Mineralization of acetone

Stefan, M.I., Hoy, A.R., and Bolton, J.R., Kinetics and mechanism of the degradation and mineralization of acetone in dilute aqueous solution sensitized by the UV photolysis of hydrogen peroxide, Environ. Sci. Technol., 30, 2382-2390, 1996. 

Stefan MI, Hoy AR, Bolton JR (1996) Kinetics and Mechanism of the Degradation and Mineralization of Acetone in Dilute Aqueous Solution Sensitized by the UV Photolysis of Hydrogen Peroxide, Environ. Sci. Technol. 30, No. 7 2382-2390. 

Fig. 7.5 On the way to complete mineralization of acetone (2-propanone) structures of the main and minor intermediate products during H2O2-UV treatment of a diluted aque-...

Fig. 2 Mineralization of acetone extract of PE (EPITDPA ) after peroxidation (ACQ) compared with cellulose (CELL) and low molar mass hydrocarbon analogues of polyolefins. DOC is docosane (C22H46), SQUA is 2,6,10,15,-19,23-hexamethyl tetracosane, squalane and ACDOC is docosanoic acid (C22H44O2).

Acetone-Alkali coloration. Dissob-e a few crystals in i-2 ml. of acetone and add a few drops of aqueous XaOlI solution. A deep violet coloration is produced, and is turned red by acetrc acid but destroyed by mineral acids (see Test 4(6) for Ketones, p. 346, and also Test 2(0) p. 274). 

In ethyl acetoacetate the methylene group is united to —CO.CH3 and —COOR. Free acetoacetic acid is even much less stable than malonic acid and, on merely warming in solution, decomposes in fundamentally similar fashion, into acetbne and carbon dioxide. Since all synthetic derivatives of ethyl acetoacetate behave in the same way, so that the acetoacetic acids, obtained by hydrolysis of their esters with aqueous mineral acids, decompose spontaneously with loss of carbon dioxide when heated, numerous derivatives of acetone are made available by this synthesis, by what is called Icetonic hydrolysis, e.g. 

Ketals of acetone and cyclohexanone with methyl, butyl, isopropyl and cyclohexyl alcohols are hydrogenolyzed to ethers and alcohols by catalytic hydrogenation. While platinum and ruthenium are inactive and palladium only partly active, 5% rhodium on alumina proves to be the best catalyst which, in the presence of a mineral acid, converts the ketals to ethers and alcohols in yields of 70-100% [933]. 

Tribromomethane [75-25-2] (bromoform), CHBr3, is usually sold mixed with up to 3—4% ethanol as a stabilizer. The pure liquid has mp, 7.7°C bp, 149.5°C cP A, 2.8912 g/mL 19D 1.5980 (87). Water solubility is about 0.3 g/100 g at 25°C. Bromoform is prepared from chloroform by the replacement procedures indicated (88). The classical method of preparation involves reaction of acetone and sodium hypobromite the latter may be generated from sodium hypochlorite and a bromide (89). Uses have been found in syntheses, in pharmacy as a sedative and antitussive, in gauge fluids, and as a dense liquid for separating minerals. Traces of bromoform and bromochloroforms are likely to be present in municipal waters and wastes as a result of chlorination in the presence of naturally occurring bromide ions and humic substances (90). Removal can be accomplished by adsorption on activated charcoal. 

Sepiolite clay (<100 mesh) was heated in air at 120°C in order to remove the zeolitic and surface bound water molecules. The partially dehydrated clay mineral was subsequently exposed to acetone vapor at room temperature for a period of four days. H and 29Si CP MAS-NMR experiments revealed that the acetone molecules penetrated into the microporous channels of the sepiolite structure. Broad line 2H NMR studies using acetone-d6 revealed that, in addition to fast methyl group rotations, the guest acetone-d6 molecules were also undergoing 2-fold re-orientations about the carbonyl bond. The presence of acetone-d6 molecules adsorbed on the exterior surfaces of the sepiolite crystals was also detected at room temperature. 

Sepiolite (SepSp-1) was obtained from the Source Clay Mineral Repository (University of Missouri) and was used without additional purification. Thermal treatment was carried out for 19-20 hours under air in a baffle furnace, using 0. l-0.2g sepiolite that had been gently ground in a mortar and passed through a 100-mesh sieve. The vials containing dried sepiolite were transferred into capped bottles containing a few milliliters of acetone (acetone-d6 for the broad line 2H NMR experiments) and then remained in contact with the acetone vapor at room temperature for 4 days. 

Aminopenicillanic acid (2.16 g) is dissolved in 20 ml of a one molar aqueous solution of potassium bicarbonate and 10 ml of acetone. The resultant solution is cooled in an ice-water bath and to it is added with stirring a solution of 2.7 g of alpha-methoxy-3,4-dichloro-phenylacetyl chloride in 10 ml of acetone. The pH is adjusted to 7-8 and upon completion of the addition the reaction medium is stirred for 15 min at ice bath temperature and then for 2.5 h at room temperature, maintaining the pH range between 7 and 8. The solution is extracted once with ether and then adjusted to pH 2.5 with 20% phosphoric acid. The acidic solution is extracted once with 30 ml of butyl acetate and again with 10 ml of butyl acetate. These combined butyl acetate extracts are thereafter successively washed twice with water and reextracted at pH 7 with 0.5 N aqueous potassium hydroxide solution. The aqueous layer is washed twice with ether and the remaining organic solvent is then removed by evaporation under reduced pressure. The washed aqueous layer is then lyophilized and the residue thus obtained taken up in acetone. The crystal line product is collected by filtration and dried to yield the potassium salt of 6-(a-methoxy-3,4-dichlorophenylacetamido)penicillanic acid. Upon treatment with mineral acid of an aqueous solution of the compound so prepared, there is obtained the free acid, 6-(a-methoxy-3,4-dichlorophenylacetamido)penicillanic acid. 

More recently, this method has been successfully extended by us18 to form the inverse systems, i.e. water core/polymer shell particles dispersed, initially in oil, but then transferred to an aqueous continuous phase. Clearly, whether one needs an oil or a water core depends on the nature of the active material to be released. Now one starts with a water/oil emulsion, rather than an oil/water emulsion, but the basic principles are very similar. A variety of shell polymer systems were prepared, including PMMA and poly(tetrahydrofuran) [PTHF]. The high vapor pressure liquid used in this case was in general, acetone. It turned out, however, that these water core systems are intrinsically more difficult to make than the equivalent oil core systems, because large amounts of acetone were required to dissolve the polymers initially in the water-acetone mixtures. An oil was then required which did not mix too well with acetone. In general, mineral oil worked reasonably well. In order to transfer the water core capsules into an aqueous continuous phase, the particles were centrifuged in... 

Soluble 1 in 6250 of water, 1 in 550 of ethanol, and 1 in 60 of acetone slightly soluble in chloroform very slightly soluble in ether soluble in dilute mineral acids and in solutions of alkali hydroxides and carbonates. 

Very slightly soluble in water sparingly soluble in ethanol soluble 1 in 25 of acetone and 1 in 400 of chloroform practically insoluble in ether freely soluble in dilute mineral acids and solutions of alkali hydroxides. 

Consistency. Lecithins are available in both fluid and plastic (solid) forms. Fluid lecithins generally follow Newtonian flow characteristics. The viscosity profile of lecithins is a complex function of acetone-insoluble content, moisture, mineral content, acid value, and the combined effects of assorted additives such as vegetable oils and surfactants. Generally, higher AI and/or moisture content yields higher viscosity, whereas an increased AV often decreases viscosity. Certain divalent minerals, such as calcium and others, can also adjust the viscosity level. 

Triamcinolone acetonide is prepared by the reaction of acetone with triamcinolone in the presence of catalytic amounts of mineral acid Fried and Heller used perchloric acid, Bernstein hydrochloric acid. An alternative... 

In this alternative procedure, the free base is dissolved in two or three volumes of acetone. Concentrated hydrochloric acid (37%) is then added to the acetone while stirring until the mixture becomes acid to litmus paper. Indicating pH paper should show a pH of 4 or lower. The hydrochloride is then precipitated from solution by slowly adding ether with stirring. It will take the addition of 10 to 20 volumes of ether to fully precipitate the hydrochloride. Toluene or mineral spirits may be substituted for the ether. Then the crystals are filtered out using a Buchner funnel as described before, and set aside to dry. The filtrate... 

The latter steps, essentially irreversible, control the overall reaction. Thus 2,4-dimethylbenzodiazepine gives acetone and 2-methylbenzimida-zole,2 5 23 while 2-methyl-4-phenylbenzodiazepine gives a mixture of acetone, acetophenone, and 2-methyl- and 2-phenylbenzimidazoles.2 The same ring contraction also ensues when aqueous solutions of benzodiazepines or their salts are kept at room temperature. It seems likely that with solutions of the salts, free base, present to some extent in equilibrium with the cation, may be the species involved in hydrolysis, since addition of traces of mineral acid greatly retards the rate of formation of benzimidazole.23 Solutions in methanol are much more stable and solutions in methanol containing small amounts of mineral acid apparently keep indefinitely.23... 

Acetic acid is known to undergo a vapor-phase ketonization reaction with formation of acetone on Brpnsted acids in general, and on proton-zeolites in particular. On large-pore zeolites in their proton form, the ketonization reaction is followed by acid-catalysed self-condensation amounting to mesitylene, mesityl oxide and phorone as main products [1], the chemistry being essentially identical to that in mineral acids. In H-pentasil zeolites with suitable acid site density, phorone isomerises to isophorone, which is cracked to yield 2,4-xylenol [1]. With propionic acid a similar chemistry occurs, but the formation of phenolics is severely suppressed by transition-state shape-selectivity effects... 

In a well-ventilated hood a 2-L, two-necked, round-bottom flask is equipped with a magnetic stirring bar, stopper, and a pressure-equalizing dropping funnel fitted with a gas inlet T-tube connected to a mineral oil bubbler. The flask is flushed with nitrogen and charged with 150 mL of dry dichloromethane and 60.0 g (0.141 mol) of 126. The mixture is stirred and cooled to -78°C in a dry-ice/2-propanol bath, and 23.9 g (0.141 mol) of 1-trimethylsiloxycy-clohexene is added dropwise over a few minutes. The mixture is stirred at — 78 C for 4 h. After the solution is warmed to room temperature, dichloromethane is removed under reduced pressure and replaced with 400 mL of acetone. The dark-red solution of the alkyne complex is cooled to —78 °C and 175 g (0.32 mol) of ceric ammonium nitrate is added in portions. The mixture is stirred until the gas evolution (carbon monoxide ) ceases (ca. 4 h). The reaction mixture is warmed to room temperature, poured into 1 L of saturated brine solution, and extracted with four 250-mL portions of diethyl ether. The combined ether extracts are dried over magnesium sulfate, filtered, and concentrated on a rotary evaporator. The residual red oil is distilled at reduced pressure to afford 15.0-15.2 g (71-72%) of 127 as a pale-yellow liquid, bp 57-60°C (10 mm). 

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