Sodium ethoxide, preparation

To an ethanolic solution of sodium ethoxide prepared by addition of 0.46 g (0.02 mole) of freshly cut sodium metal in 100 mL of absolute ethanol was slowly added 5.10 g (0.02 mole) of ethyl 4-nitrobenzylthioacetate 28 with stirring at 5°C. The mixture was refluxed for about 4 to 6 hours until the reaction was complete (monitored by tic). The resultant mixture was allowed to cool to room temperature and then added into an ice-water mixture. The solution was neutralized with slow addition of dilute aqueous hydrochloric acid (10%). The precipitated solid was removed by filtration, washed with water, and recrystallized from a dimethylformamide-ethanol (T.l) mixture yielding 2.10 g (76 %) of 29 as a light brown crystalline solid, mp 227°C ir (nujol) (neat (1710 cm ms m/z Til (NT). Anal. Calcd. For C13H11NO4S C, 56.31 H, 3.97 N, 5.05 S, 11.55. Found C, 56.36 H, 3.95 N, 5.01 S, 11.49. 

Diphenyl telluropyran-4-one (typicalprocedure)7° 120 mL (0.12 mol) of a 1.0 M solution of lithium triethylborohydride in tetrahydrofuran are added to 7.65 g (60 mmol) of powdered tellurium under nitrogen, and the mixture stirred at 20°C for 4 h. A solution of sodium ethoxide (prepared from 5.52 g (0.24 mol) of sodium and 240 mL of absolute alcohol) is added to the dilithium telluride, 13.8 g (60 mmol) of bis(phenylethynyl) ketone are dissolved in a mixture of 150 mL of tetrahydrofuran and 150 mL of 1 M sodium ethoxide in ethanol this solution is poured as quickly as possible into the deep-purple-coloured dilithium telluride soluhon. The flask containing the reaction mixture is immediately placed in a water bath at 50°C and the temperature slowly increased over 30 min until ethanol begins to condense on the side of the flask. The water bath is removed and the mixture is stirred overnight at 20°C. Dichloromethane (400 mL) is then added, the resultant mixture is washed with 800 mL of water, and the organic phase is separated and concentrated to an oil. The oil is dissolved in 600 mL of dichloromethane, and the solution is filtered through a pad of sand. The filtrate is washed with 200 mL of 2% aqueous sodium chloride soluhon, dried with anhydrous sodium sulphate, filtered and evaporated. The brownish solid residue is triturated with 20 mL of butanenitrile and the fine yellow solid is collected by filtration yield 10.9 g (51%) m.p. 126-129°C (from acetonitrile). 

The apparatus used is shown in Fig. 2 (Note 1). A solution of sodium ethoxide prepared by dissolving 2.5 g. of clean sodium metal (0.11 gram atom) in 230 g. (292 ml., 5 moles) of absolute ethanol under anhydrous conditions is added to the reaction tube C. The tube C thus charged is weighed, and placed in position with the gas inlet tube, fitted with fritted-glass dispersion cylinder D, extending nearly to the bottom. Several inches of ethanol is placed in the tube G, which serves as a flow indicator. The... 

Diethyl oxalate (29.2 g, 0.20mol) and 4-bromo-2-nitrotoluene (21.6 g, O.lOmol) were added to a cooled solution of sodium ethoxide prepared from sodium (4.6 g, 0.20 mol) and ethanol (90 ml). The mixture was stirred overnight and then refluxed for 10 min. Water (30 ml) was added and the solution refluxed for 2 h to effect hydrolysis of the pyruvate ester. The solution was cooled and concentrated in vacuo. The precipitate was washed with ether and dried. The salt was dissolved in water (300 ml) and acidified with cone. HC1. The precipitate was collected, washed with water, dried and recrystallizcd from hexane-EtOAc to give 15.2 g of product. 

Tellurium Tetraethoxide2 188.3 g (0.5 mol) of diammonium hexachlorotellurate are suspended in 500 ml of absolute ethanol and a cooled solution of sodium ethoxide, prepared by careful addition of 50 g (2.17 mol) of sodium in small pieces to 400 ml of ethanol, is added dropwise. The mixture is healed under reflux until evolution of ammonia has ceased, filtered to remove sodium chloride, and ethanol is distilled from the filtrate. The residue is distilled under vacuum to give the product as a colorless oil b.p. 10770.3 torr. 

To a solution of sodium ethoxide prepared using 4.6 g sodium and 100 ml ethyl alcohol was added 2-hydroxy-3-(l-propenyl)-propionphenone (10 g), 71.2g diethyl oxalate dissolved in 160 ml toluene, and the reaction stirred at 50°C 3.5 hours. Thereafter 16 ml 98% H2SO4 was added dropwise, the reaction stirred an addition 30 minutes at 50°C, cooled, and the organic phase washed 3 times with 200 ml water. The crude product was isolated in 62% yield, mp = 131-135 °C. 

Preparation of phenylnitromethane. A solution of sodium ethoxide prepared from 2 g. atoms of sodium and 400 ml. of absolute ethanol is treated with 100 ml. of absolute ethanol and cooled to 0°, when the sodium ethoxide separates as a hard cake. A second 100 ml. portion of ethanol is added, and a chilled mixture of 2 moles of benzyl cyanide and 2.8 moles of methyl nitrate is added with shaking at 5-15°. The reaction proceeds smoothly, with separation of the nci-nitro sodium salt (1). I he salt is collected (300-320 g.), placed in a 4-1. beaker, and treated with a solution... 

To a solution of dibromophenylbismuthine (8.92 g, 20 mmol) in ethanol (50 ml) cooled to —50°C was added dropwise a solution of sodium ethoxide (prepared from sodium 0.92 g in ethanol), and the reaction mixture was allowed to warm to -10°C gradually. As the reaction proceeded, sodium bromide and phenylbismuth diethoxide precipitated as a white solid. The reaction mixture was allowed to stand at room temperature for a short time and then filtered to remove sodium bromide. The filtrate was rapidly cooled to —20°C to give phenylbismuth diethoxide as a colorless microcrystalline solid, which was filtered at low temperature and... 

NP(0CH2CH )2]jj a solution of (NPGl ) in benzene was added slowly to a stirred solution of sodium ethoxide prepared from sodium and ethanol in a nitrogen atomosphere. The reaction was allowed to proceed at 25°C for 5 days. The mixture was added to distilled water and the polymer precipitate was isolated by filtration. Purification of the polymer was carried out in THF-ethanol. 

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