Acetone, electrolytic oxidation

Subject Phenyl acetones by electrolytic oxidation From "guest" ... 

Appendix - Phenyl acetones by electrolytic oxidation. Process for 3,4-dimethoxyphenyl-acetone preparation. European Patent Application 0247526, Filed 02.12.87 to LARK S.p.a. Milan. 

Tripotassium hexakiscyanoferrate [13746-66-2] K2[Fe(CN)g], forms anhydrous red crystals. The crystalline material is dimorphic both orthorhombic and monoclinic forms are known. The compound is obtained by chemical or electrolytic oxidation of hexacyanoferrate(4—). K2[Fe(CN)g] is soluble in water and acetone, but insoluble in alcohol. It is used in the manufacture of pigments, photographic papers, leather (qv), and textiles and is used as a catalyst in oxidation and polymerisation reactions. 

Oxidation. Nitroparaffins are resistant to oxidation. At ordinary temperatures, they are attacked only very slowly by strong oxidi2ing agents such as potassium permanganate, manganese dioxide, or lead peroxide. Nitronate salts, however, are oxidi2ed more easily. The salt of 2-nitropropane is converted to 2,3-dimethyl-2,3-dinitrobutane [3964-18-9], acetone, and nitrite ion by persulfates or electrolytic oxidation. With potassium permanganate, only acetone is recovered. 

Ttinitroparaffins can be prepared from 1,1-dinitroparaffins by electrolytic nitration, ie, electrolysis in aqueous caustic sodium nitrate solution (57). Secondary nitroparaffins dimerize on electrolytic oxidation (58) for example, 2-nitropropane yields 2,3-dimethyl-2,3-dinitrobutane, as well as some 2,2-dinitropropane. Addition of sodium nitrate to the anolyte favors formation of the former. The oxidation of salts of i7k-2-nitropropane with either cationic or anionic oxidants generally gives both 2,2-dinitropropane and acetone (59) with ammonium peroxysulfate, for example, these products are formed in 53 and 14% yields, respectively. Ozone oxidation of nitroso groups gives nitro compounds 2-nitroso-2-nitropropane [5275-46-7] (propylpseudonitrole), for example, yields 2,2-dinitropropane (60). 

As a neutral marker, an organic molecule that is non-polar at the pH of the electrolyte used and easily detected by absorption in the near UV, is selected (e.g. acetone, mesityl oxide or benzyl alcohol). 

Electrolytic oxidation of anthracene in 20 per cent sulfuric acid solution with 1 per cent of vanadium pentoxide present is carried out at 80° C. with lead electrodes and a current density of 300 amperes per square meter at 1.6 volts. Good yields have been claimed 10 for this process. Air under pressure has been used for the oxidation of anthracene in the form of dispersions in aqueous ferric sulfate solutions,20 or as a solution iu pyridine or dispersion in aqueous alkaline solutions preferably in the presence of catalysts 21 of copper, cobalt, nickel or lead compounds. Vanadium compounds have been found more active than chromium compounds for use as oxidation catalysts in the form of suspensions in the liquid phase, as in the preparation of aniline black.22 Anthracene suspended in water or dilute sulfuric arid or dissolved in a solvent as acetone is oxidized with ozone, or ozonized oxygen at ordinary temperatures.28... 

Ufheil J., Wiirsig A., Schneider O. D., Novak P. Acetone as oxidative decomposition product in propylene carbonate containing battery electrolyte, Electrochem. Commun. 2005, 7,... 

Ufheil, J. Wursig, A. Schneider, O. D. Novak, P., Acetone as Oxidative Decomposition Product in Propylene Carbonate Containing Battery Electrolyte. Electrochem. Commun. 2005, 7,1380-1384. 

In 1859, Friedel electrolytically oxidized acetone and found a mixture of formic, acetic, and carbonic acids with evolution of carbon dioxide and oxygen at the anode in an acetone-sulfuric acid mixture. Further studies on ketones were not reported until 1931, when a similar study was carried out resulting in the formation of methane, ethane, and unsaturated hydrocarbons, in addition to carbon dioxide and oxygen at platinum anodes. The first anodic oxidation of benzene was reported in 1880, with the observation that the electrolytic oxidation of benzene in an ethanolic-sulfuric acid medium yielded unidentifiable substances. A few years later Gotterman and Friedrichs reported that hydrocarbons were obtained from the anodic oxidation of benzene in alcoholic-sulfuric acid solution at platinum anodes. 

Figure 3 shows the cyclic vo1tammogram of an aceton i tr i 1 e solution containing 9-fluorenone on a bare Pt electrode and on a Polv-1 coated Pt electrode using II as the electrolyte. The only significant difference between the vo1tammograms is the presence of the poly-I reduction and oxidation waves for the coated electrode. We have previously determined by other means that poly-I films should not be permeable to molecules as large as 9-... 

Phenylacetamide has been obtained by a wide variety of reactions from benzyl cyanide with water at 250-260° 6 from benzyl cyanide with water and cadmium oxide at 240° 6 from benzyl cyanide with sulfuric acid 7 8 by saturation of an acetone solution of benzyl cyanide with potassium hydrosulfide 9 from benzyl cyanide with sodium peroxide 10 by electrolytic reduction of benzyl cyanide in sodium hydroxide 11 from ethyl phenyl-acetate with alcoholic 12 or aqueous 13 ammonia from phenyl-acetic acid with ammonium acetate 14 or urea 15 from diazoacetophenone with ammoniacal silver solution 16 from phenyl-acetic acid imino ether hydrochloride and water 17 from acetophenone with ammonium poly sulfide at 215° 18 from benzoic acid 19 and by heating the ammonium salt of phenyl-acetic acid.20... 

The densities and volumetric specific heats of some alkali halides and tetraalkylammonium bromides were undertaken in mixed aqueous solutions at 25°C using a flow digital densimeter and a flow microcalorimeter. The organic cosolvents used were urea, p-dioxane, piperadine, morpholine, acetone, dime thy Isulf oxide, tert-butanol, and to a lesser extent acetamide, tetrahydropyran, and piperazine. The electrolyte concentration was kept at 0.1 m in all cases, while the cosolvent concentration was varied when possible up to 40 wt %. From the corresponding data in pure water, the volumes and heat capacities of transfer of the electrolytes from water to the mixed solvents were determined. The converse transfer functions of the nonelectrolyte (cosolvent) at 0.4m from water to the aqueous NaCl solutions were also determined. These transfer functions can be interpreted in terms of pair and higher order interactions between the electrolytes and the cosolvent. 

Acetone, acetic acid, formic acid, and carbonic acid are formed. The oxidation takes place more easily than in the case of the primary alcohols, and yields up to 70% acetone, which, however, is readily oxidized further. In alkaline electrolytes the alcohols are converted at the anode into complicated condensation products of the aldehydes. 

In order to verify that the entire system is working correctly, frequent measurements of a well-dehned reversible voltammetric redox couple are strongly recommended. Suggested redox couples include the oxidation of ferrocene, Fc (7) in most organic solvents (i.e. acetone, acetonitrile and dichloromethane) containing 0.1 M of a typical organic electrolyte (e.g. 

Ketogenesis is an important metabolic function in the liver. It is the result of an increase in lipolysis in the fatty tissue, with a rise in fatty acids. Insulin inhibits ketogenesis, whereas it is accelerated by fasting as well as by glucagons and insulin deficiency. Ketones (acetacetate, 3-hydroxybutyrate, acetone) are synthesized by means of P-oxidation from acetyl-CoA, assuming the production of this substance exceeds the amount required by the hepa-tocytes (and glucose metabolism is simultaneously reduced). The liver itself does not require any ketones acetone is expired, whereas 3-hydroxybutyrate and acetacetate serve as a source of energy. Ketonaemia can lead to metabolic acidosis and electrolyte shifts. 

The electrically neutral marker substance employed to measure the velocity of the electro-osmotic flow has to fulfill the following requirements. The compound must be soluble in the electrolyte solution and neutral in a wide pH range and no interaction with the capillary wall must occur. In addition, the electrically neutral marker substance should be easily detectable in order to allow a small amount to be injected. If the electrically neutral marker interacts with the capillary wall or becomes partially charged by complexation with the components of the electrolyte solution, the measured electro-osmotic velocity may appear slower or faster than the real flow. Some compounds that adequately serve as electrically neutral markers include benzyl alcohol, riboflavin, acetone, dimethyl-formamide, dimethyl sulfoxide, and mesityl oxide. 

In the modern industrial manufacturing proce.ss, the reduction to d-sorbitol is accomplished either electrolytically or by catalytic hydrogenation (Ha/CuCrOa). Additionally, it has been found that the reaction of sorbose with acidified acetone at low temperature (— 5 °C) gives a greatly increased yield of the di-O-isopropylidenyl (as opposed to the 2,3-mono-O-isopropylidenyl) derivative. The oxidation of this protected sorbose (2,3 4,6-di-0-isopropylidene-L-sorbofuranose or diacetone sorbose ) to the corresponding 2,3 4,6-di-0-isopropylidene-2-... 

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