Transformations of cyanoacetylenic alcohols in the presence of the cyanide ion

Abstract

The transformation of 4-hydroxy-4-methylpent-2-ynenitrile in the presence of KCN in methanol (20–25 °C, 1 h) leads to ( Z )-2-(1-hydroxy-1-methyl)but-2-enedinitrile, 4-hydroxy-3-methoxy-4-alkylalk-2-enenitrile and 2-imino-5,5-dimethyl-4-methoxycarbimide-2,5-dihydrofuran. In dioxane at room temperature, KCN catalyses the auto-transformation of cyanoacetylene to 2,2-dimethyl-3,4-di(cyanomethylene)oxetane and 2,5-di(cyanomethylene)-3,3,6,6-tetramethyl-1,4-dioxane; in aqueous dioxane (20–25 °C, 4 h), the reaction affords 5-amino-2,2-dimethyl-3(2 H )-furanone.