Hexanenitrile

Application

Acetonitriles belong to the nitrile class of compounds and are important precursor compounds for many products, such as polyamides, pigments and dyes, pharmaceuticals, and agrochemicals. The application of nitrile compounds in the fragrance industry has recently developed rapidly, offering advantages such as long-lasting aroma, stable performance, and non-irritating properties, making them a major class of novel synthetic fragrances. The cyano group in nitrile compounds is easily converted into other functional groups, such as carboxylic acids, amides, aldehydes, and primary amines, and is widely used in the total synthesis research of natural products.

Chemical Properties

Colorless liquid. Melting point -80.3℃, boiling point 163.6℃, 47.2℃ (1.33kPa), relative density 0.8051 (20/4℃), refractive index 1.4068, flash point 43℃. Soluble in ethanol, ether, very slightly soluble in water.

Synthesis Reference(s)

Canadian Journal of Chemistry, 58, p. 2271, 1980 DOI: 10.1139/v80-365
The Journal of Organic Chemistry, 46, p. 4111, 1981 DOI: 10.1021/jo00334a001

Synthesis

Protected by nitrogen, in a 100 mL three-necked flask equipped with a thermometer, anhydrous acetonitrile (10 mL), dimethylsulfoxide (0.03 mmol, 2.5 mg, 0.01 equiv), n-hexanamide (3 mmol, 345 mg, 1.0 equiv), and triethylamine (1.04 mL, 7.5 mmol, 2.5 equiv) were added sequentially, and the temperature was set at room temperature A solution of oxalyl chloride (0.31 mL, 3.6 mmol, 1.2equiv) in anhydrous acetonitrile (5 mL) was slowly added dropwise with a constant pressure dropping funnel. After dropwise addition, continue stirring for 40 min, filtration, filtrate spin dry, add distilled water (15 mL), extract with ethyl acetate (3x 10 mL), combine the organic phases, washed with saturated aqueous sodium chloride solution (30 mL), anhydrous sodium sulfate dry. Filtration, spinning to remove the solvent to obtain the crude product, purified by column chromatography separation (petroleum ether / ethyl acetate = 9:1), to obtain 233 mg of hexanenitrile, the yield was 80%.

Purification Methods

Wash the nitrile twice with half-volumes of conc HCl, then with saturated aqueous NaHCO3, dry over MgSO4, filter and distil it. [Beilstein 2 H 324, 2 I 141, 2 II 286, 2 III 733, 2 IV 930.]