Acetic Acid → 2-Cyano-3-(4-methylphenyl)prop-2-enoic acid

反応式

[C:1]1([CH3:9])[C:2](C=O)=[CH:3][CH:4]=[CH:5][CH:6]=1.[C:10]([CH2:12][C:13]([OH:15])=[O:14])#[N:11].[C:16](O)(=O)C.C([O-])(=O)C.[NH4+]>C(O)C>[C:10]([C:12](=[CH:9][C:1]1[CH:6]=[CH:5][C:4]([CH3:16])=[CH:3][CH:2]=1)[C:13]([OH:15])=[O:14])#[N:11]

参加物

実験手順

Tolualdehyde (400 g), cyanoacetic acid (311 g), acetic acid (60 ml) and ammonium acetate (25.6 g) were refluxed in ethyl alcohol (1.6 l) for 4 hours with heating. After the reaction, the mixture was concentrated to 600 ml by removing ethyl alcohol under a reduced pressure, followed by pouring into 1 liter of ice water to separate crystals. The separated crystals were collected by suction filtration and recrystallized from 2 liters of ethyl alcohol to obtain 560 g of 2-cyano-3-(4-methylphenyl)acrylic acid which melted at 210° to 215° C. The resulting compound (320 g) and thionyl chloride (252 g) were dissolved in acetonitrile (200 ml) with heating for 1 hour. After the reaction, the acetonitrile and the thionyl chloride were distilled off under a reduced pressure, and the resulting solid was added to a solution consisting of hydroxyethyl methacrylate (244.8 g), pyridine (149 g) and acetonitrile (2 l). The reaction was carried out for 2 hours while keeping the reaction temperature below 40° C. After the reaction, the reaction solution was poured into ice water to separate crystals, and the resulting crystals were recrystallized from ethyl alcohol (3 l) to obtain 360 g of the desired compound which melted at 74° to 75° C.