Zum Mechanismus der Autoxydation metallorganischer Verbindungen

Abstract

Metallorganische Verbindungen reagieren in verschiedener Weise mit molekularem Sauerstoff. Alkyl‐Metall‐Verbindungen werden zu Metallalkyl‐peroxyden oxydiert. Aus den Alkali‐Addukten aromatischer Kohlenwasserstoffe entstehen Alkali‐peroxyd und Kohlenwasserstoff. Aryl‐Metall‐Verbindungen schließlich ergeben als Hauptreaktionsprodukte Phenole und Diaryle. Die Mechanismen der primären Reaktion mit Sauerstoff sowie der Folge‐ und Nebenreaktionen werden diskutiert.

200 Years of Lithium and 100 Years of Organolithium Chemistry

“…Several years later, Hock was able to isolate the n ‐butyl peroxide by conducting the reaction at –75 °C with 30 % yield . Similar reactions using aryllithium compounds produce more complicated results . Besides the peroxides also phenols and biaryls are found in the product mixtures.…”

The Chemistry of Organomettallic and Organometalloid Peroxides

“…On the basis of this estimate it can be expected that organoperoxides of groups la and Ila of the periodic table will have mostly ionic character. As one proceeds through groups lib and Benzyllithium Benzyl alcohol However, a concerted mechanism can also be invoked to explain the formation of biaryl and phenol (95) ArOOLi + RLi Ar Li Ar^-Li Li~Ar ArOLi + Ar2 + Li20…”

Stereospecific Polymerization of Isobutyl Vinyl Ether with (EtClAl)2NPh and Its Nuclear-Substituted Derivatives

“…6, 1973 Stereospecific Polymerization of Isobutyl Vinyl Ether with (EtC1Al)2NPh aluminum compounds react to form alkylaluminum alcoholates through peroxides as intermediates. 7 Nevertheless, ethylchloroaluminum ethylate, Et(EtO)AlCl, and the reaction product of (EtC1Al)2NPh with ethanol in a molar ratio (1 : 1 and 1 : 2) at 80°C for 3 hr had no catalytic activity for the polymerization of IBVE, and also IBVE did not polymerize with radical initiators such as benzoyl peroxide and acetyl peroxide, while no information was obtained about the polymerization of IBVE with organometallic peroxides. In the authors' experiments, high-vacuum technique was used in the polymerization, but extremely dried system could not be obtained.…”