THE PROTON-TRANSFER REACTION BETWEEN BIS(2,4-DINITROPHENYL)METHANE AND NITROGEN BASES IN DIMETHYL-SULFOXIDE AND TOLUENE SOLVENTS

被引：14

作者：

JARCZEWSKI, A ^{[1
]}

SCHROEDER, G ^{[1
]}

LEFFEK, KT ^{[1
]}

机构：

[1] ADAM MICKIEWICZ UNIV,DEPT CHEM,PL-61712 POZNAN,POLAND

来源：

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE | 1991年 / 69卷 / 03期

关键词：

PROTON TRANSFER; BIS(2,4-DINITROPHENYL)METHANE; DEUTERIUM ISOTOPE EFFECTS;

D O I：

10.1139/v91-070

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Rate constants have been measured for the proton and deuteron transfer reactions of bis(2,4-dinitrophenyl)methane (1) with 1,1,3,3-tetramethylguanidine (TMG) and 1,5-diazabicyclo[5.4.0]undec-7-ene (DBU) in dimethyl sulfoxide (DMSO) and toluene solvents. Equilibrium constants, primary deuterium kinetic isotope effects, and activation parameters are reported. The reaction of 1 with DBU is faster than that with TMG by factors of 5 and 50 in toluene and DMSO respectively. The primary deuterium kinetic isotope effects, k(H)/k(D) = 7-9, which are independent of the polarity of the solvent, indicate an uncoupled mechanism of proton transfer and are in the "classical" region with little or no indication of a tunnelling contribution to the enthalpy of activation for these reactions.

引用

页码：468 / 473

页数：6

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