SOLVENT AND SUBSTITUENT NATURE EFFECT ON THE 2-NITROAZOBENZENES HYDROGENATION SELECTIVITY ON SKELETAL NICKEL

Abstract

The elucidation of the reasons and character of the influence of nature substituent and solvent composition on the kinetic features and selectivity of liquid-phase catalytic hydrogenation of compounds containing several reactive capable groups is a theoretical and practically significant task. In the presented work the process of 2-nitroazobenzene derivatives hydrogenation with various substituents was investigated in order to obtain the corresponding benzotriazoles on a skeletal nickel catalyst in a neutral azeotropic aqueous solution of 2-propanol, and in the presence of acetic acid or sodium hydroxide. According to the data obtained, the solvent composition has a decisive influence on the selectivity of this process. The transformation of azo- and nitro groups, included in the initial compound, proceeds in parallel stages, and the introduction of acidic or basic additives leads to а change in the rate ratio of these stages. Appropriately, selectivity of 2-nitroazobenzene derivatives hydrogenation changes with respect to reaction products containing a triazole ring, in particular, with respect to N-oxides of substituted benzotriazoles, and also with respect to nitrohydrazo compounds. The greatest influence of substituent nature on the hydrogenation selectivity in a solvent with any composition is manifested for the group whose transformation rate in a given medium is higher. In the presence of acid the substituent variation is more strongly reflected in the hydrogenation rate of azo group, and in the basic medium – of nitro group. It was found that the change in the transformation rate of both reactive capable groups corresponds to the Hammett constant alteration. The electron acceptor substituent has a deactivating effect on the transformation rate of nitro as well azo group. To increase the selectivity of substituted 2-nitroazobenzenes hydrogenation with respect to compounds containing a triazole ring, it is recommended to introduce a base into the aqueous solution of 2-propanol. For citation: Lefedova O.V., Nemtzeva M.P., Sharonov N.Yu. Solvent and substituent nature effect on the 2-nitroazobenzenes hydrogenation selectivity on skeletal nickel. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 5. P. 110-119. DOI: 10.6060/ivkkt.20236605.6772.