Anhydrous ethanol with liquid solvent

Extractive distillation with liquid solvent is used commercially for the production of anhydrous ethanol from ethanol-water mixtures. This method uses a relatively nonvolatile liquid solvent, such as ethylene glycol, which is fed into a distillation column some trays above the ethanol feed tray. The presence of the solvent at relatively high concentration in the liquid on the trays alters the volatility of one of the feed components more than the other, so a separation of the feed components can be made in the column. 

Diphenyl Tellurium2 A 500-ml, three-necked flask fitted with a dry ice/ethanol cold finger condenser, a nitrogen inlet, and a magnetic stirrer is charged with 250 ml of liquid ammonia. 1.6 g (4 mmol) of diphenyl ditellurium are added followed by 0.2 g (8.7 mmol) of sodium in small pieces which are added over 20 min until the blue color persists. Then, 1.6 g (8 mmol) iodobenzene arc added and the stirred mixture is irradiated with a 250 W UV lamp for 220 min. The reaction is quenched by addition of 10 m/ of distilled water, the ammonia is allowed to evaporate, the residue is treated with 100 ml of water, and the solution is extracted with three 100 ml portions of diethyl ether. The combined extracts are dried with anhydrous sodium sulfate, the solvent is evaporated, and the residue is distilled or converted to diphenyl tellurium dibromide by treatment with bromine yield 2.0 g (90%) b.p. 182"/14torr. 

The crude bromo ester is mixed with 82.5 ml. (0.70 mole) of pure quinoline (Note 3) in a 250-ml. round-bottomed flask equipped with an air condenser, and the mixture is heated for 3 hours with an oil bath maintained at 160-170°. The black mixture is cooled, treated with 150 ml. of 20% hydrochloric acid, then shaken thoroughly with 200 ml. of petroleum ether (Note 2) until most of the tarry material has dissolved (Note 4). The aqueous phase is separated and washed with an additional 200 ml. of petroleum ether, and the combined organic extracts are washed with 10% hydrochloric acid and then with water. This washing cycle is repeated until the washes are colorless (two acid washes usually suffice) finally, the petroleum ether solution is washed once more with water. The organic layer is dried over anhydrous sodium sulfate, the solvent is flash-distilled as described above, and the residual liquid ester is distilled through a 61-cm. Pod-bielniak-type column (Note 5). The colorless unsaturated ester (Note 6) distils at 153-154°/14.5 mm. after a small fore-run. The yield is 22-27 g. (70-85.5% based on 2-methyldodecanoic acid), 1.4520-31, Xmax 214 me 12,300, in hexane (Note 7), Xmax 217 mii, e 12,800, in 95% ethanol. 

Application of solid-liquid extraction in the field of Inorganic Chemistry can be illustrated by taking the examples of separation of (i) lithium chloride from the chlorides of other members of the alkali metal group and (ii) calcium nitrate from the nitrates of other members of the alkaline earth group. The solubilities of sodium chloride and potassium chloride are very small in -hexanol and 2-ethylhexanol, whereas the solubility of lithium chloride is large enough so that it can be separated from a mixture of the three chlorides by extraction with these solvents. Similarly, using a 50-50 per cent mixture of absolute ethanol and ether calcium nitrate can be removed from a mixture of the anhydrous nitrates of calcium, barium and strontium. 

Dodecylaniline (10). Anhydrous ethanol (50 mL), 3-(l -dodecynyl)nitrobenzene (14.21 g, 49.51 mmol) and 10% Pd/C (2.50 g) were placed in a Parr flask. The flask was purged with H2 before pressurizing to 65 psi and heating to 65 °C. The pressure was maintained at 65 psi for 5 h. The Pd/C was then filtered and the solvent removed in vacuo to afford 12.54 g (97%) of the title compound as a brown liquid that solidified upon standing into... 

Extraction of DLTDP from the liquid paraffin extractant DLTDP could not be determined in the liquid paraffin extractant in amoimts of less than 100 ppm by direct infrared spectroscopy, nor was it possible to devise a preliminary solvent extraction procedure to obtain a DLTDP concentrate as was achieved in the case of the aqueous extractants. The results obtained in trial extractions of liquid paraffin with various solvents (Table 4.2) indicate that neat or anhydrous methanol (10%), ethanol or... 

B. 1-Benzylindole. The slurry of indole sodium is cooled to 0° (ice bath), and 2.30 ml. (2.53 g., 0.02 mole) of benzyl chloride (Note 5) is added as rapidly as possible to the stirred mixture. The mixture is then stirred for 8-15 hours (overnight), during which time the ice in the ice bath melts and the temperature of the reaction flask gradually rises to room temperature. The mixture is then diluted with 15 ml. of water and extracted with three 25-ml. portions of ether. The combined ethereal extracts are washed with two 40-ml. portions of water and dried with anhydrous magnesium sulfate. After filtration the solvent is removed at reduced pressure, and 4.4 g. of crude 1-benzylindole is obtained as a liquid. After bulb-to-bulb distillation of this material in a Kiigelrohr oven [120-130° (0.0025 mm.)], crystallization of the distillate from 15 ml. of hot ethanol affords 3.46-3.61 g. (83-87%) of 1-benzylindole. A second crop amounting to 0.17-0.26 g. (4-6%) is obtained on concentration of the mother liquors to 6 ml. The total yield of 1-benzylindole, m.p. 43-44°, is 3.72-3.78 g. (90-91%) (Notes 6 and 7). 

Electrolytes are ubiquitous and indispensable in all electrochemical devices, and their basic function is independent of the much diversified chemistries and applications of these devices. In this sense, the role of electrolytes in electrolytic cells, capacitors, fuel cells, or batteries would remain the same to serve as the medium for the transfer of charges, which are in the form of ions, between a pair of electrodes. The vast majority of the electrolytes are electrolytic solution-types that consist of salts (also called electrolyte solutes ) dissolved in solvents, either water (aqueous) or organic molecules (nonaqueous), and are in a liquid state in the service-temperature range. [Although nonaqueous has been used overwhelmingly in the literature, aprotic would be a more precise term. Either anhydrous ammonia or ethanol qualifies as a nonaqueous solvent but is unstable with lithium because of the active protons. Nevertheless, this review will conform to the convention and use nonaqueous in place of aprotic .]... 

Similar results were achieved when benzene was reduced with alkali metals in anhydrous methylamine at temperatures of 26-100°. Best yields of cyclohexene (up to 77.4%) were obtained with lithium at 85° [396]. Ethylamine [397] and especially ethylenediamine are even better solvents [398]. Benzene was reduced to cyclohexene and a small amount of cyclohexane [397, 398] ethylbenzene treated with lithium in ethylamine at —78° gave 75% of 1-ethyl-cyclohexene whereas at 17° a mixture of 45% of 1-ethylcyclohexene and 55% of ethylcyclohexane was obtained [397], Xylenes m- and p-) yielded non-conjugated 2,5-dihydro derivatives, l,3-dimethyl-3,6-cyclohexadiene and 1,4-dimethyl-1,4-cyclohexadiene, respectively, on reduction with sodium in liquid ammonia in the presence of ethanol (in poor yields) [399]. Reduction of diphenyl with sodium or calcium in liquid ammonia at —70° afforded mainly 1-phenylcyclohexene [400] whereas with sodium in ammonia at 120-125° mainly phenylcyclohexane [393] was formed. 

The hydrated chloride, bromide and iodide (Table 9) are soluble in ethanol, butanol and other organic solvents, but in many systems traces of water cause oxidation, hydrolysis or failure to complex with weak donor ligands. Water can be avoided by dissolving the metal in THF, ethanol or diethyl ether through which hydrogen chloride is bubbled.24,74 75 It is also possible to dissolve or suspend in organic solvents the anhydrous acetate or the halides CrX2 (Table 9), and dehydration of the hydrated halides with 2,3-dimethoxypropane in ethanol, followed by vacuum removal of the liquid, produces mixed alcoholates suitable for use in water-free conditions.76 Triethyl orthoformate may be used similarly. 

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