Desiccants sodium hydroxide

A very effective universal filling for vacuum desiccators is obtained by having concentrated sulphuric acid C in the bottom of the desiccator, and flake sodium hydroxide D in the inverted glass collar supported on the shoulders of the desiccator, the collar then being covered... 

Both forms sublime very readily, even at room temperature a small sample on exposure to the air will completely volatilise in a short time, particularly on a warm day or if the sample is exposed to a gentle current of air. Hence the above method for rapid drying. A sample confined in an atmospheric desiccator over calcium chloride rapidly disappears as the vapour is adsorbed by the calcium chloride. A sample of the hexahydrate similarly confined over sodium hydroxide undergoes steady dehydration with initial liquefaction, for the m.p. of the hydrated-anhydrous mixture is below room temperature as the dehydration proceeds to completion, complete resolidification occurs. 

Aluminium isopropoxide can be obtained as a fine powder from technical sources. When the bottle has once been opened however, the stopper should be firmly replaced and covered with wax more conveniently, the stoppered bottle can be kept in an atmospheric desiccator over calcium chloride or sodium hydroxide, preferably in the dark. 

It is advisable in any case before an experiment to place the weighed aluminium isopropoxide overnight in a shallow dish in a vacuum desiccator over sodium hydroxide. The isopropanol should be dried over anhydrous sodium sulphate, and the clear liquid decanted off before use. 

Add 10 g. of the crude hydrazobenzene to 80 ml. of ethanol contained in a flask fitted with a reflux water-condenser. Heat the mixture on a water-bath until the ethanol bolls, and then add 10 g. of zinc dust and 30 ml. of 30% aqueous sodium hydroxide solution. Remove the flask from the water-bath and shake the contents vigorously from time to time. After about 10 minutes, replace the flask on the water-bath and boil the contents for 3-5 minutes. Filter the mixture at the pump, transfer the filtrate to a beaker and cool in ice-water with stirring. The hydrazobenzene separates as colourless crystals, which are filtered off at the pump and drained. A portion when dried in a desiccator has m.p. 124°. 

Preparation of REAOENTS.t It is essential for this preparation that the zinc powder should be in an active condition. For this purpose, it is usually sufficient if a sample of ordinary technical zinc powder is vigorously shaken in a flask with pure ether, and then filtered off at the pump, washed once with ether, quickly drained and without delay transferred to a vacuum desiccator. If, however, an impure sample of zinc dust fails to respond to this treatment, it should be vigorously stirred in a beaker with 5% aqueous sodium hydroxide solution until an effervescence of hydrogen occurs, and then filtered at the pump, washed thoroughly with distilled water, and then rapidly with ethanol and ether, and dried as before in a vacuum desiccator. The ethyl bromoacetate (b.p. 159 ) and the benzaldehyde (b.p. 179 ) should be dried and distilled before use. 

II This dual tilling permits the absorption of both acid smd basic vapours which may be evolved. Thus an amine hydrochloride, which has been recrystallised from concentrated hydrochloric acid, may be readily dried in such a desiccator. If concentrated sulphuric acid alone were used, so much hydrogen chloride would be liberated that tlie pressure inside the desiccator would rise considerably, smd the rate of drying would be reduced. With sodium hydroxide present, however, the hydrogen chloride is removed, smd tho water is absorbed in the normal manner by the reagents but largely by the acid. 

The crude o-phenylenediamine may be converted into the dihydrocliloride and the salt purified in the following manner. Dissolve it in 60 ml. of concentrated hydrochloric acid and 40 ml. of water containing 2 g. of stannous chloride, and treat the hot solution with 2-3 g. of decolourising carbon. Filter, add 100 ml. of concentrated hydrochloric acid to the hot colourless filtrate, and cool in a freezing mixture of ice and salt. Collect the colourless crystals of the dihydrochloride on a Buchner or sintered glass funnel, wash with a small volume of concentrated hydrochloric acid, and dry in a vacuum desiccator over sodium hydroxide. The yield is 61 g. 

Reflux a mixture of 7 3 g. of methyl myristate with a solution of 4 8 g. of sodium hydroxide in 200 ml. of 90 per cent, methanol for 2 hours, distil off the methanol on a water bath, dissolve the residue in 400 ml. of hot water, add 15 ml. of concentrated hydrochloric acid to the solution at 50° in order to precipitate the organic acid, and cool. Collect the acid by suction filtration, wash it with a little water and dry in a vacuum desiccator. The yield of myristic acid (tetradecanoic acid tetradecoic acid), m.p. 57-58°, is 5 9 g. 

The catalyst is previously prepared in an apparatus for catalytic hydrogenation, in which are placed 0.5 g. of palladous chloride, 3.0 g. of Norite, and 20 ml. of distilled water. The bottle is swept out with hydrogen and then shaken with hydrogen for 2-3 hours at 2-3 atmospheres (40 lb.) pressure. The palladium on carbon is collected on a Biichner funnel, washed with five 50-ml. portions of distilled water, then with five 50-ml. portions of 95% ethanol, and finally twice with ether. Upon drying, about 3 g. of the catalyst is obtained. It is stored in a vacuum desiccator over solid sodium hydroxide. If the reduction of the chloro-lepidine does not proceed normally, the used catalyst should be removed by suction filtration and a fresh 3-g. portion of catalyst added. Failure of the reduction step is usually due to an inactive catalyst or to impurities in the acetic acid or chlorolepidine. The palladium catalysts, prepared as described elsewhere in this volume, are presumably also satisfactory for the reduction of 2-chlorolepidine (p. 77). 

B. Palladium on carhon catalyst (5% Pd). A suspension of 93 g. of nitric acid-washed Darco G-60 (Note 10) in 1.21. of water contained in a 4-1. beaker (Notes 3 and 4) is heated to 80°. To this is added a solution of 8.2 g. (0.046 mole) of palladium chloride in 20 ml. (0.24 mole) of concentrated hydrochloric acid and 50 ml. of water (Note 2). Eight milliliters (0.1 mole) of 37% formaldehyde solution is added. The suspension is made slightly alkaline to litmus with 30% sodium hydroxide solution, constant stirring being maintained. The suspension is stirred 5 minutes longer. The catalyst is collected on a filter and washed ten times with 250-ml. portions of water. After removal of as much water as possible by filtration, the filter cake is dried (Note 11), first in air at room temperature, and then over potassium hydroxide in a desiccator. The dry catalyst (93-98 g.) is stored in a tightly closed bottle. 

The dry methosulfate, dissolved in about 30 ml. of water, is made alkaline with 2-3 ml. of 10% sodium hydroxide, and the solution is then extracted exhaustively with successive 15-ml. portions of chloroform until no more blue substance is remov ed from the aqueous solution (Note 12). The combined chloroform solutions are extracted three times with 20-ml. portions of 5% hydrochloric acid. The combined acid extracts are made alkaline to phenolphthalein with 10% sodium hydroxide and reextracted exhaustively with 25-ml. portions of chloroform until no more blue substance is removed from the aqueous solution (Note 12). The combined chloroform solutions are dried over anhydrous sodium sulfate and decanted, and the chloroform is removed by distillation under reduced pressure. The blue crystalline residue is recrystallized by dissohnng it in the least possible amount of water at 60° and then cooling the solution in an ice bath. The product is filtered on a 5-cm. Buchner funnel and dried in the dark in a v acuum desiccator over calcium chloride. The yield is 1.35 g. (58%) of dark blue needles that melt at 133° (Note 13). 

For purification the acid is crystallized from about 150 cc. of glacial acetic acid, using an acid-resistant filter for the hot solution (Note 7). Aconitic acid separates as small, colorless needles weighing 50-60 g., and about 10 g. more can be secured by concentrating the mother liquor under reduced pressure to one-third of its volume. The material is dried in the air and then in a desiccator containing sodium hydroxide in order to remove all traces of acetic acid. One crystallization usually is sufficient to bring the point of decomposition to 198-199° (Note 6). 

A stirred mixture of 11 g of 6-chloro-a-methylcarbazole-2-acetic acid ethyl ester, 100 ml ethanol and 100 ml of 3N sodium hydroxide was heated (N2 atmosphere). After 2 hours at reflux, the reaction mixture was concentrated to dryness under reduced pressure. Water (300 ml) and ice (200 g) were added to the residue and concentrated hydrochloric acid was added until the mixture was strongly acid. The acidic mixture was extracted with ether (3 X 200 ml). The ether extracts were combined, washed by extraction with water (3 x 100 ml) and dried over anhydrous magnesium sulfate. Following filtration of the desiccant and evaporation of the solvent, a yield of 9.8 g (98.2%) was obtained. Crystallization from CHCI3 yielded 6.2 g (62.0%) of 6-chloro-0 -methylcarbazole-2-acetic acid, MP 197°-198°C. A second crop of 1.6g,MP 195°-199°C was obtained from the mother liquors. 

To a well stirred suspension of 9 g of sodium phenyl acetate and 2.4 g of magnesium turnings in 25 cc of anhydrous ether, a solution of 9.4 cc of isopropyl bromide in 50 cc of anhydrous ether are added. The mixture is refluxed for one hour (during which time propane is evolved) and then 5 cc of cyclopentanone in 25 cc of anhydrous ether are added dropwise. The mixture is then refluxed for one hour and poured over ice water containing some hydrochloric acid. The ether solution is separated and extracted with 200 cc of 5% sodium hydroxide. The alkaline solution on acidification gives the free acid which is filtered off, dried in a desiccator and recrystallized from a mixture of ethylene dichloride and petroleum ether. 

Pipethanate hydrochloride Is dissolved in water and the solution is made alkaline by adding 10% sodium hydroxide solution. The crystals that are separated are filtered off and recrystallized from dilute ethanol. The monohydrate thereby obtained is dehydrated at 100°C under reduced pressure for 20 minutes. The products that are now in the form of a syrup due to loss of water of crystallization are further dehydrated for 2 days in a desiccator over phosphorus pentoxide whereupon the anhydrous pipethanate is obtained. 

The resulting rather stiff paste is chilled in an ice-water mixture for 1 hour. The solid is collected on a 15-cm. Buchner funnel and washed with 25-ml. portions of absolute ethyl alcohol until it is white and until the filtrate becomes colorless (100-200 ml. of alcohol is required). The fluffy material, after it is dried in a vacuum desiccator over flake sodium hydroxide, weighs 66 g. (40%). 

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