Alcohols, solvents

Alkoxyall l Hydroperoxides. These compounds (1, X = OR , R = H) have been prepared by the ozonization of certain unsaturated compounds in alcohol solvents (10,125,126). 2-Methoxy-2-hydroperoxypropane [10027-74 ] (1, X = OR , R" = methyl), has been generated in methanol solution and spectral data obtained (127). A rapid exothermic decomposition upon concentration of this peroxide in a methylene chloride—methanol solution at 0°C has been reported (128). 2-Bromo-l-methoxy-l-methylethylhydroperoxide [98821-14-8]has been distilled (bp 60°C (bath temp.), 0.013 kPa) (129). Two cycHc alkoxyaLkyl hydroperoxides from cyclodecanone have been reported (1, where X = OR R, R = 5-oxo-l, 9-nonanediyl) with mp 94—95°C (R" = methyl) and mp 66—68°C (R" = ethyl) (130). Like other hydroperoxides, alkoxyaLkyl hydroperoxides can be acylated or alkylated (130,131). 

Microbial-enhanced oil recovery involves injection of carefully chosen microbes. Subsequent injection of a nutrient is sometimes employed to promote bacterial growth. Molasses is the nutrient of choice owing to its low (ca 100/t) cost. The main nutrient source for the microbes is often the cmde oil in the reservoir. A rapidly growing microbe population can reduce the permeabiHty of thief zones improving volumetric sweep efficiency. Microbes, particularly species of Clostridium and Bacillus, have also been used to produce surfactants, alcohols, solvents, and gases in situ (270). These chemicals improve waterflood oil displacement efficiency (see also Bioremediation (Supplement)). 

A low temperature catalytic process has been reported (64). The process involves the divalent nickel- or zero-valent palladium-catalyzed self-condensation of halothiophenols in an alcohol solvent. The preferred halothiophenol is -bromothiophenol. The relatively poor solubiHty of PPS under the mild reaction conditions results in the synthesis of only low molecular weight PPS. An advantage afforded by the mild reaction conditions is that of making telecheHc PPS with functional groups that may not survive typical PPS polymerization conditions. 

Over 68 aerosol products containing isopropyl alcohol solvent have been reported (145). Aerosol formulations include hair sprays (146), floor detergents (147), shoe poHshes (148), insecticides (149,150), bum ointments (151), window cleaners, waxes and poHshes, paints, automotive products (eg, windshield deicer), insect repellents, flea and tick spray, air refreshers, disinfectants, veterinary wound and pinkeye spray, first-aid spray, foot fungicide, and fabric-wrinMe remover (152) (see Aerosols). 

Raw lac is first treated to remove water-soluble carbohydrates and the dye that gives lac its red color. Also removed are woody materials, insect bodies, and trash. It is further refined by either hot filtration or a solvent process. In the heat process, the dried, refined lac is filtered molten through cloth or wine screens to produce the standard grades of orange shellac. In the solvent process, lac is dissolved and refluxed in alcohol solvents, filtered to remove dirt and impurities, and concentrated by evaporation. The lac can be further decolori2ed in this process to produce very pale grades. Bleached shellac is prepared by treatment with dilute sodium hypochlorite and coalesced into slabs. 

Aldehydes can be dkeedy converted to esters using bromine in alcohol solvents with sodium bicarbonate buffer (41). 

Higher butyryl esters, formulated with acryUc polymers, provide coatings with excellent weather resistance, good colorfastness and dispersibiUty, and good flow properties (154). Formulations for a typical automotive refinishing lacquer and a wood furniture lacquer are given in Tables 12 and 13, respectively. Low viscosity, high butyryl cellulose esters tolerate substantial amounts of alcohol solvent without appreciable increase in solution viscosity. 

The wash primer is a special type of vinyl coating. This material contains a poly(vinyl butyral) resin, zinc chromate, and phosphoric acid in an alcohol-water solvent. The coating is so thin it is HteraUy washed onto a freshly blasted steel surface, where it passivates the metal surface by converting it to a thin iron phosphate-chromate coating. The alcohol solvent makes it possible to apply the coating over damp surfaces. The coating forms the first coat of... 

Irradiation of 3,5-disubstituted isoxazoles in alcoholic solvents gave reaction products such as acetals incorporating the reaction solvent. The use of triethylamine in acetonitrile media produced ketene-aminals by reductive ring cleavage. The reductive ring cleavage product was also obtained by irradiation of the isoxazole in alcohol in the presence of copper(II) salts (Scheme 3) (76JCS(P1)783). 

Because of the presence of alkali in Raney nickel, ketones are hydrogenated over this catalyst to yield the more stable, equatorial alcohol e.g. 59) as the predominant product, Similar results can be expected with platinum in basic media or with platinum oxide in an alcoholic solvent since this catalyst also contains basic impurities. 

The reaction is generally carried out in an alcoholic solvent, resulting in formation of the acetal the general scheme is called the Mattox rearrangement, and the yields are usually high. If a nonalcoholic solvent and acid are used, the aldehyde is obtained directly, but in lower yield. However, the use of zinc acetate as catalyst instead of an acid permits isolation of the aldehyde in ca. 50 % yield. Tire use of refluxing acetic acid alone... 

H2NNH2) and base (KOH) in a high-boiling alcohol solvent. 

Vinylogous amides, which have an enamine function in conjugation with a carbonyl group, constitute tridentate systems and thus open the possibility of alkylation on carbon, nitrogen, or oxygen. It has been found that the pyrrolidine enamine of acetylacetone gives rise to a carbon mcthylation but an oxygen ethylation product 41). The alkylation of cyclic 1,3-diketone-derived enamines has been studied 41,283). O Alkylation was found in alcohol solvents and predominant C alkylation in nonprotonic solvents. 

PhCHO, CHCI3, 3A molecular sieves NaBH4 alcohol solvent, 66% yield. These conditions were used to protect selectively the terminal ends of a polyamine. ... 

The first step of the Combes reaction has been reported to occur by merely mixing an aniline and diketone in an alcoholic solvent, or neat, with slight warming. Dilute aqueous acid (2 M HCl), AcOH, ZnCh as well as CaCl2, or other types of drying agents have been used to promote the first step. 

The rearrangement has been found to be substrate specific. In some cases, the reaction proceeds as described above, i.e. using alkoxide in alcoholic solvent. In other cases, these conditions do not work well, or the reaction has been found to work better under pressure at elevated temperature in alcoholic solvents, in DMSO, DMF," or toluene. Rigorous exclusion of moisture and carbon dioxide is necessary."... 

The benzothiazine equivalent of a 1,7 naphthyridine (58) has also been prepared. The reaction did not work in alcoholic solvents, but when DMF was used 57 rearranged to provide the desired product in moderate yield. 

The Beirut reaction involves the condensation of benzofurazan oxide (BFO) 1 with an enamine 2 or an enolate anion 3 in an alcohol solvent to give the corresponding quinoxaline-1,4-dioxide 4. ... 

Alcohol. Melting-point of j-nitrobenzyl Phthalate. Strength oi Alcohol Solvent. No of c.c. of Alcohol Required for about 1 3 Grams. 

Hydrogenation of carbonyls, or incipient carbonyls such as phenols (86), in lower alcohol solvents may result in the formation of ethers. The ether arises through formation of acetals or ketals with subsequent hydrogenolysis. The reaction has been made the basis of certain ether syntheses (45,97). Reaction of alcohols with carbonyls may be promoted by trace contamination, such as iron in platinum oxide (22,53), but it is also a property of the hydrogenation catalyst itself. So strong is the tendency of palladium-hydrogen to promote acetal formation that acetals may form even in basic media (61). 

Reductive alkylation by alcohol solvents may occur as an unwanted side reaction 22,39), and it is to avoid this reaction that Freifelder (20) recom mends ruthenium instead of nickel in pyridine hydrogenation. Alkylation by alcohols may occur with surprising ease 67). Reduction of 18 in ethanol over 10% palladium-on carbon to an amino acid, followed bycyclization with /V,/V-dicyclohexylcarbodiimide gave a mixture of 19 and 20 wiih the major product being the /V-ethyl derivative 49,50). By carrying out the reduction in acetic acid, 20 was obtained as the sole cyclized product 40). 

An excellent route to cyclohexylamines is by hydrogenation of the corresponding aniline over rhodium or ruthenium (17,18,19 2 36,63,64). Rhodium has proved especially useful in saturation of alkoxyanilines with minimal hydrogenolysis of the alkoxy function (45), The extent of hydrogenol ysis occurring in saturation of alkoxyanilines depends also on the solvent. Hydrogenolysis of p-methoxyaniline over Ru(OH)2 fell with alcohol solvent in the order methanol (35%) > ethanol (30%) > propanol (26%) > butanol (22%) > isopropanol (16%) > r-butanol (8%) (43). 

A variety of solvents have been used successfully. Extensive hydrolysis or alcoholysis may accompany reduction in aqueous or alcoholic solvent, attack presumably occurring on the intermediate vinyl ether (SS). 

Safety No year goes by without some widely used chemical being declared suspect on toxicity grounds. The paint industry has responded rapidly to eliminate toxic chemicals from coatings or to show how they can be used safely in an industrial environment. Examples are the elimination of specific ether-alcohol solvents and the introduction of air-fed hoods for spraying isocyanates. Of particular interest in corrosion prevention is the current pressure to eliminate chromate pigments. Currently there are no equally effective alternatives and the emphasis has had to be on safe usage. The search for replacements continues. 

Properties. Cypridina luciferin is soluble in water, methanol and other alcoholic solvents, but not in most aprotic solvents. The ultraviolet absorption spectra of luciferin and oxyluciferin are shown in Fig. 3.1.3. Luciferin in neutral solutions is yellow (lmax 432 nm ... 

The poor solubility of coelenterazine in neutral aqueous buffer solutions often hampers the use of this compound in biological applications. The simplest way to make an aqueous solution is the dilution of a methanolic 3 mM coelenterazine with a large volume of a desired aqueous buffer solution. If the use of alcoholic solvents is not permitted, dissolve coelenterazine in a small amount of water with the help of a trace amount of 1 M NaOH or NH4OH, and then immediately dilute this solution with a desired aqueous buffer solution. However, because of the rapid oxidation of coelenterazine in alkaline solutions, it is recommended that the procedure be carried out under argon gas and as quickly as possible. 

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