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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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 H2 O (20 mL) and sat. aq Na2 SO3 (3 mL) at 0 °C, and was extracted with Et2 O (3 × 15 mL). The organic layer was washed with brine and dried over Na2 SO4 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 . 1 H 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 H2 O (20 mL) and sat. aq Na2 SO3 (3 mL) at 0 °C, and was extracted with Et2 O (3 × 15 mL). The organic layer was washed with brine and dried over Na2 SO4 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.
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All nitriles gave satisfactory spectroscopic data and were identified by comparison
with commercially available authentic materials.
