HYDROGEN ROLE IN SELECTIVITY OF SUBSTITUTED NITRO-AZOBENENES HYDROGENI-ZATION ON SKELETAL NICKEL IN 2-PROPANOL AQUEOUS SOLUTIONS
Abstract
Elucidation of the substituted nitrobenzenes transformations sequence, in particular, containing several reactive groups and the development of approaches to the control of the selectivity of processes involving them is of interest from both theoretical and practical points of view. The article is devoted to the analysis of the hydrogenation kinetics of 2-nitro-2'-hydroxy-5'-methylazobenzene, 4-nitro-2'-hydroxy-5'-methyl-isobenzene, 4-nitroaniline, 4-amino-2'-hydroxy-5'-methylazobenzene on skeletal nickel in 2-propanol aqueous solutions of different composition, including with the addition of acetic acid or sodium hydroxide with various initial amounts of organic compound. The rise in the 4-nitro-2'-hydroxy-5'-methylazobenzene initial amount leads to increase in the nitro group transformation rate in the starting compound and to decrease in the azo-group transformation rate. The effect of sodium hydroxide additives in the 2-propanol aqueous solution on the nitro- and azo-groups conversion rate into 4-nitro-2'-hydroxy-5'-methyl-isobenzene is analogous to the change in the individual compounds hydrogenation rates (4-nitroaniline and 4-amino-2'-hydroxy-5'-methylazobenzene). Obtained results do not contradict the parallel-sequential scheme concept for the 4-nitro-2'-hydroxy-5'-methylazobenzene transformations. One of the directions is associated with the azo-group transformation into 4-nitro-2'-hydroxy-5'-methylazobenzene and 4-nitroaniline and 2-amino-4-methylphenol formation, and the second with the 4-nitro-2'-hydroxy-5'-methyl-isobenzene conversion through 4-amino-2'-hydroxy-5'-methyl-isobenzene by the nitro-group reducing. At the reaction end, all intermediate compounds are reduced to 2-amino-4-methylphenol and 1,4-phenylenediamine. When 2-nitro-2'-hydroxy-5'-methylazobenzene is hydrogenated, one of the directions leads to the 2-nitro-2'-hydroxy-5'-methylhydrazobenzene formation, and the second to the product containing the triazole cycle - N-oxide 2-2'-hydroxy-5'-methylphenylbenzotriazole. At the reaction end, these compounds are reduced to 2-2'-hydroxy-5'-methylphenylbenzotriazole and 2-amino-4-methylphenol and 1,2-phenylenediamine, respectively. In the solution at the sodium hydroxide presence, 2-nitro-2'-hydroxy-5'-methylhydrazobenzene transforms into the N-oxide 2-2'-hydroxy-5'-methylphenylbenzotriazole as a result of intramolecular rearrangement.
References
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.
Filippov D.V., Ulitin M.V., Merkin A.A. Thermodynamics of processes proceeding in the surface layers of skeletal nickel in bisolvent ethanol-water solvents with the participation of individual forms of hydrogen. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2008. V. 50. N 3. P. 48-51 (in Russian).
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 thethermodynamic characteristics of the individual forms of hydrogen adsorbed on thesurface of porous nickel. Russ. J. Phys. Chem. A. 2010. V. 84. N 9. P. 1605-1610.
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 admix-tures. Russ. J. Phys. Chem. A. 2007. V. 81. N 2. P. 272-276.
Loginov S.А., Ulitin M.V., Barbov A.V. Thermodynamics of Hydrogen Adsorption an Porous Nickel from Aqueous Solution. Russ. J. Phys. Chem. A. 2003. V. 77. N 1. P. 37-41.
Bond D.K., Uzle P.B. The mechanism of catalytic hydrogenation of non-limiting hydrocarbons on transition metals. Coll.: Catalysis. Physico-chemistry of heterogeneous catalysis. M.: Mir. 1987. P. 351-473 (in Russian).
Lamy - Pitara E., N’Zemba B., Barbier J., Barbot F., Miginiac L. Simple and competitive catalytic hydrogenation of nitrobenzene, allyl benzyl ether and benzyl crotyl ether in alkaline alcoholic media. J. Molec. Catal. A: Chem. 1999. V. 142. P. 39-50.
Imai H., Nishiguchi T., Fukuzumi K. Homogeneous catalytic reduction of aromatic nitro-compounds by hydrogen transfer. Chem. Lett. 1976. V. 5. N. 7. P. 655-656.
Nguyen Thi Thu Ha, Lefedova O.V., Merkin A.A. Features of the Kinetics of 4-Nitroaniline and Azoxybenzene Hydrogenation in 2-Propanol Aqueous Solutions. Russ. J. Phys. Chem. A. 2013. V. 87. N 4. P. 571-575.
Nguyen Thi Thu Ha, Merkin A.A., Latypova A.R., Lefedova O.V. The influence of the amount of skeletal nickel on the reaction rate of hydrogenation of intermediate products of nitrobenzene reduction. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2014. V. 57. N 2. P. 55-58 (in Russian).
Theory and practice of the processes of liquid-phase hydrogenation of substituted nitrobenzenes. Ed. by O.I. Koifman M.: KRASAND. 2016. 528 p. (in Russian).
Nemtseva M.P., Lefedova O.V., Zuenko M.A., Antina L.A. Kinetics of liquid-phase hydrogenation of substituted nitro- and azobenzenes in the presence of a skeleton nickel catalyst. Russ. J. Phys. Chem. A. 2004. V. 78. N 9. P. 1571-1575.
Hoang Anh, Kalashnikova V.A., Lefedova O.V., Filippov D.V. Effect of additions of sodium hydroxide 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).
Lefedova O.V., Nikolaev V.N., Nemtzeva M.P. Intermediate Products in the hydrogenization of 2-nitro-2’-hyroxy-5’-methylazobenzene and their sequential trans-formations. Russ. J. Phys. Chem. A. 2003. V. 77. N 7. P. 1183-1187.
Zuenko M.A., Nemtseva M.P., Lefedova O.V., Nikolaev V.N. Liquid phase hydrogenation of 2-nitro-2’-hydroxy-5’-methylazobenzene on skeletal nickel at low temperatures. Russ. J. Phys. Chem. A. 2004. V. 78. N 6. P. 1015-1020 (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.
Romanenko Yu.E., Merkin A.A., Lefedova O.V. Kinetic description of the hydrogenation of nitrobenzene and nitrosobenzene on skeletal nickel in aqueous solutions of
-propanol of different composition. Kinet.Katal. 2016. V. 57. N 2. P. 206-210 (in Russian).
Zollinger H. Diazo Chemistry I. Aromatic and heteroaromatic com-pounds. Weinheim; New York; Basel; Cambridge; Tokyo: VCH. 1994. 453 p.
