Mixture, organic solutes

The mixture was then poured into a solution of 10 g of KCN or NaCN and 40 g of NHi,Cl in 400 ml of water. After vigorous shaking the layers were separated and the aqueous phase was extracted four times with diethyl ether. The combined organic solutions were dried over MgSOi, and concentrated in a water-pump vacuum. 

To a mixture of 100 ml of THF and 0.10 mol of the epoxide (note 1) was added 0.5 g Of copper(I) bromide. A solution of phenylmagnesium bromide (prepared from 0.18 mol of bromobenzene, see Chapter II, Exp. 5) in 130 ml of THF was added drop-wise in 20 min at 20-30°C. After an additional 30 min the black reaction mixture was hydrolysed with a solution of 2 g of NaCN or KCN and 20 g of ammonium chloride in 150 ml of water. The aqueous layer was extracted three times with diethyl ether. The combined organic solutions were washed with water and dried over magnesium sulfate. The residue obtained after concentration of the solution in a water-pump vacuum was distilled through a short column, giving the allenic alcohol, b.p. 100°C/0.2 mmHg, n. 1.5705, in 75% yield. 

TABLE 8.21 Potentials of Reference Electrodes (in Volts) at 25°C for Water-Organic Solvent Mixtures Electrolyte solution of M HCl. 

Paste Mixing. The active materials for both positive and negative plates are made from the identical base materials. Lead oxide, fibers, water, and a dilute solution of sulfuric acid are combined in an agitated batch mixer or reactor to form a pastelike mixture of lead sulfates, the normal, tribasic, and tetrabasic sulfates, plus PbO, water, and free lead. The positive and negative pastes differ only in additives to the base mixture. Organic expanders, barium sulfate [7727-43-7] BaSO carbon, and occasionally mineral oil are added to the negative paste. Red lead [1314-41 -6] or minium, Pb O, is sometimes added to the positive mix. The paste for both electrodes is characterized by cube weight or density, penetration, and raw plate density. 

Threo-2-Azldo-1,2-dlphenylethanol (2). A mixture ot cis-stilbene oxide 1 (3 92 g, 20 mmol) and NaNa (4 46 g, 70 mmol) in 50% aqueous acetone (60 mL) was relKixed lor 3h The solvent was removed in vacuum and the resxlue extracted with CHCI3 The organic solution was washed with water, dned (MgS04) and concentrated. Distillation of the resxlue afforded 3 70 g of 2 (77%) as a pale yellow oil, tsp 122°C/0 IS mm... 

In a 2-1. flask fitted with a total-reflux, variable-take-off distillation head is placed a solution of 53 g. (0.472 mole) of dihydroresorcinol (Note 1), 2.3 g. of -toluenesulfonic acid monohydrate and 250 ml. of absolute ethanol in 900 ml. of benzene. The mixture is heated to boiling and the azeotrope composed of benzene, alcohol, and water is removed at the rate of 100 ml. per hour. When the temperature of the distilling vapor reaches 78° (Note 2), the distillation is stopped and the residual solution is washed with four 100-ml. portions of 10% aqueous sodium hydroxide which have been saturated with sodium chloride. The resulting organic solution is washed with successive 50-ml. portions of water until the aqueous washings are neutral and then concentrated under reduced pressure. The residual liquid is distilled under reduced pressure. The yield of 3-ethoxy-2-cyclohexenone (Note 3), b.p. 66-68.5°/0.4 mm. or 115-121°/11 mm., Mq 1.5015, is 46.6-49.9 g. (70-75%). 

Preparation of l9-Norandrost-A-ene-3, l-dionef A solution of 1.1 g of 10y5-cyano-19-norandrost-5-ene-3,17-dione bis-ethylene ketal in a mixture of 15 ml of ethanol and 15 ml of toluene is carefully added to a vigorously stirred suspension of 10 g of sodium in 150 ml of boiling toluene. The addition is regulated to maintain the reaction mixture at the boiling point of the solvent. Another 40 ml of anhydrous ethanol is then added at the same rate. The solution is cooled and the excess of sodium is decomposed by addition of 95% ethanol. The reaction mixture is then diluted with water, the toluene layer separated and the aqueous phase extracted twice with ether. The organic solution is washed with water, dried and evaporated to yield 1 g of an amorphous mixture of the bis-ethylene ketals of 19- norahd-rost-5- and -5(10)-ene-3,17-dione (Note 1). 

The trialkylborane is oxidized by the addition to the stirred reaction mixture of 32 ml of a 3 solution of sodium hydroxide, followed by the dropwise addition of 32 ml of 30 % hydrogen peroxide at a temperature of 30-32° (water bath). The reaction mixture is saturated with sodium chloride and the tetrahydrofuran layer formed is separated and washed with saturated sodium chloride solution. The organic solution is dried over anhydrous magnesium sulfate and the THF is removed. Distillation affords 24.5 g (80%) of 4-methyl-1-pentanol, bp I51-153°/735 mm. 

The procedure given above is applied to norbornene. However, the formation of the alcohol is accompanied by formation of moderate amounts of the acetate. Therefore, the dried tetrahydrofuran solution of the alcohol-acetate mixture is treated with 0.4 g (O.OI mole) of lithium aluminum hydride dissolved in 10 ml ofTHF. The excess hydride is decomposed by careful addition of water, followed by filtration, drying of the organic solution, and evaporation of the solvent. The residue is almost pure (>99.8%) exo-1-norborneol. It may be purified by direct distillation, bp 178-17971 atm, crystallizing slowly on cooling, mp 127-128°. 

A solution of 88.5 parts of L-phenylalanine methyl ester hydrochloride in 100 parts of water is neutralized by the addition of dilute aqueous potassium bicarbonate, then is extracted with approximately 900 parts of ethyl acetate. The resulting organic solution is washed with water and dried over anhydrous magnesium sulfate. To that solution is then added 200 parts of N-benzyloxycarbonyl-L-aspartic acid-a-p-nitrophenyl, -benzyl diester, and that reaction mixture is kept at room temperature for about 24 hours, then at approximately 65°C for about 24 hours. The reaction mixture is cooled to room temperature, diluted with approximately 390 parts of cyclohexane, then cooled to approximately -18°C in order to complete crystallization. The resulting crystalline product is isolated by filtration and dried to afford -benzyl N-benzyloxycarbonvI-L-aspartyl-L-phenylalanine methyl ester, melting at about 118.5°-119.5°C. 

Benzhydryl 3-carbamoyloxymethyl-7j3-(2-thienylacetamido)-70 -methoxydecephalosporanate (300 mg) in 0.5 ml in anisole and 2.5 ml of trifluoroacetic acid is reacted for 15 minutes at 10°C. The resulting mixture is evaporated at reduced pressure and flushed twice with anisole. The residue is dissolved in methylene chloride and extracted with 5% sodium bicarbonate solution. The aqueous solution is adjusted to pH 1. B with 5% phosphoric acid and extracted with ethyl acetate. The organic solution is dried and evaporated to yield the pure 3-carba-moyloxymethyl-70 -methoxy-7/3-(2-thienylacetamido)decephalosporanic acid, MP 165°C to 167°C. This may then be converted to the sodium salt. 

The acetic acid mother liquor, containing the rest of the reaction product, was concentrated in vacuo. The residue was dissolved in methylene chloride and washed with ice cold sodium carbonate solution. The organic solution was dried, concentrated in vacuo to a small volume and diluted with ether and petroleum ether. Fine yellow needles of 2-chloro-methyl-4-phenyl-6-chloroquinazoline 3-oxide precipitated. The pure base was recrystallized from a mixture of methylene chloride, ether and petroleum ether, MP 133° to 134°C. 

Methyl ethyl (7-methoxy-10-methyl-3-phenthiazinyl)malonate (62.2 grams) followed by methyl iodide (45.7 grams) is added to a solution of sodium (4.45 grams) in anhydrous ethanol (500 cc). The reaction mixture is heated under reflux for 1 hour at 45°C, then for 6 hours at 55°C, and finally concentrated to dryness under reduced pressure (20 mm Hg). The residue is taken up in methylene chloride (300 cc) and water (250 cc), filtered in the presence of a filtration adjuvant, washed with methylene chloride (150 cc) and water (150 cc), and decanted. The aqueous solution is extracted once again with methylene chloride (100 cc), and the combined organic solutions washed with water (100 cc), aqueous 0.1 N sodium hyposulfite solution (200 cc) and finally with water (200 cc). After drying over anhydrous sodium sulfate and evaporation to dryness under reduced pressure (20 mm Hg), there is obtained an oil (64.8 grams) which is dissolved in methylene chloride (100 cc) and... 

---