Reaction of Substituted Benzenes and Chloral. III: Reaction of N-Acetyl-p-toluidine and Chloral. (2). Constitution and Properties of Acidic Products

R-CO-COOH (II), obtained by the oxidation of R-CH (OH)-COOH (I), (R=5-acetamino-2-methylphenyl) gives R-CN (IV) on application of hydroxylamine on heating, and an oxime (III) at room temperature. The semicarbazone is stable and can be recrystallized from water. The hydrolysis product (V) of (II) possesses securely bound water of hydration and its dehydration results in the formation of a condensate, (C8H7N)xH2O (VI), which is soluble in organic solvents, insoluble in alkalis, and soluble in acids. When its hydrochloric acid solution is basified, a substance soluble in ether is obtained but attempted recrystallization causes reversion to (VI). Application of acetic anhydride to the ether solution gives R-CHO (VII) which is also obtained on warming (I) and conc. sulfuric acid at 40°. The crude acid (II) containing chlorine forms R-CH (NH2)-COOH (IX) on the application of ammonia but the product returns to (I) by the action of nitrous acid. (IX) gives a hydrolysis product (X) of m. p. 210° (decomp.), and an oxidation product of m. p. 242° (decomp.). It is certain, therefore, that R-CHCl-COOH (VIII) is present in the crude acid. It is assumed that (VIII) alone was present during the reaction and formed (I) by hydrolysis during the procedure. Another acid obtained must be R2CH-COOH (XI), which was confirmed by synthesis from (I) and RH. Liberation of nitrogen from (XI) gave di (o-tolyl) acetic acid (XII) which was also obtained from o-tolyl iodide and methyl formate.