Sodium acetate ethylate

Mono and disaccharides Kleselguhr G (sodium acetate) Ethyl acetate/propan-l-ol (65/35)... 

Ethyl acetate test. Heat i ml. of ethanol with 0-5 g. of sodium acetate and a few drops of cone. H2SO4 gently for about i minute. Cool and pour into a few ml. of water in a boiling-tube. Note fruity odour of the ethyl acetate. 

Azlactone of a-acetylaminocinnamic acid. Warm a mixture of 29 g. of acetylglycine, 39-5 g. (37 -5 ml.) of redistilled benzaldehyde (Section IV,115), 15 g. of anhydrous sodium acetate and 67 g. (62 ml.) of acetic anhydride (95 per cent.) in a 500 ml. conical flask (equipped with a reflux condenser) on a water bath with occasional stirring until solution is complete (10-20 minutes). Boil the resulting solution for 1 hour, cool and leave in a refrigerator overnight. Stir the sohd mass of yellow crystals with 60 ml. of cold water, transfer to a Buchner funnel and wash well with cold water. (If the odour of benzaldehyde is stih apparent, wash with a little ether.) Recrystallise from carbon tetrachloride or from ethyl acetate-hght petroleum. The yield of azlactone, m.p. 150°, is 35 g. 

The addition of active methylene compounds (ethyl malonate, ethyl aoeto-acetate, ethyl plienylacetate, nltromethane, acrylonitrile, etc.) to the aP-double bond of a conjugated unsaturated ketone, ester or nitrile In the presence of a basic catalyst (sodium ethoxide, piperidine, diethylamiiie, etc.) is known as the Michael reaction or Michael addition. The reaction may be illustrated by the addition of ethyl malonate to ethyl fumarate in the presence of sodium ethoxide hydrolysis and decarboxylation of the addendum (ethyl propane-1 1 2 3-tetracarboxylate) yields trlcarballylic acid ... 

Ethylcyanoacetate (227), Rj = CH2C02Et, also reacts with ethylthio-glycolate to afford the corresponding ethyl-2-thiazolylacetate (230), R, -CH2C02Et, R2 = H, after cyclization of the acyclic intennediate in the presence of sodium acetate (542). 

Sodium acetate reacts with carbon dioxide in aqueous solution to produce acetic anhydride and sodium bicarbonate (49). Under suitable conditions, the sodium bicarbonate precipitates and can be removed by centrifugal separation. Presumably, the cold water solution can be extracted with an organic solvent, eg, chloroform or ethyl acetate, to furnish acetic anhydride. The half-life of aqueous acetic anhydride at 19°C is said to be no more than 1 h (2) and some other data suggests a 6 min half-life at 20°C (50). The free energy of acetic anhydride hydrolysis is given as —65.7 kJ/mol (—15.7 kcal/mol) (51) in water. In wet chloroform, an extractant for anhydride, the free energy of hydrolysis is strangely much lower, —50.0 kJ/mol (—12.0 kcal/mol) (51). Half-life of anhydride in moist chloroform maybe as much as 120 min. Ethyl acetate, chloroform, isooctane, and / -octane may have promise for extraction of acetic anhydride. Benzene extracts acetic anhydride from acetic acid—water solutions (52). 

Commercial Sodium Acetylide A suspension (30 ml) of sodium acete-lide (20% in exylene) is centrifuged and the solid brown sodium acetylide is taken up in 25 ml of dimethyl sulfoxide. To this is added a solution of 5 g of 5a-hydroxy-6j5-methylandrostane-3-17,dione 3-ethylene ketal in 85 ml of dimethyl sulfoxide. After stirring at room temperature overnight, ice is added and the solution diluted to about 250 ml. The tan precipitate is collected, washed with water and dried yield 4.8 g mp 202-204°. Crystallization from ethyl acetate gives a product of mp 204-206°. 

In addition to varying the electrophile, efforts have also focused on different bases. Yamaguchi and coworkers used a stoichiometric amount of DBU instead of sodium acetate when they synthesized a series of ethyl o)-(3-chromonyl)alkanoates 34 in 33-64% yield from 33. ... 

This ester loses hydrogen chloride by the action of sodium acetate giving ethyl rhodinate which when reduced by sodium and absolute alcohol yields rhodinol. 

A mixture of 14 g (0.05 mol) of a A-diphenyl-7-dlmethylaminovaleronitrile, 16 g (0.2 mol) of sodium acetate, 14 g (0.2 mol) of hydroxylamine hydrochloride and 75 ml of ethyl alcohol was refluxed IB hours. The mixture was cooled, poured Into water and neutralized with ammonium hydroxide. The heavy white precipitate solidified on standing. The material was filtered and recrystallized from isopropanol. After three recrystallizations the aminopentamide product melted at 177° to 179°C. 

Sodium N-(1-methoxycarbonyl-1 -propen-2-yl)-D(-)-0 -amino-(4-hydroxyphenyl)acetate Ethyl chlorocarbonate... 

The mixture was filtered, the ethyl acetate layer separated and washed with three 100 ml portions of water, dried over Na2S04, filtered and treated with 30 ml of sodium 2-ethyl-hexanoate in n-butanol (34 ml = 0.1 mol). The oil which settled out was scratched to induce crystallization. After stirring for 20 minutes the product, sodium 7-(a-bromoacet-amido)cephalosporanate, was scraped from the sides of the flask and collected. The filter cake was washed with several portions of acetone, air dried, and dried in vacuo over P Os. The yield was 22.5 g and decomposed at 193°C. 

The solvent was evaporated off under reduced pressure, and the residual gum refluxed with concentrated hydrochloric acid (50 g) for 6 hours. The solution was aliowed to cool overnight. It was filtered from the phthalic acid crystals, and freeze-dried, and to the pink residue was added acetone (160 g) and ethyl acetate (50 g). The mixture was left in the cold room overnight and the clear pink supernatant liquid poured off. The pink gummy hydrochloride remaining in the flask was dissolved in water (20 g), saturated sodium acetate solution added until precipitation was complete, and the product collected and dried in a desiccator. The crude p-bis-(2-chloroethyl)-aminophenylalanine (3.6 g) was crystallized from methanol giving colorless needles, MP 172° to 174°C (decomp.) of p-bis-(2-chloroethyl)-aminophenylalanine. 

The resulting mixture does not crystalize and is converted into a mixture of oximes by treatment of a solution of the mixture in 20 ml of ethanol with a solution of 1.8 g of hydroxylamine sulfate in 3 ml of water. 1.B g of sodium acetate In 5 ml of water is added, and the mixture is refluxed for 5 hours, then extracted with ethyl acetate, and the ethyl acetate solution is washed with a saturated aqueous sodium chloride solution and dried over Sodium sulfate. After evaporating the solvent, the residue is triturated with warm ether and 1.1 g of a crystalline oxime is obtained, MP 16B° to 171°C. 

The reaction of l//-l,2-diazepines with palladium(II) acetate in the presence of sodium acetate gives dienes in low yield, e.g. the reaction of ethyl l/f-l,2-diazepine-l-carboxylate (1).91,92... 

The submitters used the following reagents as supplied iodine, ether, and sodium acetate from Mallinckrodt Chemical Works, dinitrogen tetroxide from Matheson Gas Company, and ethyl acrylate from Aldrich Chemical Company, inc. The checkers obtained dinitrogen tetroxide from Matheson Gas Company and the other reagents from Wako Pure Chemical Industries, Ltd., Japan. 

This procedure for the synthesis of ethyl 3-nitroacrylate is essentially that of Stevens and Emmons.2 Four major changes have been introduced by the submitters rapid introduction of dinitrogen tetroxide no purification of the intermediate nitro iodo ester use of dry, finely powdered sodium acetate for elimination of hydroiodic acid and percolation of the final product through a mat of alumina. With these modifications, the preparation is reproducible and highly efficient (80-90% overall). 

---