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Green Synthesis and Characterization of 3-Carboxycoumarin and Ethylcoumarin-3-carboxylate via Knoevenagel Condensation
Corresponding Author(s) : Amir Azam Khan
Asian Journal of Chemistry,
Vol. 29 No. 2 (2017): Vol 29 Issue 2
Abstract
Environmentally benign, simple, efficient and clean syntheses of 3-carboxycoumarins and ethyl coumarin-3-carboxylate have been synthesized via Knoevenagel condensation using green catalysts such as aqueous extract of Acacia concinna pods and amino acids. These syntheses were carried out in solvents as well as solvent-less media. The yields obtained (between 86 % to 96 %) for the reactions were equal or better than those previously reported. The products were isolated, purified and characterized through melting points, TLC, IR, GC Mass and 1H NMR spectroscopy. The characterized molecules showed structural and compositional conformity with the predicted reactions. The green route used for these reactions has shown to be efficient in reducing the time of reaction and in avoiding the toxic nature of the catalysts employed in classical reaction.
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- K. Budde, F. Quella, A. Mathes, W. Melchior, H. Müller, O. Nuyken and S. Spiegel, Angew. Makromol. Chem., 194, 103 (1992).
- G. Jones, Org. React., 15, 204 (1967).
- B. Alm, Psychopharmacology, 50, 301 (1976).
- E.C. Gaudino, S. Tagliapietra, K. Martina, G. Palmisano and G. Cravotto, RSC Adv., 6, 46394 (2016).
- K. Sakthivel, W. Notz, T. Bui and C.F. Barbas, J. Am. Chem. Soc., 123, 5260 (2001).
- A.J. Cobb, D.M. Shaw, D.A. Longbottom, J.B. Gold and S.V. Ley, Org. Biomol. Chem., 3, 84 (2005).
- N.V. Shitole, K.F. Shelke, S.S. Sonar, S.A. Sadaphal, B.B. Shingate and M.S. Shingare, ChemInform, 41, i (2010).
- S.S. Shafqat, M.A. Khan, A. Zulkharnain, S. Hamdan, H. Rigit, A. Ragai and A.A. Khan, Asian J. Chem., 26, 8463 (2014).
- A.M. Zafar, M.N. Khan, M. Azad, M.A. Munawar and M.A. Khan, Asian J. Chem., 25, 3244 (2013).
- F. Ijaz, M.N. Khan, S. Naureen, M.A. Khan, M.A. Munawar and A.M.R. Bernardino, Asian J. Chem., 24, 5114 (2012).
- F. Chaudhry, N. Asif, S.S. Shafqat, A.A. Khan, M.A. Munawar and M.A. Khan, Synth. Commun., 46, 701 (2016).
- H.V. Chavan and B.P. Bandgar, ACS Sustain. Chem.& Eng., 1, 929 (2013).
- K. Mote, S. Pore, G. Rashinkar, S. Kambale, A. Kumbhar and R. Salunkhe, Arch. Appl. Sci. Res., 2, 74 (2010).
- R. Menegatti, in eds.: M. Kidwai and N.K. Mishra, Green Chemistry-Aspects for the Knoevenagel Reaction, Chap. 2, InTech (2012).
- A. Thakur, R. Singla and V. Jaitak, Eur. J. Med. Chem., 101, 476 (2015).
- K.V. Sairam, B.M. Gurupadayya, R.S. Chandan, D.K. Nagesha and B. Vishwanathan, Curr. Drug Deliv., 13, 186 (2015).
- A. Behrami, K. Vaso and I. Krasniqi, J. Int. Environ. Appl. Sci., 10, 247 (2010).
- S.U. Rehman, Z.H. Chohan, F. Gulnaz and C.T. Supuran, J. Enzyme Inhib. Med. Chem., 20, 333 (2005).
- G. Cravotto, G.M. Nano, G. Palmisano and S. Tagliapietra, Tetrahedron Asym., 12, 707 (2001).
- G. Melagraki, A. Afantitis, O. Igglessi-Markopoulou, A. Detsi, M. Koufaki, C. Kontogiorgis and D.J. Hadjipavlou-Litina, Eur. J. Med. Chem., 44, 3020 (2009).
- J. Nawrot-Modranka, E. Nawrot and J. Graczyk, Eur. J. Med. Chem., 41, 1301 (2006).
- K.N. Venugopala, V. Rashmi and B. Odhav, BioMed. Res. Int., Article ID 963248 (2013).
- D. Yu, M. Suzuki, L. Xie, S.L. Morris-Natschke and K.H. Lee, Med. Res. Rev., 23, 322 (2003).
- L.G. de Souza, M.N. Rennó and J.D. Figueroa-Villar, Chem. Biol. Interact., 254, 11 (2016).
- P. Anand, B. Singh and N. Singh, Bioorg. Med. Chem., 20, 1175 (2012).
- C. Sproll, W. Ruge, C. Andlauer, R. Godelmann and D.W. Lachenmeier, Food Chem., 109, 462 (2008).
- N.K. Mal, M. Fujiwara, Y. Tanaka, T. Taguchi and M. Matsukata, Chem. Mater., 15, 3385 (2003).
- A. González-González, D.M. Aparicio-Solano, H. Aguilar-Mariscal, A. Gómez-Rivera, L.F. Roa, C. Alvarado-Sánchez, C.E. Lobato-García and N. Romero-Ceronio, Am. J. Org. Chem., 6, 17 (2016).
- R.H. Vekariya and H.D. Patel, Synth. Commun., 44, 2756 (2014).
- G. Brahmachari, ACS Sustain. Chem. Eng., 3, 2350 (2015).
- L.L. Woods and J. Sapp, J. Org. Chem., 30, 312 (1965).
References
K. Budde, F. Quella, A. Mathes, W. Melchior, H. Müller, O. Nuyken and S. Spiegel, Angew. Makromol. Chem., 194, 103 (1992).
G. Jones, Org. React., 15, 204 (1967).
B. Alm, Psychopharmacology, 50, 301 (1976).
E.C. Gaudino, S. Tagliapietra, K. Martina, G. Palmisano and G. Cravotto, RSC Adv., 6, 46394 (2016).
K. Sakthivel, W. Notz, T. Bui and C.F. Barbas, J. Am. Chem. Soc., 123, 5260 (2001).
A.J. Cobb, D.M. Shaw, D.A. Longbottom, J.B. Gold and S.V. Ley, Org. Biomol. Chem., 3, 84 (2005).
N.V. Shitole, K.F. Shelke, S.S. Sonar, S.A. Sadaphal, B.B. Shingate and M.S. Shingare, ChemInform, 41, i (2010).
S.S. Shafqat, M.A. Khan, A. Zulkharnain, S. Hamdan, H. Rigit, A. Ragai and A.A. Khan, Asian J. Chem., 26, 8463 (2014).
A.M. Zafar, M.N. Khan, M. Azad, M.A. Munawar and M.A. Khan, Asian J. Chem., 25, 3244 (2013).
F. Ijaz, M.N. Khan, S. Naureen, M.A. Khan, M.A. Munawar and A.M.R. Bernardino, Asian J. Chem., 24, 5114 (2012).
F. Chaudhry, N. Asif, S.S. Shafqat, A.A. Khan, M.A. Munawar and M.A. Khan, Synth. Commun., 46, 701 (2016).
H.V. Chavan and B.P. Bandgar, ACS Sustain. Chem.& Eng., 1, 929 (2013).
K. Mote, S. Pore, G. Rashinkar, S. Kambale, A. Kumbhar and R. Salunkhe, Arch. Appl. Sci. Res., 2, 74 (2010).
R. Menegatti, in eds.: M. Kidwai and N.K. Mishra, Green Chemistry-Aspects for the Knoevenagel Reaction, Chap. 2, InTech (2012).
A. Thakur, R. Singla and V. Jaitak, Eur. J. Med. Chem., 101, 476 (2015).
K.V. Sairam, B.M. Gurupadayya, R.S. Chandan, D.K. Nagesha and B. Vishwanathan, Curr. Drug Deliv., 13, 186 (2015).
A. Behrami, K. Vaso and I. Krasniqi, J. Int. Environ. Appl. Sci., 10, 247 (2010).
S.U. Rehman, Z.H. Chohan, F. Gulnaz and C.T. Supuran, J. Enzyme Inhib. Med. Chem., 20, 333 (2005).
G. Cravotto, G.M. Nano, G. Palmisano and S. Tagliapietra, Tetrahedron Asym., 12, 707 (2001).
G. Melagraki, A. Afantitis, O. Igglessi-Markopoulou, A. Detsi, M. Koufaki, C. Kontogiorgis and D.J. Hadjipavlou-Litina, Eur. J. Med. Chem., 44, 3020 (2009).
J. Nawrot-Modranka, E. Nawrot and J. Graczyk, Eur. J. Med. Chem., 41, 1301 (2006).
K.N. Venugopala, V. Rashmi and B. Odhav, BioMed. Res. Int., Article ID 963248 (2013).
D. Yu, M. Suzuki, L. Xie, S.L. Morris-Natschke and K.H. Lee, Med. Res. Rev., 23, 322 (2003).
L.G. de Souza, M.N. Rennó and J.D. Figueroa-Villar, Chem. Biol. Interact., 254, 11 (2016).
P. Anand, B. Singh and N. Singh, Bioorg. Med. Chem., 20, 1175 (2012).
C. Sproll, W. Ruge, C. Andlauer, R. Godelmann and D.W. Lachenmeier, Food Chem., 109, 462 (2008).
N.K. Mal, M. Fujiwara, Y. Tanaka, T. Taguchi and M. Matsukata, Chem. Mater., 15, 3385 (2003).
A. González-González, D.M. Aparicio-Solano, H. Aguilar-Mariscal, A. Gómez-Rivera, L.F. Roa, C. Alvarado-Sánchez, C.E. Lobato-García and N. Romero-Ceronio, Am. J. Org. Chem., 6, 17 (2016).
R.H. Vekariya and H.D. Patel, Synth. Commun., 44, 2756 (2014).
G. Brahmachari, ACS Sustain. Chem. Eng., 3, 2350 (2015).
L.L. Woods and J. Sapp, J. Org. Chem., 30, 312 (1965).