Preparation of Trifluoromethylated (Arylaminomethylene)malononitriles Suitable for Synthesis of 4-Amino-2-(trifluoromethyl) quinoline Derivatives by Intramolecular Friedel–Crafts Reaction

Abstract

An approach for the synthesis of 4-amino-2-(trifluoromethyl)quinolines via the intramolecular Friedel–Crafts reaction of 2-(1-(arylamino)-2,2,2-trifluoroethylidene)malononitrile derivatives is reported. This simple protocol provides a wide variety of 4-amino-2-(trifluoromethyl)quinolines in good to excellent yields, without any purification. Furthermore, the 2-(1-(arylamino)-2,2,2-trifluoroethylidene) malononitrile derivatives used in this project have been synthesized by the reaction of N-aryl-2,2,2-trifluoroacetimidoyl chlorides and malononitrile at ambient temperature and under microwave irradiation in excellent yields, for the first time.

Key words

4-amino-2-(trifluoromethyl)quinolones - intramolecular Friedel–Crafts reaction - trifluoromethylated (arylaminomethylene)malononitriles - trifluoroacetimidoyl chlorides - trifluoromethylated compounds

• References

• 1 Afzal O. Kumar S. Haider MR. Ali MR. Kumar R. Jaggi M. Bawa S. Eur. J. Med. Chem. 2015; 97: 871
• 2 Bawa S. Kumar S. Drabu S. Kumar R. J. Pharm. BioAllied Sci. 2010; 2: 64
• 3 Wall ME. Wani MC. Cook CE. Palmer KH. McPhail AI. Sim GA. J. Am. Chem. Soc. 1966; 88: 3888
• 4 Nagai T. Nishioka G. Koyama M. Ando A. Miki T. Kumadaki I. J. Fluorine Chem. 1992; 57: 229
• 5a Organofluorine Chemistry: Principles and Commercial Applications . Banks RE. Smart BE. Tatlow JC. Plenum Press; New York: 1994
• 5b Organofluorine Compounds in Medicinal Chemistry and Biomedical Applications . Filler R. Kobayashi Y. Yagupolskii LM. Elsevier; Amsterdam: 1993
• 5c Hiyama T. Organofluorine Compounds. Chemistry and Application. Springer-Verlag; Berlin: 2000
• 6a Welch JT. Tetrahedron 1987; 43: 3123
• 6b McClinton MA. McClinton DA. Tetrahedron 1992; 48: 6555
• 6c Lin P. Jiang J. Tetrahedron 2000; 56: 3635
• 6d Burton DJ. Yang Z.-Y. Tetrahedron 1992; 48: 189
• 7a Cahard D. Xu X. Couve-Bonnaire S. Pannecoucke X. Chem. Soc. Rev. 2010; 39: 558
• 7b Serdyuk O. Butin A. Abaev V. J. Fluorine Chem. 2010; 131: 296
• 7c Sorochinsky AE. Soloshonok VA. J. Fluorine Chem. 2010; 131: 127
• 7d Smits R. Cadicamo CD. Burger K. Koksch B. Chem. Soc. Rev. 2008; 37: 1727
• 7e Brunet VA. O’Hagan D. Angew. Chem. Int. Ed. 2008; 47: 1179
• 7f Prakash GK. S. Beier P. Angew. Chem. Int. Ed. 2006; 45: 2172
• 7g Shimizu M. Hiyama T. Angew. Chem. Int. Ed. 2005; 44: 214
• 7h Roze S. Acc. Chem. Res. 2005; 38: 803
• 7i Singh RP. Shreeve JM. Acc. Chem. Res. 2004; 37: 31
• 7j Adams DJ. Clark JH. Chem. Soc. Rev. 1999; 28: 225
• 7k Rozen S. Acc. Chem. Res. 1996; 29: 243
• 8 Swarts F. Bull. Acad. R. Belg. 1892; 24: 309
• 9 Uneyama K. Organofluorine Chemistry . Blackwell Publishing; Oxford: 2006: 292
• 10a Ma JA. Cahard D. J. Fluorine Chem. 2007; 128: 975
• 10b Dolbier WR. Chem. Rev. 1996; 96: 1557
• 10c Shibata N. Matsnev A. Cahard D. Beilstein J. Org. Chem. 2010; 6
• 11a Schäfer G. Ahmetovic M. Abele S. Org. Lett. 2017; 19: 6578
• 11b Wu W. Wang J. Wang Y. Huang Y. Tan Y. Weng Z. Angew. Chem. Int. Ed. 2017; 129: 10612
• 12a Kowalski MK. Mlostoń G. Obijalska E. Linden A. Heimgartner H. Tetrahedron 2016; 72: 5305
• 12b Grzelak P. Utecht G. Jasiński M. Mlostoń G. Synthesis 2017; 49: 2129
• 12c Mlostoń G. Kowalski MK. Obijalska E. Heimgartner H. J. Fluorine Chem. 2017; 199: 92
• 13 Uneyama K.; Chemistry of Trifluoroacetimidoyl Halides as Versatile Fluorine-containing Building Blocks; TCIMAIL, 2009, No. 137.
• 14 Kobayashi M. Sadamune K. Mizukami H. Uneyama K. J. Org. Chem. 1994; 59: 1909
• 15 Lopez SE. Reese G. Robert JG. Ion G. William RD. J. Fluorine Chem. 2017; 193: 118
• 16 Li CL. Zhang XG. Tang RY. Zhong P. J. Org. Chem. 2010; 75: 7037
• 17 Dong X. Xu Y. Liu JJ. Hu Y. Xiao T. Zhou L. Chem. Eur. J. 2013; 19: 16928
• 18 Rahmani F. Darehkordi A. Notash B. J. Fluorine Chem. 2014; 166: 84
• 19 Rahmani F. Darehkordi A. Synlett 2017; 28: 1224
• 20 Uneyama K. Morimoto O. Yamashita F. Tetrahedron Lett. 1989; 30: 4821
• 21 Zhang Y. Yan W. Wang Y. Weng Z. Org. Lett. 2017; 19: 5478
• 22 CCDC 1048265 (2a) contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures; structural parameters for 2a: C₁₁H₅ClF₃N₃, M _r = 271.63, monoclinic system, space group P2₁, a = 7.5522(15) Å, b = 5.2370(10) Å, c = 14.730(3) Å, V = 564.29(19) ų, Z = 2.