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Current Organic Synthesis

Editor-in-Chief

ISSN (Print): 1570-1794
ISSN (Online): 1875-6271

Review Article

The Chemistry of 4-(dicyanomethylene)-3-methyl-l-phenyl-2-pyrazoline-5-ones as a Privileged Scaffold in the Synthesis of Heterocycles

Author(s): Mohsen A.-M. Gomaa* and Huda A. Ali

Volume 18 , Issue 1 , 2021

Published on: 24 September, 2020

Page: [75 - 90] Pages: 16

DOI: 10.2174/1570179417666200924150340

Price: $65

Abstract

Background: The reactivity of 4-(dicyanomethylene)-3-methyl-l-phenyl-2-pyrazoline-5-one DCNP 1 and its derivatives makes it valuable as a building block for the synthesis of heterocyclic compounds like pyrazolo- imidazoles, -thiazoles, spiropyridines, spiropyrroles, spiropyrans, and others. As a number of publications have reported on the reactivity of DCNP and its derivatives, we compiled some features of this interesting molecule.

Objective: This article aims to review the preparation of DCNP, its reactivity, and application in heterocyclic and dyes synthesis.

Conclusion: In this review, we have provided an overview of recent progress in the chemistry of DCNP and its significance in the synthesis of various classes of heterocyclic compounds and dyes. The unique reactivity of DCNP offers unprecedentedly mild reaction conditions for the generation of versatile cynomethylene dyes from a wide range of precursors, including amines, α-aminocarboxylic acids, their esters, phenols, malononitriles, and azacrown ethers. We anticipate that more innovative transformations involving DCNP will continue to emerge in the near future.

Keywords: 4-(dicyanomethylene)-3-methyl-l-phenyl-2-pyrazoline-5-one, dyes, amines, indole, pyrrole, oxonols, cyanine dyes.

Graphical Abstract
[1]
Gupta, P.; Gupta, J.K.; Halve, A.K. Synthesis and biological significance of pyrazolones. Int. J. Pharm. Sci. Res., 2015, 6(6), 2291-2310.
[2]
Arnost, M.; Pierce, A.; ter Haar, E.; Lauffer, D.; Madden, J.; Tanner, K.; Green, J. 3-Aryl-4-(arylhydrazono)-1H-pyrazol-5-ones: Highly ligand efficient and potent inhibitors of GSK3β. Bioorg. Med. Chem. Lett., 2010, 20(5), 1661-1664.
[http://dx.doi.org/10.1016/j.bmcl.2010.01.072] [PMID: 20138514]
[3]
Kawai, H.; Nakai, H.; Suga, M.; Yuki, S.; Watanabe, T.; Saito, K.I. Effects of a novel free radical scavenger, MCl-186, on ischemic brain damage in the rat distal middle cerebral artery occlusion model. J. Pharmacol. Exp. Ther., 1997, 281(2), 921-927.
[PMID: 9152402]
[4]
Gürsoy, A.; Demirayak, S.; Capan, G.; Erol, K.; Vural, K. Synthesis and preliminary evaluation of new 5-pyrazolinone derivatives as analgesic agents. Eur. J. Med. Chem., 2000, 35(3), 359-364.
[http://dx.doi.org/10.1016/S0223-5234(00)00117-3] [PMID: 10785562]
[5]
Castagnolo, D.; Manetti, F.; Radi, M.; Bechi, B.; Pagano, M.; De Logu, A.; Meleddu, R.; Saddi, M.; Botta, M. Synthesis, biological evaluation, and SAR study of novel pyrazole analogues as inhibitors of Mycobacterium tuberculosis: Part 2. Synthesis of rigid pyrazolones. Bioorg. Med. Chem., 2009, 17(15), 5716-5721.
[http://dx.doi.org/10.1016/j.bmc.2009.05.058] [PMID: 19581099]
[6]
Parekh, N.; Maheria, K.; Patel, P.; Rathod, M. Study on antibacterial activity for multidrug resistance stain by using phenyl Pyrazolones Substituted 3-amino 1H-pyrazolon [3,4-b]quinoline derivative in vitro condition. Int. J. Pharm. Tech. Res., 2011, 3(1), 540-548.
[7]
Mariappan, G.; Saha, B.P.; Sutharson, L.; Haldar, A. Synthesis and bioactivity evaluation of pyrazolone derivatives. Indian J. Chem., 2010, 49, 1671-1674.
[8]
Manojkumar, P.; Ravi, T.K.; Subbuchettiar, G. Synthesis of coumarin heterocyclic derivatives with antioxidant activity and in vitro cytotoxic activity against tumour cells. Acta Pharm., 2009, 59(2), 159-170.
[http://dx.doi.org/10.2478/v10007-009-0018-7] [PMID: 19564141]
[9]
Himly, M.; Jahn-Schmid, B.; Pittertschatscher, K.; Bohle, B.; Grubmayr, K.; Ferreira, F.; Ebner, H.; Ebner, C. IgE-mediated immediate-type hypersensitivity to the pyrazolone drug propyphenazone. J. Allergy Clin. Immunol., 2003, 111(4), 882-888.
[http://dx.doi.org/10.1067/mai.2003.163] [PMID: 12704373]
[10]
Kakiuchi, Y.; Sasaki, N.; Satoh-Masuoka, M.; Murofushi, H.; Murakami-Murofushi, K. A novel pyrazolone, 4,4-dichloro-1-(2,4-dichlorophenyl)-3-methyl-5-pyrazolone, as a potent catalytic inhibitor of human telomerase. Biochem. Biophys. Res. Commun., 2004, 320(4), 1351-1358.
[http://dx.doi.org/10.1016/j.bbrc.2004.06.094] [PMID: 15303281]
[11]
Wu, T.W.; Zeng, L.H.; Wu, J.; Fung, K.P. Myocardial protection of MCI-186 in rabbit ischemia-reperfusion. Life Sci., 2002, 71(19), 2249-2255.
[http://dx.doi.org/10.1016/S0024-3205(02)01965-3] [PMID: 12215372]
[12]
Rajendra Prasad, Y.; Lakshmana Rao, A.; Prasoona, L.; Murali, K.; Ravi Kumar, P. 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., 2005, 15(22), 5030-5034.
[http://dx.doi.org/10.1016/j.bmcl.2005.08.040] [PMID: 16168645]
[13]
Junek, H.; Klade, M.; Sterk, H.; Fabian, W. Dicyanmethylenpyrazolinone und deren bedeutung als chromophor. Synthesen mit nitrilen. Monatsh. Chem., 1988, 119, 993-1010.
[http://dx.doi.org/10.1007/BF00810108]
[14]
Junek, H.; Aigner, H. Synthesen mit nitrilen, XXXV. Reaktionen von tetracyanäthylen mit heterocyclen. Chem. Ber., 1973, 106, 914-921.
[http://dx.doi.org/10.1002/cber.19731060323]
[15]
Holzer, W.; Hallak, L. Synthesis and NMR spectroscopic investigations with 3-amino-, 3-hydroxy-, and 3-methoxy-4-acyl-1-phenyl-2-pyrazolin-5-ones. Heterocycles, 2004, 63(6), 1311-1334.
[http://dx.doi.org/10.3987/COM-04-10046]
[16]
Hennig, L.; Schellenberg, C.; Franke, K. α-Arylamino-cyanomethylen-pyrazolinone aus azomethinfarbstoffen und malonsauredinitril. J. Prakt. Chem., 1993, 335, 368-370.
[http://dx.doi.org/10.1002/prac.19933350411]
[17]
Wichern, J. Entwicklung donor-akzeptor substituierter chromophore für die nichtlineare optik.. . Ph D Thesis, TU Braunschweig, Germany, 2000., https://publikationsserver.tu-braunschweig.de/receive/dbbs_mods_000011062000.
[18]
Metwally, S.A.M.; El Naggar, G.M.; Younis, M.I.; El-Emary, T.I.; Elnagdi, M.H. Reactions of 4‐(dicyanomethylene)‐3‐methyl‐1‐phenyl‐2‐pyrazolin‐5‐one towards amines and phenols. Liebigs Ann. Chem., 1989, 1037-1040.
[http://dx.doi.org/10.1002/jlac.198919890262]
[19]
Atta, A.H. Reactions of 1 -(2-benzothiazolyl)-4-(dicyanomethylene)-3-methyl-2-pyrazolin-5-one towards Amines. Heterocycl. Commun., 1999, 5(3), 243.
[http://dx.doi.org/10.1515/HC.1999.5.3.243]
[20]
Göckel, A.B.; Fabian, W.M.F.; Junek, H. Syntheses with nitriles, xcviii synthesis and characterization of (aminocyanomethylene)indandione and ‐pyrazolone chromoionophores as extractants for alkali metal ions. Liebigs Ann. Chem., 1996, 397-402.
[21]
Gomaa, M.A-M. Reaction of N1,N2-Diarylamidines with 2-(3-methyl-5-oxo-1-phenyl-1H-pyrazol-4(5H)-ylidene)propanedinitrile. J. Chem. Res., 2001, 387-389.
[22]
Junek, H.; Klade, M.; Biza, P.; Geringer, M.; Steric, H. Synthesen mit nitrilen, LXXXVII. Chromoionophore durch Addition von N‐Phenyl(aza‐15‐krone‐5) an reactive dicyanmethylenverbindungen. Liebigs Ann. Chem., 1990, 741-744.
[http://dx.doi.org/10.1002/jlac.1990199001139]
[23]
Junek, H.; Biza, P.; Geringer, M. Diphenyldiaza-18-krone-6-bis-pyrazoliden-acetonitril, ein neuer Chromoionophor Synthesen mit Nitrilen, 90. Mitt. Monatsh. Chem., 1992, 123, 581-585.
[http://dx.doi.org/10.1007/BF00816852]
[24]
Dworczak, R.; Fabian, W.M.F.; Sterk, H.; Kratky, C.; Junek, H. Syntheses with Nitriles, IXC. preparation, structure, and color of 4‐[(cyano)indolylmethylene]‐ and 4‐[(cyano)pyrrolylmethylene]‐1H‐pyrazol‐5(4H)‐ones. Liebigs Ann. Chem., 1992, 7-14.
[http://dx.doi.org/10.1002/jlac.199219920103]
[25]
Reidlinger, C.; Dworczak, R.; Fabian, W.M.F.; Junek, H. Structur-color correlations of penta- and heptamethines. syntheses with Nitriles XCIV. Dyes Pigments, 1994, 24, 185-204.
[http://dx.doi.org/10.1016/0143-7208(94)80009-X]
[26]
Dworczak, R.; Glaser, H.; Biza, P.; Junek, H. Hydroxyphenyl-pyrazolyl-tmlononitriles, a new Class of polymethine-Type color forums. Syntheses with Nitriles Dye. Pig., 1993, 21, 75-86.
[http://dx.doi.org/10.1016/0143-7208(93)85006-L]
[27]
Metwally, S.A.M.; El Naggar, G.M.; Younis, M.I.; El-Emary, T.I.; Elnagdi, M.H. Reactions of 4-(dicyanomethylene)-3-methyl-l-phenyl-2-pyrazolin-5-one towards active methylene compounds. Liebigs Ann. Chem., 1991, 961-962.
[http://dx.doi.org/10.1002/jlac.1991199101164]
[28]
Metwally, S.A.; Aly, M.F.; Abd‐Alla, M.A.; Atta, F.M.; Abd‐El‐Monem, M.E. Azomethine ylides from the reaction of 4‐(dicyanomethylene)‐3‐methyl‐1‐phenyl‐2‐pyrazoline‐5‐one with α‐amino acids and their esters. Liebigs Ann. Chem., 1991, (4), 387-389.
[http://dx.doi.org/10.1002/jlac.199119910168]
[29]
Gomaa, M.A-M. Reaction of 2-(3-methyl-5-oxo-1-phenyl-1H-pyrazol-4(5H)-ylidene)propanedinitrile with 1,3-dicarbonyl Compounds. Pharmazie, 1999, 54, 352-354.
[http://dx.doi.org/10.1002/chin.199940113]
[30]
Gomaa, M.A-M.; Ali, H.A. An efficient and facile synthesis of new tetracyclic fused pyrazolo[4,3-c][1,2,4]triazino[4,5-a]quinolin-4(5H)-ones. Mol. Divers., 2018, 22(4), 969-977.
[http://dx.doi.org/10.1007/s11030-018-9849-9] [PMID: 29971615]

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