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Preparative, mechanistic and tautomeric investigation of 1-phenyl and 1-methyl derivative of 3-methyl-5-pyrazolone

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Abstract

1-Phenyl and 1-methyl derivative of 3-methyl-5-pyrazolone were prepared quantitatively via a scalable solvent-free reaction of corresponding hydrazine derivative with ethyl acetoacetate. Different mechanisms have been proposed for the reaction of hydrazine derivatives (methyl or phenyl) with ethyl acetoacetate and also the tautomeric aspects of the targeted compounds have been discussed.

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Synopsis: 13C NMR and quantitative proportional amount of different tautomeric forms of 1,3-dimethyl-5-pyrazolone in DMSO-d6.

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References

  1. Jamwal A, Javed A and Bhardwaj V 2013 A review on Pyrazole derivatives of pharmacological potential J. Pharm. Bio. Sci. 3 114

    Google Scholar 

  2. Faisal M, Aamer Saeed M, Hussain S, Dar P and Larik FA 2019 Recent developments in synthetic chemistry and biological activities of pyrazole derivatives J. Chem. Sci. 131 70

    Article  Google Scholar 

  3. Watanabe T, Tahara M and Todo S 2008 The Novel antioxidant edaravone: From bench to bedside Cardiovasc. Ther. 26 101

    Article  CAS  Google Scholar 

  4. Paspe Cruz M 2018 A novel neuroprotective agent for the treatment of amyotrophic lateral sclerosis Pharm. Ther. 43 25

    Google Scholar 

  5. Deruiter J, Carter D A and Arledge W S 1987 Synthesis and reactions of 4-isopropylidene-1-aryl-3-methyl-2-pyrazolin-5-ones J. Heterocycl. Chem. 24 149

    Article  CAS  Google Scholar 

  6. Xu Y, Smith R and Vivoli M 2017 A blue print for the discovery of non-substrate-like inhibitors for bacterial glycosyltransferases Bioorg. Med. Chem. 25 3182

    Article  CAS  Google Scholar 

  7. Kulangiappar K, Anbukulandainathan M and Raju T 2014 Nuclear versus side-chain bromination of 4-methoxy toluene by an electrochemical method Synth. Commun. 1 2494

    Article  Google Scholar 

  8. Reddy Vaddula B, Varma R S and Leazer J 2013 Solvent-free and catalyst-free synthesis of pyrazoles and diazepines Tetrahedron Lett. 54 1538

    Article  Google Scholar 

  9. Shrivastava P, Singh P and Kumar Tewari A 2012 Synthesis of pyrazole-based 1,5-diaryl compounds as potent anti-inflammatory agents Med. Chem. Res. 21 2465

    Article  CAS  Google Scholar 

  10. Nasseri M, Salimi M and Esmaeili A 2014 Cellulose sulfuricacid as a bio-supported and efficient solid acidcatalyst for synthesis of pyrazoles in aqueous medium RSC Adv. 4 61193

    Article  CAS  Google Scholar 

  11. Sun P, Yang D, Wei W, Zhang W, Zhang H, Wang Yu and Wang H 2017 Metal- and solvent-free, iodine-catalyzed cyclocondensation and C-H bond sulphenylation: A facile access to C-4 sulfenylated pyrazoles via a domino multicomponent reaction Tetrahedron 73 2022

    Article  CAS  Google Scholar 

  12. Sun B, Liu K, Han J, Zhao Li SuX, Lin B, Zhao D and Cheng M 2015 Design, synthesis, and biological evaluation of amide imidazole derivatives as novel metabolic enzyme CYP26A1 inhibitors Bioorg. Med. Chem. 23 6763

    Article  CAS  Google Scholar 

  13. Zhou S, Ren J, Liu M, Ren L, Liu Y and Gong P 2014 Design, synthesis and pharmacological evaluation of 6,7-disubstituted-4-phenoxyquinoline derivatives as potential antitumor agents Bioorg. Chem. 57 30

    Article  CAS  Google Scholar 

  14. Lu B, Cui S and Xie Z 2018 A kind of synthetic method of pyrazolone and its derivative. Chinese. Patent No. 107652237

  15. Jianfeng T, Huiwei C, Jianting W, Xue Y and Ying L 2020 Pyrazole compound and salt and application thereof. Chinese. Patent No. CN110903279

  16. Dai H, Huang M, Qian J, Liu J, Meng C, Li Y, et al. 2019 Excellent antitumor and antimetastatic activities based on novelcoumarin/pyrazole oxime hybrids Eur. J. Med. Chem. 166 470

    Article  CAS  Google Scholar 

  17. Theodorescu D, Wempe M F, Ross D, Meroueh S, Schwartz M A and Reigan P 2016 Anti-cancer compounds targeting RAL Gtpases and methods of using the same U.S. Patent No. 2016,0280715

  18. Yan C, Theodorescu D, Miller B, Kumar A, Kumar V, Ross D and Wempe M F 2016 Synthesis of novel Ral inhibitors: An in vitro and in vivo study Bioorg. Med. Chem. Let. 26 5815

    Article  CAS  Google Scholar 

  19. Park H J, Lee K, Park S J, Ahn B, Lee J C, Cho H and Lee K I 2005 Identification of antitumor activity of pyrazole oxime ethers Bioorg Med. Chem. Let. 15 3307

    Article  CAS  Google Scholar 

  20. Anshu D, Vijay P, Shyam G and Kuldeep S R 2013 Pyrazolones synthesis using nanocatalyst J. Mol. Cat. 373 61

    Article  Google Scholar 

  21. Sankar B, Harikrishnan M, Raja R, Sadhasivam V, Malini N, Murugesan S and Siva A 2019 Design of a simple and efficient synthesis for bioactive novel pyrazolyl–isoxazoline hybrids New J. Chem. 43 10458

    Article  CAS  Google Scholar 

  22. Oslob J, Auble D, Kim J, Sang Y and Zhong M 2016 4-Methylsulfonyl-Substituted Piperidine Urea Compounds U.S. Patent No. 2016/243100 2016

  23. Nam N and Grandberg I 2006 Condensation of N-3-substituted 5-pyrazolones with esters of β-keto acids. Synthesis of pyrano[2,3-c]pyrazol-6-ones Chem. Heterocycl. Compd. 42 326

    Article  CAS  Google Scholar 

  24. Neelima G, Lakshmi K and Sesha Maheswaramma K 2019 Development of novel pyrazolones by using SiO2/ZnCl2 – green approach J. Chem. Sci. 131 105

    Article  Google Scholar 

  25. Karrouchi K, Radi S, Ramli Y, Taoufik J, Mabkhot Y N, Al-aizari F A and Ansar M 2018 Synthesis and pharmacological activities of pyrazole derivatives Molecules 23 134

    Article  Google Scholar 

  26. Singh S P, Kumar D, Batra H, Naithani R, Rozas I and Elguero J 2000 The reaction between hydrazines and β-dicarbonyl compounds: proposal for a mechanism Can. J. Chem. 78 1109

    Article  CAS  Google Scholar 

  27. Nigst T A, Antipova A and Mayr H 2012 Nucleophilic reactivities of hydrazines and amines: The futile search for the α-effect in hydrazine reactivity J. Org. Chem. 77 8142

    Article  CAS  Google Scholar 

  28. Kaur N 2014 Benign approaches for the microwave-assisted synthesis of five-membered 1,2-N,N-heterocycles J. Heterocycl. Chem. 52 953

    Article  Google Scholar 

  29. Abdou M M, Bondock S, El Desouky S I and Metwally M A 2012 Pyrazol-5-ones: tautomerism, synthesis and reactions Int. J. Modern. Org. Chem. 1 19

    Google Scholar 

  30. Elguero J, Marzin C, Linda P and Katritzky A R 1976 The Tautomerism of Heterocycles (Academic Press: New York) p. 655

    Google Scholar 

  31. Cornago P, Cabildo P, Claramunt R M, Bouissane L, Pinilla E, Torres M R and Elguero J 2009 The annular tautomerism of the curcuminoid NH-pyrazoles J. New J. Chem. 33 125

    Article  CAS  Google Scholar 

  32. Alkorta I, Elguero J and Liebman J F 2006 Tautomerism of imidazoles and pyrazoles Structural: The possible existence of nonaromatic forms Struct. Chem. 17 439

    Article  CAS  Google Scholar 

  33. Alkorta I and Elguero J 2005 Barriers to the intramolecular N- to N-transfer of different groups in pyrazoles: Prototropy vs. Elementotropy Heteroatom. Chem. 16 628

    Article  CAS  Google Scholar 

  34. Claramunt R M, López C, Elguero J, Rheingold A L, Zakharov L N and Trofimenkoc S 2003 Structure of 3(5)-[(4-iphenylphosphinoyl) phenyl]pyrazole in the solid state (X-ray and CPMAS NMR) and in solution (NMR): Tautomerism and hydrogen bonds ARKIVOC X 209

  35. Muruganantham R and Namboothiri I N N 2010 Phosphonylpyrazoles from Bestmann−Ohira reagent and nitroalkenes: Synthesis and Dynamic NMR Studies J. Org. Chem. 75 2197

    Article  CAS  Google Scholar 

  36. Pal S, Mareddy J and Devi N S 2008 High speed synthesis of pyrazolones using microwave-assisted neat reaction technology J. Braz. Chem. Soc. 19 1207

    Article  CAS  Google Scholar 

  37. Okafor E C 1980 Structures of l-Phenyl-3-methyl-pyrazolone-5 and its Benzoyl Derivatives Z. Naturforsch. 35b 1019

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, Imam Hossein University, Tehran, Iran

    Hossein Fakhraian & Yaser Nafari

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  1. Hossein Fakhraian
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  2. Yaser Nafari
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Correspondence to Hossein Fakhraian.

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Fakhraian, H., Nafari, Y. Preparative, mechanistic and tautomeric investigation of 1-phenyl and 1-methyl derivative of 3-methyl-5-pyrazolone. J Chem Sci 133, 40 (2021). https://doi.org/10.1007/s12039-021-01902-9

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  • DOI: https://doi.org/10.1007/s12039-021-01902-9

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