HYDROGENIZATION OF SUBSTITUTED NITRO-, AZOBENZENES, THEIR MIXTURE AND SUBSTITUTED NITROAZOBENZEN ON SKELETAL NICKEL IN AQUEOUS 2-PROPANOL SOLUTIONS
Abstract
The article is devoted to the investigation of the hydrogenation of 4-nitroaniline, 4-amino-2'-hydroxy-5'-methylazobenzene, their mixture and 4-nitro-2'-hydroxy-5'-methylazobenzene on skeletal nickel in an aqueous solution of 2-propanol with azeotropic composition (x2 = 0.68) and this solvent with the addition of acid (0.01 M CH3COOH) or sodium hydroxide (0.01 M NaOH). The elucidation of the reasons and the development of approaches to the selective control of the staged transformations of substituted nitroazobenzenes containing two reactive groups in a molecule under the conditions of hydrogenation are of interest from theoretical and practical points of view. The rate of formation of intermediate products during the hydrogenation of nitroazobenzenes is largely determined by the activation of nitro and azo groups. The aim of the work is to conduct a comparative analysis of the rates of conversion of nitro- and azogroups in individual compounds with the rates of hydrogenation of their mixture and the rate of conversion of nitroazobenzene, which simultaneously contains nitro- and azogroups, to discuss the reasons for the influence of the solvent composition on the conversion rates of mono- and disubstituted benzenes. UV-spectroscopic data indicate that the electronic state of the hydrogenated compounds in the solvent compositions used does not undergo significant changes, since the absorption maxima are shifted by no more than 1 nm, both with the addition of acid and base. On the contrary, the observed rates of hydrogenation of mono- and disubstituted benzenes vary within fairly wide limits. A comparative analysis of the rates of hydrogenation of individual compounds, their mixtures and disubstituted benzene allows us to conclude that the priority of reduction of one or another group in 4-nitro-2'-hydroxy-5'-methyl-azobenzene can be made on the basis of calculating the quantitative ratio of the reaction products. When a mixture of compounds containing nitro and azo groups is hydrogenated, their adsorption rather than reactivity begins to play the primary role.
References
Theory and practice of the processes of liquid-phase hy-drogenation of substituted nitrobenzenes. Ed. by O.I. Koifman. M.: KRASAND. 2016. 528 p. (in Russian).
Lauwiner M., Roth R., Rys P. Reduction of aromatic nitro compounds with hydrazine hydrate in the presence of an iron oxide/hydroxide catalyst. III. Selective reduc-tion of nitro groups in aromatic azo compounds. Appl. Catal. A. Gen. 1999. V. 177. P. 9-14. DOI: 10.1016/S0926-860X(98)00247-6.
Rakhimov A.I., Brunilina L.L. Reactions of diazotiza-tion and azo coupling: method. Volgograd: IUNL Volg GTU. 2012. 8 p. (in Russian).
Nishchenkova L.G., Timofeyeva V.F., Gostikin V.P., Fasman A.B., Blinichev V.N. Catalytic activity of skele-tal nickel catalysts. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 1980.V. 23. N 12. P. 1495-1501 (in Rus-sian).
Hoang Anh, Nemtzeva M.P., Lefedova O.V. Concentra-tion Effect in the Hydrogenation of 4-Nitro-2’-Hyroxy-5’-Methylazobenzene over Skeletal Nickel in an Aqueous 2-Propanol Solution. Russ. J. Phys. Chem. A. 2018. V. 92. N 4. P. 669-673. DOI: 10.1134/S0036024418040131.
Hoang Anh, Nemtseva M.P., Lefedova O.V. Effect of individual solvents on the rates of hydrogenization for substituted nitro-, azo-, and nitroazobenzenes on Skeletal Nickel. Russ. J. Phys. Chem. A. 2017. V. 91. N 11. P. 1995-1998. DOI: 10.1134/S0036024417110085.
Hoang Anh, Kalashnikova V.A., Lefedova O.V., Filippov D.V. The effect of sodium hydroxide additives on the kinetics of hydro-genation of 4-nitro-2'-hydroxy-5'-methylazobenzene on skeletal nickel in an aqueous solution of 2-propanol. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 8. P. 66-72 (in Rus-sian). DOI: 10.6060/ivkkt201861008.5752.
Hoang Anh, Kalashnikova V.A., Lefedova O.V. Kinetics of hy-drogenation of 4-nitro-2'-hydroxy-5'-methylazobenzene on skeletal nickel in an aqueous solution of 2-propanol. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 3. P. 10-15 (in Rus-sian). DOI: 10.6060/tcct.20186103.5604.
Budanov M.A., Sharonov N.Yu., Ulitin M.V. The influ-ence of the composition of the binary solvent 2-propanol-water on the magnitude of the adsorption of aniline by the skeletal nickel catalyst. Mat. XII Th. All-Russian Symposium "Actual problems of the theory of adsorp-tion, porosity and adsorption selectivity." M.: Izd. 2008. P. 145 (in Russian).
Romanenko Yu.E., Merkin A.A., Lefedova O.V. Kinetic descrip-tion of the hydrogenation of nitrobenzene and nitrosobenzene on skeletal nickel in aqueous solutions of 2-propanol of different com-position. Kinet. Katal. 2016. V. 57. N 2. P. 206 (in Russian).
Romanenko Yu.E., Merkin A.A., Komarov A.A., Lefedova O.V. Kinetics and models of hydrogenation of phenilhydroxilamin and asobenzene on nickel catalyst in aqueous 2-propanol solutions. Russ. J. Phys. Chem. A. 2014. V. 88. N 8. P. 1323-1328. DOI: 10.1134/S0036024414080251.
Budanov M.A., Lefedova O.V., Ulitin M.V., Nguyen Thi Thu Xa. Features of the phenylhydroxylamine cata-lytic hydrogenation in water solutions of 2-propanole on skeletal nickel. Rus. J. Phys. Chem. A. 2010. V. 84. N 11. P. 1901-1904. DOI: 10.1134/S0036024410110142.
Budanov M.A., Ulitin M.V., Sharonov N.Yu. Adsorption of phenylhydroxylamine on skeletal nickel under the re-action conditions of liquid-phase hydrogenation. Mat. XII Th. All-Russian Symposium "Actual problems of the the-ory of adsorption, porosity and adsorption selectivity". M.: Izd. 2008. P. 146 (in Russian).
Lefedova O.V., Nguyen Thi Thu Ha, Komarov A.A., Budanov M.A. Peculiarities of azobenzene catalytic hy-drogenation in 2-propanol aqueous solutions with acid or base additives. Russ. J. Phys. Chem. A. 2012. V. 86. N 1. P. 32-35. DOI: 10.1134/S0036024412010207.
Merkin A.A., Latypova A.R., Nguyen Thi Thu Ha, Lefedova O.V. Kinetics of hydrogenation of a mixture of nitrobenzene and azoxybenzene on skeletal nickel in an aqueous solution of 2-propanol. Russ. J. Phys. Chem. A. 2015.V. 89. N 10. P. 1772-1775. DOI: 10.1134/S0036024415100222.
Filippov D.V., Ulitin M.V., Merkin A.A. Thermodynam-ics of processes occurring in the surface layers of skeletal nickel in ethanol-water binary solvents with the participa-tion of individual forms of hydrogen. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2008. V. 50. N 3. P. 48-51 (in Russian).
Barbov A.V., Merkin A.A., Shepelev M.V., Ulitin M.V. Using solvents to control hydrogen adsorption on skeletal nickel. Russ. J. Phys. Chem. A. 2014. V. 88. N 12. P. 2197-2202. DOI: 10.1134/S0036024414120036.
Barbov A.V., Denisov S.V., Ulitin M.V., Korosteleva P.O. The heats of hydrogen adsorption on Raney nickel from aqueous -organic solvents with acid and base ad-mixtures. Russ. J. Phys. Chem. A. 2007. V. 81. N 2. P. 272-276. DOI: 10.1134/S0036024407020215.
Filippov D.V., Ulitin M.V., Barbov A.V. The effect of pH on the adsorption equilibrium of individual forms of hydrogen in the surface layers of nickel catalysts in the ethanol-water system. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2006. V.49. N 9. P. 28-30 (in Russian).
Barbov A.V., Shepelev M.V., Filippov D.V., Ulitin M.V. Effects of the nature and composition of the solvent on the thermodynamic characteristics of the individual forms of hydrogen adsorbed on the surface of porous nickel. Russ. J. Phys. Chem. A. 2010. V. 84. N 9. P. 1605-1610. DOI: 10.1134/S0036024410090281.
