Silver ethyl , decomposition

Over the temperature range — 60-0 °C kt = 5.5 x10s exp(— 10,500/RT) sec-1. Silver ethyl also undergoes decomposition by Ag-C bond rupture... 

A kinetic study of the previously reported substitution of aromatic nitro groups by tervalent phosphorus has established an aromatic 5n2 mechanism. Similarities in values of activation energies, and in relative reactivities of phosphite and phosphonite esters, between this displacement and the Arbusov reaction suggest a related mechanism (31), while the lack of reactivity of p-dinitrobenzene is attributed to the need for intramolecular solvation (32). The exclusive formation of ethyl nitrite, rather than other isomers, is confirmed from the decomposition of triethoxy-(ethyl)phosphonium fluoroborate (33) in the presence of silver nitrite. A mechanism involving quinquevalent phosphorus (34) still seems applicable, particularly in view of the recent mechanistic work on the Arbusov reaction. ... 

The higher decomposition points were obtained when adrenochrome methyl and ethyl ethers were prepared by oxidation of the appropriate catecholamine in methanol with silver oxide. The BOlid aminochromes were then obtained as microcrystalline solids on addition of dry ether and cooling the resultant solution to — 80°. The slightly less pure products were obtained when the oxidation was carried out in acetonitrile. [R. A. Heacock and B. D. Scott, loc. cit. (footnote c )]. 

Similar products were obtained in the decomposition of the silver salt of 2.4.6-trichlorophenol, however, in this case higher temperature (60° C) was necessary and ethyl iodide did not initiate the reaction. Polymers were also obtained from several other trihalophenols. 

An extension of this reaction leading to a general synthesis of N-substituted (3-lactams involves the addition of a primary amine to a freshly prepared solution of cyclopropanone, conversion of the resulting carbinol amine to the N-chloro derivative, and then decomposition of this intermediate with silver ion in acetonitrile. 87a> The method permits one to prepare N-substituted (3-lactams of great variety (Table 14), including those constructed from amino acid esters. 87b The use of valine ethyl ester (123) as a nitrogen source leading to 124 is illustrated. 

Paneth22 first demonstrated that the decomposition by heat of certain organic compounds furnished products which removed metallic mirrors of silver, tellurium and other metals from the walls of the tube. For example when vapor of lead tetraethyl was heated a silver coating on the inside of the exit tube was removed for a considerable distance. The results were interpreted to mean that ethyl radicals were liberated in the thermal decomposition and... 

DOT CLASSIFICATION Forbidden SAFETY PROFILE A poison. Can explode spontaneously. The solid, liquid and vapor are shock-sensitive explosives. Concentrated solutions in organic solvents may explode. Moderate fire hazard in the form of vapor by chemical reaction. A powerful oxidant. Moderately explosive when exposed to heat. The liquid explodes on contact with arsenic, sodium, silver foil, or phosphorus. Incompatible with Sb, ethyl ether, Ag, metals. When heated to decomposition it... 

This results in 63 per cent, yield when the same quantities of materials are used as in the preceding preparation, the 2-bromo-6-methylphenyl-arsinic acid being replaced by 2-bromo-4-methylphenylarsinic acid. The compound crystallises in colourless needles, melting with decomposition at 158° to 159° C., readily soluble in acetic acid, methyl and ethyl alcohols, and acetone, very sparingly soluble in water. The sodium, potassium and ammonium salts are readily soluble in water the silver, mercuric and lead salts form white, flocculent precipitates, insoluble in cold or hot water the silver salt is soluble in ammonia the mercurous, calcium and barium salts arc white precipitates, insoluble in cold but soluble in hot water. The magnesium salt is obtained when a solution of the ammonium salt is boiled with magnesia mixture. 

In contrast to silver-catalysed cumene oxidation, the evidence concerning the mechanism of copper-catalysed reactions favours radical initiation via surface hydroperoxide decomposition. Gorokhovatsky has shown that the rate of ethyl benzene oxidation responds to changes in the amount of copper(ii) oxide catalyst used, in a manner which is characteristic of this mechanism. Allara and Roberts have studied the oxidation of hexadecane over copper catalysts treated in various ways to produce different surface oxide species, Depending on the catalyst surface area and surface oxide species present, a certain critical hydroperoxide concentration was necessary in order to produce a catalytic reaction. At lower hydroperoxide levels, the reaction was inhibited by the oxidized copper surface. XPS surface analysis of the copper catalysts showed a... 

The first, unsuccessful, attempts to prepare alkylsilver compounds were made as early as 1859 by Buckton5a and 1861 by Wanklyn and Carius5b. The reaction of silver chloride with diethylzinc yielded only metallic silver, and a mixture of ethylene, ethane and butane. Due to their low thermal stability alkylsilver compounds were entirely unknown until 1941, when Semerano and Riccoboni6 reported the formation of some alkylsilver complexes by the reaction of silver nitrate with tetraalkyllead in alcoholic solution at low temperatures (equation 1). The yellow to brown precipitates of the formula RAg (R = methyl, ethyl, propyl) were stable at —80 °C for several hours, but upon warming to room temperature rapid decomposition took place with formation of metallic silver and... 

Bis(ethylenediamine)copper(II) diiodocuprate(I) is a chocolate-brown, crystalline compound which melts with decomposition at 267°. It is insoluble in cold water and in organic solvents such as ethanol, acetone, and ethyl ether. Boiling water decomposes it immediately to insoluble copper(I) iodide and a purplish-blue solution of bis-(ethylenediamine) copper(II) iodide. The solid instantaneously reduces a cold aqueous silver nitrate solution to elemental silver. 

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