Microwave-assisted synthesis of pyrazoles - a mini-review

Abstract

Heterocyclic compounds including pyrazole have a serious area in the field of medicinal chemistry and modern drug development studies. Pyrazole is a five-membered ring system containing two adjacent nitrogen atoms. Pyrazole attracts great attention due to its wide biological activity scale and potential in the development of new drug molecules. Traditional methods have been used in the general synthesis methods of pyrazole for a long time, but since these methods can be performed within certain limits, it is necessary to benefit from new and sustainable methodologies. In this review, the use and benefits of microwave (MW)-assisted techniques under the general title of green chemistry will be emphasized. The use of MW techniques stands out with its advantages such as increasing the efficiency of synthesis, obtaining selective products and preventing environmental pollution. The area of use of the MW method in pyrazole synthesis, synthesis mechanisms, organic synthesis methods and benefits are examined in this study. The MW method used in the synthesis of the pyrazole ring, which stands out with its bioactive diversity, will be encountered much more in the coming years.

Keywords

• pyrazole
• microwave
• green chemistry

References

1. Majumder A, Gupta R, Jain A. Microwave-assisted synthesis of nitrogen-containing heterocycles. Green Chem Lett Rev. (2013); 6(2): 151–82. https://doi.org/10.1080/17518253.2012.733032
2. Balaban AT, Oniciu DC, Katritzky AR. Aromaticity as a cornerstone of heterocyclic chemistry. Chem Rev. (2004); 104(5): 2777–812. https://doi.org/10.1021/cr0306790
3. Sheldon RA. Catalysis: The key to waste minimization. In: Journal of Chemical Technology and Biotechnology., John Wiley & Sons Ltd. (1997); 381–8. https://doi.org/fm7wx6
4. Alam MA. Pyrazole: an emerging privileged scaffold in drug discovery. Vol. 15, Future Medicinal Chemistry. Newlands Press Ltd. (2023); 2011–23. https://doi.org/10.4155/fmc-2023-0207
5. Henary M, Kananda C, Rotolo L, Savino B, Owens EA, Cravotto G. Benefits and applications of microwave-assisted synthesis of nitrogen containing heterocycles in medicinal chemistry. Vol. 10, RSC Advances. Royal Society of Chemistry. (2020); 14170: 97. https://doi.org/10.1039/D0RA01378A
6. Ansari A, Ali A, Asif M, others. Biologically active pyrazole derivatives. New J of Chem. (2017); 41(1): 16–41.
7. Anastas PT, Beach ES. Green chemistry: the emergence of a transformative framework. Green Chem Lett Rev. (2007); 1(1): 9–24. https://doi.org/10.1080/17518250701882441
8. Tucker JL. Green chemistry, a pharmaceutical perspective. Org Process Res Dev. (2006); 10(2): 315–9. https://doi.org/10.1021/op050227k

9. Villar H, Frings M, Bolm C. Ring closing enyne metathesis: A powerful tool for the synthesis of heterocycles. Chem Soc Rev. (2007); 36(1): 55–66.
10. Anastas PT, Beach ES. Green chemistry: the emergence of a transformative framework. Green Chem Lett Rev. (2007); 1(1): 9–24. https://doi.org/10.1080/17518250701882441
11. Daştan A, Kulkarni A, Török B. Environmentally benign synthesis of heterocyclic compounds by combined microwave-assisted heterogeneous catalytic approaches. Green chemistry. (2012); 14(1): 17–37. https://doi.org/10.1039/C1GC15837F
12. De La Hoz A, Díaz-Ortiz Á, Moreno A, Sanchéz-Migallón A, Prieto P, Carrillo R, et al. Microwave-Assisted Reactions in Heterocyclic Compounds with Applications in Medicinal and Supramolecular Chemistry. CCHTS. (2007); 7: 877-902. https://doi.org/10.2174/138620707783220347
13. Paul S, Nanda P, Gupta R, Loupy A. Zinc mediated friedel-crafts acylation in solvent-free conditions under microwave irradiation. Synthesis (Stuttg). 2003; (18): 2877–81. https://doi.org/10.1055/s-2003-42485
14. Hoz A dl, Diaz-Ortiz A, Moreno A, Sanchez-Migallon A, Prieto P, Carrillo JR, et al. Microwave-assisted reactions in heterocyclic compounds with applications in medicinal and supramolecular chemistry. CCHTS. (2007); 10(10): 877–902. https://doi.org/10.2174/138620707783220347
15. Larhed M, Hallberg A. Microwave-assisted high-speed chemistry: a new technique in drug discovery. Drug Discov Today. (2001); 6(8): 406–16. https://doi.org/10.1016/S1359-6446(01)01735-4
16. Will H, Scholz P, Ondruschka B. Heterogene gasphasenkatalyse im mikrowellenfeld. Chemie Ingenieur Technik. (2002); 74(8): 1057–67. https://doi.org/10.1002/1522-2640(20020815)74:8<1057::AID CITE1057>3.0.CO;2-3
17. Langa F, De La Cruz P, Espldora E, Garca JJ, Pérez MC, la Hoz A. Fullerene chemistry under microwave irradiation. Carbon N Y. (2000); 38(11–12): 1641–6. https://doi.org/10.1016/S0008-6223(99)00284-5
18. de la Hoz A, Diaz-Ortis A, Moreno A, Langa F. Cycloadditions under microwave irradiation conditions: Methods and applications. European J Org Chem. (2000); (22): 3659–73. https://doi.org/fdcvcm
19. Elander N, Jones JR, Lu SY, Stone-Elander S. Microwave-enhanced radiochemistry. Chem Soc Rev. (2000); 29(4): 239–49. https://doi.org/10.1002/9783527619559.ch18
20. Kappe CO, Stadler A, Dallinger D. Microwaves in organic and medicinal chemistry. John Wiley & Sons. (2012); 52:26-37.
21. Polshettiwar V, Varma RS. Microwave-assisted organic synthesis and transformations using benign reaction media. Acc Chem Res. (2008); 41(5): 629–39. https://doi.org/10.1021/ar700238s
22. Polshettiwar V, Varma RS. Aqueous microwave chemistry: a clean and green synthetic tool for rapid drug discovery. Chem Soc Rev. (2008); 37(8): 1546–57. https://doi.org/10.1039/b716534j
23. Cao X, Sun Z, Cao Y, Wang R, Cai T, Chu W, et al. Design, synthesis, and structure–activity relationship studies of novel fused heterocycles-linked triazoles with good activity and water solubility. J Med Chem. . (2014); 57(9): 3687–706. dx.doi.org/10.1021/jm4016284
24. Salem MS, Sakr SI, El-Senousy WM, Madkour HMF. Synthesis, antibacterial, and antiviral evaluation of new heterocycles containing the pyridine moiety. Arch Pharm (Weinheim). (2013); 346(10): 766–73. https://doi.org/10.1002/ardp.201300183
25. El-Sawy ER, Ebaid MS, Abo-Salem HM, Al-Sehemi AG, Mandour AH. Synthesis, anti-inflammatory, analgesic and anticonvulsant activities of some new 4, 6-dimethoxy-5-(heterocycles) benzofuran starting from naturally occurring visnagin. Arabian Journal of Chemistry. (2014); 7(6): 914–23. https://doi.org/10.1016/j.arabjc.2012.12.041
26. Mabkhot YN, Barakat A, Al-Majid AM, Alshahrani S, Yousuf S, Choudhary MI. Synthesis, reactions and biological activity of some new bis-heterocyclic ring compounds containing sulphur atom. Chem Cent J. (2013); 7: 1–9.
27. Abd El-Salam NM, Mostafa MS, Ahmed GA, Alothman OY. Synthesis and Antimicrobial Activities of Some New Heterocyclic Compounds Based on 6-Chloropyridazine-3 (2H)-thione. J Chem. (2013); 2013(1),890617: 1-8 https://doi.org/10.1155/2013/890617.
28. Alkahtani HM, Almehizia AA, Al-Omar MA, Obaidullah AJ, Zen AA, Hassan AS, et al. In vitro evaluation and bioinformatics analysis of schiff bases bearing pyrazole scaffold as bioactive agents: antioxidant, anti-diabetic, anti-alzheimer, and anti-arthritic. Molecules. (2023); 28(20): 7125. https://doi.org/10.3390/molecules28207125
29. Hossain M, Nanda AK. A review on heterocyclic: Synthesis and their application in medicinal chemistry of imidazole moiety. Science (1979). (2018); 6(5): 83–94. https://doi.org/10.11648/j.sjc.20180605.12
30. Sharma M, Sandhu N, Saraswat V. Microwave assisted facile one pot synthesis of novel pyrazole derivative for multi-analyte detection (Fe3+ and Zn2+) and its solvatochromic studies. J Mol Struct. (2024); 1318: 139-183. https://doi.org/10.1016/j.molstruc.2024.139183
31. Karrouchi K, Radi S, Ramli Y, Taoufik J, Mabkhot YN, Al-Aizari FA, et al. Synthesis and pharmacological activities of Pyrazole derivatives: A review. Molecules. (2018); 23(1): 134. https://doi.org/10.3390/molecules23010134
32. Alcazar J, Diels G, Schoentjes B. Applications of the combination of microwave and parallel synthesis in medicinal chemistry. Comb Chem High Throughput Screen. (2007); 10(10): 918–32. https://doi.org/10.2174/138620707783220383
33. Leadbeater NE. Microwave heating as a tool for sustainable chemistry. CRC press. (2010); 1: 290. https://doi.org/10.1201/9781439812709
34. Dallinger D, Lehmann H, Moseley JD, Stadler A, Kappe CO. Scale-up of microwave-assisted reactions in a multimode bench-top reactor. Org Process Res Dev. (2011); 15(4): 841–54. https://doi.org/10.1021/op200090k
35. Ju Y, Varma RS. Aqueous N-heterocyclization of primary amines and hydrazines with dihalides: Microwave-assisted syntheses of N-azacycloalkanes, isoindole, pyrazole, pyrazolidine, and phthalazine derivatives. Journal of Organic Chemistry. (2006); 71(1): 135–41. https://doi.org/10.1021/jo051878h
36. Humphries PS, Finefield JM. Microwave-assisted synthesis utilizing supported reagents: A rapid and versatile synthesis of 1,5-diarylpyrazoles. Tetrahedron Lett. (2006); 47(14): 2443–6. https://doi.org/10.1016/j.tetlet.2006.01.100
37. Corradi A, Leonelli C, Rizzuti A, Rosa R, Veronesi P, Grandi R, et al. New “Green” Approaches to the Synthesis of Pyrazole Derivatives. Molecules. (2007); 12: 1482–95. https://doi.org/10.3390/12071482
38. Sauzem PD, Machado P, Rubin MA, da S. Sant’Anna G, Faber HB, de Souza AH, et al. Design and microwave-assisted synthesis of 5-trifluoromethyl-4,5-dihydro-1H-pyrazoles: Novel agents with analgesic and anti-inflammatory properties. Eur J Med Chem. (2008); 43(6): 1237–47. https://doi.org/10.1016/j.ejmech.2007.07.018
39. Polshettiwar V, Varma RS. Nano-organocatalyst: magnetically retrievable ferrite-anchored glutathione for microwave-assisted Paal-Knorr reaction, aza-Michael addition, and pyrazole synthesis. Tetrahedron. (2010); 66(5): 1091–7. https://doi.org/10.1016/j.tet.2009.11.015
40. Abdel-Aziz HA, El-Zahabi HSA, Dawood KM. Microwave-assisted synthesis and in-vitro anti-tumor activity of 1,3,4-triaryl-5-N-arylpyrazole-carboxamides. Eur J Med Chem. (2010); 45(6): 2427–32. https://doi.org/10.1016/j.ejmech.2010.02.026
41. Antre R V., Cendilkumar A, Goli D, Andhale GS, Oswal RJ. Microwave assisted synthesis of novel pyrazolone derivatives attached to a pyrimidine moiety and evaluation of their anti-inflammatory, analgesic and antipyretic activities. Saudi Pharmaceutical Journal. (2011); 19(4): 233–43. https://doi.org/10.1016/j.jsps.2011.05.006
42. Sahu PK, Sahu PK, Gupta SK, Thavaselvam D, Agarwal DD. Synthesis and evaluation of antimicrobial activity of 4H-pyrimido[2,1-b] benzothiazole, pyrazole and benzylidene derivatives of curcumin. Eur J Med Chem. (2012); 54: 366–78. https://doi.org/10.1016/j.ejmech.2012.05.020
43. Alam MM, Marella A, Akhtar M, Husain A, Yar MS, Shaquiquzzaman M, et al. Microwave assisted one pot synthesis of some pyrazole derivatives as a safer anti-inflammatory and analgesic agents. Acta Pol Pharm. (2013); 70(3): 435–41.
44. Selvam TP, Kumar PV, Saravanan G, Prakash CR (2014). Microwave-assisted synthesis, characterization and biological activity of novel pyrazole derivatives. Journal of Saudi Chemical Society., 18(6),1015–21.
45. Bagley MC, Baashen M, Chuckowree I, Dwyer JE, Kipling D, Davis T. Microwave-assisted synthesis of a MK2 inhibitor by Suzuki-Miyaura coupling for study in werner syndrome cells. Pharmaceuticals. (2015); 8(2): 257–76. https://doi.org/10.3390/ph8020257
46. Farmani HR, Mosslemin MH, Sadeghi B. Microwave-assisted green synthesis of 4,5-dihydro-1H-pyrazole-1-carbothioamides in water. Mol Divers. (2018); 22(3): 743–9. https://doi.org/10.1007/s11030-018-9814-7
47. Mótyán G, Gopisetty MK, Kiss-Faludy RE, Kulmány Á, Zupkó I, Frank É, et al. Anti-cancer activity of novel dihydrotestosterone-derived ring a-condensed pyrazoles on androgen non-responsive prostate cancer cell lines. Int J Mol Sci. (2019); 20(9): 2170. https://doi.org/10.3390/ijms20092170
48. Goulart TB, Neves AM, Soares MSP, Stefanello FM, Campos PT, Moura S, et al. Design, synthesis, and structure of alkyl 1H-pyrazolecarboxylates from a raspberry ketone methyl ether. Chem Heterocycl Compd (N Y). (2020); 56(10): 1314–20. https://doi.org/10.1007/s10593-020-02816-z
49. Masaret GS. Synthesis of new Spiropyrazole derivatives under microwave irradiation and docking study for inhibition the microbes and COVID-19. J Mol Struct. (2022); 1269. https://doi.org/10.1016/j.molstruc.2022.133581
50. Anwer KE, Sayed GH, Essa BM, Selim AA. Green synthesis of highly functionalized heterocyclic bearing pyrazole moiety for cancer-targeted chemo/radioisotope therapy. BMC Chem. (2023); 17(1). https://doi.org/10.1186/s13065-023-01053-7
51. Kumar KS, Robert AR, Rao AV, Thainana SK, Harikrishna S, Maddila S. A rapid, efficient microwave-assisted synthesis of novel bis-pyrazole analogues using non-toxic and cost-effective catalyst under green solvent medium. CDC. (2024); 54. https://doi.org/10.1016/j.cdc.2024.101165
52. Sharma M, Sandhu N, Saraswat V. Microwave assisted facile one pot synthesis of novel pyrazole derivative for multi-analyte detection (Fe3+ and Zn2+) and its solvatochromic studies. J Mol Struct. (2024); 1318. https://doi.org/10.1016/j.molstruc.2024.139183