1. School of Chemical Engineering, Xiangtan University, Xiangtan 411105, China 2. National & Local United Engineering Research Center for Chemical Process Simulation and Intensification, Xiangtan University, Xiangtan 411105, China
Metal salts with highly electronegative cations have been used to effectively catalyze the liquid-phase nitration of benzene by NO2 to nitrobenzene under solvent-free conditions. Several salts including FeCl3, ZrCl4, AlCl3, CuCl2, NiCl2, ZnCl2, MnCl2, Fe(NO3)3·9H2O, Bi(NO3)3·5H2O, Zr(NO3)4·5H2O, Cu(NO3)2·6H2O, Ni(NO3)2·6H2O, Zn(NO3)2·6H2O, Fe2(SO4)3, and CuSO4 were examined and anhydrous FeCl3 exhibited the best catalytic performance under the optimal reaction conditions. The benzene conversion and selectivity to nitrobenzene were both over 99%. In addition, it was determined that the metal counterion and the presence of water hydrates in the salt affects the catalytic activity. This method is simple and efficient and may have potential industrial application prospects.
. [J]. Frontiers of Chemical Science and Engineering, 2017, 11(2): 205-210.
Shenghui Zhou, Kuiyi You, Zhengming Yi, Pingle Liu, Hean Luo. Metal salts with highly electronegative cations as efficient catalysts for the liquid-phase nitration of benzene by NO2 to nitrobenzene. Front. Chem. Sci. Eng., 2017, 11(2): 205-210.
Schofield K. Aromatic Nitration.Cambridge: Cambridge University Press, 1980
2
Ma X, Li B, Lv C, Lu M, Wu J, Liang L. An efficient and eco-friendly MoO3-SiO2 solid acid catalyst for electrophilic aromatic nitration with N2O5. Catalysis Letters, 2011, 141(12): 1814–1820 https://doi.org/10.1007/s10562-011-0721-0
3
Olah G A, Malhotra R, Narang S C. Nitration: Methods and Mechanisms.New York: VCH, 1989
4
Smith K, Musson A, De Boos G A. A novel method for the nitration of simple aromatic compounds. Journal of Organic Chemistry, 1998, 63(23): 8448–8454 https://doi.org/10.1021/jo981557o
5
Kalbasi R J, Ghiaci M, Massah A R. Highly selective vapor phase nitration of toluene to 4-nitro toluene using modified and unmodified H3PO4/ZSM-5. Applied Catalysis A, General, 2009, 353(1): 1–8 https://doi.org/10.1016/j.apcata.2008.10.013
6
Kulal A B, Dongare M K, Umbarkar S B. Sol-gel synthesised WO3 nanoparticles supported on mesoporous silica for liquid phase nitration of aromatics. Applied Catalysis B: Environmental, 2016, 182: 142–152 https://doi.org/10.1016/j.apcatb.2015.09.020
7
Mao W, Ma H, Wang B. A clean method for solvent-free nitration of toluene over sulfated titania promoted by ceria catalysts. Journal of Hazardous Materials, 2009, 167(1): 707–712 https://doi.org/10.1016/j.jhazmat.2009.01.045
8
Bernasconi S, Pirngruber G D, Prins R. Influence of the properties of zeolite BEA on its performance in the nitration of toluene and nitrotoluene. Journal of Catalysis, 2004, 224(2): 297–303 https://doi.org/10.1016/j.jcat.2004.03.015
9
Zhao X, Han Y, Sun X, Wang Y. Structure and catalytic performance of H3PW12O40/SiO2 prepared by several methods. Chinese Journal of Catalysis, 2007, 28(1): 91–95 https://doi.org/10.1016/S1872-2067(07)60011-4
10
Parida K M, Pattnayak P K. Sulphated zirconia: An efficient paraselective catalyst for mononitration of halobenzenes. Catalysis Letters, 1997, 47(3-4): 255–257 https://doi.org/10.1023/A:1019073525356
11
Yadav G D, Nair J J. Selectivity engineering in the nitration of chlorobenzene using eclectically engineered sulfated zirconia and carbon molecular sieve catalysts. Catalysis Letters, 1999, 62(1): 49–52 https://doi.org/10.1023/A:1019066131736
12
Sato H, Nagai K, Yoshioka H, Nagaokab Y. Vapor phase nitration of benzene over solid acid catalysts IV. Nitration with nitric acid (3); supported sulfuric acid catalyst with co-feeding of a trace amount of sulfuric acid. Applied Catalysis A, General, 1999, 180(1-2): 359–366 https://doi.org/10.1016/S0926-860X(98)00367-6
13
Gong S, Liu L, Cui Q, Ding J. Liquid phase nitration of benzene over supported ammonium salt of 12-molybdophosphoric acid catalysts prepared by sol-gel method. Journal of Hazardous Materials, 2010, 178(1-3): 404–408 https://doi.org/10.1016/j.jhazmat.2010.01.095
14
Olah G A, Krishnamurthy V V, Narang S C. Aromatic substitution. 50. Mercury (II)-promoted azeotropic nitration of aromatics over Nafion-H solid superacidic catalyst. Journal of Organic Chemistry, 1982, 47(3): 596–598 https://doi.org/10.1021/jo00342a052
15
Shi M, Cui S C. Electrophilic aromatic nitration using perfluorinated rare earth metal salts in fluorous phase. Chemical Communications, 2002, (9): 994–995 https://doi.org/10.1039/b202308n
16
You K Y, Deng R J, Jian J, Liu P L, Ai Q H, Luo H A H. 3PW12O40 synergized with MCM-41 for the catalytic nitration of benzene with NO2 to nitrobenzene. RSC Advances, 2015, 5(89): 73083–73090 https://doi.org/10.1039/C5RA15679C
17
Ma X M, Li B D, Lu M, Lv C X. Selective nitration of aromatic compounds catalyzed by Hβ zeolite using N2O5. Chinese Chemical Letters, 2012, 23(7): 809–812 https://doi.org/10.1016/j.cclet.2012.05.016
18
Ma X M, Li B D, Lu M, Lv C X. Rare earth metal triflates catalyzed electrophilic nitration using N2O5. Chinese Chemical Letters, 2012, 23(1): 73–76 https://doi.org/10.1016/j.cclet.2011.09.021
19
Samajdar S, Becker F F, Banik B K. Surface-mediated highly efficient regioselective nitration of aromatic compounds by bismuth nitrate. Tetrahedron Letters, 2000, 41(42): 8017–8020 https://doi.org/10.1016/S0040-4039(00)01397-6
20
Iranpoor N, Firouzabadi H, Heydari R, Shiri M. Nitration of aromatic compounds by Zn(NO3)2·2N2O4 and its charcoal-supported system. Synthetic Communications, 2005, 35(2): 263–270 https://doi.org/10.1081/SCC-200048450
21
Pervez H, Onyiriuka S O, Rees L, Rooney J R, Suckling C J. Selective functionalization: Part 10. The nitration of phenols by pyridine derivatives carrying a transferable nitro group. Tetrahedron, 1988, 44(14): 4555–4568 https://doi.org/10.1016/S0040-4020(01)86158-5
22
Cheng G, Duan X, Qi X, Lu C. Nitration of aromatic compounds with NO2/air catalyzed by sulfonic acid-functionalized ionic liquids. Catalysis Communications, 2008, 10(2): 201–204 https://doi.org/10.1016/j.catcom.2008.08.019
23
Smith K, Almeera S, Petersa C. Regioselective mononitration of aromatic compounds by zeolite/dinitrogen tetroxide/air in a solvent-free system. Chemical Communications, 2001, (24): 2748–2749 https://doi.org/10.1039/b108952h
24
Bosch E, Kochi K. Thermal and photochemical nitration of aromatic hydrocarbons with nitrogen dioxide. Journal of Organic Chemistry, 1994, 59(12): 3314–3325 https://doi.org/10.1021/jo00091a018
25
Suzuki H, Yonezawa S, Nonoyama N, Mori T. Iron(III)-catalysed nitration of non-activated and moderately activated arenes with nitrogen dioxide–molecular oxygen under neutral conditions. Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry, 1996, (19): 2385–2389 https://doi.org/10.1039/P19960002385
Shiri M, Zolfigol M A, Kruger H G, Tanbakouchian Z. Advances in the application of N2O4/NO2 in organic reactions. Tetrahedron, 2010, 66(47): 9077–9106 https://doi.org/10.1016/j.tet.2010.09.057
28
Tang B, Wei S, Peng X. Acid-catalyzed regioselective nitration of o-xylene to 4-nitro-o-xylene with nitrogen dioxide: Brønsted acid versus Lewis acid. Synthetic Communications, 2014, 14(44): 2057–2065 https://doi.org/10.1080/00397911.2013.873468