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Synlett 2014; 25(2): 193-196
DOI: 10.1055/s-0033-1340088
DOI: 10.1055/s-0033-1340088
letter
Synthesis of 2,4,6-Triarylpyridines Using ZrOCl2 under Solvent-Free Conditions
Weitere Informationen
Publikationsverlauf
Received: 03. August 2013
Accepted after revision: 06. Oktober 2013
Publikationsdatum:
13. November 2013 (online)
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Abstract
An efficient procedure for the synthesis of 2,4,6-triarylpyridines (Kröhnke pyridines) by the one-pot multicomponent condensation of aldehydes (1 equiv) with acetophenones (2 equiv) and ammonium acetate (1.2 equiv) in the presence of catalytic amounts of oxozirconium(IV) chloride (ZrOCl2) under solvent-free conditions is described. In this work, four products have been reported for the first time. Easy work-up, simple methodology, clean reaction and reusability of the catalyst are some advantages of this work.
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References and Notes
- 1 Zhu J, Bienayme H. Multicomponent Reactions . Wiley-VCH; Weinheim: 2005
- 2 Hasaninejad A, Zare A, Shekouhi M, Ameri Rad J. J. Comb. Chem. 2010; 12: 844
- 3 Zolfigol MA, Khazaei A, Moosavi-Zare AR, Zare A, Khakyzadeh V. Appl. Catal., A 2011; 400: 70
- 4 Khazaei A, Zolfigol MA, Moosavi-Zare AR, Zare A, Parhami A, Khalafi-Nezhad A. Appl. Catal., A 2010; 386: 179
- 5 Khazaei A, Zolfigol MA, Moosavi-Zare AR, Zare A, Khojasteh M, Asgari Z, Khakyzadeh V, Khalafi-Nezhad A. Catal. Commun. 2012; 20: 54
- 6 Balasubramanian M, Keay JG In Comprehensive Heterocyclic Chemistry II . Vol.5. Katritzky AR, Rees CW, Scriven EV. F. Pergamon Press; London: 1996: 245
- 7 Constable EC, Housecroft CE, Neuburger M, Phillips D, Raithby PR, Schofield E, Sparr E, Tocher DA, Zehnder M, Zimmermann Y. J. Chem. Soc., Dalton Trans. 2000; 2219
- 8 Kim BY, Ahn JB, Lee HW, Kang SK, Lee JH, Shin JS, Ahn SK, Hong CI, Yoon SS. Eur. J. Med. Chem. 2004; 39: 433
- 9 Enyedy IJ, Sakmuri S, Zaman WA, Johnson KM, Wang S. Bioorg. Med. Chem. Lett. 2004; 13: 513
- 10 Pillai AD, Rathod PD, Franklin PX, Patel M, Nivarsarkar M, Vasu KK, Padh H, Sudarsanam V. Biochem. Biophys. Res. Commun. 2003; 301: 183
- 11 Klimesova V, Svoboda M, Waisser K, Pour M, Kaustova J. Farmaco 1999; 54: 666
- 12 Nagarapu L, Peddiraju AR, Apuri S. Catal. Commun. 2007; 8: 1973
- 13 Potts KT, Cipullo MJ, Ralli P, Theodoridis G. J. Am. Chem. Soc. 1981; 103: 3584
- 14 Kobayashi T, Kakiuchi H, Kato H. Bull. Chem. Soc. Jpn. 1991; 64: 392
- 15 Palacios F, de Retana AM. O, Oyarzabal J. Tetrahedron Lett. 1996; 37: 4577
- 16 Cave GW. V, Raston CL. Chem. Commun. 2000; 2199
- 17 Tu S, Li T, Shi F, Fang F, Zhu S, Wei X, Zong Z. Chem. Lett. 2005; 34: 732
- 18 Adib M, Tahermansouri H, Koloogani SA, Mohammadi B, Bijanzadeh HR. Tetrahedron Lett. 2006; 47: 5957
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Synthesis of 2,4,6-Triarylpyridines with ZrOCl2; General Procedure: A mixture of aldehyde (1 mmol), acetophenone (2 mmol), NH4OAc (1.2 mmol) and ZrOCl2 (15 mol%) was stirred in an oil-bath (100 °C) for the appropriate time (Figure 1). After completion of the reaction (progress monitored by TLC), hot ethyl acetate was added to the mixture, which was then centrifuged for 10 min and the insoluble catalyst was filtered off. The filtrate was evaporated, and the residue was purified by preparative plate chromatography on silica (n-hexane–EtOAc, 5:1) to give the pure product.
Analytical data for novel compounds:
4-(2-Chlorophenyl)-2,6-bis(4-methoxyphenyl)pyridine (1): 1H NMR (400 MHz, CDCl3): δ = 8.18 (s, 1 H), 8.13 (s, 1 H), 8.03 (d, J = 8.8 Hz, 4 H), 7.52 (s, 1 H), 7.30–7.46 (m, 3 H), 6.98 (d, J = 8.7 Hz, 4 H), 3.88 (s, 6 H). 13C NMR (100 MHz, CDCl3): δ = 163.8, 140.1, 135.3, 133.4, 130.9, 130.8, 130.2, 127.7, 127.0, 124.7, 113.9, 55.4. IR (KBr): 3081, 2962, 1594, 1519, 1346, 855 cm–1. MS: m/z = 401 [M]+. 4-(4-Chlorophenyl)-2,6-bis(4-nitrophenyl)pyridine (5): 1H NMR (400 MHz, CDCl3): δ = 7.41 (s, 4 H), 7.28 (s, 4 H), 6.98–7.06 (m, 2 H), 6.85 (s, 1 H), 6.80 (s, 1 H), 6.58 (d, J = 10 Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ = 150.3, 148.8, 144.5, 142.6, 136.0, 133.8, 131.3, 130.0, 129.4, 128.1, 124.3, 122.9. IR (KBr): 3055, 1664, 1606, 1587, 1492, 716 cm–1. MS: m/z = 431 [M]+. 2,4,6-Tris(4-chlorophenyl)pyridine (6): 1H NMR (400 MHz, CDCl3): δ = 7.14–7.23 (m, 4 H), 6.96–7.03 (m, 3 H), 6.80 (s, 1 H), 6.75 (s, 1 H), 6.58–6.69 (m, 3 H), 6.56 (d, J = 9.6 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 150.3, 148.8, 144.5, 142.6, 136.0, 133.8, 131.3, 130.4, 130.0, 129.4, 128.1, 124.3, 122.9. IR (KBr): 3087, 1656, 1603, 1488, 742 cm–1. MS: m/z = 410 [M]+. 2,6-Bis(4-chlorophenyl)-4-(4-nitrophenyl)pyridine (10): 1H NMR (400 MHz, CDCl3): δ = 8.39–8.41 (m, 1 H), 8.38 (d, J = 2.4 Hz, 1 H), 8.14–8.15 (m, 2 H), 8.11–8.13 (m, 2 H), 7.87–7.90 (m, 2 H), 7.85 (s, 2 H), 7.50–7.51 (m, 2 H), 7.48–7.49 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ = 156.8, 148.2, 135.7, 129.7, 129.5, 129.0, 128.4, 128.3, 128.2, 127.9, 124.4, 124.0, 117.0. IR (KBr): 3069, 1596, 1548, 1428, 1347, 827 cm–1. MS: m/z = 421 [M]+ .