Alcohol continued pour point

In a i-l. round-bottom flask are placed 250 cc. of glacial acetic acid, 15 g. of red phosphorus and 5 g. of iodine. The mixture is allowed to stand for fifteen to twenty minutes until the iodine has reacted, and then 5 cc. of water and 100 g. of benzilic acid are added. A reflux condenser is attached and the mixture is boiled continuously for at least two and a half hours. After the reaction is complete, the hot mixture is filtered with suction to remove the excess red phosphorus (Note 2). The hot filtrate is slowly poured into a cold, well-stirred, filtered solution of 20-25 g- °f sodium bisulfite in 1 1. of water (Note 3). This procedure removes the excess iodine and precipitates the diphenylacetic acid as a fine white or slightly yellow powder (Note 4). The product is filtered with suction, washed with cold water and dried thoroughly on filter paper. The yield is 88-90 g. (94-97 per cent of the theoretical amount) of a solid melting at 141-1440 (Note 5). If a crystalline product is desired, the acid is dissolved in about 500 cc. of hot 50 per cent alcohol and then cooled. The melting point after recrystallization is 144-1450. 

To a stirred suspension of 4.6 g (13.8 mmoles) of the (S)-3-(2-hydroxyethyl)-5-(2-oxo-l,3-oxazolidin-4- ylmethyl)-lH-indol-2-carboxylic acid ethyl ester in 42 ml of dichloromethane were added 4.2 ml of pyridine, 3.9 g (20.7 mmoles) oftosyl chloride and 170 mg (1.38 mmoles) of dimethylaminopyridine and the stirring continued at room temperature for 20 hours. The reaction mixture was poured over 20 ml of 3 N, HCI precooled to 0°C and extracted twice with dichlormethane. The organic phases were washed with brine, dried on anhydrous sodium sulphate and the solvent evaporated to dryness. The evaporated solid was crystallised with isopropyl alcohol to give 6.4 g (95%) of the title compound as a white crystalline solid. Melting point 166.4°-168.2°C. 

In a 2-1. two-neck ilask fitted with a short reflux condenser and mechanical stirrer (Note 1) are placed 400 cc. of dry xylene (Note 2) and 29 g. (1.26 moles) of clean sodium (Note 3) cut in small pieces. The flask is surrounded by an oil-bath and heated until the sodium has melted. At this point the stirrer is started and the sodium is broken up into very small particles (Note 4). The oil-bath is removed but stirring is continued until the sodium has solidified as very fine particles. The xylene is then poured off, and to the sodium is added 455 cc. (4.7 moles) of absolute ethyl acetate (Note 5) containing 3-4 cc. of absolute ethyl alcohol (Note 6). The flask is quickly cooled to o° and 106 g. (1 mole) of pure benzaldehyde (Note 7) is added slowly from a separatory funnel while the mixture is stirred. The temperature is held between o° and 50 (Note 8). The reaction starts as soon as the benzaldehyde is added, as is shown by the production of a reddish substance on the particles of the sodium. About one and a half to two horns are required for this addition. The stirring is continued until practically all of the sodium has reacted (one hour after all the aldehyde has been added). When most of the sodium (Note 9) has disappeared, 90-95 cc. of glacial acetic acid is added and the mixture is carefully diluted with... 

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