Patent GB-664580-A (GB)
Title: Improvements in and relating to the production of photographic colour couplers
IPC: G03C7/32
Filed: 1949-11-04
Abstract: Amino-phenyl-alkylamines are acylated in the side chain with an ester and subsequently acylated in the nucleus, either the first or second acylating agents having a group which is reactive with the oxidation product of a primary aromatic amino developing agent.  Amines specified are m- or p-amino-b -phenyl-ethylamine, p-amino-D -phenylbutylamine, p-amino - Z - phenylhexylamine and p - amino - phenylmethylamine.  The acylating ester may be of a carboxylic or sulphonic acid and lower alkyl, e.g. ethyl and butyl esters, may be used although phenyl esters are preferred.  The second acylation may be effected with an ester, acid chloride or anhydride.  The first acylation is desirably effected at below 80 DEG  C., when phenyl carboxylic esters are used.  In examples: (1) m-amino-b -phenethylamine is reacted with phenyl methane sulphonate and with ethyl benzoyl acetate to give benzoyl-acet-3-(b -methanesulphonamidoethyl) anilide; (2) p-amino-b -phenethylamine is reacted with phenyl-1-hydroxy-2-naphthoate and acetic acid, sodium acetate and acetyl chloride to give 1-hydroxy-b -[b -(41-acetamido) phenethyl] naphthamide and phenyl salicylate may replace the naphthoate and methane- or p-toluene-sulphonyl chlorides may replace acetyl chloride; (3) the 1-hydroxy-2-(b -41-amino-phenethyl) naphthamide of (2) is reacted with 2-(21 : 41-diamylphenoxy)-5-nitrobenzoyl chloride to produce 1-hydroxy-2-{b -{41-[211 - (2111 : 4111 - diamylphenoxy) - 511 - (311 : 5111-dichlorosulphonylbenzamido)] benzamido} phenethyl} naphthamide after reduction with iron and acetic acid and acylation with 2 : 4 -disulphobenzoyl trichloride; (4) uses the p-amino isomer of the alkyl-amine of (1) to produce benzoylacet - 4 - (b  - methanesulphonamido ethyl) anilide; (5) p-amino-b -phenethylamine is heated with phenyl-2-(21 : 41-diamylphenoxy)-5-nitrobenzoate and ethyl benzoyl acetate, reduced with iron and acetic acid and acylated with 2 : 4-disulphobenzoyl trichloride to give benzoylacet - 4 - {b - [21 - (211 : 411 - diamylphenoxy) - 5 - (31 : 51 - dichlorosulphonyl - benzamido) benzamido] ethyl} anilide; (6) p-amino-b -phenethylamine is reacted with 1-phenyl-3-carboxyphenyl - 5 - pyrazolone and 2 - (21 : 41-diamylphenoxy) - 5 - nitrobenzoyl chloride, reduced and acylated with 2 : 4-disulphobenzoyl trichloride to give 1 - phenyl - 3 - {b  - {41 - [211-(2111 : 4111 - diamylphenoxy) - 5 - (31 : 51 - dichlorosulphonylbenzamido)] benzamido} phenethyl} pyrazolone; (7) p-amino-b -phenethylamine is heated with 2 : 4-diamylphenoxyphenyl acetate and benzoyl phenyl acetate to yield benzoylacet - 4 - [b  - (21 : 41 - diamylphenoxyacetamido) ethyl] anilide; (8) p-amino-2-phenethylamine is heated with benzoyl phenyl acetate or other acylaceto ester and with 2 : 4-diamyl phenoxy acetyl chloride to yield 4 - [b  - (benzoylacetamido) ethyl] - 21 : 41 - diamylphenoxyacetanilide; (9) p-amino-phenyl benzoate is reacted with ethyl benzoylacetate and the product, first with p-amino-b -phenethylamine and then acetylthioglycolyl chloride (made as in Specification 595,844) to give benzoylacet - {4 - [b  - (41 - acetylthioglycolamido) phenethyl] carbamyl} anilide; (10) 1-phenyl - 3 - [b  - (41 - acetamido) phenethyl] carbamyl - 5 -, 1 - phenyl - 3 - {b  - [41 - (211 : 411 - diamylphenoxy) acetamido] phenethyl} carbamyl-5-, and 1-phenyl-3-[b -(acetylthioglycolamido) phenethyl] carbamyl-5-pyrazolones are made by reacting p-amino-b -phenethylamine with the appropriate pyrazolone ester and with acetyl, 2 : 4 - diamylphenoxy - acetyl - or acetylthioglycolyl chloride respectively; (11) 1-hydroxy-2 - {b  - 4 - [41 - (211 : 411 - diamylphenoxy) acetamido] phenethyl} and 1-hydroxy-2-[b -(41-acetyl - thioglycolamido) phenethyl] naphthamides are made by acylating p-amino-b -phenylethylamine with phenyl-1-hydroxy-2-naphthoate and either 2 : 4-diamylphenoxyacetyl or acetylthioglycolyl chlorides; (12) p-amino-b -phenethylamine is reacted with phenyl-p-toluene sulphonate and phenyl-1-hydroxy-2-naphthoate to give 1-hydroxy-2-{41-[b -(411-toluene sulphonamido) ethyl]} naphthanilide; and (13) 3-[b -(benzoylacetamido) ethyl]-21 : 41-diamylphenoxyacetanilide and 1-phenyl-3-[31-(b -acetamido-ethyl) phenyl] carbamyl-5-pyrazolone are made by reacting p-amino-b -phenethylamine with phenyl benzoyl acetate and 2 : 4-diamylphenoxy acetyl chloride or phenyl acetate and 1-phenyl-3-carbonyl chloride - 5 - pyrazolone respectively.  The products are of use as photographic colour couplers (see Group XX). The alkylamines are made by reduction of the corresponding amino - phenyl - alkyl - nitrile or nitro - phenyl - alkyl - amine. Thus p - amino - phenylacetonitrile is reduced in liquid ammonia and methanol using Raney nickel catalyst and hydrogen.  In the Specification as open to inspection under Sect. 91 the nucleus of the amine may contain halogen, alkyl or phenoxy groups. This subject-matter does not appear in the Specification as accepted.