ベンゼン置換体とクロラールの反応について (第4報)

N-Acetyl-p-toluidineとクロラールの反応 その3 中性物質の構造について

抄録

Of the three neutral substances obtained by the reaction of N-acetyl-p-toluidine and chloral, two were determined as 4-methyl-3-(α, β, β, β-tetrachloroethyl)acetanilide (I), m. p. 166-168°, and 5-acetamido-2-methylbenzaldehyde (II), m. p. 129°, while the third of m. p. 268° (decomp.) was too small to be submitted to structural determination. (I) forms an N, N-diacetyl cmpound of m. p. 134-136° with acetic anhydride, its deacetylated compound of m. p. 120-122°, and loses 1 mole of hydrogen chloride by treatment with ethanolic sodium hydroxide. It is reduced with zinc dust and glacial acetic acid to 4-methyl-3-(β, β-dichloroethyl) acetanilide (VI), m. p. 135-136°, which is also obtained by its reduction with hydriodic acid and red phosphorus, followed by acetylation. (VI) forms a vinyl derivative (VII), m. p. 132-134°, with ethanolic sodium hydroxide and oxidation of (VII) gives 5-acetamido-2-methylbenzoic acid (VIII). Heating of (I) with conc. sulfuric acid for 18 hours at 60-70° yields 5-acetamido-2-methylphenylglycolic acid, m. p. 229°(decomp.), and an attempt to change the chlorine in the α-position of (I) alone to hydroxyl group did not succeed.
5-Acetamido-2-methylbenzaldehyde (II) (oxime, m. p. 165-167°: semicarbazone, m. p. 268-270° (decomp.)) also forms on boiling 5-acetamido-2-methylphenylglycine and 5-amino-2-methylphenylglyoxylic acid with Al³⁺.