Iodine-Mediated Synthesis of Novel Pyrazole Derivatives

Abstract

The reaction between N,2-diarylhydrazinecarbothioamide (generated from arylhydrazines and aryl isothiocyanates) and malononitrile in the presence of iodine/triethylamine in N,N-dimethylform­amide at 80 °C afforded novel pyrazoles, 5-amino-1-aryl-3-(arylamino)-1H-pyrazole-4-carbonitriles, in good yields. In this strategy, iodine served as a versatile desulfurizing agent, efficiently promoting the cyclization reaction.

Key words

pyrazoles - molecular iodine - heterocycles - isothiocyanates - malononitrile

• References

• 1 Tekale SU, Kauthale SS, Dake SA, Sarda SR, Pawar RP. Curr. Org. Chem. 2012; 16: 1485
• 2 Moulay S. Des. Monomers Polym. 2014; 17: 501
• 3 Rahimizadeh M, Bakavoli M, Shiri A, Eshghi H. Bull. Korean Chem. Soc. 2009; 30: 1699
• 4 Das B, Krishnaiah M, Venkateswarlu K, Reddy VS. Tetrahedron Lett. 2007; 48: 81
• 5 Sun J, Dong Y, Cao L, Wang X, Wang S, Hu Y. J. Org. Chem. 2004; 69: 8932
• 6 Gao S, Tzeng T, Sastry MN. V, Chu CM, Liu JT, Lin C, Yao C.-F. Tetrahedron Lett. 2006; 47: 1889
• 7 Yadav JS, Reddy BV. S, Chaya DN, Kumar GG. K. S. N, Aravind S, Kunwar AC, Madavi C. Tetrahedron Lett. 2008; 49: 3330
• 8 Mori N, Togo H. Tetrahedron 2005; 61: 5915
• 9a Shibahara F, Kitagawa A, Yamaguchi E, Murai T. Org. Lett. 2006; 8: 5621
• 9b Yella R, Khatun N, Rout SK, Patel BK. Org. Biomol. Chem. 2011; 9: 3235
• 9c Nath J, Patel BK, Jamir L, Sinha UB, Satyanarayana KV. V. V. Green Chem. 2009; 11: 1503
• 10 Küçükgüzel ŞG, Şenkardeş S. Eur. J. Med. Chem. 2015; 97: 786
• 11 Maggio B, Daidone G, Raffa D, Plescia S, Mantione L, Cutuli VM. C, Mangano NG, Caruso A. Eur. J. Med. Chem. 2001; 36: 737
• 12 Tanitame A, Oyamada Y, Ofuji K, Fujimoto M, Suzuki K, Ueda T, Terauchi H, Kawasaki M, Nagai K, Wachi M, Yamagishi J. Bioorg. Med. Chem. 2004; 12: 5515
• 13 Aragade P, Kolhe S, Kamble H, Baheti D, Maddi V. Int. J. Drug Discovery 2012; 3: 688
• 14 Dominquez JN, Charris JE, Caparelli M, Riggione F. Arzneimittelforschung 2002; 52: 482
• 15 Li Y, Zhang H, Lıu J, Yang X, Liu Z. J. Agric. Food Chem. 2006; 54: 3636
• 16 Castagnolo D, De Logu A, Radi M, Bechi B, Manetti F, Magnani M, Supino S, Meleddu R, Chisu L, Botta M. Bioorg. Med. Chem. 2008; 16: 8587
• 17 Bandgar BP, Gawande SS, Bodade RG, Gawande NM, Khobragade CN. Bioorg. Med. Chem. 2009; 17: 8168
• 18 Anzaldia M, Macciò C, Mazzeia M, Bertolottob M, Ottonellob L, Dallegrib F, Balbi A. Chemistry & Biodiversity 2009; 6: 1674
• 19 Dong W, Xu J, Xıong L, Liu X, Li Z. Chin. J. Chem. 2009; 27: 579
• 20 Faria JV, dos Santos MS, Bernardino AM. R, Becker KM, Machado GM. C, Rodrigues RF, Canto-Cavalheiro MM, Leon LL. Bioorg. Med. Chem. Lett. 2013; 23: 6310
• 21 Kasımoğulları R, Bülbül M, Arslan BS, Gökçe B. Eur. J. Med. Chem. 2010; 45: 4769
• 22 Cottineau B, Toto P, Marot C, Pipaud A, Chenault J. Bioorg. Med. Chem. Lett. 2002; 12: 2105
• 23a Fustero S, Simón-Fuentes A, Sanz-Cervera JF. Org. Prep. Proced. Int. 2009; 41: 253
• 23b Makino K, Kim HS, Kurasawa Y. J. Heterocycl. Chem. 1999; 36: 321
• 24 Kumar SV, Yadav SK, Raghava B, Saraiah B, Ila H, Rangappa KS, Hazra A. J. Org. Chem. 2013; 78: 4960
• 25 Ahmed MS. M, Kobayashi K, Mori A. Org. Lett. 2005; 7: 4487
• 26 Panda N, Jena AK. J. Org. Chem. 2012; 77: 9401
• 27 Zhang G, Ni H, Chen W, Shao J, Liu H, Chen B, Yu Y. Org. Lett. 2013; 15: 5967
• 28 Reddy CR, Vijaykumar J, Grée R. Synthesis 2013; 45: 830
• 29a Mahdavi M, Bialam M, Saeedi M, Jafarpour F, Foroumadi A, Shafiee A. Synlett 2015; 26: 173
• 29b Goli-Garmroodi F, Omidi M, Saeedi M, Sarrafzadeh F, Rafinejad A, Mahdavi M, Bardajee GR, Akbarzadeh T, Firoozpour L, Shafiee A, Foroumadi A. Tetrahedron Lett. 2015; 56: 743
• 29c Saeedi M, Mahdavi M, Foroumadi A, Shafiee A. Tetrahedron 2013; 69: 3506
• 29d Rasouli MA, Mahdavi M, Saeedi M, Ranjbar PR, Shafiee A, Foroumadi A. J. Heterocycl. Chem. 2015; 52: 386
• 29e Esmaeili-Marandi F, Saeedi M, Mahdavi M, Yavari I, Foroumadi A, Shafiee A. Synlett 2014; 25: 2605
• 29f Saeedi M, Ansari S, Mahdavi M, Sabourian R, Akbarzadeh T, Foroumadi A, Shafiee A. Synth. Commun. 2015; 45: 2311
2930
• 30a Britto MM, Almeida TM. G, Leitão A, Donnici CL, Lopes MT. P, Montanari CA. Synth. Commun. 2006; 36: 3359
• 30b Ram VJ. Indian J. Appl. Chem. 1970; 33: 394