Sodium—continued phenols

Dissolve 3-8 g. of sodium in 75 mi. of rectified spirit, using otherwise the same conditions as in the preparation of anisole. Then add 15 g. of phenol, and to the clear solution add 13 2 ml. (19-1 g., n mois.) of ethyl bromide. Continue precisely as in the preparation of anisole, shaking the ethereal extract with sodium hydroxide solution as before in order to eliminate any unchanged phenol. Finally collect the fraction boiling at 168-172°. Yield, 14 g. 

Cautiously add 250 g. (136 ml.) of concentrated sulphuric acid in a thin stream and with stirring to 400 ml. of water contained in a 1 litre bolt-head or three-necked flask, and then dissolve 150 g. of sodium nitrate in the diluted acid. Cool in a bath of ice or iced water. Melt 94 g. of phenol with 20 ml. of water, and add this from a separatory funnel to the stirred mixture in the flask at such a rate that the temperature does not rise above 20°. Continue the stirring for a further 2 hours after all the phenol has been added. Pour oflF the mother liquid from the resinous mixture of nitro compounds. Melt the residue with 500 ml. of water, shake and allow the contents of the flask to settle. Pour oflF the wash liquor and repeat the washing at least two or three times to ensure the complete removal of any residual acid. Steam distil the mixture (Fig. II, 40, 1 or Fig. II, 41, 1) until no more o-nitrophenol passes over if the latter tends to solidify in the condenser, turn oflF the cooling water temporarily. Collect the distillate in cold water, filter at the pump, and drain thoroughly. Dry upon filter paper in the air. The yield of o-nitrophenol, m.p. 46° (1), is 50 g. 

P-Hydroxy-a-naphthaldehyde, Equip a 1 litre three-necked flask with a separatory funnel, a mercury-sealed mechanical stirrer, and a long (double surface) reflux condenser. Place 50 g. of p-naphthol and 150 ml. of rectified spirit in the flask, start the stirrer, and rapidly add a solution of 100 g. of sodium hydroxide in 210 ml. of water. Heat the resulting solution to 70-80° on a water bath, and place 62 g. (42 ml.) of pure chloroform in the separatory funnel. Introduce the chloroform dropwise until reaction commences (indicated by the formation of a deep blue colour), remove the water bath, and continue the addition of the chloroform at such a rate that the mixture refluxes gently (about 1 5 hours). The sodium salt of the phenolic aldehyde separates near the end of the addition. Continue the stirring for a further 1 hour. Distil off the excess of chloroform and alcohol on a water bath use the apparatus shown in Fig. II, 41, 1, but retain the stirrer in the central aperture. Treat the residue, with stirring, dropwise with concentrated hydrochloric acid until... 

Guyot A continuous sulfonation process for making phenol. Sodium sulfite is a byproduct and must be sold if the process is to be economic. 

Phosgene addition is continued until all the phenolic groups are converted to carbonate functionalities. 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-alkali 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. 

Stirring and heating were continued for a total of 2 h after which the mixture was cooled, poured into water and extracted with ether. The combined ether extract was washed several times with 2 N sodium hydroxide to remove phenol, dried over anhydrous sodium sulfate, and evaporated. The residue was distilled under water-pump vacuum to give pure 2-(3-methoxy-phenoxy)-propionitrile, boiling point 152-154°C/13 mm. 

This sequence explains Price s observations adequately and seems to be required in this particular case. The oxidative elimination of halide ion from salts of phenols does not always follow this course, however. In the peroxide-initiated condensation of the sodium salt of 2,6-dichloro-4-bromophenol (Reaction 23) molecular weight continues to increase with reaction time after the maximum polymer yield is obtained (Figure 5) (8). Furthermore, Hamilton and Blanchard (15) have shown that the dimer of 2,6-dimethyl-4-bromophenol (VIII, n = 2) is polymerized rapidly by the same initiators which are effective with the monomer. Obviously, polymer growth does not occur solely by addition of monomer units in either Reaction 22 or 23 some process leading to polymer—polymer coupling must also be possible. Hamilton and Blanchard explained the formation of polymer from dimer by redistribution between polymeric radicals to form monomer radicals, which then coupled with polymer, as in Reaction 11. Redistribution has indeed been shown to occur under... 

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