Petroleum, ethanol from

Place I g. of powdered 3,5-dinitrobenzoyl chloride in a small conical flask, add 2 5 ml. of dry methanol, and warm on a water-bath until the solid has dissolved. Cool and filter off the 3,5-dinitrobenzoate which has separated. Recrystallise from ethanol or petroleum (b.p. 60-80°). The ester separates in colourless crystals, m.p. 108°. Yield,... 

Ethanol s use as a chemical iatemiediate (Table 8) suffered considerably from its replacement ia the production of acetaldehyde, butyraldehyde, acetic acid, and ethyUiexanol. The switch from the ethanol route to those products has depressed demand for ethanol by more than 300 x 10 L (80 x 10 gal) siace 1970. This decrease reflects newer technologies for the manufacture of acetaldehyde and acetic acid, which is the largest use for acetaldehyde, by direct routes usiag ethylene, butane (173), and methanol. Oxo processes (qv) such as Union Carbide s Low Pressure Oxo process for the production of butanol and ethyUiexanol have totaUy replaced the processes based on acetaldehyde. For example, U.S. consumption of ethanol for acetaldehyde manufacture declined steadily from 50% ia 1962 to 37% ia 1964 and none ia 1990. Butadiene was made from ethanol on a large scale duriag World War II, but this route is no longer competitive with butadiene derived from petroleum operations. 

Ethylene. Where ethylene is ia short supply and fermentation ethanol is made economically feasible, such as ia India and Bra2il, ethylene is manufactured by the vapor-phase dehydration of ethanol. The production of ethylene [74-85-1] from ethanol usiag naturally renewable resources is an active and useful alternative to the pyrolysis process based on nonrenewable petroleum. This route may make ethanol a significant raw material source for produciag other chemicals. 

Solid esters are easily crystallisable materials. It is important to note that esters of alcohols must be recrystallised either from non-hydroxylic solvents (e.g. toluene) or from the alcohol from which the ester is derived. Thus methyl esters should be crystallised from methanol or methanol/toluene, but not from ethanol, n-butanol or other alcohols, in order to avoid alcohol exchange and contamination of the ester with a second ester. Useful solvents for crystallisation are the corresponding alcohols or aqueous alcohols, toluene, toluene/petroleum ether, and chloroform (ethanol-free)/toluene. Esters of carboxylic acid derived from phenols... 

Ethanol in the past has been used commercially to synthesize dozens of other high-volume chemical commodities. However, at present, it has been substituted in many applications by less costly petrochemical feedstocks, e.g., ethylene. The availability of low-cost ethanol and the rising cost of ethylene, however, may change this scenario. For example, there is interest in producing ethylene from ethanol [71-73], while the opposite reaction is commercially current. Already, in markets with abundant agricultural products, but a less developed petrochemical infrastructure, such as the People s Republic of China, Pakistan, India, and Brazil, ethanol can be used to produce chemicals, including ethylene and butadiene, that would be produced from petroleum in the West. For example, ethanol may substitute alkenes for the alkylation of aromatics [82]. 

The partition of different lipids between two immiscible solvents (countercurrent distribution) is useful for crude fractionation of lipid classes with greatly differing polarities. Repeated extractions in a carefully chosen solvent pair increase the effectiveness of the separation but in practice mixtures of lipids are still found in each fraction. A petroleum ether-ethanol-water system can be used to remove polar contaminants (into the alcoholic phase) when interest lies in the subsequent analysis of neutral glycerides, which may be recovered from the ether phase. Carbon... 

The situation with regard to ethanol is much clearer there is long industrial experience in the manufacture of ethanol from wood, by fermentation of the sugars in the waste effluents of pulp mills, or of the sugars made by wood hydrolysis ( ). In the years following World War II, wood hydrolysis plants have been unable to compete economically with petroleum-based ethanol synthesis, mainly by hydration of ethylene, and they have been shut down in most countries. However, in the Soviet Union, we understand, there are still about 30 wood hydrolysis plants in operation (10). Many of these are used for fodder yeast production (11) but the wood sugars are also available for ethanol production. 

These two ethers are used as blending agents (antiknock effect) in the petroleum industry. Especially, ethyl ferf-butyl ether is expected to become the most widely used octane booster on gasoline blending. Ethyl fcrf-butyl ether is mainly produced on an industrial scale by the reaction of isobutene with an excess of ethanol. Thus, the separation from ethanol is very important. 

In a distillation apparatus fitted with mechanical stirrer, thermometer, and provisions for adding solids, to an agitated mixture of 26.7 gm (0.187 mole) erf 2-naphthylamine (CAUTION carcinogenic material) and 20 gm (0.163 mole) of nitrobenzene maintained at 180°C is added slowly 17 gm of powdered sodium hydroxide over a 20 min period. After completion of the addition, heating is continued for 10 min. After cooling, the reaction mixture is treated repeatedly with dilute hydrochloric acid. The excess nitrobenzene is then separated by steam distillation. The residue from the steam distillation is treated with ethanol at 70°C to precipitate insoluble impurities which are removed by filtration. On cooling the filtrate, product cyrstals separate which, after filtration, are taken up in petroleum ether, leaving petroleum ether-insoluble impurities behind. The petroleum ether extract is evaporated to dryness and the residue is recrystallized from ethanol at 75°C yield 17 gm (41 %), m.p. 84°C. 

To separate the components of this reaction mixture, the crude product is dissolved in a minimum quantity of petroleum ether. The solution is then passed through a 2 x 20 cm chromatography column packed with aluminum oxide. The nitro and azo compounds are eluted from the column first with sufficient petroleum ether. The azoxy compound is eluted with petroleum ether containing 1 % of methanol. The eluting solvent is evaporated and the residual product is recrystallized from ethanol, m.p. 117°-118°C, nematic-liquid transition point 134°C. 

Composition. Crystals deposited from ethanol solution as well-formed thin plates. The fatty acid content of the crystals is given in Table I. For all chain lengths the acid content approximates closely that required for 1 to 1 stoichiometry. This is also the case for most of the acid-soaps prepared by the petroleum ether route the low values of titratable acid in some instances are ascribable to the presence of free soap. 

Figure I. Differential thermograms of potassium acid-soaps (Hormel and Baker fatty acids) prepared from ethanol and petroleum ether...

To prepare DCC from dicyclohexylurea recrystallise the recovered urea from ethanol m.p. 234 °C. Add dropwise with stirring 17.1 g (47 ml, 0.11 mol) of phosphorus oxychloride to 22.5 g (0.1 mol) of dicyclohexylurea in 50 ml of pyridine at 50 °C, and heat at 60-90 °C for 1.5 hours. Pour the reaction product on to crushed ice, extract with light petroleum (b.p. 60-80 °C) and dry the extract over anhydrous sodium sulphate. Remove the solvent using a rotary evaporator and distil the residual oil under reduced pressure. The yield of diimide, b.p. 157-159°C/15mmHg (131 °C/3-4mmHg), is about 14g (68%). 

The Schotten-Baumann method of benzoylation with benzoyl chloride in the presence of aqueous sodium hydroxide may be used. Full details are given under Primary and secondary amines, Section 9.6.21, p. 1273. Alternatively, dissolve 1.0 g of the phenol in 3 ml of dry pyridine and add 0.5 g of benzoyl chloride. After the initial reaction has subsided, warm the mixture over a small flame for a minute or two and pour, with vigorous stirring, into 10-15 ml of water. Allow the precipitate to settle, decant the supernatant liquid, stir the residue thoroughly with 5-10 ml of m sodium carbonate solution, filter and recrystallise from ethanol or from light petroleum. 

Dissolve 0.5 g of the phenol in 4-5 ml of dry pyridine, add 1.3 g of 3,5-dinitro-benzoyl chloride and reflux for 25-30 minutes. Pour the cold reaction mixture into 40 ml of c. 2 M-hydrochloric acid. Decant the supernatant aqueous liquid from the precipitated solid or oil and stir it vigorously with about 10 ml of m sodium carbonate solution. Filter off the solid derivative and wash it with water. Recrystallise from ethanol, dilute ethanol, toluene-acetone or toluene-light petroleum (b.p. 60-80 °C). 

Dissolve 0.5 g of the phenol in 2.5 ml of pyridine, and add one equivalent of diphenylcarbamoyl chloride (or 0.4—0.5 g if the molecular weight is uncertain). Reflux the mixture for 30-60 minutes on a boiling-water bath, and then pour into about 25 ml of water. Filter the derivative, wash with a little sodium hydrogen carbonate solution and recrystallise from ethanol, toluene, light petroleum (b.p. 60-80 °C) or dichloromethane. 

For water-insoluble aldehydes or ketones, the following alternative procedure may be used. Reflux a mixture of 0.5 g of the aldehyde or ketone, 0.5 g of hydroxylamine hydrochloride, 5 ml of ethanol and 0.5 ml of pyridine on a water bath for 15-60 minutes. Remove the ethanol either by distillation (water bath) or by evaporation of the hot solution in a stream of air (water pump). Add 5 ml of water to the cooled residue, cool in an ice bath and stir until the oxime crystallises. Filter off the solid, wash it with a little water and dry. Recrystallise from ethanol (95% or more dilute), benzene or benzene-light petroleum (b.p. 60-80 °C). 

An amount of 40 g. of 2,3,4,6-tetra-O-acetyl-a-D-glucosyl bromide is warmed with 12 g. of diethylamine in 20 ml. of dry benzene at 60° until dissolved. (Benzene is often replaced by chloroform, and the initial warming is often omitted.) After 32 hours at room temperature, the reaction mixture is extracted with dry ether, and the diethylamine hydrobromide is removed by filtration. The filtrate is washed once with dilute sulfuric acid and twice with water and is dried over calcium chloride. After evaporation of the ether under diminished pressure, the residue is dissolved in the least possible amount of hot alcohol. Crystallization occurs after the addition, with stirring, of petroleum ether to the cooled solution. Yield of crude 2,3,4,6-tetra-0-acetyl-(2-hy-droxy-D-glucal), 17 g. (51% of the theoretical). Itecrystallization is effected from hot water or from ethanol with the addition of water to turbidity.1 2... 

To a mixture of sugar bromide (5.84 g) in toluene (100 ml) were added Bu3SnH (12.34 g, 42.4 mmol) and AIBN (0.2 g, 1.2 mmol) under a nitrogen atmosphere. The mixture was heated at 95 °C for 75 min. After the reaction, the mixture was cooled and was poured into petroleum ether. The mixture obtained was filtered and washed with petroleum ether. The solids were recrystallized from ethanol to give 3/-deoxyadenosine in 41% yield [30]. 

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