Ethyl acetate-calcium chloride

A method of prediction of the salt effect of vapor-liquid equilibrium relationships in the methanol-ethyl acetate-calcium chloride system at atmospheric pressure is described. From the determined solubilities it is assumed that methanol forms a preferential solvate of CaCl296CH OH. The preferential solvation number was calculated from the observed values of the salt effect in 14 systems, as a result of which the solvation number showed a linear relationship with respect to the concentration of solvent. With the use of the linear relation the salt effect can be determined from the solvation number of pure solvent and the vapor-liquid equilibrium relations obtained without adding a salt. 

The author selected the system containing salt which is not dissolved with other components but only with a particular component of a solvent mixture as a system with which the phenomenon of preferential solvate can be understood easily. Calcium chloride is dissolved with alcohol but it is not dissolved well with ester. Thus, calcium chloride forms a preferential solvate with alcohol and does not with ester. For the component system which consists of calcium chloride, alcohol, and ester, the author selected the following three systems for which vapor-liquid equibrium relations have been measured methanol-ethyl acetate-calcium chloride (I) methyl acetate-methanol-calcium chloride (3) and n-butyl acetate-n-butanol-calcium chloride (3). 

Figure 7. Result of prediction for methanol-ethyl acetate-calcium chloride system at 1 atm (O), observed (—), calculated.

Fit a 750 ml, bolt-head flask (also by a rubber stopper) to a reflux water-condenser closed at the top by a calcium chloride tube ensure that flask and condenser are quite dr). Place 150 ml. of the dried ethyl acetate in the flask and add 15 g. of sodium. The sodium for this purpose should preferably be added in the form of wire directly from a sodium press (Fig. 55, p. 82) alternatively the sodium may be added as thin slices, but in this case each slice should be quickly pressed between drying-paper before being added to the acetate to remove the wet film which may have formed during the weighing and cutting of the metal. 

Place 50 g. of anhydrous calcium chloride and 260 g. (323 ml.) of rectified spirit (95 per cent, ethyl alcohol) in a 1-litre narrow neck bottle, and cool the mixture to 8° or below by immersion in ice water. Introduce slowly 125 g. (155 ml.) of freshly distilled acetaldehyde, b.p. 20-22° (Section 111,65) down the sides of the bottle so that it forms a layer on the alcoholic solution. Close the bottle with a tightly fitting cork and shake vigorously for 3-4 minutes a considerable rise in temperature occurs so that the stopper must be held well down to prevent the volatilisation of the acetaldehyde. Allow the stoppered bottle to stand for 24-30 hours with intermittent shaking. (After 1-2 hours the mixture separates into two layers.) Separate the upper layer ca. 320 g.) and wash it three times with 80 ml. portions of water. Dry for several hours over 6 g. of anhydrous potassium carbonate and fractionate with an efficient column (compare Section 11,17). Collect the fraction, b.p. 101-104°, as pure acetal. The yield is 200 g. 

Pure commercial ethyl acetate is allowed to stand for 2 days over anhydrous calcium chloride, the desiccant removed by filtration, and the ester is then finally dried over anliydrous calcium sulphate for several hours. 

The live fireflies are dried over calcium chloride in a vacuum desiccator, and then their lanterns are separated by hand. An acetone powder prepared from the dried lanterns is extracted with boiling water. The cooled aqueous extract is extracted with ethyl acetate at pH 3.0, and the ethyl acetate layer is concentrated under reduced pressure. The concentrated luciferin is adsorbed on a column of Celite-Fuller s earth mixture. The column is washed with water-saturated ethyl acetate, and eluted with alkaline water at pH 8.0-8.5. The aqueous eluate of luciferin is adjusted to pH 3.0 with HCl and luciferin is... 

A solution of sodium ethylate is prepared from 60 g. (2.6 gram atoms) of clean sodium and 700 cc. of absolute alcohol (Note 1) in a 2-1. round-bottomed flask, equipped with a reflux condenser. To the hot solution is added a mixture of 234 g. (2 moles) of pure benzyl cyanide (Note 2) and 264 g. (3 moles) of dry ethyl acetate (Note 3). The mixture is thoroughly shaken, the condenser closed with a calcium chloride tube, and the solution heated on the steam bath for two hours before standing overnight (Note 4). The next morning the mixture is stirred with a wooden rod to break lumps, cooled in a freezing mixture to — io°, and kept at this temperature for two hours. The sodium salt is collected on a 6-in. Buchner funnel and washed four times on the funnel with 250-cc. portions of ether. The filter cake is practically colorless and corresponds to 250-275 g. of dry sodium salt, or 69-76 per cent of the calculated amount. The combined filtrates are placed in the freezing mixture until they can be worked up as indicated below. 

B. 2-Acetyl-6,l-dimethoxy-l-methylene-l,2,3,4-tetrahydroisoquinoline [Isoquinoline, 2-acetyl-l,2, A,4-tetrahydro-6,7-dimethoxy-l-methylene-]. A 1-1., three-necked, round-bottomed flask equipped with a mechanical stirrer, a reflux condenser topped with a calcium chloride drying tube, and a thermometer is charged with 110 ml. of acetic anhydride, 110 ml. of pyridine, and 45.0 g. (0.22 mole) of the dihydroisoquinoline prepared in Part A. The reaction mixture is stirred and heated at 90-95° for 30 minutes, stored at room temperature overnight, and concentrated by distillation at 50° using a rotary evaporator. The residue is diluted with 20 ml. of ethyl acetate, and another evaporation under reduced pressure gives material that can be crystallized from 75 ml. of ethyl acetate to yield 38.5 41.0 g. (72-77%) of product, m.p. 106-107° (Note 11). 

Ethyl 2-(D-amiino-tetrahydroxybutyl)-5-methyl-4-furoate (5.5 g.) is mixed with 80 ml. of dry benzene and 20 ml. of glacial acetic acid, and cooled in ice plus water. While stirring and cooling, 182 g. of lead tetraacetate (purity, 99.7%)62 is added during about sixty minutes stirring is continued until all the oxidant has been consumed. The lead dioxide is then removed by filtration, and the benzene solution is extracted twice with water.58 The benzene layer is dried with calcium chloride and the solvent is evaporated under diminished pressure, giving an oily residue which rapidly crystallizes in colorless plates yield, 3.6 g. (quantitative). The product is purified by recrystallization from dilute acetic acid or by steam distillation m.p., 57°. 

For acetone, chloroform, ethyl acetate, carbon bisulphide calcium chloride. 

Finely powdered sodamide (34 g.),a which is kept in a closed container, is added gradually in small portions to a mixture of 120 c.c. of ethyl acetate (purified as for the preparation of ethyl acetoacetate) and 32 c.c. of dry acetone. During the addition of the sodamide the mixture is cooled in a freezing mixture. The flask is provided with a cork or rubber stopper carrying a calcium chloride tube. A vigorous evolution of ammonia at once begins. After all the soda-... 

The ethyl acetate layer is washed with water, sodium bisulfite solution, saturated calcium chloride solution, and again with water. It is further purified as in Note 6, giving 316-400 g. of recovered ester. The amount of recovered ester depends somewhat upon the length of time the two layers are allowed to remain in contact before separating. 

Ethyl Acetoacetate. 250 g of ethyl acetate are shaken with a sodium carbonate solution, separated and allowed to stand for 23 hours over anhydrous calcium chloride. Filter and distill taking care to keep moisture or water from the reaction. 

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