IJOC  Vol.1 No.4 , December 2011
Vilsmeier Haack Adducts as Effective Reagents for Regioselective Nitration of Aromatic Compounds under Conventional and Non-Conventional Conditions
Abstract: Nitration of aromatic Compounds is triggered by Vilsmeier-Haack reagent (DMF/POCl3) or (DMF/SOCl2) in the presence of KNO3 or NaNO2 under conventional and non-conventional conditions. The reactions af- forded corresponding Nitro derivatives in very good yield with high regioselectivity. The results obtained in non-conventional methods (Micro wave irradiation, Grinding, Sonication) are comparable with those ob- tained under conventional conditions, but the reaction times of former conditions are substantially shorter than that of the latter.
Cite this paper: nullK. Rajanna, M. Kumar, P. Venkanna, S. Ramgopal and M. Venkateswarlu, "Vilsmeier Haack Adducts as Effective Reagents for Regioselective Nitration of Aromatic Compounds under Conventional and Non-Conventional Conditions," International Journal of Organic Chemistry, Vol. 1 No. 4, 2011, pp. 250-256. doi: 10.4236/ijoc.2011.14036.

[1]   G. A. Olah, R. Malhotra and S. C. Narang, “Nitration Methods and Mechanisms,” VCH, New York, 1989.

[2]   J. G. Hoggett, R. B. Monodie, J. R. Penton and K. Scho- field, “Nitration and Aromatic Reactivity,” Cambridge University Press, London, 1971.

[3]   N. Ono, “The Nitro Group in Organic Synthesis,” Wiley- VCH, New York, 2001.

[4]   G. K. Surya Prakash and T. Mathew, “Ipso-Nitration of Arenes,” Angewandte Chemie International Edition, Vol. 49, No. 10, 2010, pp. 1726-1728.

[5]   A. Kogelbauer, D. Vassena, R. Prins and J. N Armor, “So- lid Acids as Substitutes for Sulfuric Acid in the Liquid Phase Nitration of Toluene to Nitrotoluene and Dini Tro- toluene,” Catalysis Today, Vol. 55, No. 1-2, 2000, pp. 151-160.

[6]   J. M. Riego, Z. Sedin, J. M. Zaldivar, N. C. Marziano and C. Tortato, “Sulfuric Acid on Silica-Gel: An Inexpensive Catalyst for Aromatic Nitration,” Tetrahedron Letters, Vol. 37, 1996, pp. 513-516. doi:10.1016/0040-4039(95)02174-4

[7]   X. Peng, H. Suzuki and C. Lu, Zeolite-Assisted Nitration of Neat Toluene and Chlorobenzene with a Nitrogen Dioxide/Molecular Oxygen System. Remarkable Enhancement of Para-Selectivity,” Tetrahedron Letters, Vol. 42, 2001, pp. 4357-4359. doi:10.1016/S0040-4039(01)00750-X

[8]   S. P. Dagade, S. B. Waghmode, V. S. Kadam and M. K. Dongare, “Vapor Phase Nitration of Toluene Using Dilute Nitric Acid and Molecular Modeling Studies over Beta Zeolite,” Applied Catalysis A, Vol. 226, No. 1-2, 2002, pp. 49-61.

[9]   R. B. Radoslaw and J. S. Andrew, “A Fast and Mild Method for the Nitration of Aromatic Rings,” Tetrahe- dron Letters, Vol. 42, No. 38, 2001, pp. 6767-6769. doi:10.1016/S0040-4039(01)01378-8

[10]   N. Iranpoor, H. Firouzabadi, R. Heydari, “Silica-Polyethy- leneglycols/N2O4 Complexes as Heterogeneous Nitrating and Nitrosating Agents,” Phosphorus, Sulfur and Silicon, Vol. 178, No. 5, 2003, pp. 1027-1035. doi:10.1080/10426500307863

[11]   J. A. R. Rodrigues, A. P. Oliveira Filho, P. J. S. Moran and R. Custodio, “Regioselectivity of the Nitration of Phenol by Acetyl Nitrate Adsorbed On Silica Gel,” Tet- rahedron, Vol.55, No. 22, 1999, pp. 6733-6738. doi:10.1016/S0040-4020(99)00320-8

[12]   J. A. R. Rodrigues, A. P. Oliveira Filho, P. J. S. Moran and R. Custodio, “Regioselectivity of the Mononitration of Alkylbenzenes by Immobilized Acyl Nitrates,” Syn- thetic Communications, Vol. 29, No. 12, 1999, pp. 2169- 2174. doi:10.1080/00397919908086213

[13]   L. Delaude, P. Laszlo, K. Smith, “Heightened Selectivity in Aromatic Nitrations and Chlorinations by the Use of Solid Supports and Catalysts,” Accounts of Chemical Re- search, Vol. 26, No. 12, 1993, pp. 607-613. doi:10.1021/ar00036a001

[14]   P. Laszlo, “Catalysis of Organic Reactions by Inorganic Solids,” Accounts of Chemical Research, Vol. 19, No. 4, 1986, pp. 121-127. doi:10.1021/ar00124a004

[15]   A. R. Hajipour and A. E. Ruoho, “A Fast and Mild Me- thod for Nitration of Aromatic Rings,” Phosphorus, Sul- fur, and Silicon and the Related Elements, Vol. 179, No. 2, 2004, pp. 221-226. doi:10.1080/10426500490274655

[16]   J. J. Paul Selvam, V. Suresh, K. Rajesh, S. Ravinder Red- dy and Y. Venkateswarlu, “Highly Efficient Nitration of Phenolic Compounds by Zirconyl Nitrate,” Tetrahedron Letters, Vol. 47, No. 15, 2006, pp. 2507-2509. doi:10.1016/j.tetlet.2006.02.057

[17]   H. Firouzabadi, N. Iranpoor and M. A. Zolfigol, “A Reinvestigation of Nitration of Phenols with Metal Nitrates under Non-Aqueous and Aprotic Conditions,” Iranian Jour- nal of Chemistry and Chemical Engineering, Vol. 16, No. 2, 1997, pp. 48-58.

[18]   M. M. Ali, Tasneem, K. C. Rajanna, P. K Saiprakash, “An Efficient and Facile Synthesis of 2-Chloro-3-formyl- quinolines from Acetanilides in Micellar Media by Vilsmeier-Haack Cyclization,” Synlett, Vol. 32, No. 22,2001, pp. 251-253.

[19]   Tasneem, “Vilsmeier-Haack Reagent” Synlett, Vol. 138- 139, No. 1, 2003, pp. 138-139.

[20]   A. Chakradhar, R. Roopa, K. C. Rajanna and P. K. Saip- rakash, “Vilsmeier-Haack Bromination of Aromatic Com- pounds with KBr and N-Bromosuccinimide Under Sol- vent-Free Conditions,” Synthetic Communications, Vol. 39, No. 10, 2009, pp. 1817-1824.

[21]   S. Ramgopal, K. Ramesh, N. Maasi Reddy, A. Chakrad- har and K. C. Rajanna, “Metal Nitrate Driven nitro Huns- diecker Reaction with α,β-Unsaturated Carboxylic Acids under Solvent-Free Conditions,” Tetrahedron Letters, Vol. 48, No. 23, 2007, pp. 4043-4045. doi:10.1016/j.tetlet.2007.04.026

[22]   K. C. Rajanna, N. Maasi Reddy, M. Rajender Reddy and P. K. Saiprakash, “Micellar Mediated Halodecarboxyla- tion of α,β-Unsaturated Aliphatic and Aromatic Carbox- ylic Acids—A Novel Green Hunsdiecker-Borodin Reac- tion,” Journal of Dispersion Science and Technology, Vol. 28, No. 4, 2007, pp. 613-616. doi:10.1080/01932690701282690

[23]   G. R. Desiraju and B. S. Goud, “Reactivity of Solids. Present, Past, and Future,” V. V. Boldyrev, Ed., Black- well Sciences, London, 1995, p. 223.

[24]   F. Toda, “Solid State Organic Reactions,” Synlett, No.5, 1993, pp. 303-312. doi:10.1021/ar00060a003

[25]   K. Tanaka and F. Toda, “Solvent-Free Organic Synthe- sis,” Chemical Reviews, Vol. 100, No. 3, 2000, pp. 1025- 1074.

[26]   J. D. Lou and Z. N. Xu, “Selective Oxidation of Primary Alcohols with Chromium Trioxide under Solvent Free Conditions,” Tetrahedron Letters, Vol. 43, No. 35, 2002, pp. 6095-6097. doi:10.1016/S0040-4039(02)01333-3

[27]   R. S. Varma, “Microwaves: Theory and Application in Material Processing IV,” D. E. Clark, W. H. Sutton and D. A. Lewis, Eds., American Ceramic Society, Westerville, Ohio, 1997, p. 357.

[28]   J. Hamelin, J. P. Bazureau, F. Texier-Boullet, A. Louby, “Microwave in Organic Synthesis,” Wiley-VCH, Wein- heim, 2002, p. 253.

[29]   A. Vilsmeier and A. Haack, Ber. 60, 1927, p. 119.

[30]   W. Su, Y. Weng, L. Jiang, Y. Yang, L. Zhao, Z. Chen and Z. Li, “Recent Progress in the Use of Vilsmeier-Type Reagents,” Organic Preparations and Procedures Inter- national, Vol. 42, No. 6, 2010, pp. 503-555. doi:10.1080/00304948.2010.513911

[31]   I. M. A. Awad, “Studies on the Vilsmeier-Haack Reaction. Part XIII: Novel Heterocyclo-Substituted 4,4’-Bi-pyrazo- lyl Dithiocarbamate Derivatives,” Chemical Technology and Biotechnology, Vol. 56, No.4, 1992, pp. 339-345. doi:10.1002/jctb.280560403

[32]   I. M. A. Awad, “Studies in the Vilsmeier-Haack Reaction, Part VII: Synthesis and Reaction of 3-Methyl-l-phenyl-4- acetyl Hydrazono 2-Pyrazoline-5-one(-5-thione),” Monat- shefte für Chemie, Vol. 121, No. 12, 1990, pp. 1023-1030

[33]   T. J. Mason and J. P. Lorimer, “Sono Chemistry Theory, Applications and Uses of Ultrasound in Chemistry,” Ellis Horwood, New York, 1989.

[34]   T. J. Mason, “Chemistry with Ultrasound,” Critical Reports in Applied Chemistry, No. 28, 1990.

[35]   M. H. Entezari and A. A. Shameli, “Shameli, Phase-Trans- fer catalysis and Ultrasonic Waves I. Cannizzaro Reac- tion,” Ultrasonics Sonochemistry, Vol. 7, No. 4, 2000, pp. 169-172. doi:10.1016/S1350-4177(00)00037-7