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Synlett 2016; 27(17): 2455-2458
DOI: 10.1055/s-0035-1562464
letter
© Georg Thieme Verlag Stuttgart · New York

A Convenient Approach for the Synthesis of 1,3-Diphenyl-1H-pyrazole-5-carbonitrile

Abdolali Alizadeh*
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran   Email: aalizadeh@modares.ac.ir   Email: abdol_alizad@yahoo.com
,
Atefeh Roosta
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran   Email: aalizadeh@modares.ac.ir   Email: abdol_alizad@yahoo.com
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Further Information

Publication History

Received: 03 April 2016

Accepted after revision: 03 June 2016

Publication Date:
14 July 2016 (online)

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Abstract

An operationally simple and efficient protocol for the synthesis of unsymmetrical substituted 1,3-pyrazole derivatives has been developed via a three-component coupling reaction involving hydrazonoyl chloride, 4-oxo-4H-chromene-3-carbaldehyde, and hydroxylamine hydrochloride.

Key words

hydrazonoyl chloride - hydroxylamine hydrochloride - 4-oxo-4H-chromene-3-carbaldehyde - pyrazole - multicomponent reaction
 

  • References and Notes

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  • 25 General Procedure A mixture of 4-oxo-4H-chromene-3-carbaldehyde (1 mmol) and hydroxylamine hydrochloride (1 mmol) in EtOH (2 mL) was stirred at reflux for 12 h. Then hydrazonoyl chloride 1 (1 mmol) was added to the mixture followed by the dropwise addition of Et3N (1 mmol). The mixture was stirred at room temperature until completion (2 h), monitoring by TLC. The solvent was removed, and the residue purified by column chromatography (hexane–EtOAc, 1:10) to afford the pure products 2a–g. Representative Analytical Data 1,3-Diphenyl-1H-pyrazole-5-carbonitrile (2a) White powder, mp 135–137 °C, 0.20 g, yield 82%. IR (KBr): νmax = 3131 (CH), 2227 (CN), 1593 (C=N), 1496 (Ar) cm–1. Anal. Calcd (%) for C16H11N3 (245.28): C, 78.35; H, 4.52; N, 17.13. Found: C, 78.39; H, 4.57; N, 17.10. 1H NMR (300 MHz, CDCl3): δ = 7.32 (1 H, s, CH4), 7.42 (2 H, t, 3 J HH = 6.9 Hz, 2 CH para of 2 Ph), 7.48 (2 H, t, 3 J HH = 8.7 Hz, 2 CH meta of Ph), 7.58 (2 H, t, 3 J HH = 7.5 Hz, 2 CH meta of Ph), 7.81 (2 H, d, 3 J HH = 8.1 Hz, 2 CH ortho of Ph), 7.89 (2 H, d, 3 J HH = 7.8 Hz, 2 CH ortho of Ph). 13C NMR (75.0 MHz, CDCl3): δ = 111.07 (CCN), 113.08 (CH4), 114.97 (CN), 122.84 (2 CH ortho of Ph), 125.94 (2 CH ortho of Ph), 128.90 (CH para of 2 Ph), 128.94 (2 CH meta of Ph), 129.08 (CH para of Ph), 129.62 (2 CH meta of Ph), 131.08 (C ipso C3), 138.63 (C ipso N), 152.72 (C3). 3-(4-Chlorophenyl)-1-phenyl-1H-pyrazole-5-carbonitrile (2b) Cream powder, mp 150 °C, 0.22 g, yield 77%. IR (KBr): νmax = 3129 (CH), 2228 (CN), 1596 (C=N), 1601 and 1495 (Ar) cm–1. Anal. Calcd (%) for C16H10ClN3 (279.73): C, 68.70; H, 3.60; N, 15.02. Found: C, 68.77; H, 3.64; N, 15.06. 1H NMR (300 MHz, CDCl3): δ = 7.28 (1 H, s, CH4), 7.43 (2 H, d, 3 J HH = 8.5 Hz, 2 CH of Ar), 7.51 (1 H, t, 3 J HH = 7.2 Hz, CH para of Ph), 7.57 (2 H, t, 3 J HH = 7.9 Hz, 2 CH meta of Ph), 7.78 (2 H, d, 3 J HH = 7.4 Hz, 2 CH of Ar), 7.81 (2 H, d, 3 J HH = 7.4 Hz, 2 CH ortho of Ph). 13C NMR (75.46 MHz, CDCl3): δ = 111.07 (CCN), 113.06 (CH4), 115.31 (CN), 122.97 (2 CH ortho of Ph), 127.30 (2 CH of Ar), 129.21 (CH para of Ph), 129.30 (2 CH meta of Ph), 129.70 (C ipso C3), 129.79 (2 CH of Ar), 135.10 (C ipso Cl), 138.61 (C ipso N), 151.74 (C3). 3-(4-Methylphenyl)-1-phenyl-1H-pyrazole-5-carbonitrile (2d) White powder, mp 124–126 °C, 0.22 g, yield 85%. IR (KBr): νmax = 3131 (CH), 2228 (CN), 1593 (C=N), 1500 and 1430 (Ar) cm–1. Anal. Calcd (%) for C17H13N3 (259.31): C, 78.74; H, 5.05; N, 16.20. Found: C, 78.70; H, 5.09; N, 16.25. 1H NMR (300 MHz, CDCl3): δ = 2.42 (3 H, s, CH3), 7.28 (1 H, s, CH4), 7.283 (2 H, d, 3 J HH = 8.7 Hz, 2 CH of Ar), 7.50 (1 H, t, 3 J HH = 7.2 Hz, CH para of Ph), 7.57 (2 H, t, 3 J HH = 7.3 Hz, 2 CH meta of Ph), 7.78 (2 H, d, 3 J HH = 8.7 Hz, 2 CH of Ar), 7.81 (2 H, d, 3 J HH = 7.4 Hz, 2 CH ortho of Ar). 13C NMR (75.46 MHz, CDCl3): δ = 21.37 (CH3), 111.21 (CCN), 112.91 (CH4), 114.83 (CN), 122.81 (2 CH ortho of Ph), 125.83 (2 CH of Ar), 128.29 (C ipso C3), 128.83 (CH para of Ph), 129.59 (2 CH meta of Ph), 129.62 (2 CH of Ar), 138.68 (C ipso N), 139.08 (C ipso Me), 152.80 (C3).