Poly Ethylene Glycols as Efficient Media for the Synthesis of β-Nitro Styrenes from α, β-Unsaturated Carboxylic Acids and Metal Nitrates under Conventional and Non-Conventional Conditions
Author(s)
Kamatala Chinna Rajanna,
Kola Ramesh,
Soma Ramgopal,
Somannagari Shylaja,
Pochampally Giridhar Reddy,
Pondichery Kuppuswamy Saiprakash
ABSTRACT
Poly ethylene glycols (PEG-200, 400, 600, 4000 and 6000) supported reactions were conducted with certain α, β-unsaturated acids in presence of metal nitrates under solvent free (solid state) and mineral acid free conditions. The reactants were ground in a mortar with a pestle for about 30 minutes. The aromatic acids underwent nitro decarboxylation and afforded β-nitro styrene derivatives in very good yield while α, β-unsaturated aliphatic carboxylic acids gave corresponding nitro derivatives. Addition of PEG accelerated rate of the reaction enormously. Reaction times substantially decreased from several hours to few minutes followed by highly significant increase in the product yield. Among the several PEGs PEG-300 has been found to be much more effective than other PEGs.
Poly ethylene glycols (PEG-200, 400, 600, 4000 and 6000) supported reactions were conducted with certain α, β-unsaturated acids in presence of metal nitrates under solvent free (solid state) and mineral acid free conditions. The reactants were ground in a mortar with a pestle for about 30 minutes. The aromatic acids underwent nitro decarboxylation and afforded β-nitro styrene derivatives in very good yield while α, β-unsaturated aliphatic carboxylic acids gave corresponding nitro derivatives. Addition of PEG accelerated rate of the reaction enormously. Reaction times substantially decreased from several hours to few minutes followed by highly significant increase in the product yield. Among the several PEGs PEG-300 has been found to be much more effective than other PEGs.
KEYWORDS
Poly Ethylene Glycols (PEG), Rate Accelerations, α, β-Unsaturated Acids; Metal Nitrates, Solvent Free (Solid State), β-Nitro Styrene Derivatives, α, β-Unsaturated Aliphatic Acids, Nitro Derivatives
Poly Ethylene Glycols (PEG), Rate Accelerations, α, β-Unsaturated Acids; Metal Nitrates, Solvent Free (Solid State), β-Nitro Styrene Derivatives, α, β-Unsaturated Aliphatic Acids, Nitro Derivatives
Cite this paper
nullK. Rajanna, K. Ramesh, S. Ramgopal, S. Shylaja, P. Reddy and P. Saiprakash, "Poly Ethylene Glycols as Efficient Media for the Synthesis of β-Nitro Styrenes from α, β-Unsaturated Carboxylic Acids and Metal Nitrates under Conventional and Non-Conventional Conditions," Green and Sustainable Chemistry, Vol. 1 No. 4, 2011, pp. 132-148. doi: 10.4236/gsc.2011.14022.
nullK. Rajanna, K. Ramesh, S. Ramgopal, S. Shylaja, P. Reddy and P. Saiprakash, "Poly Ethylene Glycols as Efficient Media for the Synthesis of β-Nitro Styrenes from α, β-Unsaturated Carboxylic Acids and Metal Nitrates under Conventional and Non-Conventional Conditions," Green and Sustainable Chemistry, Vol. 1 No. 4, 2011, pp. 132-148. doi: 10.4236/gsc.2011.14022.
References
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[1] P. Anastas and J. Warner, “Green Chemistry: Theory and Practice,” Oxford University Press, New York, 1998. [2] L. El Ka?m, L. Gautier, L. Grimaud, L. M. Harwood and V. Michaut, “The Mannich Reaction of Hydrazones: Im- proved Reactivity under Solvent-Free Conditions,” Green Chemistry, Vol. 5, No. 4, 2003, pp. 477-479. doi:10.1039/b306242b [3] G. R. Desiraju and B. S. Goud, “Reactivity of Solids: Pre- sent, Past and Future,” In: V. V. Boldyrev, Ed., Blackwell Sciences, London, 1995, p. 223. [4] K. Tanaka, “Solvent-Free Organic Synthesis,” Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2003. doi:10.1016/S0040-4039(02)01333-3 [5] 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. [6] C. L.Raston and J. L. Scott,” Solvent-Free Synthesis of 3- Carboxycoumarins,” Green Chemistry, Vol. 49, No. 5, 2000, pp. 245-247. [7] M. M. Ali, Tasneem, K. C. Rajanna and P. K. Saiprakash, “An Efficient and Facile Synthesis of 2-Chloro-3-formyl Quinolines from Acetanilides in Micellar Media by Vils- meier-HaackCyclisation,” Synlett, Vol. 2, 2001, pp. 251- 253. [8] K. C. Rajanna, M. M. Ali, S. Sana, Tasneem andP. K. Saiprakash, “Ultrasonically Accelerated Vilsmeier-Haack Cyclisation and formylation Reactions,” Synthetic Comunications, Vol. 132, No. 9, 2002, pp. 1351-1356. [9] K. C. Rajanna, M. Moazzam Ali, S. Sana, Tasneem and P. K. Saiprakash, “Vilsmeier Haack Acetylation in Micellar Media: An Efficient One Pot Synthesis of 2-Chloro, 3- acetyl Quinolines,” Journal of Dispersion Science and Technology, Vol. 25, No. 1, 2004, pp. 17-21. doi:10.1081/DIS-120027663 [10] K. C. Rajanna, N. Maasi-Reddy, M. Rajender-Reddy and P. K. Saiprakash, “Micellar Mediated Halo decarboxyla- 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 [11] S. Sana, Tasneem, M. Moazzam-Ali, K. C. Rajanna and P. K. Saiprakash, “Efficient and Facile Method for the Nitration of Aromatic Compounds by Nitric Acid in Mi- cellar Media,” Synthetic Comunications, Vol. 39, No. 10, 2009, pp. 2949-2953. doi:10.1080/00397910802711318 [12] K. C. Rajanna, M. M. Ali, S. Sana, P. K. Saiprakash, “Mild, Efficient and Selective Nitration of Anilides, Non- Activated and Moderately Activated Aromatic Com- pounds with Ammonium Molybdate and Nitric Acid as a New Nitrating Agent,” Chemical Letters, Vol. 1, 2000, pp. 48-49. [13] K. C. Rajanna, M. Moazzam Ali, S. Sana, Tasneem and P. K. Saiprakash, “Ammonium Nickel Sulphate Mediated Nitration of Aromatic Compounds with Nitric Acid,” Synthetic Comunications, Vol. 31, No. 7, 2001, pp. 1123- 1127. doi:10.1081/SCC-100103545 [14] C. Hunsdiecker and H. Hunsdiecker, “über den Abbau der Salze aliphatischer S?uren durch Brom Ber,” Chemis- che Berichte, Vol. 75 No. 3, 1942, pp. 291-297. [15] A. Borodin, “Ueber Bromvalerians?ure und Brombutter- s?ure”. Justus Liebigs Annalen der Chemie, Vol. 119, No. 1, 1861, pp. 121-123. [16] R. G. Johnson and R. K. Ingham, “The Degradation Of Carboxylic Acid Salts By Means Of Halogen The Huns- diecker Reaction”, Chemical Reviews, Vol. 56, 1956, pp. 219-269. doi:10.1021/cr50008a002 [17] D. Naskar and S. Roy, “Catalytic Hunsdiecker Reaction and One-Pot Catalytic Hunsdiecker–Heck Strategy: Synthesis of α, β-Unsaturated Aromatic Halides, α-(Dihalome- thyl)benzenemethanols, 5-Aryl-2,4-pentadienoic acids, Die- noates and Dienamides,” Tetrahedron, Vol. 56, No. 10, 2000, pp. 1369-1377. doi:10.1016/S0040-4020(99)01035-2 [18] D. Naskar and S. Roy, “Synthesis of α-Bromo-β-lactam via a Novel Catalytic Hunsdiecker Like Protocol,” Jour- nal of the Chemical Society Perkin Transactions, Vol. 1, No. 17, 1999, pp. 2435-2436. doi:10.1039/a904515e [19] D. Naskar, S. Roy, S. Das, K. L. Giribabu and B. G. Maiya, “Novel Catalytic Hunsdiecker?Heck (CHH) Stra- tegy toward All-E Stereocontrolled Ferrocene-Capped Conjugated Push?Pull Polyenes,” Oraganometallics, Vol. 19, No. 8, 2000, pp. 1464-1469. doi:10.1021/om000020+ [20] S. Roy, C. Guin and G. Maiti, “A Mild and Efficient Me- thod for Oxidative Halodecarboxylation of α, β-Unsatu- rated Aromatic Acids Using Lithium Bromide/Chloride and Ceric Ammonium Nitrate,” Tetrahedron Letters, Vol. 42, No. 52, 2001, pp. 9253-9255. doi:10.1016/S0040-4039(01)01936-0 [21] F. Homsi and G. Rousseau, “Chemistry of Hydrazinopeptides: A New Hydroperoxydeamination Process,” Tetrahedron Letters, Vol. 40, No. 8, 1999, pp. 1491-1494. doi:10.1016/S0040-4039(99)00020-9 [22] S. J. Cristol and W. C. Firth, Jr., “A Convenient Synthesis of Alkyl Halides from Carboxylic Acids,” Journal of Organic Chemistry, Vol. 26, No. 1, 1961, pp. 280-280. doi:10.1021/jo01060a628 [23] C. Kuang, H. Senboku and M. Tokuda, “Stereoselective Synthesis of (E)-β-Arylvinyl Halides by Microwave-In- duced Hunsdiecker Reaction,” Synlett, No. 10, 2000, pp. 1439-1442. [24] G. V. Ramanarayanan, V. G. Shukla and K. G. 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Rajanna, “Metal Nitrate Driven Nitro Hunsdiecker 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 [29] T. J. Dickerson, N. N. Reed and K. D. Janda, “Soluble Polymers as Scaffolds for Recoverable Catalysts and Re- agents”, Chemical Reviews, Vol. 102, No. 10, 2002, pp. 3325-3344. doi:10.1021/cr010335e [30] B. Das, V. S. Reddy and M. Krishnaiah,” An Efficient Catalyst-Free Synthesis of Thiiranes from Oxiranes Using Polyethylene Glycol as the Reaction Medium,” Tetra- hedron Letters, Vol. 47, No. 48, 2006, pp. 8471-8473. doi:10.1016/j.tetlet.2006.09.153 [31] S. Chandrasekhar, N. R. Reddy, S. S. Sultana, C. Nar- sihmulu and K. V. Reddy, “l-Proline Catalysed Asym- metric Aldol Reactions in PEG-400 as Recyclable Medium and Transfer Aldol Reactions,” Tetrahedron, Vol. 62, No. 2-3, 2006, 334-338. doi:10.1016/j.tet.2005.09.122 [32] J. -H. Li, X. -C. Hu, Y. Liang and Y. -X. Xie, “PEG-400 Promoted Pd(OAc)2/DABCO-Catalyzed Cross-Coupling Reactions in Aqueous Media,” Tetrahedron, Vol. 62, No. 1, 2006, pp. 31-38. doi:10.1016/j.tet.2005.09.138 [33] S. Chandrasekhar, C. Narsihmulu, B. Saritha and S. S. Sulthana, “Poly(ethyleneglycol) (PEG): A Rapid and Recyclable Reaction Medium for the DABCO-Catalyzed Baylis–Hillman Reaction,” Tetrahedron Letters, Vol. 45, No. 30, 2004, pp. 5865-5867. doi:10.1016/j.tetlet.2004.05.153 [34] B. Das, M. Krishnaiah, P. Thirupathi and K. Laxminarayana, “An Efficient Catalyst-Free Regio- and stereoselective Ring-Opening of Epoxides with Phenoxides Using Polyethylene Glycol as the Reaction Medium,” Tetrahedron Letters, Vol. 48, No. 24, 2007, pp. 4263-4265. doi:10.1016/j.tetlet.2007.04.062 [35] A. I. Vogel, “Text Book of Practical Organic Chemistry,” 4th Edition, Longman, London and New York, 1986. [36] M. J. Thompson and P. Zeegers, “A Theoretical Study on the Two-Phase Nitration of Phenols,” Tetrahedron, Vol. 45, No. 1, 1989, pp. 191-202. doi:10.1016/0040-4020(89)80046-8 [37] D. Gaudea, R. Le Goallera and J. L. Pierrea, “Nitration of Phenols with Nitrates in a Two-Phase System,” Synthetic Comunications, Vol. 16, No. 1, 1986, pp. 63-68. doi:10.1080/00397918608057689 [38] G. Kaupp, “Mechanochemistry: The Varied Applications of Mechanical Bond-Breaking,” CrystEngCommunity, Vol. 11, No. 3, 2009, pp. 388-403. doi:10.1039/b810822f