Patent GB-954269-A (GB)
Title: Process for the production of beta-keto amides
Inventor: HOFFSTADT WALTER FREDERICK
IPC: G03C7/36
Filed: 1962-03-28
Abstract: Amides of the formula RC(O)CH2C(O)NHR1, where R and R1 are aromatic or heterocyclic nuclei, are prepared by reacting methylaryl ketones of the formula RC(O)CH3 with isocyanates of the formula R1NCO or with urethanes of the formula R1NHC(O)OR2, where R2 is a methyl, ethyl or propyl group.  The reaction is effected in the presence of a highly basic condensing agent and yields, in the first instance, a salt of the enolic form of the desired amide, which is then converted into the ketonic form by acidification.  The preferred condensing agents are alkali-metal alkoxides, but lithium alkyls, lithium aniline or alkali-metal salts of triphenyl-methyl may also be used.  The reaction is preferably effected at a raised temperature in the presence of a solvent, a number of which are specified. Examples are given of the preparation of (1) benzoylacetanilide, from phenyl urethane and acetophenone, (2) 2-methoxybenzoyl-acetanilide from phenyl urethane and o-meth-oxyacetophenone. (3) 4, 7-dimethoxy-1-naphthoylacetanilide from phenyl unethane and 4.7-dimethoxy-1-naphthyl methyl ketone, (4) 4-chlorobenzoylacetanilide from phenyl urethane and p-chloroacetophenone. (5) 4, 41-bis (benzoylacetanilide from phenyl urethane (2 mols) and 4, 41-biphenylacetophenone, (6) p-cyanobenzoylacetanilide from phenyl urethane and p-cyanoacetophenone, (7) 4-diethylaminobenzoy-lacetanilide from phenyl urethane and p-diethy-aminoacetophenone, (8) 1-naphthoyl-41-pheny-lacetanilide from 4 phenyl phenyl urethane and methyl 1-naphthyl ketone, (9) 4-fluorobenzoyl-1 1-naphthyl amide from 1-naphthyl urethane and p-fluoroacetophenone.  (10) 4-ethoy benzoxyl-41-acetaminopyridine from the corresponding urethane and p-ethoxyacetophenone, (11) 4-phenylbenzanilide from phenyl urethane and p-phenylacetophenone, (12) the reaction product of p-fluorophenylurethane and 5-methoxy-thienyl-2-methyl ketone, (13) 4-cyano-31-fluorobenzanilide from m-fluorophenyl urethane and p-cyanoacetophenone, and (14) 4-phenyl-11, 21, 31, 41-benzanilide from 2, 3, 5, 6-tetramethyl urethane and p-phenylacetophenone. Other specfied products obtainable according to the invention include those from 4-fluorophenyl urethane and 4-chloroacetophenone, 4-chloro-3-trifluoromethylphenyl urethane and acetophenone, 4-pyridyl urethane and 2-pyridyl methyl ketone, phenyl urethane and a methylthiazole or a diethylthiazole methyl ketone, phenyl urethane and quinoline-6-methyl ketone, p-phenylphenyl urethane and 2-chlorothiophene methyl ketone 2, 4-dimethyl-6-butoxyphenyl urethane and quinoline-4 methyl ketone 3-bromophenyl urethane and acetophenone, 2, 4-dichlorophenyl urethane and 2-naphthyl methyl ketone, phenyl urethane and pyridine-3 methyl ketone, 3-fluorophenyl urethane and 4-cyanoacetophenone, phenyl urethane and 4-hydroxy-5, 6, 7, 8-tetrahydronaphthyl-2 methyl ketone, 4-pyridyl urethane and 4-ethoxyacetophenone, 3-pyridyl urethane and 2-naphthyl methyl ketone, 1-naphthyl urethane and pyridine-4 methyl ketone, thiophene-2 urethane and 4-cyanoacetophenone, furane-2 urethane and acetophenone and 2-naphthyl urethane and 4-ethoxyacetophenone. The products are useful in colour photography.