Green Chemistry - Development of Environment Benain Oxidation

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In the course of our continuous investigation of organic reactions utilizing bismuth compounds, we have been interested in oxidation reaction using bismuth compounds. Namely, we found that tributylbismuthine reacts with acid chlorides or carboxylic acids in hexane at room temperature under an oxygen atmosphere to give the corresponding butyl carboxylates in good yields. It was also found that aldehydes reacted smoothly with hydrogen peroxide in methanol at room temperature in the presence of a catalytic amount of bismuth trichloride to give the corresponding hydrogen peroxides.We have reported the oxidative esterification of aldehydes. Several aldehydes were treated with hydrogen peroxide in the presence of a catalytic amount of bismuth trichloride in refluxing methanol to give the corresponding methyl esters in high yields.This oxidative esterification was applied to the preparation of adipic acid from 2-hydroxycyclohexanone. When 2-hydroxycyclohexanone was reacted under the same reaction conditions, dimethyl adipate was obtained in good yield. Fortunately, we found that adipic acid was obtained when the reaction was tried without methanol.We have also reported the oxidative chlorination of ketones. Several ketones were treated with hydrogen peroxide in the presence of bismuth trichloride in refluxing methanol to give the corresponding α-chlorinated products in high yields.