Pyrimidine誘導体の合成研究 (第9報)
2-Dialkoxymethyl-3-alkoxypropionitrile, 2-Dialkoxymethyl-acrylonitrile及び2-Alkoxymethylene-3-alkoxypropionitrileの相互変換について
1958 年 78 巻 6 号 p. 643-646
詳細
1958 年 78 巻 6 号 p. 643-646
Formation of 2-dialkoxymethyl-acrylonitrile, formed together with 2-alkoxymethylene-3-alkoxypropionitrile by the alkylation of 2-sodioformyl-3-alkoxypropionitrile with dialkyl sulfate, was revealed to result by the catalytic effect of unreacted dialkyl sulfate on the 2-alkoxymethylene-3-alkoxypropionitrile first formed. This catalytic reaction is also effected, besides the dialkyl sulfate, by conc. sulfuric acid, p-toluenesulfonic acid, H acid, and ammonium sulfonate. When a few drops of conc. sulfuric acid is added to 2-dialkoxymethyl-3-alkoxypropionitrile and this is submitted to low-pressure distillation at 100° and 30mm.Hg, alcohol liberates immediately to form 2-alkoxymethylene-3-alkoxypropionitrile, while elevation of the bath temperature to around 170° results in the formation of 2-dialkoxymethyl-acrylonitrile. It follows, therefore, that the choice of reaction conditions will easily afford 2-dialkoxymethyl-3-alkoxypropionitrile, 2-dialkoxymethylene-3-alkoxypropionitrile, or 2-dialkoxymethyl-acrylonitrile.
