Abstract
Abstract The effects of the amine, the alcohol, the solvent, and the reaction temperature on the isomerization esterification of crotonyl chloride to the vinylacetic acid ester were investigated. Amines can be divided into three groups. The first group includes the amines with pka-values as high as 10; they give the isomerized product, ethyl vinylacetate (IEt), in a ca. 90% yield. The second includes the amines with pKa-values lower than 7.2; they give the normal product, ethyl trans-crotonsite (IIIEt). The third includes the remaining amines with intermediate pKa-values; they give various amounts of the two products. Ethyl cis-crotonate (IIEt) is always formed in only a small quantity. Alcohols favored the product ratio of IEt in the order: MeOH<EtOH<i-BuOH<i-PrOH<t-BuOH. Various aliphatic and aromatic solvents gave almost identical product ratios, regardless of their polarities. Below room temperature, the formation of IEt was predominant (ca. 95—97%), but above that temperature IIEt and IIIEt increased. It was understood that the steric factors of amine and alcohol influenced the extent of the double-bond shift and that the reaction proceeded via the ketene intermediate. The course of the reaction has been discussed.
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