RSS-Feed abonnieren
Bitte kopieren Sie die angezeigte URL und fügen sie dann in Ihren RSS-Reader ein.
https://www.thieme-connect.de/rss/thieme/de/10.1055-s-00000083.xml
Synlett 2014; 25(08): 1111-1115
DOI: 10.1055/s-0033-1340979
DOI: 10.1055/s-0033-1340979
letter
Ligand-Free Copper(I) Oxide Nanoparticle Catalyzed Three-Component Synthesis of 2H-Indazole Derivatives from 2-Halobenzaldehydes, Amines and Sodium Azide in Polyethylene Glycol as a Green Solvent
Weitere Informationen
Publikationsverlauf
Received: 15. Januar 2014
Accepted after revision: 19. Februar 2014
Publikationsdatum:
24. März 2014 (online)
![](https://www.thieme-connect.de/media/synlett/201408/lookinside/thumbnails/10.1055-s-0033-1340979-1.jpg)
Abstract
An efficient synthesis of 2H-indazole derivatives based on the one-pot three-component reaction of 2-chloro- and 2-bromobenzaldehydes, primary amines and sodium azide is described. The reaction is catalyzed by copper(I) oxide nanoparticles (Cu2O-NP) under ligand-free conditions in polyethylene glycol (PEG 300) as a green solvent.
Key words
Cu2O nanoparticle - 2H-indazole derivatives - ligand-free - three-component - green solventSupporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
References and Notes
- 1 Han W, Pelletier JC, Hodge CN. Bioorg. Med. Chem. Lett. 1998; 8: 3615
- 2 Picciola G, Ravenna F, Carenini G, Gentili P, Riva M. Farmaco Ed. Sci. 1981; 36: 1037
- 3a Qian S, Cao J, Yan Y, Sun M, Zhu H, Hu Y, He Q, Yang B. Mol. Cell. Biochem. 2010; 345: 13
- 3b Baraldi PG, Balboni G, Pavani MG, Spalluto G, Tabrizi MA, De Clercq E, Balzarini J, Bando T, Sugiyama H, Romagnoli R. J. Med. Chem. 2001; 44: 2536
- 4a Cerecetto H, Gerpe A, Gonzalez M, Aran VJ, Ochoa de Ocariz C. Mini-Rev. Med. Chem. 2005; 5: 869
- 4b De Angelis M, Stossi F, Carlson K, Katzenellenbogen B, Katzenellenbogen J. J. Med. Chem. 2005; 48: 1132
- 4c Li X, Chu S, Feher VA, Khalili M, Nie Z, Margosiak S, Nikulin V, Levin J, Sparankle KG, Fedder ME, Almassy R, Appelt K, Yager KM. J. Med. Chem. 2003; 46: 5663
- 5 Lee FY, Lien JC, Huang LJ, Huang TM, Tsai SC, Teng CM, Wu CC, Cheng FC, Kuo SC. J. Med. Chem. 2001; 44: 3746
- 6a Chen CJ, Hsu MH, Huang LJ, Yamori T, Chung FG, Lee FY, Teng CM, Kuo SC. Biochem. Pharm. 2008; 75: 360
- 6b Yakaiah T, Lingaiah BP. V, Narsaiah B, Shireesha B, Kumar BA, Gururaj S, Parthasarathy T, Sridhar B. Bioorg. Med. Chem. Lett. 2007; 17: 3445
- 7 Cekaviciute M, Simokaitiene J, Grazulevicius JV, Buika G, Jankauskas V. Dyes Pigments 2011; 92: 654
- 8a Mills AD, Maloney P, Hassanein E, Haddadin MJ, Kurth MJ. J. Comb. Chem. 2007; 9: 171
- 8b Grimmet MR, Barton SD, Ollis WD. Comprehensive Organic Chemistry . Pergamon Press; New York: 1997. Vol. 4 357
- 8c Stadlbauer W. Science of Synthesis: Houben-Weyl Methods of Molecular Transformations. Vol. 12. Neier R. Thieme; Stuttgart: 2002: 227
- 8d Huang LJ, Shih ML, Chen HS, Pan SL, Teng CM, Lee FY, Kuo SC. Bioorg. Med. Chem. 2006; 14: 528
- 9a Wu C, Fang Y, Larock RC, Shi F. Org. Lett. 2010; 12: 2234
- 9b Lam PY. S, Clark CG, Saubern S, Adams J, Winters MP, Chan DM. T, Combs A. Tetrahedron Lett. 1998; 39: 2941
- 9c Lopez-Alvarado P, Avendano C, Menendez JC. J. Org. Chem. 1995; 60: 5678
- 9d Fedorov AY, Finet J.-P. Tetrahedron Lett. 1999; 40: 2747
- 9e Claramunt RM, Elguero J, Garceran R. Heterocycles 1985; 23: 2895
- 9f Slade DJ, Pelz NF, Bodnar W, Lampe JW, Watson PS. J. Org. Chem. 2009; 74: 6331
- 10a Kumar MR, Park A, Park N, Lee S. Org. Lett. 2011; 13: 3542
- 10b Halland N, Nazare M, Rkyek O, Alonso J, Urmann M, Lindenschmidt A. Angew. Chem. Int. Ed. 2009; 48: 6879
- 10c Stokes BJ, Vogel CV, Urnezis LK, Pan M, Driver TG. Org. Lett. 2010; 12: 2884
- 10d Haag B, Peng Z, Knochel P. Org. Lett. 2009; 11: 4270
- 10e Lee KY, Gowrisankar S, Kim JN. Tetrahedron Lett. 2005; 46: 5387
- 10f Song JJ, Yee NK. Org. Lett. 2000; 2: 519
- 10g Prasad AN, Srinivas R, Reddy BM. Catal. Sci. Technol. 2013; 3: 654
- 11 Tang BX, Wang F, Li JH, Xie YX, Zhang MB. J. Org. Chem. 2007; 72: 6294
- 12 Xu HJ, Zhao XY, Deng J, Fu Y, Feng YS. Tetrahedron Lett. 2009; 50: 434
- 13 Bao W, Liu Y, Lv X, Qian W. Org. Lett. 2008; 10: 3899
- 14 Shen G, Lv X, Qian W, Bao W. Tetrahedron Lett. 2008; 49: 4556
- 15 Qu Y, Pan L, Wu Z, Zhou X. Tetrahedron 2013; 69: 1717
- 16 Wang JH, Pan CW, Li YT, Meng FF, Zhou HG, Yang C, Zhang Q, Bai CG, Chen Y. Tetrahedron Lett. 2013; 54: 3406
- 17 Correa A, Bolm C. Adv. Synth. Catal. 2007; 349: 2673
- 18a Sharghi H, Aberi M, Doroodmand MM. Adv. Synth. Catal. 2008; 350: 2380
- 18b Sharghi H, Beyzavi MH, Doroodmand MM. Eur. J. Org. Chem. 2008; 4126
- 18c Sharghi H, Aberi M, Doroodmand MM. J. Iran Chem. Soc. 2012; 9: 189
- 18d Sharghi H, Beyzavi MH, Safavi A, Doroodmand MM, Khalifeh R. Adv. Synth. Catal. 2009; 351: 2391
- 18e Sharghi H, Khalifeh R, Doroodmand MM. Adv. Synth. Catal. 2009; 351: 207
- 18f Sharghi H, Khalifeh R, Mansouri SG, Aberi M, Eskandari MM. Catal Lett. 2011; 141: 1845
- 18g Sharghi H, Khoshnood A, Doroodmand MM, Khalifeh R. J. Iran. Chem. Soc. 2012; 9: 231
- 18h Sharghi H, Ebrahimpourmoghaddam S, Doroodmand MM. J. Organomet. Chem. 2013; 738: 41
- 18i Sharghi H, Ebrahimpourmoghaddam S, Doroodmand MM. Tetrahedron 2013; 69: 4708
- 18j Khalifeh R, Sharghi H, Rashidi Z. Heteroat. Chem. 2013; 24: 372
- 19 Colacino E, Villebrun L, Martinez J, Lamaty F. Tetrahedron 2010; 66: 3730
-
20
General Procedure: To a mixture of 2-bromobenzaldehyde (1.0 mmol) or 2-chlorobenzaldehyde (1.0 mmol), amine (1.1 mmol) and NaN3 (2.0 mmol) in polyethylene glycol (PEG 300; 3.0 mL) was added the Cu2O-NP catalyst (5 mol%) and the mixture was stirred at 120 °C for 2-bromobenzaldehyde or at 170 °C for 2-chlorobenzaldehyde. The progress of the reaction was monitored by TLC using n-hexane–EtOAc (10:1). After completion of the reaction, the reaction mixture was cooled to r.t., the mixture was poured into EtOAc (30.0 mL) and washed with deionized H2O (3 × 20.0 mL) and brine (3 × 20.0 mL). The organic layer was dried (CaCl2), filtered and evaporated in vacuo to give the crude product, which was purified by silica gel column chromatography employing n-hexane–EtOAc (10:1) as eluent.
Typical Characterization Data for Some Compounds:
2-p-Tolyl-2H-indazole (4a): pale yellow solid; mp 98–100 °C. IR (KBr): 748, 786, 817, 1041, 1118, 1195, 1380, 1450, 1519, 1620, 2947, 3039, 3129 cm–1. 1H NMR (250 MHz, CDCl3): δ = 2.43 (s, 3 H), 7.08–7.14 (m, 1 H), 7.30–7.35 (m, 3 H), 7.71 (d, J = 8.5 Hz, 1 H), 7.77–7.82 (m, 3 H), 8.37 (d, J = 0.7 Hz, 1 H). 13C NMR (62.9 MHz, CDCl3): δ = 21.0, 117.8, 120.3, 120.4, 120.8, 122.3, 122.7, 126.7, 130.1, 137.9, 138.2, 149.6. MS: m/z (%) = 210 (9.0) [M+ + 2], 209 (89.6) [M+ + 1], 208 (100.0) [M+], 165 (51.4), 91 (61.1), 65 (68.1). Anal. Calcd for C14H12N2 (208.262): C, 80.74; H, 5.81; N, 13.45. Found: C, 80.70; H, 5.87; N, 13.51. 4-(2H-Indazol-2-yl)-N,N-dimethylaniline (4f): orange solid; mp 185–187 °C. IR (KBr): 732, 779, 817, 941, 1049, 1141, 1195, 1226, 1350, 1434, 1519, 1596, 2923, 3055 cm–1. 1H NMR (250 MHz, CDCl3): δ = 3.02 (s, 6 H), 6.80 (d, J = 9.0 Hz, 2 H), 7.07–7.13 (m, 1 H), 7.27–7.33 (m, 1 H), 7.68–7.75 (m, 3 H), 7.79 (d, J = 8.5 Hz, 1 H), 8.29 (s, 1 H). 13C NMR (62.9 MHz, CDCl3): δ = 40.5, 111.7, 112.4, 117.6, 119.9, 120.2, 121.9, 122.1, 122.6, 124.0, 126.1, 130.4, 149.3, 150.1. MS: m/z (%) = 239 (13.7) [M+ + 2], 238 (73.4) [M+ + 1], 237 (100.0) [M+], 208 (47.5), 165 (32.0), 118 (21.3), 69 (38.2). Anal. Calcd for C15H15N2 (237.304): C, 75.92; H, 6.37; N, 17.71. Found: C, 75.97; H, 6.48; N, 17.82. 2-(4-Chlorophenyl)-2H-indazole (4h): white solid; mp 139–141 °C. IR (KBr): 748, 817, 948, 1002, 1087, 1195, 1380, 1419, 1488, 15.21, 1627, 3062, 3132 cm–1. 1H NMR (250 MHz, CDCl3): δ = 7.09–7.15 (m, 1 H), 7.30–7.36 (m, 1 H), 7.47–7.50 (m, 2 H), 7.69 (d, J = 8.5 Hz, 1 H), 7.78 (d, J = 8.7 Hz, 1 H), 7.83–7.86 (m, 2 H), 8.36 (s, 1 H). 13C NMR (62.9 MHz, CDCl3): δ = 117.9, 120.2, 120.4, 121.9, 122.7, 122.9, 127.1, 129.6, 133.5, 138.9, 149.9. MS: m/z (%) = 230 (35.1) [M+ + 2], 229 (79.8) [M+ + 1], 228 (100.0) [M+], 193 (57.4), 166 (77.7), 139 (24.5), 111 (51.1), 75 (60.6). Anal. Calcd for C13H9ClN2 (228.681): C, 68.28; H, 3.97; N, 12.25. Found: C, 68.22; H, 4.07; N, 12.32.