STUDY OF THE DISSOCIATION OF THE PRODUCTS OF SOME PROTON-TRANSFER REACTIONS IN ACETONITRILE SOLVENT

被引:27
作者
GALEZOWSKI, W
JARCZEWSKI, A
机构
来源
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE | 1992年 / 70卷 / 03期
关键词
ION-PAIR DISSOCIATION; PROTON TRANSFER REACTIONS; KINETIC ISOTOPE EFFECTS;
D O I
10.1139/v92-126
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The conductometric study of the products of the proton transfer reactions of C-acids (nitriles, nitroalkanes, and 2,4,6-trinitrotoluene) with the strong amine bases (1,1,3,3-tetramethylguanidine (TMG), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,8-bis(dimethylamino)naphthalene (DMAN), and piperidine) in acetonitrile shows their large degree of dissociation into free ions. The dissociation constant values have been estimated at 25-degrees-C to be larger than 1 X 10(-4) M. This weakens the formalism commonly accepted in spectrophotometric kinetic studies of these systems of reactions, based on the assumption that the product is an ion pair. Spectrophotometric equilibrium and kinetic measurements provided evidence that reverse reaction is a second-order process (pseudo-first order because cation concentration is controlled by side reactions). The influence of the common cation (TMGH+) on the equilibria of the proton abstraction from 2-methyl-1-4-nitrophenyl)-1-nitropropane and 4-nitrophenylcyanomethane with TMG base in acetonitrile at 25-degrees-C was examined and was found to be compatible with the assumption of large dissociation of the reaction product for free ions. "Equilibrium constants" estimated by the Benesi and Hildebrand method (which assumes an ion-pair product) decreased with increasing concentration of added TMGH+ cation, but these "equilibrium constants" multiplied by [TMGH+] are constant. The observed pseudo-first-order rate constants of the proton transfer reaction, measured at large excess of the base over C-acid, grow with the cation concentration due to the increase of the backward reaction rate. The concentration of added common cation shows a negligible influence on the observed rate constants of deuteron transfer reaction. Thus, as a result of side reactions, in which extra amounts of cation are formed, some second-order rate constants k(f)H and also kinetic isotope effects (KIEs) (k(f)H/k(f)D) that have been measured in acetonitrile can be substantially overestimated.
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收藏
页码:935 / 942
页数:8
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