k2) increase with increasing polarity of the medium. The deuterium isotope effect (k2H/k2D) is ca. 1·0 in each solvent system and a linear Brønsted plot is observed with a number of tertiary amines over a range of five pKa units. Activation parameters are reported for the reaction with triethylamine and the kinetic results are interpreted in terms of a E1CB reaction involving fast proton loss to form an ion-pair, followed by rate-determining elimination of cyanide ion from the ion-pair intermediate.

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Article information

DOI
https://doi.org/10.1039/J29710000220
Article type
Paper

J. Chem. Soc. B, 1971, 220-224

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The kinetics and mechanism of the reaction of cyclopentadienylidenetriarylphosphoranes with cyano-olefins. Part III. Elimination of hydrogen cyanide from 2-(1-phenyl-1,2,2-tricyanoethyl)cyclopentadienylidenetriphenylphosphorane; an E1CB reaction via an ion-pair

E. Lord, M. P. Naan and C. D. Hall, J. Chem. Soc. B, 1971, 220 DOI: 10.1039/J29710000220

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