Abstract
With the increase in environmental awareness, developing a highly efficient and environmentally benign nitration process has very important academic and applied industrial values in the synthesis of nitro-compounds. Towards this goal, we have developed an efficient and environmentally friendly approach for solvent-free liquid phase nitration of toluene by employing NO2 as a nitrating agent and sulfated SO4 2−/WO3 as a catalyst replacing traditional nitric acid–sulfuric acid under mild conditions. The results indicate that SO4 2−/WO3 as an effective and eco-friendly catalyst exhibits excellent catalytic activity and reusability for the nitration of toluene with NO2. In addition, the possible pathway for liquid phase nitration of toluene with NO2 over sulfated SO4 2−/WO3 catalyst was suggested. The present method makes this nitration process safe and environmentally friendly, and has the potential to enable a sustainable production of nitro-compounds from the liquid phase nitration of aromatic hydrocarbon with NO2 in industrial applications.
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References
G.A. Olah, R. Malhotra, S.C. Narang, Nitration: Methods and Mechanisms (VCH, New York, 1989)
J.P. Agrawal, R.D. Hodgson, Organic Chemistry of Explosive (Wiley, New York, 2007)
J.P. Agrawal, High Energy Materials propellants, Explosives and Pyrotechnics (Wiley, New York, 2010)
R.W. Millar, A.W. Arber, R.M. Endsor, J. Hamid, M.E. Colclouth, J. Energ. Mater. 29, 88–114 (2011)
R. Fareghi-Alamdari, F. Zandi, M.H. Keshavarz, RSC Adv. 5, 71911–71921 (2015)
K. Smith, A. Musson, G.A. DeBoos, J. Org. Chem. 63, 8448–8454 (1998)
T. Esakkidurai, K. Pitchumani, J. Mol. Catal. A Chem. 185, 305–309 (2002)
S.P. Dagade, V.S. Kadam, M.K. Dongare, Catal. Commun. 3, 67–70 (2002)
B.M. Choudary, M. Sateesh, M.L. Kantam, K.K. Rao, K.V.R. Prasad, K.V. Raghavan, J.A.R.P. Sarma, Chem. Commun. 1, 25–26 (2000)
A. German, T. Akouz, F. Figueras, J. Catal. 147, 163–170 (1994)
M.G. Kuba, R. Prins, G.D. Pirngruber, Appl. Catal. A Gen. 333, 78–89 (2007)
W. Skupinski, M. Malesa, Appl. Catal. A Gen. 236, 223–234 (2002)
S.K. Maurya, M.K. Gurjar, K.M. Malshe, P.T. Patil, M.K. Dongare, E. Kemnitz, Green Chem. 5, 720–723 (2003)
S.B. Umbarkar, A.V. Biradar, S.M. Mathew, S.B. Shelke, K.M. Malshe, P.T. Patil, S.P. Dagde, S.P. Niphadkar, M.K. Dongare, Green Chem. 8, 488–493 (2006)
X.M. Ma, B.D. Li, C.X. Lv, M. Lu, J. Wu, L.J. Liang, Catal. Lett. 141, 1814–1820 (2011)
A.B. Kulal, M.K. Dongare, S.B. Umbarkar, Appl. Catal. B Environ. 182, 142–152 (2016)
S.M. Kemdeo, V.S. Sapkal, G.N. Chaudhari, J. Mol. Catal. A Chem. 323, 70–77 (2010)
J.M. Riego, Z. Sedin, J.M. Zaldivar, N.C. Nunziata, C. Tortato, Tetrahedron Lett. 37, 513–516 (1996)
H. Sato, K. Nagai, H. Yoshioka, Y. Nagaoka, Appl. Catal. A Gen. 180, 359–366 (1999)
J. Adamiak, D. Kalinowska-Alichnewicz, P. Maksimowski, W. Skupinski, J. Mol. Catal. A Chem. 351, 62–69 (2011)
K.M. Parida, P.K. Pattnayak, Catal. Lett. 47, 255–257 (1997)
K.R. Sunajadevi, S. Sugunan, Mater. Lett. 60, 3813–3817 (2006)
A.S. Khder, A.I. Ahmed, Appl. Catal. A 354, 153–160 (2009)
S. Mallick, K.M. Parida, Catal. Commun. 8, 1487–1492 (2007)
S.W. Gong, L.J. Liu, J.L. Zhang, Q.X. Cui, Process Saf. Environ. Protect. 92, 577–582 (2014)
S.W. Gong, L.J. Liu, Q. Zhang, L.Y. Wang, Bull. Korean Chem. Soc. 33, 1279–1284 (2012)
G.B. Cheng, X.F. Qi, C.X. Lu, Cent. Eur. J. Energ. Mater. 4, 59–65 (2007)
V.V. Brei, S.V. Prudius, O.V. Melezhyk, Appl. Catal. A Gen. 239, 11–16 (2003)
T. Mishra, K.M. Parida, J. Mol. Catal. A Chem. 121, 91–96 (1997)
T. Mishra, Catal. Commun. 9, 21–26 (2008)
H. Sato, K. Hirose, Appl. Catal. A 174, 77–81 (1998)
T. Mori, H. Suzuki, Synlett 5, 383–392 (1995)
X. Peng, H. Suzuki, Org. Lett. 3, 3431–3434 (2001)
X. Peng, H. Suzuki, C. Lu, Tetrahedron Lett. 42, 4357–4359 (2001)
H. Suzuki, S. Yonezawa, N. Nonoyama, N. Mori, J Chem Soc Perkin Trans. 1, 2385–2389 (1996)
K. You, R. Deng, J. Jian, P. Liu, Q. Ai, H. Luo, RSC Adv. 5, 73083–73090 (2015)
N. Iranpoor, H. Firouzabadi, M.A. Zolfigol, Synth. Commun. 28, 2773–2781 (1998)
R.R. Bak, A.J. Smallridge, Tetrahedron Lett. 42, 6767–6769 (2001)
X.M. Ma, B.D. Li, L. Chen, M. Lu, C.X. Lv, Chin. Chem. Lett. 23, 809–812 (2012)
B. Shokrolahi, A. Zali, M.H. Keshavarz, Chin. Chem. Lett. 18, 1064–1066 (2007)
H. Pervez, S.O. Onyiriuka, L. Rees, C.J. Suckling, Tetrahedron 44, 4555–4568 (1988)
R. Fareghi-Alamdari, M. Golestanzadeh, N. Zekri, New J. Chem. 40, 3400–3412 (2016)
H. Naeimi, M. Golestanzadeh, New J. Chem. 39, 2697–2710 (2015)
R. Fareghi-Alamdari, M. Golestanzadeh, N. Zekri, Z. Mavedatpoor, J. Iran. Chem. Soc. 12, 537–549 (2015)
M. Golestanzadeh, H. Naeimi, Z. Zahraie, Mater. Sci. Eng., C 71, 709–717 (2016)
K. Tanabe, Solid acid and base catalysts, in Catalysis Science and Technology, vol. 2, ed. by J.R. Anderson, M. Boudart (Springer, Berlin, 1981), pp. 231–273
L.R. Pizzio, P.G. Vazquez, C.V. Caceres, M.N. Blanco, Appl. Catal. A Gen. 256, 125–139 (2003)
B. Tyagi, M.K. Mishra, A. Tasra, J. Mol. Catal. A Chem. 301, 67–78 (2009)
K.N. Rao, K.M. Reddy, N. Lingaiah, I. Suryanarayana, P.S.S. Prasad, Appl. Catal. A Gen. 300, 139–146 (2006)
A.E.R.S. Khder, H.M.A. Hassan, M.S. El-Shall, Appl. Catal. A Gen. 411–412, 77–86 (2012)
M.V. Landau, S.B. Kogan, D. Tavor, M. Herskowitz, J.E. Koresh, Catal. Today 36, 497–510 (1997)
Acknowledgements
The authors are grateful for the financial support for this work by the National Natural Science Foundation of China (21276216 and 21402048), Collaborative Innovation Center of New Chemical Technologies for Environmental Benignity and Efficient Resource Utilization, and Project of Technological Innovation and Entrepreneurship Platform for Hunan Youth (2014).
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Jiao, Y., Zhu, M., Deng, R. et al. Sulfated SO4 2−/WO3 as an efficient and eco-friendly catalyst for solvent-free liquid phase nitration of toluene with NO2 . Res Chem Intermed 43, 3961–3974 (2017). https://doi.org/10.1007/s11164-016-2856-5
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DOI: https://doi.org/10.1007/s11164-016-2856-5