Oxidative Conversion of Primary Alcohols, and Primary, Secondary, and Tertiary Amines into the Corresponding Nitriles with 1,3-Diiodo-5,5-dimethylhydantoin in Aqueous NH₃

Abstract

Various primary alcohols, and primary, secondary, and tertiary amines were oxidatively and efficiently converted into the corresponding nitriles in good yields, by 1,3-diiodo-5,5-dimethylhydantoin (DIH) in aqueous ammonia (NH₃) at 60 °C.

Key words

primary alcohols - primary amines - secondary amines - tertiary amines - 1,3-diiodo-5,5-dimethylhydantoin - nitriles - aqueous ammonia

References and Notes

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8

Typical Experimental Procedure for Oxidative Conversion of Primary Alcohols into Nitriles:⁹ To a mixture of dodecanol (186.3 mg, 1 mmol) and aq NH₃ (3.0 mL, 45 mmol) was added DIH (731.9 mg, 2.0 mmol) at r.t. under an empty balloon. The obtained mixture was stirred at 60 °C. After 32 h at the same temperature, the reaction mixture was quenched with H₂O (20 mL) and sat. aq Na₂SO₃ (3 mL) at 0 °C, and was extracted with Et₂O (3 × 15 mL). The organic layer was washed with brine and dried over Na₂SO₄ to provide lauronitrile in 97% yield in an almost pure state. If necessary, the product was purified by column chromatography on silica gel (hexane-EtOAc, 4:1) to give pure lauronitrile in 97% yield as a colorless oil. IR (NaCl): 2250 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 0.88 (t, J = 7.0 Hz, 3 H), 1.29 (br, 14 H), 1.45 (quin, J = 7.1 Hz, 2 H), 1.66 (quin, J = 7.1 Hz, 2 H), 2.34 (t, J = 7.1 Hz, 2 H). The product was identified by comparison with the commercially available authentic compound.
Typical Experimental Procedure for Oxidative Conversion of Primary Amines into Nitriles:⁹ To a mixture of dodecylamine (185.4 mg, 1 mmol) and aq NH₃ (3.0 mL, 45 mmol) was added DIH (439.1 mg, 1.2 mmol) at r.t. under an empty balloon. The obtained mixture was stirred at 60 °C. After 6 h at the same temperature, the reaction mixture was quenched with H₂O (20 mL) and sat. aq Na₂SO₃ (3 mL) at 0 °C, and was extracted with Et₂O (3 × 15 mL). The organic layer was washed with brine and dried over Na₂SO₄ to provide lauronitrile in 88% yield in an almost pure state. If necessary, the product was purified by column chromatography on silica gel (hexane-EtOAc, 4:1) to give pure lauronitrile as a colorless oil.

9

All nitriles gave satisfactory spectroscopic data and were identified by comparison with commercially available authentic materials.