Synlett 2016; 27(03): 417-421
DOI: 10.1055/s-0035-1560365
letter
© Georg Thieme Verlag Stuttgart · New York

An Efficient Synthesis of 2,4,6-Triarylpyridines by Use of Benzyl Halides under Neat Conditions

Mehdi Adib*
a   School of Chemistry, College of Science, University of Tehran, P. O. Box 14155-6455 Tehran, Iran   Email: madib@khayam.ut.ac.ir
,
Neda Ayashi
a   School of Chemistry, College of Science, University of Tehran, P. O. Box 14155-6455 Tehran, Iran   Email: madib@khayam.ut.ac.ir
,
Peiman Mirzaei
b   Department of Chemistry, Shahid Beheshti University, Tehran, Iran
› Author Affiliations
Further Information

Publication History

Received: 14 August 2015

Accepted after revision: 04 October 2015

Publication Date:
24 November 2015 (online)


Abstract

An efficient synthesis of 2,4,6-triarylpyridines is described. Heating a mixture of an acetophenone, a benzyl halide, and ammonium acetate under neat conditions afforded the corresponding Kröhnke pyridines in excellent yields.

 
  • References and Notes

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  • 17 General Procedure for the Preparation of 2,4,6-Triarylpyridines 3a–r, Exemplified with Compound 3a A mixture of acetophenone (1 mmol), benzyl chloride (2 mmol), and NH4OAc (3 mmol) in a 5 mL round-bottomed flask was magnetically stirred at 150 °C for 8 h. Progress of the reaction was followed by TLC monitoring. The reaction mixture was cooled to ambient temperature, H2O (2.5 mL) was added, and the product was extracted into CH2Cl2 (2 × 2.5 mL). The combined organic phases were dried over Na2SO4, filtered, the solvent was removed, and the residue was purified by crystallization from absolute EtOH. TAP 3b,c,km were purified by column chromatography using n-hexane–EtOAc (6:1) as eluent. The solvent was removed, and the solid residue was recrystallized from absolute EtOH. 2,4,6-Triphenylpyridine (3a) Yield 0.116 g (97%, in respect to acetophenone); colorless crystals; mp 135–136 °C (136–137 °C).18a 1H NMR (500.1 MHz, CDCl3): δ = 7.40–7.60 (m, 9 H, 9 × CH), 7.78 (d, J = 8.0 Hz, 2 H, 2 × CH), 7.92 (s, 2 H, 2 × CH), 8.23 (d, J = 8.0 Hz, 4 H, 4 × CH). 13C NMR (125.8 MHz, CDCl3): δ = 117.2 (CH), 127.2 (CH), 127.3 (CH), 128.8 (CH), 129.0 (C), 129.1 (CH), 129.2 (CH), 139.1 (C), 139.6 (CH), 150.2 (C), 157.5 (C). 4-(4-Methoxyphenyl)-2,6-diphenylpyridine (3c) Yield 0.104 g (87%, in respect to acetophenone); colorless crystals; mp 100–101 °C (99–100 °C).18a 1H NMR (500.1 MHz, CDCl3): δ = 3.87 (s, 3 H, OCH3), 7.04 (d, J = 8.7 Hz, 2 H, 2 × CH), 7.44 (t, J = 7.2 Hz, 2 H, 2 × CH), 7.52 (t, J = 7.7 Hz, 4 H, 4 × CH), 7.70 (d, J = 8.7 Hz, 2 H, 2 × CH), 7.85 (s, 2 H, 2 × CH), 8.20 (d, J = 7.2 Hz, 4 H, 4 × CH). 13C NMR (125.8 MHz, CDCl3): δ = 55.4 (OCH3), 114.5 (CH), 116.6 (CH), 127.1 (CH), 128.3 (CH), 128.6 (CH), 129.0 (CH), 131.2 (C), 139.6 (C), 149.6 (C), 157.4 (C), 160.5 (C).
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