α-シアノアクリル酸エステルのアクリル酸メチルを出発原料とする製造方法について

α-シアノアクリル酸エステルの研究(第8報)

抄録

Methyl acrylate is cony erted quantitatively to methyl α, β-dichloropropionate by chlorination at room temperature in the presence of 4 mol-% DMF as the catalyst.
Methyl α, β-dichloropropionate is then methoxylated by reaction with an equimolar amount of Na-methylate in one hour without a catalyst at -20 to -35°C in mately 90% yield.
Methyl α-chloro-β-methoxypropionate is let to react with an equimolar amount of potassiumcyanide at 30°C in a homogeneous solution. The yield is about 95%, but part of the produced α-cyano-β-methoxy propionate changes into poly-α-cyanoacrylate. Therefore, the true cyanation yield appears to be between 60 to 70%.
Then crude methyl α-cyano-β-methoxypropionate is converted to methyl α-cyanoacrylate at rather high temperature, since the reaction involves the degradation of poly-α-cyanoacrylate. The reaction is carried out at 170250°C/39mmHg in a SO₂ stream in the presence of 3 mole-% sulfuric acid and 100 g of DOP. Approximately 80% yield is attained.