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Kinetics of methoxy-NNO-Azoxymethane hydrolysis in strong acids

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Abstract

The kinetics of methoxy-NNO-azoxymethane (I) hydrolysis in concentrated solutions of strong acids (HBr, HCl, HClO4, and H2SO4) has been investigated by a manometric method. The gas evolution rate is described by the equation corresponding to two consecutive first-order reactions, with the rate constant of the second reaction considerably exceeding the rate constant of the first reaction, i.e., k 2 {ie17-1} k 1. The temperature dependences of k 1 (s−1) in 47.59% HBr in the temperature range from 60 to 90°C and in 64.16% H2SO4 between 80 and 130°C are described by Arrhenius equations with IogA= 12.7 ± 1.5 and 13.6 ± 1.4 and E a = 115 ± 10 and 137 ± 10 kJ/mol, respectively. The parameters of the Arrhenius equation for the rate constant k 2 for the reaction in 64.16% H2SO4 between 80 and 130°C are IogA= 9.1 ± 2.5 and E a = 91 ± 18 kJ/mol. An analysis of the UV spectra of compound I in concentrated H2SO4 shows that I is a weak base \( (pK_{BH^ + } \approx - 6) \). The rate-determining step of the hydrolysis of I is the attack of the nucleophile on the carbon atom of the MeO group of the protonated molecule of I. The resulting methyldiazene dioxide decomposes via a complicated mechanism to evolve N2, NO, and N2O. The pseudo-first-order rate constant k 1 of the reaction at 80°C depends strongly on the acid concentration and on the type of nucleophile (Br−, Cl−, or H2O). The relationship between k 1 and the rate constant k of the bimolecular nucleophilic substitution reaction (SN2) is given by the linear equation log\( [k_1 /(C_H + C_{Nu} )] = m^ \ne m*X_0 + \log (k/K_{BH^ + } ) \), where \( C_{H^ + } \) and C Nu are the concentrations of H+ and nucleophile, respectively; X 0 is the excess acidity; and m ≠ and m* are coefficients. The Swain-Scott equation log\( (k_{Nu} /k_{H_2 O} ) = ns \), where n is the nucleophilicity factor and s is the substrate constant (s = 0.72), is applicable to the rate constants k of the SN2 reactions of the protonated molecule of I with Br−, Cl−, and H2O.

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  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432, Russia

    I. N. Zyuzin & D. B. Lempert

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  1. I. N. Zyuzin
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Original Russian Text © I.N. Zyuzin, D.B. Lempert, 2011, published in Kinetika i Kataliz, 2011, Vol. 52, No. 1, pp. 19–27.

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Zyuzin, I.N., Lempert, D.B. Kinetics of methoxy-NNO-Azoxymethane hydrolysis in strong acids. Kinet Catal 52, 17–25 (2011). https://doi.org/10.1134/S0023158411010228

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