Nitro acetanilide

White crystals, m.p. 114" C. Manufactured by reacting aniline with excess ethanoic acid or ethanoic anhydride. Chief use is in the manufacture of dye intermediates such as p-nitro-acetanilide, p-nitroaniline and p-phenylene-diamine, in the manufacture of rubber, and as a peroxide stabilizer. 

Hydrolysis to p-Nitroaniline. For this purpose use 70 sulphuric acid, the usual reagent employed for the hydrolysis of anilides (p. 108). Add 5 g. of the recrystallised />-nitro-acetanilide to 30 ml. of 70%sulphuric acid, and boil the mixture gently under a reflux water-condenser for 20 minutes. Then pour the clear hot solution into about 150 ml. of cold water, and finally add an excess of sodium hydroxide solution until precipitation of the yellow p-nitroaniline is complete. Coo the mixture in ice-water if necessary, and then filter at the pump, wash well... 

Another side reaction which occurs is reduction in the reaction the —N2C1 or —N(NO)COCH3 group is replaced by hydrogen. wi-Bromo-toluene was isolated in 6% yield from the reaction between the sodium diazotate from 2-bromo-4-methylaniline and benzene, and in 10% yield in a similar reaction from 2-methyl-4-bromoaniline.4 Some nitrobenzene is obtained in the preparation of 3-nitrobiphenyl from nitroso-w-nitro-acetanilide (p. 250). The source of the hydrogen effecting the reduction has not been determined. f... 

In the meantime a mixture of one volume of 50 per cent aqueous potassium hydroxide, 4 volumes of water, and one volume of alcohol is prepared, cooled to o°, and the nitration product thoroughly rubbed up (in portions) in a chilled mortar with about 600 cc. of the solution. The o-nitro-acetanilide dissolves, while the bora- compound remains insoluble in the cold mixture and is sucked off and washed with a little of the cold... 

To obtain p-nitroaniline from the anilide proceed as follows HOOD.—In a beaker covered with a watch-glass boil the p-nitro-acetanilide with ten times its weight of dilute hydrochloric acid (sp. gr. 1.12) for about 20 minutes. Cool the solution, add about an equal volume of water and an excess of concentrated ammonia. When the solution is cold, filter off the p-nitroaniline,... 

Nitration of aniline as the acetyl derivative by mixed acid gives p-nitro-acetanilide as the main product, together with a little of the ortho-compound. The relative amounts are shifted very greatly in favor of the ortho-compound... 

The highly active amino function present in aniline is duly protected by acetylating it with acetic anhydride to obtain acetanilide and the elimination of a mole of acetic acid. The acetanilide is now subjected to nitration by concentrated sulphuric acid and fuming nitric acid to obtain the two products, namely para-nitro acetanilide ( 90%) and ortho-miro acetanilide ( 10%). Finally, the para-nitroaniline is obtained by carrying out the hydrolysis of the corresponding p-nitro acetanilide with 70% sulphuric acid. 

A soln. of m-(hydroxymethyl) phenoxyacetic acid in thionyl chloride refluxed 3 hrs., evaporated in vacuo, the residue dissolved in ethylene dichloride, and again evaporated in vacuo —crude m-(chloromethyl) phenoxyacetyl chloride (Y 96%) dissolved in methylene chloride, a soln. of 2 moles of m-nitraniline in the same solvent added with stirring during ca. 15 min., stirring continued for 10 min., treated with anhydrous HCl until the yellow color of free m-nitraniline has disappeared, filtered, crude 2-[(m-chloromethyl)phenoxy]-3 -nitro-acetanilide isolated from the filtrate, dissolved in chloroform containing diethanolamine, and refluxed 6 hrs. 2-(m-[bis-(2-hydroxyethyl) aminomethyl]-... 

HuoT-S-nitro-acetanilid 12 1 355." CaHyFNaOa 6-FIuor-3-mtxo.4-oxy.1>enzaldehyd-... 

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