Selective Nitration of Phenols via H6PMo9V3O40/SiO2 catalysts

doi:10.3724/SP.J.1095.2014.30261

Chinese Journal of Applied Chemistry

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Selective Nitration of Phenols via H₆PMo₉V₃O₄₀/SiO₂ catalysts

WU Jinming¹, SHI Lei¹, SHEN Aibao^1*, TANG Yanfeng¹, LU Tianhong^2,3

(1.School of Chemistry and Chemical Engineering,Nantong University,Nantong 226019,China;
2.Jiangsu Key Laboratory of New Power Batteries,School of Chemistry and
Material Science,Nanjing Normal University,Nanjing 210097,China;
3.Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 226019,China)

Received:2013-05-22 Revised:2013-08-05 Published:2014-04-10 Online:2014-04-10
Contact: shen aibao

Abstract

Abstract: To establish a clean and efficient nitration process of phenolic compounds, heteropolyacid H6PMo9V3O40(PMAV3) and chromatographic silica gel were respectively chosen as active component and carrier for the preparation of a series of supported catalysts(PMAV3/SiO2) via the conventional impregnation method. The catalysts were characterized by Fourier transform infrared spectroscopy(FTIR), X-ray diffraction(XRD)，N2 adsorption-desorption and thermogravimetry-differential scanning calorimetry(TG-DSC). The catalytic performance of catalysts was evaluated for the nitration of phenols. The results reveals that PMAV3/SiO2 exhibits excellent catalytic activity and regioselectivity for the nitration of phenols, the nitration yield is in the range of 83.7%～94.5%. For salicylic acid, the para-selectivity is nearly 100%, but for phenol, 2-methylphenol, 2-chlorophenol and 2-fluorphenol, the ortho-selectivity is observed. The textural properties of PMAV3/SiO2 are close to that of PMAV3, but BET of the supported catalysts is decreased with the rise of PMAV3 loading. PMAV3/SiO2 shows better thermal stability than PMAV3. The catalyst can be recovered easily and reused for five times without noticeable drop in activity.

Key words: catalyst, heteropolyacid, H6PMo9V3O40, silica gel, nitration, phenolic compound

CLC Number:

WU Jinming1, SHI Lei1, SHEN Aibao1*, TANG Yanfeng1, LU Tianhong2,3. Selective Nitration of Phenols via H₆PMo₉V₃O₄₀/SiO₂ catalysts[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30261.

References

[1] Olah G A,Malhotra R,Narang S C. Nitration Methods and Mechanism[M]. New York:VCH Press,1989:5-15.

[2] Zaldivar J M,Molgab E,Alos M A,et al. Aromatic Nitrations by Mixed Acid. Fast Liquid-Liquid Reaction Regime[J]. Chem Eng Process,1996,35(2):91-105.

[3] Mellor J M,Mittoo S,Parkes R,et al. Improved Nitrations Using Metal Nitrate-Sulfuric Acid Systems[J]. Tetrahedron,2000,56(40):8019-8024.

[4] Selvam J J P,Suresh V,Rajesh K,et al. Highly Efficient Nitration of Phenolic Compounds by Zirconyl Nitrate[J]. Tetrahedron Lett,2006,47(15):2507-2509.

[5] Anuradha V,Srinivas P V,Aparna P,et al. p-Toluenesulfonic Acid Catalyzed Regiospecific Nitration of Phenols with Metal Nitrates[J]. Tetrahedron Lett,2006,47(28):4933-4935.

[6] Pourali A R,Fatemi F. Selective Nitration of Phenols Using Bismuth Subnitrate/Charcoal in the Presence of Trichloroisocyanuric Acid under Aprotic Conditions[J]. Chinese Chem Lett,2010,21(11):1283-1286.

[7] Nowrouzi N,Jonaghani M Z. Nitration of Aromatic Compounds under Neutral Conditions Using the Ph2PCl/I2/AgNO3 Reagent System[J]. Tetrahedron Lett,2011,52(39):5081-5082.

[8] Wang P C,Lu M. Regioselectivity Nitration of Aromatics with N2O5 in PEG-based Dicationic Ionic Liquid[J]. Tetrahedron Lett,2011,52(13):1452-1455.

[9] Ma X M,Li B D,Chen L,et al. Selective Nitration of Aromatic Compounds Catalyzed by H beta Zeolite Using N2O5[J]. Chinese Chem Lett,2012,23(7):809-812.

[10] Parida K M,Rath D. Studies on MCM-41:Effect of Sulfate on Nitration of Phenol[J]. J Mol Catal A:Chem,2006,258(1/2):381-387.

[11] Khder A S,Ahmed A I. Nitration of Phenol over Nanosized Tungsten Oxide Supported on Sulfated SnO2 as a Solid Acid Catalyst[J]. Appl Catal A,2009,354(1/2):153-160.

[12] Kemdeo S M,Sapkal V S,Chaudhari G N. TiO2-SiO2 Mixed Oxide Supported MoO3 Catalyst:Physicochemical Characterization and Activities in Nitration of Phenol[J]. J Mol Catal A:Chem,2010,323(1/2):70-77.

[13] Timofeeva M N. Acid Catalysis by Heteropoly Acids[J]. Appl Catal A,2003,256(1/2):19-35.

[14] Shaabani A,Behnam M,Rezayan A H. Tungstophosphoric Acid (H3PW12O40) Catalyzed Oxidation of Organic Compounds with NaBrO3[J]. Catal Commun,2009,10(7):1074-1078.

[15] Rafiee E,Joshaghani M,Tork F,et al. Esterification of Mandelic Acid Catalyzed by Heteropoly Acid[J]. J Mol Catal A:Chem,2008,283(1/2):1-4.

[16] Feng S J,Zhang L,Ren Y H,et al. Catalytic Hydroxylation of Benzene to Phenol with Hydrogen Peroxide over Cesium Salts of Keggin-type Heteropoly Acids[J]. Acta Chim Sin,2012,70(22):2316-2322.

[17] Mallick S,Parida K M. Selective Nitration of Phenol over Silicotungstic Acid Supported Zirconia[J]. Catal Commun,2007,8(10):1487-1492.

[18] Kumar A S H,Rao K T V,Upendar K,et al. Nitration of Methyl 5-Nitrosalicylate Catalyzed by H6PMoV3O40 Supported on Silica Gel[J]. Catal Commun,2012,18:37-40

[19] WU Jinming,SHEN Aibao. Synthesis of Methyl 5-Nitrosalicylate Catalyzed by H6PMoV3O40 Supported on Silica Gel[J]. Fine Chem,2011,28(6):603-605(in Chinese).

吴锦明，沈爱宝. 硅胶负载H6PMo9V3O40催化制备5-硝基水杨酸甲酯[J]. 精细化工,2011,28(6):603-605.

[20] WU Jinming,TANG Yanfeng,SHEN Aibao. Synthesis of 5-Nitrosalicylaldehyde Catalyzed by H6PMo9V3O40 Supported on Silica Gel[J]. Chinese J Appl Chem,2012,29(5):545-550(in Chinese).

吴锦明,汤艳峰,沈爱宝. 硅胶负载H6PMo9V3O40催化合成5-硝基水杨醛[J]. 应用化学,2012,29(5):545-550.

[21] PEI Supeng,YUE Bin,CHENG Jifang,et al. Selective Oxidation of Methane on SBA-15 Supported P-Mo-V Oxide Catalysts[J]. Acta Chim Sin,2008,66(8):902-908(in Chinese).

裴素朋,岳斌,程记芳,等. 负载型 P-Mo-V/SBA-15催化剂上的甲烷选择氧化反应[J]. 化学学报,2008,66(8):902-908.

[22] Rodrigues J A R,Filho A P O,Moran P J S,et al. Regioselectivity of the Nitration of Phenol by Acetyl Nitrate Adsorbed on Silica Gel[J]. Tetrahedron,1999,22(55):6733-6738.

[23] HE Yigong,LI Fen,WANG Peng,et al. Adsorption, Acidity and Physico-chemical Properties of Heteropolyacid Catalysts[J]. Pet Process Petrochem,1996,27(8):12-16(in Chinese).

何奕工，李奋，王蓬，等. 杂多酸催化剂的吸附、酸性和物化性质[J]. 石油炼制与化工,1996,27(8):12-16.

[24] QIAN Hua,LIU Dabin,YE Zhiwen. Selective Nitration of Chlorobenzene with N2O5 Assisted by Heteropolyacids[J]. Chiense J Appl Chem,2009,26(6):676-680(in Chinese).

钱华，刘大斌，叶志文. 负载杂多酸催化下N2O5对氯苯的选择性硝化[J]. 应用化学,2009,26(6):676-680.

Selective Nitration of Phenols via H₆PMo₉V₃O₄₀/SiO₂ catalysts

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