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Hydrogenation of Dinitrobenzenes to Corresponding Diamines Over Cu–Al Oxide Catalyst in a Flow Reactor

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Abstract

The catalytic hydrogenation of dinitroaromatic compounds is an important reaction for the production of phenylenediamine derivatives, which are widely used in industry. In this work, the catalytic properties of a Cu–Al mixed oxide obtained from double layered hydroxide have been investigated in liquid-phase hydrogenation of 1,3-dinitrobenzenes under continuous-flow conditions. The reaction was carried out at temperature of 120 °C, total pressure of 30 bar, using methanol or methanol/isopropanol mixture as a solvent. It was found that hydrogenation of 1,3-dinitrobenzene, 2,4-dinitrotoluene, 2,4-dinitroanisole and 2,4-dinitromesitylene provides the selective formation of the corresponding diamines, which were isolated in the form of salts with sulfuric acid stable in storage. The effect of the reaction temperature, pressure, H2 flow rate, and solvent nature on the catalyst performance was studied.

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References

  1. Downing RS, Kunkeler PJ, van Bekkum H (1997) Catalytic syntheses of aromatic amines. Catal Today 37:121–136. https://doi.org/10.1016/S0920-5861(97)00005-9

    Article  Google Scholar 

  2. Rajashekharam MV, Nikalje DD, Jaganathan R, Chaudhari RV (1997) Hydrogenation of 2,4-dinitrotoluene using a Pd/Al2O3 catalyst in a slurry reactor: a molecular level approach to kinetic modeling and nonisothermal effects. Ind Eng Chem Res 36:592–604. https://doi.org/10.1021/ie960365l

    Article  Google Scholar 

  3. Neri G, Musolino MG, Milone C, Galvagno S (1995) Kinetic modeling of 2,4-dinitrotoluene hydrogenation over Pd/C. Ind Eng Chem Res 34:2226–2231. https://doi.org/10.1021/ie00046a003

    Article  Google Scholar 

  4. Neri G, Musolino MG, Milone C, Visco AM, Di Mario A (1995) Mechanism of 2,4-dinitrotoluene hydrogenation over Pd/C. J Mol Catal A Chem 95:235–241. https://doi.org/10.1016/1381-1169(94)00002-6

    Article  Google Scholar 

  5. Janssen HJ, Kruithof AJ, Steghuis GJ, Westerterp KR (1990) Kinetics of the catalytic hydrogenation of 2,4-dinitrotoluene. 1. Experiments, reaction scheme, and catalyst activity. Ind Eng Chem Res 29:754–766. https://doi.org/10.1021/ie00101a008

    Article  Google Scholar 

  6. Pinna E, Selva M, Signoretto M, Strukul G, Boccuzzi E, Benedetti A, Canton P, Fagherazzi G (1990) Pd-Fe/SiO2 catalysts in the hydrogenation of 2,4-dinitrotoluene. J Catal 150:356–367. https://doi.org/10.1006/jcat.1994.1354

    Article  Google Scholar 

  7. Formenti D, Ferretti F, Scharnagl FK, Beller M (2019) Reduction of nitro compounds using 3d-non-noble metal catalysts. Chem Rev 119:2611–2680. https://doi.org/10.1021/acs.chemrev.8b00547

    Article  PubMed  Google Scholar 

  8. Ren B, Zhao M, Dong L, Li G (2014) Catalytic hydrogenation of 2,4-dinitroethylbenzene to 2,4-diaminoethylbenzene over Ni/HY catalysts: the solvent effect. Catal Commun 50:92–96. https://doi.org/10.1016/j.catcom.2014.02.029

    Article  Google Scholar 

  9. Malyala RV, Chaudhari RV (1999) Hydrogenation of 2,4-dinitrotoluene using a supported Ni catalyst: reaction kinetics and semibatch slurry reactor modeling. Ind Eng Chem Res 38:906–915. https://doi.org/10.1021/ie980423y

    Article  Google Scholar 

  10. Wei Z, Mao S, Sun F, Wang J, Mei B, Chen Y, Li H, Wang Y (2018) The synergic effects at the molecular level in CoS2 for selective hydrogenation of nitroarenes. Green Chem 20:671–679. https://doi.org/10.1039/c7gc03122j

    Article  Google Scholar 

  11. Formenti D, Ferretti F, Topf C, Surkus AE, Pohl MM, Radnik J, Schneider M, Junge K, Beller M, Ragaini F (2017) Co-based heterogeneous catalysts from well-defined α-diimine complexes: discussing the role of nitrogen. J Catal 351:79–89. https://doi.org/10.1016/j.jcat.2017.04.014

    Article  Google Scholar 

  12. Pisiewicz S, Formenti D, Surkus AE, Pohl MM, Radnik J, Junge K, Topf C, Bachmann S, Scalone M, Beller M (2016) Synthesis of nickel nanoparticles with N-doped graphene shells for catalytic reduction reactions. ChemCatChem 8:129–134. https://doi.org/10.1002/cctc.201500848

    Article  Google Scholar 

  13. Wei Z, Wang J, Mao S, Su D, Jin H, Wang Y, Xu F, Li H, Wang Y (2015) In situ-generated Co0-Co3O4/N-doped carbon nanotubes hybrids as efficient and chemoselective catalysts for hydrogenation of nitroarenes. ACS Catal 5:4783–4789. https://doi.org/10.1021/acscatal.5b00737

    Article  Google Scholar 

  14. Shuvalova EV, Kirichenko OA, Kapustin GI, Kustov LM (2016) Silica-supported copper nanoparticles as efficient catalysts for the liquid-phase selective hydrogenation of p-dinitrobenzene by molecular hydrogen. Russ Chem Bull 65:2850–2854. https://doi.org/10.1007/s11172-016-1667-6

    Article  Google Scholar 

  15. Shesterkina AA, Shuvalova EV, Kirichenko OA, Strelkova AA, Nissenbaum VD, Kapustin GI, Kustov LM (2017) Application of silica-supported Fe–Cu nanoparticles in the selective hydrogenation of p-dinitrobenzene to p-phenylenediamine. Russ J Phys Chem A 91:201–204. https://doi.org/10.1134/S0036024417020285

    Article  Google Scholar 

  16. Bukhtiyarova MV (2019) A review on effect of synthesis conditions on the formation of layered double hydroxides. J Solid State Chem 269:494–506. https://doi.org/10.1016/j.jssc.2018.10.018

    Article  Google Scholar 

  17. Nuzhdin AL, Shchurova IA, Bukhtiyarova MV, Bulavchenko OA, Alekseyeva NA, Sysolyatin SV, Bukhtiyarova GA (2022) Flow hydrogenation of 1,3,5-trinitrobenzenes over Cu-based catalysts as an efficient approach for the preparation of phloroglucinol derivatives. Synthesis 54:3605–3612. https://doi.org/10.1055/a-1807-3188

    Article  Google Scholar 

  18. Kumalaputri AJ, Bottari G, Erne PM, Heeres HJ, Barta K (2014) Tunable and selective conversion of 5-HMF to 2,5-Furandimethanol and 2,5-dimethylfuran over copper-doped porous metal oxides. Chemsuschem 7:2266–2275. https://doi.org/10.1002/cssc.201402095

    Article  PubMed  Google Scholar 

  19. Bukhtiyarova MV, Bulavchenko OA, Bukhtiyarov AV, Nuzhdin AL, Bukhtiyarova GA (2022) Selective hydrogenation of 5-acetoxymethylfurfural over Cu-based catalysts in a flow reactor: effect of Cu–Al layered double hydroxides synthesis conditions on catalytic properties. Catalysts 12:878. https://doi.org/10.3390/catal12080878

    Article  Google Scholar 

  20. Nuzhdin AL, Bukhtiyarova MV, Bulavchenko OA, Bukhtiyarova GA (2020) Flow hydrogenation of 5-acetoxymethylfurfural over Cu-based catalysts. Mol Catal 494:111132. https://doi.org/10.1016/j.mcat.2020.111132

    Article  Google Scholar 

  21. Kühl S, Friedrich M, Armbrüster M, Behrens M (2012) Cu, Zn, Al layered double hydroxides as precursors for copper catalysts in methanol steam reforming – pH-controlled synthesis by microemulsion technique. J Mater Chem 22:9632–9638. https://doi.org/10.1039/c2jm16138a

    Article  Google Scholar 

  22. Shao Y, Li Q, Dong X, Wang J, Sun K, Zhang L, Zhang S, Xu L, Yuan X, Hu X (2021) Cooperation between hydrogenation and acidic sites in Cu-based catalyst for selective conversion of furfural to γ-valerolactone. Fuel 293:120457. https://doi.org/10.1016/j.fuel.2021.120457

    Article  Google Scholar 

  23. Yu T, Jiao J, Song P, Nie W, Yi C, Zhang Q, Li P (2020) Recent progress in continuous-flow hydrogenation. Chemsuschem 13:2876–2893. https://doi.org/10.1002/cssc.202000778

    Article  PubMed  Google Scholar 

  24. Masuda K, Ichitsuka T, Koumura N, Sato K, Kobayashi S (2018) Flow fine synthesis with heterogeneous catalysts. Tetrahedron 74:1705–1730. https://doi.org/10.1016/j.tet.2018.02.006

    Article  Google Scholar 

  25. de C Crater W (1943) Manufacture of dinitrotoluene. U.S. Patent 2362743

  26. Zhao X, Li Z, Lin F, Zhan T, Zhang K (2015) Novel viologen compounds and preparation method thereof. CN Patent 104292151

  27. Geng H, Ni L, Yuan J, Yang G (2016) Synthesis method of 2,4,6-trimethyl-m-phenylenediamine. CN Patent 105461567

  28. Yu Z, Wu K (2017) Method for synthesizing 2,4-dinitroanisol. CN Patent 106748798

  29. Bems B, Schur M, Dassenoy A, Junkes H, Herein D, Schlögl R (2003) Relations between synthesis and microstructural properties of copper/zinc hydroxycarbonates. Chem Eur J 9:2039–2052. https://doi.org/10.1002/chem.200204122

    Article  PubMed  Google Scholar 

  30. Kühl S, Tarasov A, Zander S, Kasatkin I, Behrens M (2014) Cu-based catalyst resulting from a Cu, Zn, Al hydrotalcite-like compound: a microstructural, thermoanalytical, and in situ XAS study. Chem Eur J 20:3782–3792. https://doi.org/10.1002/chem.201302599

    Article  PubMed  Google Scholar 

  31. Alejandre A, Medina F, Salagre P, Correig X, Sueiras JE (1999) Preparation and study of Cu−Al mixed oxides via hydrotalcite-like precursors. Chem Mater 11:939–948. https://doi.org/10.1021/cm980500f

    Article  Google Scholar 

  32. Bridier B, López N, Pérez-Ramírez J (2010) Partial hydrogenation of propyne over copper-based catalysts and comparison with nickel-based analogues. J Catal 269:80–92. https://doi.org/10.1016/j.jcat.2009.10.019

    Article  Google Scholar 

  33. Yakushkin SS, Nuzhdin AL, Artiukha EA, Plyusnin PE, Bukhtiyarova GA, Martyanov ON (2018) In situ EPR study of chemoselective hydrogenation of nitroarenes on Au/Al2O3 catalyst. Mendeleev Commun 28:536–537. https://doi.org/10.1016/j.mencom.2018.09.029

    Article  Google Scholar 

  34. Shimizu K, Miyamoto Y, Kawasaki T, Tanji T, Tai Y, Satsuma A (2009) Chemoselective hydrogenation of nitroaromatics by supported gold catalysts: mechanistic reasons of size- and support-dependent activity and selectivity. J Phys Chem C 113:17803–17810. https://doi.org/10.1021/jp906044t

    Article  Google Scholar 

  35. Bunnett JF, Zahler RE (1951) Aromatic nucleophilic substitution reactions. Chem Rev 49:273–412. https://doi.org/10.1021/cr60153a002

    Article  Google Scholar 

  36. Huang L, Megías-Sayago C, Bingre R, Zheng Q, Wang Q, Louis B (2019) Catalytic performance of layered double hydroxides (LDHs) derived materials in gas-solid and liquid-solid phase reactions. ChemCatChem 11:3279–3286. https://doi.org/10.1002/cctc.201900499

    Article  Google Scholar 

  37. Biesinger MC, Lau LWM, Gerson AR, Smart RSC (2010) Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn. Appl Surf Sci 257:887–898. https://doi.org/10.1016/j.apsusc.2010.07.086

    Article  Google Scholar 

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Acknowledgements

This research was supported by the Ministry of Science and Higher Education of the Russian Federation within the governmental order for the Boreskov Institute of Catalysis (Project No. AAAA-A21-121011390055-8) and Institute for Problems of Chemical and Energetic Technologies (Project No. 121061500029-7). The studies were carried out using the facilities of the shared research center “National Center of Investigation of Catalysts” at Boreskov Institute of Catalysis.

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Authors and Affiliations

  1. Boreskov Institute of Catalysis SB RAS, Lavrentieva Ave., 5, Novosibirsk, Russia, 630090

    A. L. Nuzhdin, M. V. Bukhtiyarova, E. Yu. Gerasimov, A. V. Bukhtiyarov & G. A. Bukhtiyarova

  2. Institute for Problems of Chemical and Energetic Technologies SB RAS, Sotsialisticheskaja Str., 1, Biysk, Russia, 659322

    I. A. Shchurova & S. V. Sysolyatin

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  1. A. L. Nuzhdin
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Nuzhdin, A.L., Shchurova, I.A., Bukhtiyarova, M.V. et al. Hydrogenation of Dinitrobenzenes to Corresponding Diamines Over Cu–Al Oxide Catalyst in a Flow Reactor. Catal Lett 154, 295–302 (2024). https://doi.org/10.1007/s10562-023-04306-1

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