Cleavage of olefinic double bonds by mediated anodic oxidation

• Published in: Electrochimica acta Vol. 48; no. 5; pp. 489 - 495
• Main Author: BAUMER, U
• Format: Journal Article
• Language: English
• Published: Oxford Elsevier Ltd 15.01.2003; Elsevier
• Subjects: Alkenes; C,C-double bond cleavage; Chemistry; Electrochemistry; Exact sciences and technology; General and physical chemistry; Kinetics and mechanism of reactions; Mediated anodic oxidation; Periodate/ruthenium trichloride; C,C-double bond cleavage; Alkenes; Periodate/ruthenium trichloride; Mediated anodic oxidation; Mixed catalyst; Alkali metal Compounds; Platinoid Compounds; Catalytic reaction; Catalyst selectivity; Transition metal Compounds; Ruthenium chloride; Experimental study; Scission; Sodium Periodates; Alkene; Anodizing; Reaction mechanism; Electrochemical reaction; Catalyst activity; Degradation product
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/S0013-4686(02)00715-6

Seven alkenes, e.g. 1-decene, methyl oleate, cyclododecene, norbornene, are cleaved by indirect anodic oxidation with IO 4 −/RuCl 3 as mediator to carboxylic acids. The best performance was achieved with two alternative ex cell-methods. Periodate is regenerated from iodate in a divided cell at a PbO 2/Ti-anode. In the chemical reactor alkene and the produced carboxylic acid are immobilized in a chromatography column on Chromosorb W and oxidized with IO 4 −/RuO 4 in CH 3CN/water. In the alternative version the alkene is oxidized in an emulsion generated by sonication and the organic phase is retained in the reactor by a separator. Acids and diacids are obtained in 61–91% chemical yield and good current yields. The amount of consumed periodate can be reduced to less than 5% of the amount needed for the chemical oxidation. The mediated anodic cleavage of alkenes is altogether an interesting alternative to ozonolysis.