Sodium—continued amines

Into a 750 ml. round-bottomed flask furnished with a reflux condenser place a solution of 34 g. (18-5 ml.) of concentrated sulphuric acid in 100 ml, of water add 33 g. of di-n-butyl cyanamide and a few fragments of porous porcelain. Reflux gently for 6 hours. Cool the resulting homogeneous solution and pour in a cold solution of 52 g. of sodium hydroxide in 95 ml. of water down the side of the flask so that most of it settles at the bottom without mixing with the solution in the flask. Connect the flask with a condenser for downward distillation and shake it to mix the two layers the free amine separates. Heat the flask when the amine with some water distils continue the distillation until no amine separates from a test portion of the distillate. Estimate the weight of water in the distillate anp add about half this amount of potassium hydroxide in the form of sticks, so that it dissolves slowly. 

Manufacture and Uses. Acetoacetic esters are generally made from diketene and the corresponding alcohol as a solvent ia the presence of a catalyst. In the case of Hquid alcohols, manufacturiag is carried out by continuous reaction ia a tubular reactor with carefully adjusted feeds of diketene, alcohol, and catalyst, or alcohol—catalyst blend followed by continuous purification (Fig. 3). For soHd alcohols, an iaert solvent is used. Catalysts used iaclude strong acids, tertiary amines, salts such as sodium acetate [127-09-3], organophosphoms compounds, and organometaHic compounds (5). 

Phosgene addition is continued until all the phenoHc groups are converted to carbonate functionahties. Some hydrolysis of phosgene to sodium carbonate occurs incidentally. When the reaction is complete, the methylene chloride solution of polymer is washed first with acid to remove residual base and amine, then with water. To complete the process, the aqueous sodium chloride stream can be reclaimed in a chlor-alkah plant, ultimately regenerating phosgene. Many variations of this polycarbonate process have been patented, including use of many different types of catalysts, continuous or semicontinuous processes, methods which rely on formation of bischloroformate oligomers followed by polycondensation, etc. 

Ryon and Lowrie (U.S. AEC ORNL-3.381, 1960). Batch and continuous extraction of uranium from aqueous sulfate solutions into kerosine -t- amines, stripping of extract with aqueous sodium carbonate baffled vessels, turbine agitated. A detailed process study. 

A mixture of 1.5 1. of water and 624 g. (6.00 moles) of sodium bisulfite in a 5-1. beaker equipped with a mechanical stirrer is stirred until solution is complete. Benzaldehyde (Note 1) (636 g., 6.00 moles) is added and the mixture is stirred for 20 minutes, during which time a slurry of the benzaldehyde-bisulfite addition product is formed. A 25% aqueous solution of dimethylamine (1100 g.) containing 275 g. (6.13 moles) of the amine is run in, and stirring is continued as most of the addition compound dissolves. The beaker is immersed in an ice bath, and 294 g. (6.00 moles) of sodium cyanide (CautionI Toxic) is added over a period of 20-25 minutes. 

Silverstein, J. L. et al., Loss Prev., 1981,14, 78 Nitrobenzene was washed with dilute (5%) sulfuric acid to remove amines, and became contaminated with some tarry emulsion that had formed. After distillation, the hot tarry acidic residue attacked the iron vessel with hydrogen evolution, and an explosion eventually occurred. It was later found that addition of the nitrobenzene to the diluted acid did not give emulsions, while the reversed addition did. A final wash with sodium carbonate solution was added to the process [1]. During hazard evaluation of a continuous adiabatic process for manufacture of nitrobenzene, it was found that the latter with 85% sulfuric acid gave a violent exotherm above 200° C, and with 69% acid a mild exotherm at 150- 170°C [2],... 

A solution of 75.6 g. (57 ml., 0.60 mole) of dimethyl sulfate (Toxic Note 4) in 200 ml. of anhydrous benzene is added through the condenser with intermittent swirling (Note 2). The mixture is then heated gently. After a short period (about 10 minutes) the reaction becomes mildly vigorous, and the heating is stopped (Note 5). The ebullition subsides after about 10 minutes. The mixture is heated under reflux for 30 minutes. It is then steam-distilled until the distillate becomes clear about 500 ml. of distillate is collected (Note 6). The residue is cooled in an ice bath, and 60 g. (1.5 moles) of sodium hydroxide is added with continuous swirling. The layers are separated, and the amine... 

Figure 1 shows how acid-gas-bearing process gases can be generally treated in industrial processes. The sulfur compounds and CO2 may be absorbed in a liquid medium, such as amines, alkali salts (NaOH, K2CO3), physical solvents (methanol, propylene carbonate), or water (3). The absorbed acid gases are released by reduction of pressure and/or by application of heat. Alternatively, the H2S and CO2 may chemically combine with the absorbent (as in NaOH scrubbing) to form salts which are removed in a liquid treatment unit. This requires continual and expensive makeup of sodium to the system. 

In a 1-1. separatory funnel there are first placed 400 ml. of ether and 75 ml. of 10% phosphoric acid (Note 10), and then the above amine salt is added (Note 11). The mixture is shaken vigorously for a few minutes, an additional 50 ml. of 10% phosphoric acid added, and the vigorous shaking continued until a ll the solid has disappeared. The ether layer is separated, washed twice with 100-ml. portions of water, and dried over anhydrous sodium sulfate. The drying agent is separated by filtration, the ether is removed at room temperature under reduced pressure using a rotary evaporator, and the residue dissolved in 40-60 ml. of boiling ethanol. The levopimaric acid is collected by suction filtration, yield 26-31 g. (10-12%), m.p. 147-150°, —265°... 

B. 2-Methoxycyclooctanone oxime. In a 500-ml., three-necked, round-bottomed flask, fitted with a mechanical stirrer, a dropping funnel, and a reflux condenser equipped with a calcium chloride tube, is placed a solution of 53.5 g. (0.252 mole) of crude 2-chlorocyclooctanone oxime hydrochloride in 250 ml. of methanol. While cooling the vessel with running water, 60.7 g. of triethyl-amine (0.60 mole) is added dropwise during 40 minutes. The reaction temperature is kept below 50° and the reaction is continued for 30 minutes with stirring. After removal of methanol under reduced pressure using an efiicient rotatory evaporator, a light brown semisolid is obtained it is treated with 200 ml. of ether and 200 ml. of water to effect complete solution. The ether layer is separated and the aqueous layer is further extracted twice with ether. The combined ether solution is washed with saturated sodium chloride and dried over sodium sulfate. Removal of ether affords 42.8 g. of crude 2-methoxycyclooctanone oxime (Note 3) as a brown oil. 

To a stirred solution of 120 ml of methylene chloride, 18 ml of dry pyridine, and 5 ml of iodine pentafluoride maintained at —10°C to —20°C in a Dry Ice-carbon tetrachloride slurry is added a solution of 13.5 gm (0.1 mole) of cumyl-amine in 10 ml of methylene chloride over a 1 hr period. The reaction mixture is stirred for another hour at —10°C, and then for 1 hr at 0°. After this time, water is added to the reaction mixture and stirring is continued until the yellow solid which had formed is dissolved. The lower organic layer is separated and washed in turn with water, 1 N hydrochloric acid, a saturated sodium thiosulfate solution, and again with water. After drying with anhydrous magnesium sulfate and filtration, the product solution is partially evaporated by means of a rotary evaporator at a temperature below 30°C. The brown solid obtained on cooling is separated and recrystallized twice from methylene chloride yield 4.75 gm (17.9%), m.p. 86.9°-88.7°C. 

The amine (0.1 mole) is dissolved in a buffered (pH 4-5) solution of 500 ml of 60 % aqueous acetic acid and 68 gm of sodium acetate. The reaction mixture is warmed to 90°C. Then 69 gm (1.0 mole) of sodium nitrite dissolved in 100 ml of water is added dropwise over a 45 min period while heating at 90°C is continued. After the addition, the reaction mixture is heated for 2 hr, cooled, poured into 200 ml of cold water, and extracted three times with 200 ml portions of ether. The ether was washed with 10 % potassium carbonate solution until basic, then with saturated sodium chloride solution, dried, stripped, and distilled to obtain the products shown in the table. 

To 450 cc. of concentrated hydrochloric acid (sp. gr. 1.19) and 500 cc. of water in a 4-I. (i-gal.) earthenware crock equipped with an efficient stirrer is added 143 g. (1 mole) of /3-naphthyla-mine. The suspension of the amine hydrochloride is cooled by the addition of 500 g. of cracked ice. When the temperature reaches 5° solid sodium nitrite (about 69 g.) is added until starch-iodide paper shows an excess. During the diazotization about 600 g. of cracked ice is introduced at such a rate as to keep the temperature at 50. The cold solution of the diazonium salt is filtered to remove a small amount of precipitate and returned to the crock. A solution of 271 g. (1 mole) of mercuric chloride in 300 cc. of concentrated hydrochloric acid is mixed with 300 g. of ice and added slowly to the rapidly stirred solution. A heavy yellow solid separates. Stirring is continued for one-half hour to secure complete reaction. The yellow addition compound of /3-naphthalene diazonium chloride and mercuric chloride is collected on a 20-cm. Buchner funnel, sucked as dry as possible, and then washed with two 400-cc. portions of water and two 150-cc. portions of acetone (Note 1). The... 

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