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An eco-friendly synthesis of 2-pyrazoline derivatives catalysed by \(\hbox {CeCl}_{3} \cdot 7\hbox {H}_{2}\hbox {O}\)

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Abstract

1,3,5-triaryl-2-pyrazoline derivatives were synthesised by a condensation reaction between chalcones and phenyl hydrazine using cerium chloride heptahydrate as a catalyst. All these reactions were carried out in ethyl lactate (70%) as a green solvent. Easy and efficient work up, recyclability of solvent and catalyst are the key merits of this protocol.

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SYNOPSIS A facile protocol for the synthesis of 1,3,5-triaryl-2-pyrazolines is described. The solvent ethyl lactate, obtained from renewable sources, is biodegradable. The catalyst \(\hbox {CeCl}_{3} \cdot 7\hbox {H}_{2}\hbox {O}\) is a water-tolerant Lewis acid with low toxicity. Easy and clean work up, recyclable solvent and catalyst are merits of the protocol. The reaction works well for all systems giving good yields of the desired products.

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References

  1. Marella A, Ali R, Alam T, Saha R, Tanwar O, Akhter M, Shaquiquzzaman M and Mumtaz Alam M 2013 Pyrazolines: A biological review Mini. Rev. Med. Chem. 13 921

    Article  CAS  Google Scholar 

  2. Manna K and Agrawal Y K 2009 Microwave assisted synthesis of new indophenazine 1,3,5-trisubstituted pyrazoline derivatives of benzofuran and their antimicrobial activity Bioorg. Med. Chem. Lett. 19 2688

    Article  CAS  Google Scholar 

  3. Abid M, Bhat A R, Athar F and Azam A 2009 Synthesis spectral studies and antiamoebic activity of new 1-N-substituted thiocarbamoyl-3-phenyl-2-pyrazolines Eur. J. Med. Chem. 44 417

    Article  CAS  Google Scholar 

  4. Kaplancikli Z A, Turan-Zitouni G, Özdemir A, Devrim Can Ö and Chevallet P 2009 Synthesis and antinociceptive activities of some pyrazoline derivatives Eur. J. Med. Chem. 44 2606

    Article  CAS  Google Scholar 

  5. Havrylyuk D, Zimenkovsky B, Vasylenko O, Zaprutko L, Gzella A and Lesyk R 2009 Synthesis of novel Thiazolone-based compounds containing pyrazoline moiety and evaluation of their anticancer activity Eur. J. Med. Chem. 44 1396

    Article  CAS  Google Scholar 

  6. Gökhan-Kelekçi N, Koyunoglu S, Yabanoglu S, Yelekçi K, Özgen Ö, Uçar G, Erol K, Kendi E and Yeşilada A 2009 New pyrazoline bearing \(4\) 3H.-quinazolinone inhibitors of monoamine oxidase: Synthesis biological evaluation and structural determinants of MAO-A and MAO-B selectivity Bioorg. Med. Chem. 17 675

    Article  Google Scholar 

  7. Barsoum F F, Hosni H M and Girgis A S 2006 Novel bis(1-acyl-2-Pyrazolines) of potential anti-Inflammatory and molluscicidal properties Bioorg. Med. Chem. 14 3929

    Article  CAS  Google Scholar 

  8. Salgado V L 1990 Mode of action of insecticidal dihydropyrazoles: Selective block of impulse generation in sensory nerves Pestic. Sci. 28 389

    Article  CAS  Google Scholar 

  9. Franck-Neumann M and Miesch M 1982 Stereospecific cyclopropenic synthesis of cis-Chrysanthemic methyl ester 2 The by-Passing Diazoalkane Way Tetrahedron Lett. 23 409

    Article  Google Scholar 

  10. Ji S J and Shi H B 2006 Synthesis and Fluorescent Property of some novel Benzothiazoyl Pyrazoline derivatives containing aromatic heterocycle Dyes Pigm. 70 246

    Article  CAS  Google Scholar 

  11. Wei X Q, Yang G, Cheng J B, Lu Z Y and Xie M G 2007 Synthesis of novel light emitting Calix [4] arene derivatives and their luminescent properties Mater. Chem. Phys. 102 214

    Article  CAS  Google Scholar 

  12. Fischer E and Knoevenagel O 1887 Ueber Die Verbindungen Des Phenylhydrazins Mit Acroleïn Mesityloxyd Und Allylbromid Justus Liebigs Ann. Chem. 239 194

    Article  Google Scholar 

  13. Li J T, Zhang X H and Lin Z P 2007 An improved synthesis of 1,3,5-triaryl-2-pyrazolines in acetic acid aqueous solution under ultrasound irradiation Beilstein J. Org. Chem. 3 13

    Article  Google Scholar 

  14. Kidwai M, Kukreja S and Thakur R 2006 \(\text{ K }_{2}\text{ CO }_{3}\)-mediated regioselective synthesis of isoxazoles and pyrazolines Lett. Org. Chem. 3 135

    Article  CAS  Google Scholar 

  15. Fazaeli R, Aliyan H, Bordbar M and Mohammadi E 2010 \(\text{ H }_{3}\text{ PW }_{12}\text{ O }_{40}\): Highly efficient catalysts for the synthesis of novel 1,3,5-triaryl-2-pyrazoline derivatives Open Catal. J. 3 79

    Article  CAS  Google Scholar 

  16. Holla B S, Mahalinga M, Poojary B, Ashok M and Akberali P M 2006 Synthesis of pyrazolines promoted by Amberlyst-15 catalyst Indian J. Chem. 45B 568

    CAS  Google Scholar 

  17. Levai A and Jeko J 2009 Simple Efficient Procedure for the Stereoselective Synthesis of trans-2, 3, 3a, 4-Tetrahydro-3-aryl-2-4-carboxyphenyl)[1] benzopyrano [4, 3-c] pyrazoles and their [1] Benzothiopyrano Analogues Acta Chim. Slovenica 56 566

    CAS  Google Scholar 

  18. Mokle S S, Vibhute A Y, Khansole S V, Zangade S B and Vibhute Y B 2010 Synthesis, characterization and antibacterial activity of some new 2-pyrazolines using triethanolamine as reaction solvent Res. J. Pharm. Biol. Chem. Sci. 1 631

    CAS  Google Scholar 

  19. Sridhar S and Rajendraprasad Y 2012 Synthesis and analgesic studies of some new 2-pyrazolines J. Chem. 9 1810

    CAS  Google Scholar 

  20. Shah S N N, Ziauddin H M, Zameer M, Khan T and Baseer M A 2011 A precious addition of some novel pyrazolines to the library of bioactive compounds Int. J. Chem. Res. 2 15

    Google Scholar 

  21. Hareesh M, Mahantia S, Sailu B, Subramanyam D, Sakam S R, Tara B, Balram B, Vasudha B and Ram B 2012 Synthesis and antibacterial evaluation of some novel pyrazoline derivatives Der Pharma Chemica 4 1637

    CAS  Google Scholar 

  22. Diaz-Tielas C, Grana E, Reigosa M J and Sanchez-Moreiras A M 2016 Biological activities and novel applications of chalcones Planta Daninha 34 607

    Article  Google Scholar 

  23. Bandgar B P, Patil S A, Gacche R N, Korbad B L, Hote B S, Kinkar S N and Jalde S S 2010 Synthesis and biological evaluation of nitrogen-containing chalcones as possible anti-inflammatory and antioxidant agents Bioorg. Med. Chem. Lett. 20 730

    Article  CAS  Google Scholar 

  24. Kalirajan R, Sivakumar S U, Jubie S, Gowramma Band Suresh B 2009 Synthesis and biological evaluation of some heterocyclic derivatives of chalcones Int. J. ChemTech. Res. 1 27

    CAS  Google Scholar 

  25. Shahar Yar M, Ahmad Siddiqui A and Ashraf Ali M 2007 Synthesis and antimycobacterial activity of novel heterocycles J. Serbian Chem. Soc. 72 5

    Article  Google Scholar 

  26. Sperry J, and García-Álvarez J 2016 Organic Reactions in Green Solvents Molecules 21 1527

    Article  Google Scholar 

  27. Uzma N, Khaja Mohinuddin Salar B M, Kumar B S, Aziz N, David M A and Reddy V D 2008 Impact of organic solvents and environmental pollutants on the physiological function in petrol filling workers Int. J. Environ. Res. Public Health 5 139

    Article  CAS  Google Scholar 

  28. Gu Y 2012 Multicomponent reactions in unconventional solvents: State of the art Green Chem. 14 2091

    Article  CAS  Google Scholar 

  29. Paul S, Pradhan K and Das A R 2016 Ethyl Lactate As a Green Solvent: A Promising Bio-Compatible Media for Organic Synthesis Curr. Green Chem. 3 111

    Article  CAS  Google Scholar 

  30. Bartoli G, Marcantoni E, Marcolini M and Sambri L 2010 Applications of \(\text{ CeCl }_{3}\) as an environmental friendly promoter in organic chemistry Chem. Rev. 110 6104

    Article  CAS  Google Scholar 

  31. Tao X, Li W, Li X, Xie X and Zhang Z 2012 Diastereo-and enantioselective asymmetric hydrogenation of \(\alpha \)-amido-\(\beta \)-keto phosphonates via dynamic kinetic resolution Org. Lett. 15 72

    Article  Google Scholar 

  32. Bartoli G, Marcantoni E and Sambri L 2003 The \(\text{ CeCl }_{3 }\cdot \text{ n }\text{ H }_{2}\text{ O }/\text{ NaI }\) System in organic synthesis: An efficient water tolerant Lewis acid promoter Synlett 1 2101

    Article  Google Scholar 

  33. Ravishankar L, Patwe S A, Gosarani N and Roy A 2010 A Cerium (III)-catalyzed synthesis of Schiff bases: A green approach Synth. Commun. 40 3177

    Article  CAS  Google Scholar 

  34. Lokhande R, Sonawane J, Roy A and Ravishankar L 2011 Solvent-free reductive amination of aromatic aldehydes catalyzed by \(\text{ CeCl }_{3}\cdot 7\text{ H }_{2}\text{ O }\) Green Chem. Lett. Rev. 4 69

    Article  CAS  Google Scholar 

  35. Vaidya S P, Shridhar G, Ladage S and Ravishankar L 2016 A facile synthesis of isoxazole derivatives catalysed by cerium chloride heptahydrate in ethyl lactate as a solvent: A green methodology Curr. Green Chem. 3 160

    Article  CAS  Google Scholar 

  36. Kumar J A, Shridhar G, Ladage S and Ravishankar L 2016 Synthesis of 1,4-dihydropyridine esters using low melting sugar mixtures as green solvents Synth. Commun. 46 1989

    Article  CAS  Google Scholar 

  37. Syam S, Abdelwahab S I, Al-Mamary M A and Mohan S 2012 Synthesis of chalcones with anticancer activities Molecules 17 6179

    Article  CAS  Google Scholar 

  38. Palleros D R 2004 Solvent-free synthesis of chalconesJ. Chem. Educ. 81 1345

    Article  CAS  Google Scholar 

  39. Alarcón E, Romero N, Aguilar H, Terán J L, Gómez A, Roa L F, Lobato C E and Escobar A 2013 Green Synthesis of Chalcone Derivates of Acetophenone Proceedings of \(\mathit{10}^{th}\) Green Chem. Conf. Barcelona -Spain

  40. Jin H, Xiang L, Wen F, Tao K, Liu Q and Hou T 2008 Improved synthesis of chalconoid-like compounds under ultrasound irradiation Ultrason. Sonochem. 15 681

    Article  CAS  Google Scholar 

  41. Maleki B, Azarifar D, Moghaddam M K, Hojati S F, Gholizadeh M and Salehabadi H 2009 Synthesis and characterization of a series of 1,3,5-trisubstituted-2-pyrazolines derivatives using methanoic acid under thermal condition J. Serbian. Chem. Soc. 74 1371

    Article  CAS  Google Scholar 

  42. Rajendra Prasad Y, Lakshmana Rao A, Prasoona L, Murali K and Ravi Kumar P 2005 Synthesis and antidepressant activity of some 1,3,5-Triphenyl-2-pyrazolines and 3-(2’-hydroxy naphthalen-1’-yl)-1,5-diphenyl-2-pyrazolines Bioorg. Med. Chem. Lett. 15 5030

  43. Samshuddin S, Narayana B, Sarojini B K, Khan M T H, Yathirajan H S, Raj C G D and Raghavendra R 2012 Antimicrobial analgesic DPPH scavenging activities and molecular docking study of some 1,3,5-triaryl-2-pyrazolines Med. Chem. Res. 21 2012

  44. Lévai A 2005 Synthesis of chlorinated 3,5-diaryl-2-pyrazolines by the reaction of chlorochalcones with hydrazines Arkivoc 9 344

    Google Scholar 

  45. Reames D C, Harris C E, Dasher L W, Sandifer R M, Hollinger W M and Beam C F 1975 Reactions of c (\(\alpha )\) N-Dilithiophenylhydrazones with aldehydes acid-cyclization to 2-pyrazolines J. Heterocycl. Chem. 12 779

    Article  CAS  Google Scholar 

  46. Fazaeli R, Aliyan H, Mallakpour S, Rafiee Z and Bordbar M 2011 Tungstophosphoric acid supported on highly organosoluble polyamide (PW12/PA): Highly efficient catalysts for the synthesis of novel 1,3,5-triaryl-2-pyrazoline derivatives Chin. J. Catal. 32 582

    Article  CAS  Google Scholar 

  47. Shandala M Y and Hamdy A M 2008 Synthesis of some new substituted 1,3,5-triaryl pyrazolines Natl. J. Chem. 30 338

    Google Scholar 

  48. Palaska E, Aytemir M, Uzbay I T and Erol D 2001 Synthesis and antidepressant activities of some 3,5-diphenyl-2-pyrazolines Eur. J. Med. Chem. 36 539

    Article  CAS  Google Scholar 

  49. Wiley R H, Jarboe C H, Hayes F N, Hansbury E, Nielsen J T, Callahan P X and Sellars M C 1958 1,3,5-triaryl-2-pyrazolines for use as scintillation solutes J. Org.Chem. 23 732

    Article  CAS  Google Scholar 

  50. Liu Y and Wen W 2015 A clean and practical catalyst free synthesis of keto and aldoximes as well as the Beckmann rearrangement by using ethyl lactate as an environmentally benign medium Curr. Green Chem. 2 399

    Article  CAS  Google Scholar 

  51. Kidwai M and Jahan A 2010 Cerium Chloride (\(\text{ CeCl }_{3}\cdot 7\text{ H }_{2}\text{ O }\)) as a highly efficient catalyst for one-pot three-component Mannich reaction J. Braz. Chem. Soc. 21 2175

    Article  CAS  Google Scholar 

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Acknowledgements

Prabhat Bhat was a National Initiative on Undergraduate Science (NIUS) chemistry fellow (Batch XI, 2014-2016) at Homi Bhabha Centre for Science Education. The authors thank Tata Institute of Fundamental Research (TIFR), for providing the NMR spectra.

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Authors and Affiliations

  1. National Initiative on Undergraduate Science (NIUS) Chemistry Programme Fellow, Homi Bhabha Centre for Science Education, Mankhurd, Mumbai, Maharashtra, 400 088, India

    Prabhat Bhat

  2. Department of Chemistry, V. K. Krishna Menon College of Commerce & S. S. Dighe College of Science, Bhandup (E), Mumbai, Maharashtra, 400 042, India

    Gomathi Shridhar

  3. Homi Bhabha Centre for Science Education (TIFR), Mankhurd, Mumbai, Maharashtra, 400 088, India

    Savita Ladage

  4. Department of Chemistry, K.E.T’s V.G. Vaze College of Arts, Science and Commerce, Mithagar Road, Mulund- (E), Mumbai, Maharashtra, 400 081, India

    Lakshmy Ravishankar

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  1. Prabhat Bhat
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  2. Gomathi Shridhar
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  4. Lakshmy Ravishankar
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Correspondence to Lakshmy Ravishankar.

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Bhat, P., Shridhar, G., Ladage, S. et al. An eco-friendly synthesis of 2-pyrazoline derivatives catalysed by \(\hbox {CeCl}_{3} \cdot 7\hbox {H}_{2}\hbox {O}\) . J Chem Sci 129, 1441–1448 (2017). https://doi.org/10.1007/s12039-017-1327-x

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