Preparation of glycerides by controlled esterification

A simple procedure for esterifying glycerides without interesterification occurring would be highly useful for preparing on a large scale a number of tailor‐made fats, including cocoa butter‐like fats. Such esterifications were carried out by employingp‐toluenesulfonic acid as catalyst and continuously removing the water of esterification by azeotropic distillation with aliphatic hydrocarbons or by stripping with vaporized hydrocarbons. Even thoughp‐toluenesulfonic acid rapidly disproportionated 1‐monostearin, even at 120C, apparently esterification was faster and only a moeerate amoung of ester‐ester interchange and acidolysis occurred. Diacid glycerides might be prepared from monoglycerides by the procedure which was employed. Saturated diglycerides were esterified with oleic acid with little ester‐ester interchange or acidolysis occurring; however, intraesterification was extensive. The reaction between 1,3‐distearin and oleic acid yielded approximately 75% 1‐oleodistearin and 25% 2‐oleodistearin. Saturated diglycerides were esterified with sebacic acid, again with little or no interesterification occurring.