Alcohols electrolytes

Alcohol Electrolyte Current density (mA/cm ) Yield carboxylic acid (%)... 

Acidic-alcoholic electrolytes may be used 377), but divided cells have to be employed in this case. In electrolytes consisting of amines and Li salts, the aromatic B ring in steroids can be converted selectively into the 9-a-H-dihydro compound 378) ... 

Ethoxylated Sulfate Surfactants onto Mineral Oxides and Sandstone Cores. Various features of anionic surfactant systems in EOR have been illustrated in a series of studies using ethoxylated sulfates as the primary surfactants with additives which included co-surfactants, alcohols, electrolytes, polyethylene oxide and polymers [63-70], The solids included kaolinite, quartz, sandstone cores, Berea cores, and oil containing reservoir cores. 

If an alcohol surfactant is incorporated in the electroljde, then the porosity of a layer will depend on the dilution used, higher porosities being obtained with higher alcohol content. As mentioned previously, the in situ chemical leaching of a layer (with or without electrical bias) in HF-alcohol electrolytes can be used to good effect to increase porosity (Halimaoui 1994 Herino et al. 1987) and pore size (Herino et al. 1987 Herino 1997). 

Two new routes to allyl vinyl ethers, suitable substrates for Claisen rearrangement, are summarized in Scheme 41 and equation (22) one involves copper-catalysed solvolytic cleavage by an allylic alcohol of (E)-alkenylpentafluorosili-cates available from hydrosilylation of alkynes," and the other is based on the base-promoted reaction of dimethyl diazomethylphosphonate with aliphatic ketones in the presence of an allylic alcohol." Electrolytic synthesis of allylic ethers direct from alkenes has been discussed earlier in this Report (Scheme 11). ... 

Cationic surfactants may be used [94] and the effect of salinity and valence of electrolyte on charged systems has been investigated [95-98]. The phospholipid lecithin can also produce microemulsions when combined with an alcohol cosolvent [99]. Microemulsions formed with a double-tailed surfactant such as Aerosol OT (AOT) do not require a cosurfactant for stability (see, for instance. Refs. 100, 101). Morphological hysteresis has been observed in the inversion process and the formation of stable mixtures of microemulsion indicated [102]. 

Reduction. These hydroxybenzaldehydes can be reduced by catalytic hydrogenation over palladium or platinium to yield the corresponding hydroxybenzyl alcohols, but the electrolytic reduction in an alkaline medium gives the coupling product l,2-bis(4-hydroxyphenyl)ethane-l,2-diol in very good yield from 4-hydroxybenzaldehyde (49—51). 

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. 

The molten carbonate fuel ceU uses eutectic blends of Hthium and potassium carbonates as the electrolyte. A special grade of Hthium carbonate is used in treatment of affective mental (mood) disorders, including clinical depression and bipolar disorders. Lithium has also been evaluated in treatment of schizophrenia, schizoaffective disorders, alcoholism, and periodic aggressive behavior (56). 

The covalent character of mercury compounds and the corresponding abiUty to complex with various organic compounds explains the unusually wide solubihty characteristics. Mercury compounds are soluble in alcohols, ethyl ether, benzene, and other organic solvents. Moreover, small amounts of chemicals such as amines, ammonia (qv), and ammonium acetate can have a profound solubilizing effect (see COORDINATION COMPOUNDS). The solubihty of mercury and a wide variety of mercury salts and complexes in water and aqueous electrolyte solutions has been well outlined (5). 

Micellar properties are affected by changes in the environment, eg, temperature, solvents, electrolytes, and solubilized components. These changes include compHcated phase changes, viscosity effects, gel formation, and Hquefication of Hquid crystals. Of the simpler changes, high concentrations of water-soluble alcohols in aqueous solution often dissolve micelles and in nonaqueous solvents addition of water frequendy causes a sharp increase in micellar size. 

Reduction of vanillin by means of platinum black in the presence of ferric chloride gives vanillin alcohol in excellent yields. In 1875, Tiemann reported the reduction of vanillin to vanillin alcohol by using sodium amalgam in water. The yields were poor, however, and there were a number of by-products. High yields of vanillin alcohol have been obtained by electrolytic reduction. 

Almost 40 years later the Lummus Co. patented an integrated process involving the addition of chlorine along with the sodium chloride and sodium hydroxide from the cathode side of an electrolytic cell to a tertiary alcohol such as tertiary butanol to produce the tertiary alkyl hypochlorite. The hypochlorite phase separates, and the aqueous brine solution is returned to the electrolytic cells. The alkyl hypochlorite reacts with an olefin in the presence of water to produce a chlorohydrin and the tertiary alcohol, which is returned to the chlorinator. With propylene, a selectivity to the chlorohydrin of better than 96% is reported (52). A series of other patents covering this technology appeared during the 1980s (53—56). 

Latex Types. Latexes are differentiated both by the nature of the coUoidal system and by the type of polymer present. Nearly aU of the coUoidal systems are similar to those used in the manufacture of dry types. That is, they are anionic and contain either a sodium or potassium salt of a rosin acid or derivative. In addition, they may also contain a strong acid soap to provide additional stabUity. Those having polymer soUds around 60% contain a very finely tuned soap system to avoid excessive emulsion viscosity during polymeri2ation (162—164). Du Pont also offers a carboxylated nonionic latex stabili2ed with poly(vinyl alcohol). This latex type is especiaUy resistant to flocculation by electrolytes, heat, and mechanical shear, surviving conditions which would easUy flocculate ionic latexes. The differences between anionic and nonionic latexes are outlined in Table 11. 

The o-nitrobenzyl and p-nitrobenzyl ethers can b prepared and cleaved by many of the methods described for benzyl ethers. The p-nitrobenzyl ether is also prepared from an alcohol and p-nitrobenzyl alcohol (trifluoroacetic anhydride, 2,6-lutidine, CH2CI2, 67% yield). In addition, the o-nitrobenzyl ether can be cleaved by irradiation (320 nm, 10 min, quant, yield of carbohydrate " 280 nm, 95% yield of nucleotide ). The p-nitrobenzyl ether has been cleaved by electrolytic reduction (—1.1 V, DMF, R4N X, 60% yield) and by reduction with Na2S204 (pH 8-9, 80-95% yield). These ethers can also be cleaved oxidatively (DDQ or electrolysis) after reduction to the aniline derivative. ... 

The p-cyanobenzyl ether, prepared from an alcohol and the benzyl bromide in the presence of sodium, hydride (74% yield), can be cleaved by electrolytic reduction (—2.1 V, 71% yield). It is stable to electrolytic removal ( — 1.4 V) of a tritylone ether [i.e., 9-(9-phenyl-10-oxo)anthiyl ether]. ... 

Picolyl ethers are prepared from their chlorides by a Williamson ether synthesis (68-83% yield). Some selectivity for primary versus secondary alcohols can be achieved (ratios = 4.3-4.6 1). They are cleaved electrolytically ( — 1.4 V, 0.5 M HBF4, MeOH, 70% yield). Since picolyl chlorides are unstable as the free base, they must be generated from the hydrochloride prior to use. These derivatives are relatively stable to acid (CF3CO2H, HF/anisole). Cleavage can also be effected by hydrogenolysis in acetic acid. ... 

The tritylone ether is used to protect primary hydroxyl groups in the presence of secondary hydroxyl groups. It is prepared by the reaction of an alcohol with 9-phenyl-9-hydroxyanthrone under acid catalysis (cat. TsOH, benzene, reflux, 55-95% yield).It can be cleaved under the harsh conditions of the WolfT-Kishner reduction (H2NNH2, NaOH, 200°, 88% yield), " and by electrolytic reduction (-1.4 V, LiBr, MeOH, 80-85% yield). It is stable to 10% HCl, 55 h. ... 

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