A comparative study of the direct anodic oxidation of olefins and acetylenes in non aqueous solvents

✍ Scribed by M. Katz; H. Wendt

• Publisher: Elsevier Science
• Year: 1976
• Tongue: English
• Weight: 433 KB
• Volume: 21
• Category: Article
• ISSN: 0013-4686
• DOI: 10.1016/0013-4686(76)80008-4

✦ Synopsis

Abstmct-The results of electrode kinetic, preparative and theoretical studies of the direct anodic oxidation of related olefms and acetylenes are compared (phenylacetylene/styrene; vinylacetylene/butadiene; I,4-diphenylbutadiene/l,4_diphenylbutadiyne).

Modified HMO-calculation @modification according to bond lengths) predict the observed difference of the half wave potentiais of related olefins and acetylenes qualitatively. However the HMO-calculations do not allow the precise prediction of the reactivities of anodically formed radical cations of the acetylenes except for the highly conjugated diphenylbutadiyne. Electrode kinetic and preparative data of the olefin and acetylene oxidation show that both react in the same way ie, are oxidized in the adsorbed state to yield monomeric and dimeric products. The remarkably low dimer yield in the acetylene oxidation is supposed to be due to the decreased adsorbability of the acetylenes at the higher anode potentials which are necessary to oxidize them. This phenomenon is observed, too, if olefins with different half wave potentials are compared.