Patent GB-932935-A (GB)
Title: Process for the manufacture of aminoalkyl hydrooxyarly ketones, aminoalky alkoxyaryl ketones and aminoalkyl alkythioaryl ketones
IPC: C07D209/48
Filed: 1959-10-15
Abstract: Products containing ketonic, amino and hydroxy, alkoxy or alkylthio groups are prepared by reacting (a) straight-chain linked aminoacid or lactam polycondensation products with (b) hydroxyaryl, alkoxyaryl or alkylthioaryl compounds, which may be substituted in the nucleus by a halogen atom or an alkoxy or a nitro group.  Specified aminoacid or lactam starting materials are the low molecular polyamides of g -aminobutyric acid and the fairly high-molecular polyamides of S -caprolactam or of 8-aminocaprylic acid.  Specified aryl compounds are phenol, anisole, thioanisole, phenetole, n-butylphenyl ether, o- and p-cresol, p-tert.-butylphenol, 2- and 4-methoxytoluene, p-chlorophenol, resorcinol and its mono- and di-methyl ethers, dithioresorcinol dimethyl ether, 4-methyl- and 2-nitro-resorcinol, pyrogallol and its mono-, di- and tri-methyl ethers, and a - and b -naphthol and their methyl ethers.  No specific examples are given.ALSO:Substituted alkyl-aromatic aminoketones are prepared by reacting (a) an aliphatic aminocarboxylic acid, the amino group of which is linked to a saturated carbon atom and is separated from the carboxy group by at least 3 carbon atoms, with (b) a hydroxyaryl compound or an alkyl ether thereof or an alkyl thioaryl ether, the reaction being effected in the presence of a polyphosphoric acid. The aminocarboxylic acid may be substituted on the nitrogen atom by a hydrocarbon radical and (or) an acyl group, and the aromatic reagent may be substituted in the nucleus by a chlorine atom or an alkyl or a nitro group.  The polyphosphoric acid may be taken as such or formed in situ from syrupy phosphoric acid and phosphorus pentoxide. Specified aminocarboxylic acids and derivatives are 6-aminocaproic acid, 6-acetyl-, 6-benzoyl-, 6-succinimido-, 6-phthalimido-and 6-dimethyl-aminocaproic acids, N : N : N-trimethyl-6-aminocaproic acid betaine, 6-guanidino- and 6-ureido-caproicacids, N,N1-carbonyl-bis-6-aminocaproic acid, 8-amino- and 8-formylamino- or 8-benzoylamino-caprylic acids, 11-amino-, 11-formylamino- or 11-methylamino-undecanic acid. N-methyl- N-benzoyl- 11-undecanic acid, N : N1- hexamethylenebis- (6-aminocaproic acid), piperazine-N : N1-bis(e -caproic acid), N-allyl-11-amino-undecanic acid, 4-acetylaminobutyric acid, N-methyl-N-benzoyl-4-amino-butyric acid, 4-benzoylaminobutyric acid, 5-benzoylaminovaleric acid, 5-ureidovaleric acid, carbonyl-bis-(5-aminovaleric acid) and N : N-dimethyl-4-aminobutyric acid.  Straightchain linked aminoacid or lactam polycondensation products, e.g. polyamides of 4-aminobutyric acid or of 8-aminocaprylic acid or polyamides of e -caprolactam may also be used.  Specified hydroxyaryl, alkoxyaryl or alkylthioaryl compounds are phenol, anisole, thioanisole, phenetole, n-butylphenyl ether, o- and p-cresol, p-tert.-butylphenol, 2-and 4-methoxytoluene, p-chlorophenol, resorcinol and its mono- and dimethyl ethers, dithioresorcinol dimethyl ether, 4-methyl- and 2-nitro-resorcinol, pyrogallol and its mono, di- and tri-methyl ethers, and a - or b -naphthol and their methyl ethers.  Examples are given in which (1) 11-aminoundecanic acid and phenol yield 10-aminodecyl-4-hydroxy-phenyl ketone, which is purified by conversion into its N-acetyl derivatives followed by hydrolysis of the acetyl group; (2) 8-aminocaprylic acid and phenol yield 7-aminoheptyl-4-hydroxyphenyl ketone, which is purified as in Example 1; (3) 6-benzoyl-aminocaproic acid and phenol yield 5-benzoylaminopentyl-4-hydroxyphenyl ketone, and corresponding products are obtained from 6-acetaminocaproic acid and 6-aminocaproic acid; (4) acetaminobutyric acid and phenol yield 3- acetaminopropyl- 4- hydroxyphenyl ketone; the corresponding benzoylamino product is also prepared; (5) 11-aminoundecanic acid and p-cresol yield 10-aminodecyl-2-hydroxy-5-methylphenyl ketone; (6) 6-benzoyl-aminocaproic acid and p-cresol yield 5-benzoylaminopentyl-2-hydroxy- 5-methylphenyl ketone; (7) 11-aminoundecanic acid and anisole yield 10-aminodecyl-4-methoxyphenyl ketone; (8) 8-aminocaprylic acid and anisole yield 7-aminoheptyl-4-methoxyphenyl ketone; (9) 6-aminocaproic acid and phenetole yield 5-aminopentyl-4-ethoxyphenyl ketone; (10) 6-aminocaproic acid and p-tert.-butylphenol yield 5-aminopentyl-2-hydroxy-5-p-tert.-butylphenyl ketone; (11) 11-aminoundecanic acid and resorcinol yield 10-aminodecyl-2,4-dihydroxyphenyl ketone; (12) 11-aminoundecanic acid and resorcinol dimethyl ether yield 10-aminodecyl-2,4-dimethoxyphenyl ketone; (13) 8-aminocaprylic acid and resorcinol dimethyl ether yield 7-aminoheptyl-2,4-dihydroxyphenyl ketone, after treatment with sodium hydroxide solution; (14) 5-ureidovaleric acid and resorcinol dimethyl ether yield 4-ureidobutyl-2.4-dimethoxyphenyl ketone; (15) N : N1-carbonyl-5-aminovaleric acid and resorcinol dimethyl ether yield N,N1- bis-(5-(21,41-dimethoxyphenyl) - 5-oxopentyl) urea; a corresponding product from N:N1-carbonyl-6-aminocaproic acid is also prepared; (16) 6-benzoylaminocaproic acid and 1-methoxynaphthalene yield 5-benzoylaminopentyl- 1-methoxy- 4-naphtyl ketone; (17) N-methyl-11-aminoundecanic acid and resorcinol dimethyl ether yield N-methyl-10aminodecyl-2,4-dimethoxyphenyl ketone; (18) 6-dimethylaminocaproic acid and resorcinol dimethyl ether yield 5-dimethylaminopentyl2,4-dimethoxyphenyl ketone; (19) 4-dimethylaminobutyric acid and resorcinol dimethyl ether yield 3-dimethylaminopropyl-2,4-dimethoxyphenyl ketone; (20) 6-phthalimidocaproic acid and resorcinol dimethyl ether yield 5- phthalimidopentyl- 2.4- dimethoxyphenyl ketone; (21) N-methyl-N-benzoyl-4butyric acid and resorcinol dimethyl ether yield N-methyl- N-benzoylamino- 3-aminopropyl-2,4-dimethoxyphenyl ketone; (22) acetaminocaproic acid and thioanisole yield 5acetaminopentyl- 4- methylmercaptophenyl ketone.