Vilsmeier Haack Adducts as Effective Reagents for Regioselective Nitration of Aromatic Compounds under Conventional and Non-Conventional Conditions — Oak Academic Publishing
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Vilsmeier Haack Adducts as Effective Reagents for Regioselective Nitration of Aromatic Compounds under Conventional and Non-Conventional Conditions
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.
KeywordsNitrationKNO3 or NaNO2Vilsmeier-Haack ReagentMicrowave Irradiation (MWI)GrindingSonication
G. A. Olah, R. Malhotra and S. C. Narang, “Nitration Methods and Mechanisms,” VCH, New York, 1989.
J. G. Hoggett, R. B. Monodie, J. R. Penton and K. Scho- field, “Nitration and Aromatic Reactivity,” Cambridge University Press, London, 1971.
N. Ono, “The Nitro Group in Organic Synthesis,” Wiley- VCH, New York, 2001.
G. K. Surya Prakash and T. Mathew, “Ipso-Nitration of Arenes,” Angewandte Chemie International Edition, Vol. 49, No. 10, 2010, pp. 1726-1728.
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.
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
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
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.
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
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
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
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
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
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
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
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
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.
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.
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.
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
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
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.
F. Toda, “Solid State Organic Reactions,” Synlett, No.5, 1993, pp. 303-312. doi:10.1021/ar00060a003
K. Tanaka and F. Toda, “Solvent-Free Organic Synthe- sis,” Chemical Reviews, Vol. 100, No. 3, 2000, pp. 1025- 1074.
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
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.
J. Hamelin, J. P. Bazureau, F. Texier-Boullet, A. Louby, “Microwave in Organic Synthesis,” Wiley-VCH, Wein- heim, 2002, p. 253.
A. Vilsmeier and A. Haack, Ber. 60, 1927, p. 119.
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
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
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
T. J. Mason and J. P. Lorimer, “Sono Chemistry Theory, Applications and Uses of Ultrasound in Chemistry,” Ellis Horwood, New York, 1989.
T. J. Mason, “Chemistry with Ultrasound,” Critical Reports in Applied Chemistry, No. 28, 1990.
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