Silver acetate allylic oxidation

Codeposition of silver vapor with perfluoroalkyl iodides at -196 °C provides an alternative route to nonsolvated primary perfluoroalkylsilvers [272] Phosphine complexes of trifluaromethylsilver are formed from the reaction of trimethyl-phosphme, silver acetate, and bis(trifluoromethyl)cadmium glyme [755] The per-fluoroalkylsilver compounds react with halogens [270], carbon dioxide [274], allyl halides [270, 274], mineral acids and water [275], and nitrosyl chloride [276] to give the expected products Oxidation with dioxygen gives ketones [270] or acyl halides [270] Sulfur reacts via insertion of sulfur into the carbon-silver bond [270] (equation 188)... 

Allyl olefines are mainly used and, from these reactants, Brace prepared diols and diacids by reacting silver acetate and by permanganic oxidation, respectively [65]. 

A combination of rtiodium(III) chloride with silver acetate, and treatment of rhodium(II) acetate in acetic acid solution with ozone, are two methods for generation of the (is-oxotrimetal-acetato complex of rhodium [Rhs0(0Ac)6 2O)3]0Ac. This RhsO complex was found to effect catalytic allylic oxidation of alkenes efficiently to give the corresponding a -unsaturated carbonyl compounds in the presence of a reoxidant such as r-butyl hydroperoxide, although in disappointing yield (equation 44). 

For primary and secondary bromides base-catalysis is required, while for tertiary bromides silver acetate or silver oxide are more effective cyclization catalysts. For tertiary substrates dehydrobromination leading to allylic hydroperoxides is a serious side reaction when base-catalysis is employed and, thus, silver ion catalysis is essential. Furthermore, the silver salts must be freshly prepared because metallic silver that might be present due to exposure to light causes decomposition of the dioxetane. The tetramethyl-l,2-dioxetane (7) was the first example prepared in this way (Eq. 13). For primary substrates, abstraction of the base-sensitive dioxetanyl hydrogens are probably responsible for the low yields. For secondary substrates, both side reactions might operate. 

Valuable products are produced from the oxidation of both ethylene and propylene (Figs. 1 and 2). Ethylene is epoxidized with oxygen in the vapor phase over a silver catalyst, and propylene is epoxidized with an alkyl hydroperoxide in the liquid phase using a molybdeniim catalyst system. Vinylic oxidation products or their stable isomers, including acetaldehyde, acetone, and vinyl acetate, have been manufactured by a series of related catalytic reactions. These reactions occur either in solutions of palladium complexes or on the surfaces of supported palladium catalysts. Bismuth molybdate is an effective catalyst for allylic oxidations of propylene, which are of paramount importance to the chemical industry. Propylene is oxidized in the vapor phase to give acrolein for acrylic acid manufacture or, in the presence of ammonia, to give acrylonitrile. Second- and third-generation catalysts,... 

CARBONIC ACID, LITHIUM SALT (554-13-2) LijCOj Aqueous solution is an organic base. Violent reaction with acids. Inconpatible with fluorine, germanium, lead diacetate, magnesium, mercurous chloride, silicon, silver nitrate, titanium. Aqueous solution incompatible with organic anhydrides, acrylates, alcohols, aldehydes, alkylene oxides, substituted allyls, cellulose nitrate, cresols, caprolactam solution, epichlorohydrin, ethylene dichloride, isocyanates, ketones, glycols, nitrates, phenols, vinyl acetate. Exothermic decomposition with maleic anhydride. Corrodes aluminum, copper, zinc in the presence of moisture. On small fires, use any extinguishing agent. 

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