Monohydrocyanation of Symmetrical Azines Using Potassium Hexacyanoferrate(II) as an Environmentally Friendly Cyanide Source

Abstract

The monohydrocyanation of symmetrical azines to synthesize α-hydrazinonitriles using potassium hexacyanoferrate(II) as cyanide source and benzoyl chloride as a promoter under catalyst-free conditions is described. The advantages of this protocol are the environmentally friendly cyanide source, high yield, and simple work-up procedure.

Key words

green chemistry - hydrocyanation - nucleophilic addition - synthetic methods - azines

• References and Notes

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• 19 Monohydrocyanation of Azines; General Procedure: A mixture of K₄[Fe(CN)₆] (0.2 mmol) and benzoyl chloride (1.2 mmol) was heated at 160 °C for 3 h. After the reaction system was cooled to room temperature, azine (1 mmol) in methanol (20 mL) was added. The resulting mixture was further stirred at 60 °C for the appropriate time indicated in Table 2. After completion of the reaction, monitored by TLC, the resulting mixture was filtered to remove the solids, the liquor was concentrated, and the residue was subjected to alkaline Al₂O₃ column chromatography (PE–EtOAc, 30:1) to give the pure product. The analytical data for representative products are given. (E)-2-(2-Benzylidenehydrazinyl)-2-phenylacetonitrile (2a): White solid; mp 100–102 °C. IR (KBr): 3241 (NH), 2226 (CN) cm^–1. ¹H NMR (CDCl₃, 400 MHz): δ = 7.77 (s, 1 H, CH), 7.60–7.63 (m, 4 H, ArH), 7.44–7.46 (m, 3 H, ArH), 7.36–7.38 (m, 3 H, ArH), 5.53 (s, 1 H, CH). ¹³C NMR (CDCl₃, 100 MHz): δ = 143.4, 134.2, 132.6, 129.5, 129.4, 129.1, 128.6, 127.7, 126.7, 118.5, 55.8 ppm. (Z)-3,4,5,6-Tetrahydro-2H-1,2-diazepine-3-carbonitrile (2m): White solid; mp 240–242 °C. IR (KBr): 3176 (NH), 2226 (CN) cm^–1. ¹H NMR (CDCl₃, 400 MHz): δ = 4.04–4.06 (m, 1 H, CH), 3.58–3.60 (m, 1 H, CH), 2.97 (s, 1 H, NH), 1.69–1.99 (m, 6 H, CH₂). ¹³C NMR (CDCl₃, 100 MHz,): δ = 115.9, 75.2, 53.8, 28.6, 28.0, 19.4.