An Introduction to Modern Scientific Chemistry

Schober, William Bush

doi:10.1126/science.13.331.707

Cited by 1 publication

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“…It leads to carboxylic acids and aldehydes or ketones, which provide starting materials for a large variety of functional group interconversions and C,C-bond forming reactions. In the laboratory the method of choice is ozonolysis [1][2][3][4][5], in a few cases it is also applied on a technical scale [6][7][8], which, however, requires costly safety precautions. Other methods are the conversion to 1,2-diols followed by a glycol cleavage [9][10][11][12][13].…”

Section: Introductionmentioning

confidence: 99%

Cleavage of alkenes by anodic oxidation

Bäumer

Schäfer

2005

J Appl Electrochem

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Oxidative cleavage of olefinic double bonds to carboxylic acids, aldehydes or ketones is one of the important reactions in organic synthesis. Ozonolysis is mostly applied for this purpose, however, high costs for safety precautions in technical scale conversions demand alternatives. For this purpose different electrochemical methods are investigated. In the direct oxidation of cyclohexene at a platinum or graphite anode no cleavage occurs, but substituted and rearranged products are obtained. At the boron doped diamond electrode (BDDE) aliphatic olefins with high oxidation potential are not converted. Electrochemical ozonolysis by oxidation of water to ozone at the lead dioxide electrode leads to carboxylic acids as cleavage products in high material yield but low current yield. Anodic bromo-formyloxylation followed by an anodic cleavage provides a two step conversion of cyclohexene to hexane-1,6-dial derivatives. Thereby anodic discharge of bromide in formic acid leads to (2-bromocyclohexyl)-formate, which is converted to cyclohexane-1,2-diol and the major part of potassium bromide is recovered for the next cycle. This electrochemical conversion appears to be an attractive alternative to chemical oxidations with oxygen and catalysts or with hydrogen peroxide. The diol is cleaved in high yield to hexane-1,6-dial or its acetal either directly or indirectly with periodate as mediator.

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