Abstract
Hexamethylenediamine (HMDA) is an important reagent for the synthesis of Nylon-6,6, and it is usually produced by the hydrogenation of adiponitrile using a toxic reagent of hydrocyanic acid. Herein, we developed an environmental friendly route to produce HMDA via catalytic reductive amination of 1,6-hexanediol (HDO) in the presence of hydrogen. The activities of several heterogeneous metal catalysts such as supported Ni, Co, Ru, Pt, Pd catalysts were screened for the present reaction in supercritical ammonia without any additives. Among the catalysts examined, Ru/Al2O3 presented a high catalytic activity and highest selectivity for the desired product of HMDA. The high performance of Ru/Al2O3 was discussed based on the Ru dispersion and the surface properties like the acid-basicity. In addition, the reaction parameters such as reaction temperature, time, H2 and NH3 pressure were examined, and the reaction processes were discussed in detail.
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References
Dros AB, Larue O, Reimond A, De Campo F, Pera-Titus M. Green Chem, 2015, 17: 4760–4772
Roundhill DM. Chem Rev, 1992, 92: 1–27
Fischer A, Mallat T, Baiker A. Catal Today, 1997, 37: 167–189
Bähn S, Imm S, Neubert L, Zhang M, Neumann H, Beller M. ChemCatChem, 2011, 3: 1853–1864
Shimizu K. Catal Sci Technol, 2015, 5: 1412–1427
Zhang Y, Qi X, Cui X, Shi F, Deng Y. Tetrahedron Lett, 2011, 52: 1334–1338
Tuteja J, Choudhary H, Nishimura S, Ebitani K. ChemSusChem, 2014, 7: 96–100
Xiao B, Zheng M, Li X, Pang J, Sun R, Wang H, Pang X, Wang A, Wang X, Zhang T. Green Chem, 2016, 18: 2175–2184
Gunanathan C, Milstein D. Angew Chem Int Ed, 2008, 47: 8661–8664
Molnár Á, Sirokmán G, Bartók M. J Mol Catal, 1983, 19: 25–33
Sirokmán G, Molnár Á, Bartók M. J Mol Catal, 1983, 19: 35–40
Fischer A, Maciejewski M, Bürgi T, Mallat T, Baiker A. J Catal, 1999, 183: 373–383
Fischer A, Mallat T, Baiker A. Angew Chem Int Ed, 1999, 38: 351–354
Fischer A, Mallat T, Baiker A. J Mol Catal A-Chem, 1999, 149: 197–204
Jenzer G, Mallat T, Baiker A. Catal Lett, 1999, 61: 111–114
Fischer A, Mallat T, Baiker A. J Catal, 1999, 182: 289–291
Imm S, Bähn S, Zhang M, Neubert L, Neumann H, Klasovsky F, Pfeffer J, Haas T, Beller M. Angew Chem Int Ed, 2011, 50: 7599–7603
Baumann W, Spannenberg A, Pfeffer J, Haas T, Köckritz A, Martin A, Deutsch J. Chem Eur J, 2013, 19: 17702–17706
Pingen D, Diebolt O, Vogt D. ChemCatChem, 2013, 5: 2905–2912
Pfützenreuter R, Rose M. ChemCatChem, 2016, 8: 251–255
Mormul J, Breitenfeld J, Trapp O, Paciello R, Schaub T, Hofmann P. ACS Catal, 2016, 6: 2802–2810
Horlenko T, Tatum HW. Process for producing hexamethylenediamine from 1-6-hexanediol. US Patent, 3268588, 1966-08-23
Winderl S, Haarer E, Corr H, Hornberger P. Production of diaminoalkanes. US Patent, 3270059, 1966-08-30
Romanelli GP, Autino JC, Blanco MN, Pizzio LR. Appl Catal A-Gen, 2005, 295: 209–215
Altass HM, Khder AERS. J Mol Catal A-Chem, 2016, 411: 138–145
Srinivas N, Venu Gopal D, Srinivas B, Kulkarni SJ, Subrahmanyam M. Microporous Mesoporous Mater, 2002, 51: 43–50
Zhao F, Ikushima Y, Arai M. J Catal, 2004, 224: 479–483
Acknowledgments
This work was supported by the National Basic Research Program of China (2016YFA0602900), Youth Innovation Promotion Association CAS (2016206), and Jilin Provincial Science and Technology Program of China (20150301012GX).
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Li, Y., Cheng, H., Zhang, C. et al. Reductive amination of 1,6-hexanediol with Ru/Al2O3 catalyst in supercritical ammonia. Sci. China Chem. 60, 920–926 (2017). https://doi.org/10.1007/s11426-017-9049-5
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DOI: https://doi.org/10.1007/s11426-017-9049-5