Acids sodium with water

Into a 500 nil. round-bottomed flask, provided with a double surface condenser, place 50 g. (63 ml.) of pure, dry acetone, 50 g. (47 ml.) of ethyl cyanoacetate (Section 111,131) and 0 -5 g. of piperidine. Allow to stand for 60 hours and heat on a water bath for 2 hours. Treat the cold reaction mixture with 100 ml. of ether, wash with dilute hydrochloric acid, then with water, and dry over anhydrous sodium or magnesium sulphate. Distil under diminished pressure and collect the ethyl fsopropylidene cyanoacetate (ethyl a-cyano-pp-dimethylacrylate) at 114-116°/14mm.(l). The yield is 39 g. 

Hydroxy-5a-pregn-l-ene-3,20-dione (44). To a solution of 7.7 g (15.6 mmoles) of the nitrone (43) in 300 ml of benzene is added 500 ml of 2 A hydrochloric acid, whereupon the deep-red benzene solution immediately turns green. The resulting mixture is stirred for 12 hr and the layers are then separated. The aqueous layer is extracted with three 300-ml portions of benzene the combined benzene layers are washed with 2 N hydrochloric acid and with water, and then dried over sodium sulfate. The benzene is evaporated under reduced pressure to give 4.8 g (93 %) of the diosphenol (44). 

Into a stirred, cooled (10°-15°C) solution of 26.2 grams (0.1 mol) of 2-amino-5-chlorobenzo-phenone (3-oxime in 150 ml of dioxane were introduced in small portions 12.4 grams (0.11 mol) of chloracetyl chloride and an equivalent amount of 3 N sodium hydroxide. The chlor acetyl chloride and sodium hydroxide were introduced alternately at such a rate so as to keep the temperature below 15°C and the mixture neutral or slightly alkaline. The reaction was completed after 30 minutes. The mixture was slightly acidified with hydrochloric acid, diluted with water and extracted with ether. The ether extract was dried and concentrated in vacuo. Upon the addition of ether to the oily residue, the product, 2-chloroacetamido-5-chlorobenzophenone (3-oxime, crystallized in colorless prisms melting at 161°-162°C. 

Reaction of sodium with water. When a very small piece of sodium is added to water, it reacts violently with the water. The OH- ions formed in the reaction turn the acid-base indicator phenolphthalein from colorless to pink. 

Mix 130 g. of the crude thiomorpholide with 270 ml. of glacial acetic acid, 40 ml. of concentrated sulphuric acid and 60 ml. of water raise the temperature of the mixture carefully to the boiling point and reflux for 6 hours. Decant the solution from a little tarry matter into 2 litres of water and keep overnight. Collect the solid by suction filtration and wash it well with cold water. Digest the solid with a solution of 50 g. of sodium hydroxide in 1 litre of water, filter and acidify the filtrate with hydrochloric acid filter off the crude p-naphthylacetic acid, wash with water and dry. The yield of the crude acid, m.p. 137-140°, is 75 g. RecrystaUisation from benzene raises the m.p. to 142-143° the loss is about 10 per cent. 

After one hour the organic solution is extracted with 0.5 N hydrochloric acid, then with water and filtered. The solvent is evaporated, the residue redissolved in hexane and the solution is stirred for one hour with 10% acetic acid in water. The solution is filtered again, the aqueous layer is discarded and the organic layer is washed three times with 5% sodium bicarbonate solution. 

In a 500 cc. round-bottom flask are placed 240 g. of hydro-bromic acid (48 per cent), 62 g. of concentrated sulfuric acid, and 71 g. of M-oclyl alcohol (b. p. 135-140° at 100 mm.). The mixture is boiled under reflux for three and a half hours. The solution is diluted with water and the bromide layer is separated, washed once with a little cold concentrated sulfuric acid, then with water and finally with dilute sodium carbonate solution, The crude yield is 102 g. this is dried over a little calcium chloride and distilled. The product is collected at iyh 200" and amounts to 96 g. (91 per cent theory). 

The following morning a precipitate of Et2NHHCI was present. The mixture was washed twice with brine, five times with 15% acetic acid, then with water, and finally with NaHC03 solution. After drying with sodium sulfate, the product was concentrated under vacuum. Unchanged starting ether was removed by treatment with neutral alumina (Alcoa F-20). 

Phenoxatellurin1 A mixture of 1.0 g (2.9 mmol) of 2-carboxyphenoxatellurin, a little copper-bronze, and 30 ml of dry quinoline is heated under reflux for 1 h. The mixture is cooled to 20° and poured into dilute acetic acid. The precipitate is filtered, washed with dilute acetic acid, then with water, and the solid is extracted with aqueous sodium carbonate solution. The insoluble material is recrystallized twice from light petroleum ether yield 0.2 g (23%) m.p. 77 19°. 

Add 8.0g (10.0ml, 0.15 mol) of redistilled acrylonitrile (Expt 5.161, Note (1)) to a stirred solution of diethyl propylmalonate (30.2 g, 0.15 mol) (Expt 5.132) and of 30 per cent methanolic potassium hydroxide (4.0 g) in t-butyl alcohol (100 g). Keep the reaction mixture at 30-35 °C during the addition and stir for a further 3 hours. Neutralise the solution with 2 M-hydrochloric acid, dilute with water and extract with ether. Dry the ethereal extract with anhydrous sodium sulphate and distil off the ether the residue [diethyl (2-cyanoethyl)-propylmalonate 11 g] solidifies on cooling in ice, and melts at 31—32 °C after recrystallisation from ice-cold ethanol. Boil the cyanoethyl ester (lOg) under reflux with 40ml of 48 per cent hydrobromic acid solution for 8 hours, and evaporate the solution almost to dryness under reduced pressure. Add sufficient water to dissolve the ammonium bromide, extract several times with ether, dry the ethereal extract and distil off the solvent. The residual oil (4.5 g, 66%) soon solidifies upon recrystallisation from water, pure 2-propylglutaric acid, m.p. 70 °C, is obtained. 

Summary 70% Nitric acid can be obtained by treating potassium or sodium nitrate with sulfuric acid, mixing with water, and then extracting the acid mixture with methylene chloride. The result is a methylene chloride solution containing 99% nitric acid. This methylene chloride/99% nitric acid solution is then mixed with a calculated amount of water, and then carefully distilled to remove the methylene chloride and leave behind 70% nitric acid. 

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