Share This Article:

Zinc Chloride Catalyzed Regioselective Nitration of Aromatic Hydrocarbons Using Tetrachlorosilane-Sodium Nitrate Homogeneous System

Abstract Full-Text HTML XML Download Download as PDF (Size:349KB) PP. 49-56
DOI: 10.4236/ijoc.2015.52006    4,839 Downloads   6,117 Views   Citations

ABSTRACT

The development of a new silane reagent derived from tetrachlorosilane (TCS) was applied in the present work. TCS-sodium nitrate (NaNO3) binary reagent and zinc chloride (ZnCl2) were reported here as a homogeneous nitrating system. The later was used for the efficient mono nitration, in most cases, with high para-regioselectivity. The nitration proceeded smoothly under mild condition, fairly clean and in good yields. This readily available and inexpensive system is superior to other methods by avoidance of the use of corrosive nitrating reagents and therefore considered to be convenient in terms of risk reduction, economic advantages and environment protection. The present protocol was convenient and applicable to a variety of aromatic hydrocarbons and could be amenable to high throughput synthesis of combinatorial libraries for potential drug development, which needs to be studied as part of future investigations.

Conflicts of Interest

The authors declare no conflicts of interest.

Cite this paper

Elmorsy, S. , Shaaban, S. , Eldesoky, F. and Kandeel, E. (2015) Zinc Chloride Catalyzed Regioselective Nitration of Aromatic Hydrocarbons Using Tetrachlorosilane-Sodium Nitrate Homogeneous System. International Journal of Organic Chemistry, 5, 49-56. doi: 10.4236/ijoc.2015.52006.

References

[1] Kilpatrick, B., Heller, M. and Arns, S. (2013) Chemoselective Nitration of Aromatic Sulfonamides with Tert-Butyl Nitrite. Chemical Communications (Cambridge), 49, 514-516.
http://dx.doi.org/10.1039/C2CC37481A
[2] Hajipour, A.R. and Ruohob, A.E. (2005) Nitric Acid in the Presence of P2O5 Supported on Silica Gel—A Useful Reagent for Nitration of Aromatic Compounds under Solvent-Free Conditions. Tetrahedron Letters, 46, 8307-8310.
http://dx.doi.org/10.1016/j.tetlet.2005.09.178
[3] Antes, J., Boskovic, D., Krause, H., Loebbecke, S., Lutz, N., Tuercke, T. and Schweikert, W. (2003) Analysis and Improvement of Strong Exothermic Nitrations in Microreactors. Chemical Engineering Research and Design, 81, 760- 765.
http://dx.doi.org/10.1205/026387603322302931
[4] Yan, G. and Yang, M. (2013) Recent Advances in the Synthesis of Aromatic Nitro Compounds. Organic Biomolecular Chemistry, 11, 2554-2566.
http://dx.doi.org/10.1039/c3ob27354g
[5] Ono, N. (2001) The Nitro Group in Organic Synthesis. Wiley, Hoboken.
http://dx.doi.org/10.1002/0471224480
[6] Olah, A.G., Malhotra, R. and Narang, C.S. (1989) Nitration. Methods and Mechanisms. VCH, New York, Weinheim.
[7] Hoggett, J.G, Moodie, R.B., Penton, J.R. and Schofield, K. (1971) Nitration and Aromatic Reactivity. Cambridge University Press, Cambridge.
[8] Esakkidurai, T. and Pitchumani, K. (2002) Zeolite-Mediated Regioselective Nitration of Phenol in Solid State. Journal of Molecular Catalysis A: Chemical, 185, 305-309.
http://dx.doi.org/10.1016/S1381-1169(02)00135-8
[9] Iranpoora, N., Firouzabadia, Habib., Nowrouzia, N. and Firouzabadib, D. (2006) Highly Chemoselective Nitration of Aromatic Amines Using the Ph3P/Br2/AgNO3 System. Tetrahedron Letters, 47, 6879-6881.
http://dx.doi.org/10.1016/j.tetlet.2006.07.054
[10] Shokrolahi, A., Zali, A. and Keshavarz, M.H. (2007) Wet Carbon-Based Solid Acid/NaNO3 as a Mild and Efficient Reagent for Nitration of Aromatic Compound under Solvent Free Conditions. Chinese Chemical Letters, 18, 1064-1066.
http://dx.doi.org/10.1016/j.cclet.2007.06.031
[11] Peng, X.H., Suzuki, H. and Lu, C.X. (2001) Zeolite-Assisted Nitration of Neat Toluene and Chlorobenzene with a Nitrogen Dioxide/Molecular Oxygen System. Remarkable Enhancement of Para-Selectivity. Tetrahedron Letters, 42, 4357-4359.
http://dx.doi.org/10.1016/S0040-4039(01)00750-X
[12] Bak, R.R. and Smallridge, J.A. (2001) A Fast and Mild Method for the Nitration of Aromatic Rings. Tetrahedron Letters, 42, 6767-6769.
http://dx.doi.org/10.1016/S0040-4039(01)01378-8
[13] Iranpoor, N., Firouzabadi, H. and Heydari, R. (1999) Ionic Complex of N2O4 with 18-Crown-6: A Highly Efficient and Selective Reagent for Nitration of Phenols. Synthetic Communications, 29, 3295-3302.
http://dx.doi.org/10.1080/00397919908085957
[14] Olah, A.G. and Kuhn, S.J. (1962) Aromatic Substitution XII. Steric Effects in Nitronium Salt Nitrations of Alkylbenzenes and Halobenzenes. Journal of the American Chemical Society, 84, 3684-3687.
[15] Nowrouzi, N. and Jonaghani, M.Z. (2011) Nitration of Aromatic Compounds under Neutral Conditions Using the Ph2PCl/I2/AgNO3 Reagent System. Tetrahedron Letters, 52, 5081-5082.
http://dx.doi.org/10.1016/j.tetlet.2011.07.097
[16] Ramana, M.M.V., Malik, S.S. and Parihar, J.A. (2004) Guanidinium Nitrate: A Novel Reagent for Aryl Nitrations. Tetrahedron Letters, 45, 8681-8683.
http://dx.doi.org/10.1016/j.tetlet.2004.09.140
[17] Strazzolini, P., Giumanini, A.G. and Runcio, A. (2001) Nitric Acid in Dichloromethane Solution. Facile Preparation From Potassium Nitrate and Sulfuric Acid. Tetrahedron Letters, 42, 1387-1389.
http://dx.doi.org/10.1016/S0040-4039(00)02253-X
[18] Bozell, J.J. and Hoberg, J.O. (1988) Catalytic Ox-idation of Para-Substituted Phenols with Nitrogen Dioxide And Oxygen. Tetrahedron Letters, 39, 2261-2264.
http://dx.doi.org/10.1016/S0040-4039(98)00242-1
[19] Iranpoor, N., Firouzabadia, H. and AliZolfigol, M. (1998) Efficient and Selective Mono and Dinitration of Phenols with Cr(NO3)3.2N2O4 as a New Nitrating Agent. Synthetic Communications, 28, 2773-2781.
http://dx.doi.org/10.1080/00397919808004851
[20] Bahulayan, D., Narayan, G., Sreekumar, V. and Lalithambika, M. (2002) Natural Bentonite Clay/Dilute HNO3 (40%)—A Mild, Efficient, and Reusable Ctatlyst/Reagent System for Selective Mono Nitration and Benzylic Oxidations. Synthetic Communications, 32, 3565-3574.
http://dx.doi.org/10.1081/SCC-120014967
[21] Mellor, J.M., Mittoo, R.S. and Millar, R.W. (2000) Improved Nitrations Using Metal Nitrate-Sulfuric Acid Systems. Tetrahedron, 56, 8019-8024.
http://dx.doi.org/10.1016/S0040-4020(00)00720-1
[22] Cornelis, A. and Laszlo, P. (1985) Clay-Supported Copper(II) and Iron(III) Nitrates: Novel Multi-Purpose Reagents for Organic Synthesis. Synthesis, 1985, 909-918.
http://dx.doi.org/10.1055/s-1985-31382
[23] Olah, G.A., Krishnamurthy, V.V. and Narang, S.C. (1982) Aromatic Substitution. 50. Mercury(II)-Promoted Azeotropic nitration of Aromatics over Nafion-H Solid Superacidic Catalyst. Journal of Organic Chemistry, 47, 596-598.
http://dx.doi.org/10.1021/jo00342a052
[24] Iranpoor, N., Firouzabadia, H., Heydaria, R. and Shiria, M. (2005) Nitration of Aromatic Compounds by Zn(NO3)2.2N2O4 and Its Charcoal-Supported System. Synthetic Communications, 35, 263-270.
http://dx.doi.org/10.1081/SCC-200048450
[25] Samajdar, S., Becker, F.F. and Banik, K.B. (2000) Surface-Mediated Highly Efficient Regioselective Nitration of Aromatic Compounds by Bismuth Nitrate. Tetrahedron Letters, 41, 8017-8020.
http://dx.doi.org/10.1016/S0040-4039(00)01397-6
[26] Parac-Vogt, T.N. and Binnemans, K. (2004) Lanthanide(III) Nosylates as New Nitration Catalysts. Tetrahedron Letters, 45, 3137-3139.
http://dx.doi.org/10.1016/j.tetlet.2004.02.084
[27] Zolfigol, A.M., Ghasemi, E. and Madrakian, E. (2003) Trichloroi-socyanuric Acid/NaNO2 as a Novel Heterogeneous System for the Selective Mononitration of Phenols under Mild Conditions. Synlett, 2, 191-194.
http://dx.doi.org/10.1055/s-2003-36791
[28] Frost, C.G., Hartley, J.P. and Grifin, D. (2002) Counterion Effects in Indium-Catalysed Aromatic Electrophilic Substitution Reactions. Tetrahedron Letters, 43, 4789-4791.
http://dx.doi.org/10.1016/S0040-4039(02)00931-0
[29] Jacoway, J., Narayana Kumar, G.G.K.S. and Laali, K.K. (2012) Aromatic Nitration with Bismuth Nitrate in Ionic Liquids and in Molecular Solvents: A Comparative Study of Bi(NO3)3.5H2O/[bmim] [PF6] and Bi(NO3)3.5H2O/1,2-DCE Systems. Tetrahedron Letters, 53, 6782-6785.
http://dx.doi.org/10.1016/j.tetlet.2012.09.137
[30] Rajagopal, R. and Srinivasan, K.V. (2003) Ultrasound Promoted Para-Selective Nitration of Phenols in Ionic Liquid. Ultrasonics Sonochemistry, 10, 41-43.
http://dx.doi.org/10.1016/S1350-4177(02)00099-8
[31] Loebbecke, S., Boskovic, D., Antes, J., Tuercke, T., Schweikert, W., Marioth, E., Schnuerer, F. and Krause, H. (2002) Application of Microreactors for the Synthesis of Energetic Materials. Process Improvements and Diagnostics. Proceedings of 33rd International Annual Conference ICT: Energetic Materials Synthesis, Production and Application, Karlsruhe, 25-28 June 2002, 42.
[32] Zolfigol, M.A., Madrakian, E. and Ghasemi, E. (2002) Silica Sulfuric Acid/NaNO2 as a Novel Heterogeneous System for the Nitration of Phenols under Mild Conditions. Molecules, 7, 734-742.
http://dx.doi.org/10.3390/71000734
[33] Dummann, G., Quittmann, U., Groeschel, L., Agar, D.W., Woerz, O. and Morgenschweis, K. (2002) Nitration of Single Ring Aromatics in a Capillary-Microreactor. Proceedings of 1st International Congress on the Process Industries, AchemAmerica, Mexico City.
[34] Olah, A.G., Reddy, V. and Prakash, S. (1992) Aromatic Nitration with Nitric Acid/Trifluoromethanesulfonic Anhydride. Synthesis, 11, 1087-1089.
http://dx.doi.org/10.1055/s-1992-26310
[35] Laali, K.K. and Gettwert, V.J. (2001) Electrophilic Nitration of Aromatics in Ionic Liquid Solvents. Journal of Organic Chemistry, 66, 35-40.
http://dx.doi.org/10.1021/jo000523p
[36] Nowrouzi, N., Mehranpour, A.M., Bashiri, E. and Shayan Z. (2012) Aromatic Nitration under Neutral Conditions Using N-Bromosuccinimide/Silver(I) Nitrate. Tetrahedron Letters, 53, 4841-4842.
http://dx.doi.org/10.1016/j.tetlet.2012.06.126
[37] Chuchev, K., Tadjer, A., Nikolova, N. and Nenov, V. (2005) Relationship between Molecular Characteristics and Biodegradation Rate of Benzene Derivates. Oxidation Communications, 28, 837-846.
[38] Datta, J. (1952) Reactions with Dry Alkaline Earth Hydroxides. 2. Reduction of Alpha Nitro Naphthalene and Dinitronaphthalene. Journal of the Indian Chemical Society, 29, 394-396.
[39] Taha, N., Sasson, Y. and Chidambaram, M. (2008) Phase Transfer Methodology for the Synthesis of Substituted Stilbenes under Knoevenagel Condensation Condition. Applied Catalysis A: General, 350, 217-224.
http://dx.doi.org/10.1016/j.apcata.2008.08.011
[40] Shi, M. and Cui, S.C. (2003) Electrophilic Aromatic Ni-tration Using a Mixed Catalyst of Lithium, Molybdenum, Ytterbium on Silica Gel. Advanced Synthesis & Catalysis, 345, 1197-1202.
http://dx.doi.org/10.1002/adsc.200303111
[41] Preiss, A. (2005) Analysis of Highly Polar Compounds in Groundwater Samples from Ammunition Waste Sites. Part I—Characterization of the Pollutant Spectrum. Magnetic Resonance in Chemistry, 43, 736-746.
http://dx.doi.org/10.1002/mrc.1609
[42] Zou, J.W., Jiang, Y.J., Guo, M., Hu, G.X., Zhang, B., Liu, H.C. and Yu, Q.S. (2005) Ab Initio Study of the Complexes of Halogen-Containing Molecules RX (X=Cl, Br, and I) and NH3: Towards Understanding the Nature of Halogen Bonding and the Electron-Accepting Propensities of Covalently Bonded Halogen Atoms. Chemistry—A European Journal, 11, 740-751.
http://dx.doi.org/10.1002/chem.200400504
[43] Dhami, K.S. and Stothers, J.B. (1965) 13C N.M.R. Studies Part III. Carbon-13 N.M.R. Spectra of Substituted Acetophenones. Indian Journal of Chemistry, 43, 479-497.
[44] Bakke, J.M. and Ranes, E. (1997) Nitration of Pyridine by Dinitrogen Pentoxide, a Study of the Reaction Mechanism. Journal of the Chemical Society, Perkin Transactions, 2, 1919-1923.
http://dx.doi.org/10.1039/a703079g
[45] Salama, A.T. and Elmorsy, S.S. (2011) Silicon Mediated Synthesis and Selected Transformations of β-Chloroketones. Chinese Chemical Letters, 22, 1171-1174.
http://dx.doi.org/10.1016/j.cclet.2011.05.007
[46] Salama, A.T., Elmorsy, S.S., Khalil, M.A. and Ismail A.M. (2007) A SiCl4-ZnCl2 Induced General, Mild and Efficient One-Pot, Three-Component Synthesis of β-Amido Ketone Libraries. Tetrahedron Letters, 48, 6199-6203.
http://dx.doi.org/10.1016/j.tetlet.2007.06.128
[47] Salama, A.T., Ismail, A.M., Khalil, M.A. and Elmorsy, S.S. (2012) Silicon-Assisted O-Heterocyclic Synthesis: Mild and Efficient One-Pot Syntheses of (E)-3-Benzylideneflavanones, Coumarin-3-Carbonitriles/Carboxamides, and Benzannulated Spiropyran Derivatives. Archive for Organic Chemistry, 2012, 242-253.
http://dx.doi.org/10.3998/ark.5550190.0013.921

  
comments powered by Disqus

Copyright © 2019 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.