1911 Encyclopædia Britannica/Acetophenone
ACETOPHENONE, or Phenyl-Methyl Ketone, C8H8O or C6H5CO⋅CH3, in chemistry, the simplest representative of the class of mixed aliphatic-aromatic ketones. It can be prepared by distilling a mixture of dry calcium benzoate and acetate,
Ca(O2CC6H5)2+(CH3CO2)2Ca=2CaCO3+2C6H5CO⋅CH3, or by condensing benzene with acetyl chloride in the presence of anhydrous
aluminium chloride (C. Friedel and J. M. Crafts), C6H6+CH3COCl=HCl+ C6H5COCH3. It crystallizes in colourless
plates melting at 20°C. and boiling at 202°C.; it is insoluble in
water, but readily dissolves in the ordinary organic solvents.
It is reduced by nascent hydrogen to the secondary alcohol
C6H5-CH-OH-CH3 phenyl-methyl-carbinol, and on oxidation forms benzoic acid. On the addition of phenylhydrazine it
gives a phenylhydrazone, and with hydroxylamine furnishes an oxime C6H5
CH3 C=N⋅OH melting at 59°C. This oxime undergoes a peculiar rearrangement when it is dissolved in ether and phosphorus pentachloride is added to the ethereal solution, the excess of ether distilled off and water added to the residue being converted into the isomeric substance acetanilide, C6H5NHCOCH3, a behaviour shown by many ketoximes and known as the Beckmann change (see Berichte, 1886, 19, p. 988). With sodium ethylate in ethyl acetate solution it forms the sodium derivative of benzoyl acetone, from which benzoyl acetone, C6H5⋅CO⋅CH2⋅CO⋅CH3, can be obtained by acidification with acetic acid. When heated with the halogens, ace top hen one is substituted in the aliphatic portion of the nucleus; thus bromine gives phenacyl bromide, C6H5CO⋅CH2Br. Numerous derivatives of acetophenone have been prepared, one of the most important being ortheaminoacetophenone, NH2⋅C6H4⋅CO⋅CH3, which is obtained by boiling orthoaminophenylpropiolic acid with water. It is a thick yellowish oil boiling between 242° C. and 250° C. It condenses with acetone in the presence of caustic soda to a quinoline. Acetanyl-acetophenone, C6H5⋅CO⋅CH2-CH2⋅CO⋅CH3, is produced by condensing phenacyl bromide with sodium acetoacetate with subsequent elimination of carbon dioxide, and on dehydration gives αα-phenyl-methyl-furfurane. Oxazoles (q.v.) are produced on condensing phenacyl bromide with acid-amides (M. Lewy, Berichte, 1887, 2, p. 2578). K. L. Paal has also obtained pyrrol derivatives by condensing acetophenone-aceto-acetic-ester with substances of the type NH2R.