Synlett 2014; 25(2): 193-196
DOI: 10.1055/s-0033-1340088
letter
© Georg Thieme Verlag Stuttgart · New York

Synthesis of 2,4,6-Triarylpyridines Using ZrOCl2 under Solvent-Free Condi­tions

Ahmad Reza Moosavi-Zare*
a   University of Sayyed Jamaleddin Asadabadi, Asadabad, 6541835583, Iran   Fax: +98(811)8257407   Email: moosavizare@yahoo.com
,
Mohammad Ali Zolfigol*
b   Faculty of Chemistry, Bu-Ali Sina University, Hamedan, 6517838683, Iran   Email: mzolfigol@yahoo.com
,
Shohreh Farahmand
b   Faculty of Chemistry, Bu-Ali Sina University, Hamedan, 6517838683, Iran   Email: mzolfigol@yahoo.com
,
Abdolkarim Zare
c   Department of Chemistry, Payame Noor University, Iran
,
Ali Reza Pourali
d   School of Chemistry, Damghan University, Damghan, Iran
,
Roya Ayazi-Nasrabadi
b   Faculty of Chemistry, Bu-Ali Sina University, Hamedan, 6517838683, Iran   Email: mzolfigol@yahoo.com
› Author Affiliations
Further Information

Publication History

Received: 03 August 2013

Accepted after revision: 06 October 2013

Publication Date:
13 November 2013 (online)


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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  • 19 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]+ .