Ammonia, drying purification

The Scientific Design, Inc. process for aminolysis of phenol is shown in Fig. 28.31. In this process, a mixed-vapor feed of phenol and ammonia is preheated and passed over a fixed catalyst bed. A unique SD-developed catalyst is used. The reactor effluent is partially condensed and then sent to an ammonia recovery still. The recovered ammonia is recycled, and the ammonia recovery still bottoms are stripped of ammonia, dried, and distilled. Nearly stoichiometric yields are said to be obtained, and the aniline is of high purity. An azeotrope of aniline and phenol from the purification still is recycled to the reactor, and a long catalyst life is claimed. A 30,000 metric ton/year plant has been operated by Mitsui Petrochemical Industries, Ltd. since 1970. In 1882, U.S. Steel put a 90,000 metric ton/year plant onstream. This process is favorable where low cost phenol is available, and when high purity aniline is desired. Capital costs are low because the nitration of benzene is avoided. Waste disposal problems are minimal. 

Cellulose for chromatography is purified by sequential washing with chloroform, ethanol, water, ethanol, chloroform and acetone. More extensive purification uses aqueous ammonia, water, hydrochloric acid, water, acetone and diethyl ether, followed by drying in a vacuum. Trace metals can be removed from filter paper by washing for several hours with O.IM oxalic or citric acid, followed by repeated washing with distilled water. 

Acids that are solids can be purified in this way, except that distillation is replaced by repeated crystallisation (preferable from at least two different solvents such as water, alcohol or aqueous alcohol, toluene, toluene/petroleum ether or acetic acid.) Water-insoluble acids can be partially purified by dissolution in N sodium hydroxide solution and precipitation with dilute mineral acid. If the acid is required to be free from sodium ions, then it is better to dissolve the acid in hot N ammonia, heat to ca 80°, adding slightly more than an equal volume of N formic acid and allowing to cool slowly for crystallisation. Any ammonia, formic acid or ammonium formate that adhere to the acid are removed when the acid is dried in a vacuum — they are volatile. The separation and purification of naturally occurring fatty acids, based on distillation, salt solubility and low temperature crystallisation, are described by K.S.Markley (Ed.), Fatty Acids, 2nd Edn, part 3, Chap. 20, Interscience, New York, 1964. 

Amides are stable compounds. The lower-melting members (such as acetamide) can be readily purified by fractional distillation. Most amides are solids which have low solubilities in water. They can be recrystallised from large quantities of water, ethanol, ethanol/ether, aqueous ethanol, chloroform/toluene, chloroform or acetic acid. The likely impurities are the parent acids or the alkyl esters from which they have been made. The former can be removed by thorough washing with aqueous ammonia followed by recrystallisation, whereas elimination of the latter is by trituration or recrystallisation from an organic solvent. Amides can be freed from solvent or water by drying below their melting points. These purifications can also be used for sulfonamides and acid hydrazides. 

To a mixture of naphthyloxazoline 71 (4.31 g, 12.97 mmol) in pyridine (4 mL) was added activated copper (1.99 g). The mixture was heated to reflux for 24 h then was cooled to rt, diluted with CH2CI2 and washed with aqueous ammonia until the copper had been completely removed. The organic phase was washed with water then dried over anhydrous magnesium sulfate, filtered, and concentrated to afford the title compound as a tan solid. This material was used without further purification. 

C. Isolation and purification of XK-62-2 100 g of the white powder obtained in the above step B are placed to form a thin, uniform layer on the upper part of a 5 cm0X 150 cm column packed with about 3 kg of silica gel advancely suspended in a solvent of chloroform, isopropanol and 17% aqueous ammonia (2 1 1 by volume). Thereafter, elution is carried out with the same solvent at a flow rate of about 250 ml/hour. The eluate is separated in 100 ml portions. The active fraction is subjected to paper chromatography to examine the components eluted. XK-62-2 is eluted in fraction Nos. 53-75 and gentamicin Cja is eluted in fraction Nos. 85-120. The fraction Nos. 53-75 are combined and concentrated under reduced pressure to sufficiently remove the solvent. The concentrate Is then dissolved in a small amount of water. After freeze-drying the solution, about 38 g of a purified preparate of XK-62-2 (free base) is obtained. The preparate has an activity of 950 units/mg. Likewise, fraction Nos. 85-120 are combined and concentrated under reduced pressure to sufficiently remove the solvent. The concentrate is then dissolved in a small amount of water. After freeze-drying the solution, about 50 g of a purified preparate of gentamicin Cja (free base) is obtained. 

This gave a viscous sludge, and some ammonia was evolved. The temp was raised steadily to 59-61° over a period of 8 minutes, and held there for 23 minutes, while stirring the mixt continuously. After the mixt was cooled to 6°, a white ppt of methylnitroguanidine (MeNGu) was filtered off, washed with 30ml of cold w and dried. The crude product weighed about lQg (84.7% yield) and melted at 151—54°. Purification of the product was achieved by crystn, first from hot w (3ml per g) and then from 95% ethanol (8ml per g)... 

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