Diethyl ketone, oxidation

Reactions involving abstraction from acetaldehyde are just as likely in diethyl ketone oxidation as reactions involving abstraction from formaldehyde in acetone oxidation. The acetyl radical so produced will oxidize as in the oxidation of acetone to give mostly carbon dioxide (from the -carbon atom of diethyl ketone71), but a little decomposition seems to occur since some carbon monoxide does not come from the original carbonyl group of the ketone.71... 

The slow combustion reactions of acetone, methyl ethyl ketone, and diethyl ketone possess most of the features of hydrocarbon oxidation, but their mechanisms are simpler since the confusing effects of olefin formation are unimportant. Specifically, the low temperature combustion of acetone is simpler than that of propane, and the intermediate responsible for degenerate chain branching is methyl hydroperoxide. The Arrhenius parameters for its unimolecular decomposition can be derived by the theory previously developed by Knox. Analytical studies of the slow combustion of methyl ethyl ketone and diethyl ketone show many similarities to that of acetone. The reactions of methyl radicals with oxygen are considered in relation to their thermochemistry. Competition between them provides a simple explanation of the negative temperature coefficient and of cool flames. 

The detection of 1,2-propylene oxide in the products from methyl ethyl ketone combustion is particularly interesting. It parallels the formation of ethylene oxide in acetone combustion (8) and of 1,2-butylene oxide in the combustion of diethyl ketone. Thus, there is apparently a group of isomerization reactions in which carbon monoxide is ejected from the transition state with subsequent closing of the C—C bond. Examination of scale molecular models shows that reactions of this type are, at any rate, plausible geometrically. 

Diethyl ketone was either purchased from the Eastman Kodak Company and redistilled, or prepared by passing propionic acid slowly over a mixture of manganous oxide and clay plate chips in a tube furnace at 420-440° 3 the apparatus was similar to one described in Organic Syntheses When prepared by this method the ketone was distilled, dried over potassium carbonate, and redistilled b.p. 100-101°. 

Oxidation of compounds of the types thus far discussed proceeds readily at room temperature. Certain compounds which show no substantial reaction with periodic acid at room temperature can be oxidized at elevated temperature.22- 23 26 Thus, at 100° in aqueous solution the acetone mole exile is split to produce acetic acid and formaldehyde diethyl ketone yields propionic acid and probably ethanol lactic acid gives acetaldehyde and carbon dioxide acetaldehyde is oxidized to formic acid and methanol, which is converted into formaldehyde and pyruvic acid yields acetic acid and carbon dioxide. 

Epoxides react with aldehydes and ketones in the presence of stannic chloride to form cyclic acetals of dihydric alcohols. Undesirable side reactions are repressed by adding the reactants, dissolved in dry carbon tetrachloride, to a dilute solution of the catalyst in the same solvent at 20° to 30°. In most instances, the reaction is practically instantaneous and the mixture may be processed immediately by washing with aqueous alkali and distilling. The yields for the interaction of y-halopropylene oxides and typical carbonyl compounds, such as propion-aldehyde, diethyl ketone, or benzophenone, are 69-70%. 

One somewhat surprising minor product is 1 2-epoxypropane. Its formation parallels the formation of ethylene oxide and 1 1-epoxybutane in the slow combustion of acetone and diethyl ketone, respectively. It may perhaps be formed via... 

The photo-oxidation of acetone [51], methyl ethyl ketone [52] and diethyl ketone [53, 54] at temperatures between 100 and 250 °C has yielded some further information on these reactions and Hoare and... 

ETHYL BENZENE ETHYL BROMIDE ETHYL CHLORIDE ETHYL ETHER ETHYLENE CHLOROHYDRIN ETHYLENE DIAMINE ETHYLENE DIBROMIDE ETHYLENE DICHLORIDE ETHYLENE GLYCOL ETHYLENEIMINE ETHYLENE OXIDE DIETHYL KETONE DIETHYLENE GLYCOL GLYCOL ETHERS, ESTERS MEA, DEA. TEA VINYL ACETATE POLYMERS. COPOLYMERS... 

CO. CHa, CO2, acetone, ketene. ethene. propene, 1-butene, benzene, toluene, mesitylene. xylene, methyl ethyl ketone, diethyl ketone, methyl-n-propyt ketone, methyl-n-butyl ketone, ethyl vinyl ketone, methyl propenyl ketone (trace), ethyl propyl ketone (trace), 3-methyl-cydopenlanone, cyclohexanone (trace), cyclohexa-2-enone, 2-methyl-cyclohexanone, 1-methyl-cydohexa-1-ene-3-one (trace), acrolein, mesityl oxide, ethanal, propanal. butanal. chain fragments, some monomer... 

CO, CH4, CO2, acetone, ketene. ethene. propene. 1-butene, benzene, toluene, xylene, cydopentene, methyl ethyl ketone, diethyl ketone, methyl-n-propyl ketone, di-n-propyl ketone, methyl vinyl ketone, methyl Isopropenyl ketone, methyl isopropyl ketone, ethyl vinyl ketone, trace amounts of methyl-n-bulyl ketone, cyclopentanone, cydohexanone. acrolein, ethanal. butanal. chain fragments, some monomer CO. CH4, COj, ketene, 1-butene, propene, acetone, methyl ethyl ketone, methyl n-propyl ketone, 1,4-cyclohexadiene. toluene, l-methy. l.3-cydohexadlene, 2-hexanone, cydopentene, 1-methyl cydopentene. mesityl oxide, xylenes, benzene, ethene, cyclopentanone, 1.3-cyclopentad iene, diethyl ketone, short chain fragments, traces of monomer CO, CH4, COi, ketene, 1-butene, propene, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl-n-propyl ketone, diethyl ketone, methyl propenyl ketone, 3-hexanone. toluene, 2-hexanone. 1,3-cydopentadiene, cyclopentanone, 2-melhylcydopenlanone, mesityl oxide, xylenes, benzene, propionaldehyde, acrolein, acetaldehyde ethene, short chain fragments, traces of monomer CO, COj, H2O, CH4. acetone, ketene, ethene, propylene, 1-butene, methyl vinyl ketone, benzene, acrylic add, toluene, xylene, short chain fragments such as dimer to octamer with unsaturated and anhydride functionalities... 

Instead of acetaldehyde, other aliphatic aldehydes such as propanal or butanal can be applied. Besides MEK, diethyl ketone or dibutyl ketone or even simply n-butane is used. It is worthwhile to point out the significant importance of co-oxi-dizing processes in the mechanistic course of autoxidation reactions. After a short induction time, the intermediates formed act as co-oxidants for the remaining starting molecules. 

DIETHYL KETONE (96-22-0) Forms explosive mixture with air (flash point 55°F/13°C). Violent reaction with strong oxidizers. May be able to form unstable peroxides on prolonged storage. Incompatible with aliphatic amines, amides, sulfuric acid, nitric acid, caustics, isocyanates. Attacks some plastics, rubber, and coatings. Flow or agitation of substance may generate electrostatic charges due to low conductivity. 

The results for diethyl ketone are similar [34], The interaction between H202 and ketones plays a great part in alcohol oxidation. 

Tetra - ethylphosphonium carbonate, [(C2H5)4P]2C03, forms highly deliquescent, needle-shaped crystals. These at 2-10° to 250° C. are decomposed with formation of triethylphosphine, triethylphosphine oxide, diethyl ketone, carbon dioxide and a gaseous hydrocarbon (C4H10 ). An acid carbonate is known, and this gives a similar result W hen decomposed by heat. 

Tetra-ethylphosphonium oxalate, [(C2115)4 ]2C2O4,—This salt separates as fine crystals wliich decompose at 200° to 230° C. into triethylphosphine oxide, triethylphospiune, diethyl ketone, ethylene, carbon dioxide and carbon monoxide. 

Reactions of Thiophen Aldehydes and Ketones.—The synthesis of bis-(4-methylpent-3-enyl)thiophens was achieved by applying the Wittig reaction to (106). A convenient method for the synthesis of (2-thienyl)ethylene oxide from thiophen-2-aldehyde and a sulphur ylide has been worked out. From 2-thenil and diethyl ketone, (107) was prepared, and its Diels-Alder reactions have been studied. The reaction of (108) with different Grignard reagents has been... 

August Sayer (U.S.P., No. 470,451) finds diethyl-ketone, dibutyl-ketone, di-pentyl-ketone, and the mixed ketones, [A] methyl-ethyl, methyl-propyl, methyl-butyl, methyl-amyl, and ethyl-butyl ketones are active solvents of pyroxyline and Paget finds that although methyl-amyl oxide is a solvent, that ethyl-amyl oxide is not. 

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