AgI-PEG400-KI Catalyzed Environmentally Benign Synthesis of Aroyl Cyanides Using Potassium Hexacyanoferrate(II) as the Cyanating Agent

Zheng Li; Shengyi Shi; Jingya Yang

doi:10.1055/s-2006-950407

LETTER

AgI-PEG400-KI Catalyzed Environmentally Benign Synthesis of Aroyl Cyanides Using Potassium Hexacyanoferrate(II) as the Cyanating Agent

Zheng Li*, Shengyi Shi, Jingya Yang
Gansu Key Laboratory of Polymer Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu, 730070, P. R. of China
Fax: +86(931)7971989; e-Mail: lizheng@nwnu.edu.cn;

Abstract

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Abstract

A practical cyanation of aroyl chlorides with 0.2 equivalent of non-toxic cyanide source, K₄[Fe(CN)₆], 3 mol% AgI, 4 mol% PEG-400, and 3 mol% KI as the catalyst system is described. The reactions were performed in DMF at room temperature and provided the corresponding aroyl cyanides in 64-89% yield, typically in less than ten hours.

Key words

green chemistry - catalysis - synthesis - phase-transfer catalysis - cyanation

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References and Notes

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General Procedure: A mixture of AgI (0.1 g, 0.45 mmol), PEG400 (0.24 g, 0.6 mmol), KI (0.08 g, 0.45 mmol), and K₄[Fe(CN)₆] (1.15 g, 3 mmol) (dried at 80 °C under vacuum for 24 h and finely powdered prior to use) in anhyd DMF (10 mL) was first stirred for 10 min, then aroyl chloride (15 mmol) was added. The mixture was stirred for the appropriate time indicated in Table [2] at r.t. The progress of the reaction was monitored by TLC (PE-EtOAc, 5:1). Then CH₂Cl₂ (20 mL) was added. The suspension was filtered to remove the solid, the filtrate was washed with cold H₂O (3 × 30 mL), and dried over anhyd MgSO₄. Then the solvent was removed by distillation and the residue was crystallized from hexane to give the product. 2-Chlorobenzoyl cyanide: IR (KBr): 2089 (C≡N), 1776 cm^-1 (C=O). ¹H NMR (CDCl₃, 400 MHz): δ = 7.29-7.81 (m, 4 H, Ph). Anal. Calcd for C₈H₄ClNO: C, 58.03; H, 2.44; N, 8.46. Found: C, 57.91; H, 2.50; N, 8.39. 3-Chlorobenzoyl cyanide: IR (KBr): 1964 (C≡N), 1793 cm^-1 (C=O). ¹H NMR (CDCl₃, 400 MHz): δ = 7.22-7.78 (m, 4 H, Ph). Anal. Calcd for C₈H₄ClNO: C, 58.03; H, 2.44; N, 8.46. Found: C, 58.11; H, 2.49; N, 8.53. 2-Furoyl cyanide: IR (KBr): 2067 (C≡N), 1758 cm^-1 (C=O). ¹H NMR (CDCl₃, 400 MHz): δ = 6.70-7.69 (m, 3 H, Furan). Anal. Calcd. for C₆H₃NO₂: C, 59.51; H, 2.50; N, 11.57. Found: C, 59.70; H, 2.43; N, 11.49. 2-Thiophenecarbonyl cyanide: IR (KBr): 2052 (C≡N), 1766 (C=O). ¹H NMR (CDCl₃, 400 MHz): δ = 7.10-7.71 (m, 3 H, Thiophene). Anal. Calcd for C₆H₃NOS: C, 52.54; H, 2.20; N, 11.66. Found: C, 52.42; H, 2.30; N, 11.72.