Kinetics and Mechanism of the Nucleophilic Substitution Reaction of Imidazole with Bis(2,4,6-trichlorophenyl) Oxalate and Bis(2,4-dinitrophenyl) Oxalate.

AndrewG. Hadd, JohnW. Birks

Index: J. Org. Chem. 61(8) , 2657-2663, (1996)

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Abstract

The kinetics of the imidazole-catalyzed decomposition of bis(2,4,6-trichlorophenyl) oxalate (TCPO) and bis(2,4-dinitrophenyl) oxalate (DNPO) was investigated by the stopped-flow technique. Pseudo-first-order rate constants were determined as a function imidazole concentration in the temperature range 6-45 degrees C by fitting the temporal changes in absorbance throughout the 245 to 345 nm wavelength range for TCPO and at 420 nm for DNPO. The reaction proceeds by release of two molecules of substituted phenol and formation of 1,1'-oxalyldiimidazole (ODI) for both esters. The identity of ODI was confirmed in the reaction of imidazole with TCPO by its UV absorbance spectrum and (13)C-NMR spectrum. The reaction of imidazole with TCPO has a second-order dependence on imidazole concentration and an observed negative activation energy of -6.2 +/- 0.3 kJ/mol, whereas the DNPO reaction has a first-order dependence on imidazole concentration and an observed positive activation energy of 12.0 +/- 0.6 kJ/mol. The differences in the temperature dependence and order of the reaction with respect to imidazole for the two oxalate esters are explained by a shift in the rate-determining step from addition to the acyl group for DNPO to imidazole-catalyzed release of the phenol leaving group for TCPO. These kinetics results are useful in interpreting the initial reaction steps in peroxyoxalate chemiluminescence.