Hydrogen peroxide solvent

CH3CH2OHCH3. B.p. 82 C. Manufactured by hydrolysis of propene. Used in the production of acetone (propanone) by oxidation, for the preparation of esters (e.g. the ethanoate used as a solvent), amines (diisopropylamines, etc.), glycerol, hydrogen peroxide. The alcohol is used as an important solvent for many resins, aerosols, anti-freezes. U.S. production 1978 775 000 tonnes. 

B). Many nitriles when treated with hydrogen peroxide in warm alkaline solution undergo hydrolysis to amides which can thus be readily obtained in high yield. Insoluble liquid nitriles can be treated directly in the aqueous suspension, but for insoluble solid nitriles the addition of a suitable organic solvent to give a complete solution may be desirable, although the completion of the hydrolysis may not then be so readily detected. 

The method is basically an application of the Wacker oxidation except that the catalyst used is palladium acetate ( Pd(AcO)2 or Pd(02CCH3)2). the solvent is acetic acid or tert-butyl alcohol and the oxygen source is the previously suggested hydrogen peroxide (H202)[17]. 

The alkene is allowed to react at low temperatures with a mixture of aqueous hydrogen peroxide, base, and a co-solvent to give a low conversion of the alkene (29). These conditions permit reaction of the water-insoluble alkene and minimise the subsequent ionic reactions of the epoxide product. Phase-transfer techniques have been employed (30). A variation of this scheme using a peroxycarbimic acid has been reported (31). 

The amount of oxygen evolved is not related to the degree of bleaching (40). Oxidative decoloring is caused by hydrogen peroxide or by the HO ions present in alkaline solution. Hydrogen peroxide is also an effective solvent for melanin (41). 

Ca.ta.lysis by Protons. The discovery of hydrogen peroxide hydroxylation of phenol in the presence of strong acids such as perchloric, trifluoromethane-sulfonic, or sulfuric acids allows suppression of all previous drawbacks of the process (18,19). This mode of hydroxylation gives high yields (85% based on H2O2 at phenol conversion of 5—6%). It can be mn without solvents and does not generate resorcinol. Its main advantage rehes on... 

Fig. 1. Time courses of the chemiluminescence intensity from oxalate—hydrogen peroxide systems in ethyl acetate as solvent, 0.7 mM TCPO. The curves correspond to the following concentrations of triethylamine (TEA) catalyst A, 0.05 mM B, 0.10 mM and C, 0.20 mM (70).

Reaction takes place ia aqueous solution with hydrogen peroxide and catalysts such as Cu(II), Cr(III), Co(II), ferricyanide, hernia, or peroxidase. Chemiluminescent reaction also takes place with oxygen and a strong base ia a dipolar aprotic solvent such as dimethyl sulfoxide. Under both conditions Qcis about 1% (light emission, 375—500 am) (105,107). 

Oxidation. Maleic and fumaric acids are oxidized in aqueous solution by ozone [10028-15-6] (qv) (85). Products of the reaction include glyoxyhc acid [298-12-4], oxalic acid [144-62-7], and formic acid [64-18-6], Catalytic oxidation of aqueous maleic acid occurs with hydrogen peroxide [7722-84-1] in the presence of sodium tungstate(VI) [13472-45-2] (86) and sodium molybdate(VI) [7631-95-0] (87). Both catalyst systems avoid formation of tartaric acid [133-37-9] and produce i j -epoxysuccinic acid [16533-72-5] at pH values above 5. The reaction of maleic anhydride and hydrogen peroxide in an inert solvent (methylene chloride [75-09-2]) gives permaleic acid [4565-24-6], HOOC—CH=CH—CO H (88) which is useful in Baeyer-ViUiger reactions. Both maleate and fumarate [142-42-7] are hydroxylated to tartaric acid using an osmium tetroxide [20816-12-0]/io 2LX.e [15454-31 -6] catalyst system (89). 

Acid-cataly2ed hydroxylation of naphthalene with 90% hydrogen peroxide gives either 1-naphthol or 2-naphthiol at a 98% yield, depending on the acidity of the system and the solvent used. In anhydrous hydrogen fluoride or 70% HF—30% pyridine solution at — 10 to + 20°C, 1-naphthol is the product formed in > 98% selectivity. In contrast, 2-naphthol is obtained in hydroxylation in super acid (HF—BF, HF—SbF, HF—TaF, FSO H—SbF ) solution at — 60 to — 78°C in > 98% selectivity (57). Of the three commercial methods of manufacture, the pressure hydrolysis of 1-naphthaleneamine with aqueous sulfuric acid at 180°C has been abandoned, at least in the United States. The caustic fusion of sodium 1-naphthalenesulfonate with 50 wt % aqueous sodium hydroxide at ca 290°C followed by the neutralization gives 1-naphthalenol in a ca 90% yield. 

The anhydride can be made by the Hquid-phase oxidation of acenaphthene [83-32-9] with chromic acid in aqueous sulfuric acid or acetic acid (93). A postoxidation of the cmde oxidation product with hydrogen peroxide or an alkaU hypochlorite is advantageous (94). An alternative Hquid-phase oxidation process involves the reaction of acenaphthene, molten or in alkanoic acid solvent, with oxygen or acid at ca 70—200°C in the presence of Mn resinate or stearate or Co or Mn salts and a bromide. Addition of an aHphatic anhydride accelerates the oxidation (95). 

Aqueous Phase. In contrast to photolysis of ozone in moist air, photolysis in the aqueous phase can produce hydrogen peroxide initially because the hydroxyl radicals do not escape the solvent cage in which they are formed (36). 

PoUowing further development (38), a two-cycle process has been adopted by industry. In the first concentration cycle, the clarified feed acid containing 100—200 mg/L U Og [1334-59-8] is oxidized, for example, with hydrogen peroxide or sodium chlorate [7775-09-9] to ensure that uranium is in its 6+ valence state is not extracted. Uranium is extracted with a solvent composed of 0.5 Af D2EHPA and 0.125 Af TOPO dissolved in an aUphatic hydrocarbon diluent. 

Amine oxides used in industry are prepared by oxidation of tertiary amines with hydrogen peroxide solution using either water or water and alcohol solution as a solvent. A typical industrial formulation is as follows ... 

Industrial specifications for aHphatic tertiary amine oxides generally requite an amine oxide content of 20—50%. These products may contain as much as 5% unreacted amine, although normally less than 2% is present. Residual hydrogen peroxide content is usually less than 0.5%. The most common solvent systems employed are water and aqueous isopropyl alcohol, although some amine oxides are available ia aoapolar solveats. Specificatioas for iadividual products are available from the producers. 

Eatty amine oxides are most frequendy prepared from alkyldimethylarnines by reaction with hydrogen peroxide. Aqueous 2-propanol is used as solvent to prepare amine oxides at concentrations of 50—60%. With water only as a solvent, amine oxides can only be prepared at lower concentrations because aqueous solutions are very viscous. Eatty amine oxides are weak cationic surfactants. 

Peracid Processes. Peracids, derived from hydrogen peroxide reaction with the corresponding carboxyUc acids in the presence of sulfuric acid and water, react with propylene in the presence of a chlorinated organic solvent to yield propylene oxide and carboxyUc acid (194—196). 

The refining process most commonly used involves treatment with hot aqueous alkaH to convert free fatty acids to soaps, followed by bleaching, usually with hydrogen peroxide, although sodium chlorite, sodium hypochlorite, and ozone have also been used. Other techniques include distillation, steam stripping, neutralization by alkaH, Hquid thermal diffusion, and the use of active adsorbents, eg, charcoal and bentonite, and solvent fractionation... 

The residue is leached to give cesium sulfate solution, which can be converted to cesium chloride by ion exchange on Dowex 50 resin and elution with 10% HCl, treatment using ammonia or lime, to precipitate the alurninum, or by solvent extraction, followed by purification at neutral pH using hydrogen peroxide or ammonia. 

The selective epoxidation of ethylene by hydrogen peroxide ia a 1,4-dioxane solvent ia the presence of an arsenic catalyst is claimed. No solvent degradation is observed. Ethylene oxide is the only significant product detected. The catalyst used may be either elemental arsenic, an arsenic compound, or both. 

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