Patent GB-866203-A (GB)
Title: Monochromatic direct positive coloured photographic images
IPC: G03C7/333
Filed: 1953-01-28
Abstract: Compounds of formulae:-  <FORM:0866203/IV(c)/1> in which X and Y represent negative groups such as-COR, -COOR, -CO.COOR, -CONR1R2, -CO.CO.NR1R2. -CH=CHR, -CN, -NO2.  -SO2R, phenyl groups which may be substituted, such as by nitro, halogen, alkyl, SO3H, COOH-groups, or heterocyclic radicals, R, R1 and R2 representing hydrogen atoms or monovalent aliphatic, aromatic or heterocyclic radicals such as methyl, ethyl, propyl, cyanomethyl, phenyl, substituted phenyl, pyridyl or benzthiazolyl radicals.  A represents a monovalent organic radical which is not split off by colour development, preferably an alkyl, cycloalkyl, aralkyl or aryl radical, such as methyl, ethyl, propyl, sulphoethyl (C2H4SO3H), carboxymethyl (CH2 COOR), cyclohexyl, benzyl, phenyl or naphthyl radical; B represents an aryl or a heteocryclic radical, such as a phenyl radical, which may be substituted as for instance by an alkyl (CH3, C2H5 or C3H7), a hydroxyl, sulphonic acid, nitro, carboxylic acid, sulphonamide, acylamide or tertiary amino groups or a halogen atom; and Z represents the atoms necessary to complete an isocyclic or heterocyclic ring, preferably a five-or six-membered ring.  The aforementioned compounds may be produced by coupling diazonium salts derived from aromatic or heterocyclic compounds in a liquid medium, preferably in an aqueous medium, with colour couplers having an active methylene group one hydrogen atom of which is substituted as disclosed above.  The pH value of the aqueous medium is preferably about 5 to 11.  Examples of suitable coupling components are:-nitriles, esters, amides, hydrazides, hydroxamic acids and other derivatives of acylacetic acids, malonic acid, cyanoacetic acid, phenylsulphonyl acetic acid; aliphatic and cyclic 1, 3-diketones such as acetylacetone, cyclohexanedione, and -cyanoketones such as cyanoacetylbenzene, nitrodiphenylmethanes such as 4-nitrodiphenylmethane, and p-nitrobenzyl-cyanides, indanediones, cyclopentanone- and cyclohexanone-2-carbonic and oxalic acid derivatives such as nitriles, esters or amides; pyrazolones; isoxazolones; 1, 2, 3-triazolones; oxindoles; coumaranones; oxythionaphthenes; oxycarbostyrils; thiohydantions; N-substituted rhodanines; benzimidazoles; benzoxazoles; benzthiazoles; 1, 3, 4-oxadiazoles; 1, 3, 4-thiodiazo pyrimidines; quinolines; quinazolines; quinazolones substituted in the 2-position by a CH2COR1 group (R1 standing for alkyl, aralkyl, aryl, amide, hydrazide, hydroxamino or an ester group) or by a CH2CN group; 1, 2, 4-oxodiazoles; 1, 2, 4-thiodiazoles, isoquinolines which are substituted in the 3-position by a CH2COR1 (R1 having the same meaning as above) or by a CH2CN group, all these compounds being substituted in the reactive methylene group by the substituent A disclosed above. Further compounds are those of formula:- <FORM:0866203/IV(c)/2> Ar standing for an aromatic radical and N for the quaternary nitogen atom of a heterocyclic ring such as pyridine or quinoline. A having the same meaning as above.  The compounds may be made by coupling 1 mol of diazotized 4-chloraniline-3-sulphonic acid with 1 mol of cyclopentanone-(1)-2-carboxylic acid anilide, 1 mol of tetrazotized 4, 41-diaminostilbene-2, 21-disulphonic acid with 2 mols of cyanogen ethyl malonic ester, 1 mol of diazotized 4-aminonitrostilbene-2, 21-disulphonic acid with 1 mol of cyclopentanone oxylylic acid ester, 1 mol of tetrazotized, 4, 41-diaminostilbene-2, 21-disulphonic acid with 2 mols of 1-benzthiazolyl-3, 41-dimethyl pyrazolone-(5), 1 mol of tetrazotized 4, 41-diamino-3, 31-methoxy diphenyl-2, 21-disulphonic acid with 2 mols of a -hydrindone-b -oxalylic ester, 1 mol of tetrazotized 4, 41-diaminostilbene-2, 21-disulphonic acid with:-2 mols of cyclopentanone-2-carboxylic acid ethyl ester, cyclopentanone-2-carboxylic acid anilide, a -hydrindone-b -oxalylic acid ethyl ester, a -tetralone-b -oxalylic acid methyl ester, cyclohexanone-2-carboxylic acid ethyl ester, cyclohexanone-2-oxalylic acid anilide or benzoyl-a -methyl-acetic acid ethyl ester; 1 mol of tetrazotized 4, 41-diamino-3, 31-dimethoxy diphenyl-2, 21-disulphonic acid with:-2 mols of 1-phenyl-3, 41-dimethyl pyrazolone-(5), a -hydrindone-b -oxalylic acid ester, or 1-(41-sulphophenyl)-3-phenyl-4-methyl pyrazolone-(5), 1 mol of cyclopentanone-2-carboxylic acid-(41-methyl stearylamino-31-sulphonic acid)-anilide with 1 mol of diazotized 4-chloraniline-3-sulphonic acid, aniline-3-sulphanilide, aniline-3-sulphamide, 4-nitroaniline-3-sulphonic acid, or 2-chlor-5-aminobenzoic acid, 1 mol of 1-phenyl-3-amino-4-methyl pyrazolone-(5) with 1 mol of diazotized 4-chlor-2-aminophenyl-5-sulphonic acid.  In examples coupling is effected between (1) tetrazotized 4, 41-diaminodibenzyl-2, 21-disulphonic acid and cyclopentanone-2-oxalylic acid ethyl ester; (2) tetrazotized 4, 41-diaminostilbene-2, 21-disulphonic acid with methyl cyclohexanone oxalyl ethyl ester; (3) tetrazotized 4, 41-diamino-3, 31-methoxy-2, 21-dibenzyl disulphonic acid and hydrindone oxalylic acid ethyl ester; (4) tetrazotized-4, 41-diamino-stilbene-2, 21-disulphonic acid and 1-benzthiazolyl-3, 4-dimethyl pyrazolone-5; (5) tetrazotized 4, 41-diamino-dibenzyl-2, 21-disulphonic acid and cyclopentanone-2-oxalylic acid ethyl ester; (6) diazotized 4-aminophenol sulphonic acid-2 and 1-(51-sulphobenzthiazolyl-21) -3-heptadecyl-4-isopropyl-pyrazolone-5; (7) diazotized 3-nitroaniline and 1-(51-sulpho-benzthiazolyl-21) - 3-heptadecyl- 4-methylpyrazolone- 5; (8) 2, 5-dichloro-4-aminobenzene sulphonic acid-1 and 1-(51-sulpho-benzthiazolyl-21)-3-heptadecyl-4-methyl pyrazolone-5; (9) 4-aminobenzoic acid and 1-(51-sulpho-benzthiazolyl-21)-3-heptadecyl-4-methyl pyrazolone-5; (10) 4-aminobenzene sulphonic acid-1 and 1-(51-sulphobenzthiazolyl-21)-3-heptadecyl-4-methyl pyrazolone-5; (11) 4-amino-anisole hydrochloride and 1-(41-sulpho-phenyl)-3-heptadecyl-4-methyl pyrazolone-5; (12) 4-aminophenetol hydrochloride and 1-(41-sulphophenyl)-3-heptadecyl-4-methyl-pyrazolone-5; (13)4-nitroaniline and 1-(31-sulpho-41-phenoxyphenyl)-3-heptadecyl-4-methyl pyrazolone-5; (14) 4, 41-diaminostilbene-2, 21-disulphonic acid and 1- -pyridyl-3, 4-dimethyl pyrazolone; (15) 4, 41-diaminostilbene-2, 21-disulphonic acid and 1-(41- -methyl quinoly)-3, 4-dimethyl pyrazolone; (17) 2-amino-5-acetamino- 41-hydroxy- 31-carboxy - diphenylsulphone and 1-(21-benzthiazolyl-51-sulpho) - 3-haptadecyl- 4- -cyanoethylpyrazolone-5; (18) 3-aminobenzonitrile and 1-(41-phenoxy- 31-sulphophenyl) - 3-heptadecyl- 4- -cyanoethylpyrazolone-5; (19) 3-aminotoluene- -sulphonic acid and 1-(41-phenoxy- 31-sulphophenyl) - 3-heptadecyl- 4- -cyanoethylpyrazolone-5 or 1-(31-lauroylaminophenyl) - 3-methyl- 4- -oxethylpurazolone-5; (20) 2-amino- 41-hydroxy- 31-carboxy-diphenyl sulphone sulphonic acid-4 and 1-(41- phenoxy- 31-sulphophenyl) - 3-heptadecyl-4-methylpyrazolone-5; (21) 4- aminodiphenyl-sulphonic acid-3 and 1-(41-phenoxy- 31-sulphophenyl) - 3-heptadecyl- 4-methylpyrazolone-5; (22) 4- aminoazobenzenecarboxylic acid-41 and 1-(41- phenoxy- 31-sulphophenyl) - 3-heptadecyl- 4-methylpyrazolone-5; (23) 3-amino-benzoic acid and 1-(41-sulphophenyl)- heptadecyl- 4-methylpyrazolone-5; (24) 3-amino-4-methyl- 41-nitrodiphenylamine- 21 -sulphonic acid and 1-(41-phenoxy- 31-sulphophenyl) - 3-heptadecyl- 4-methylpyrazolone-5; (25) sodium salt of 2- amino- 41- methyldiphenylsulphone-4-sulphonic acid and 1-(41- phenoxy- 31- sulphophenyl) - 3-heptadecyl- 4-methylpyraxolone-5; (26) 3-aminobenzonitrile and 1-(41- phenoxy- 31-sulphophenyl) - 3-heptadecyl- 4-methylpyrazolone-5; (27) 1- amino- 4-acetamino- 31-carboxy-41-hydroxy - diphenylsulphone and 2- ethyl- N-ethylbenzthiazoletosylate (ptoluene sulphonate); (28) 1- amino- 5-benzoylamino- 31-carboxy - 41- hydroxydiphenylsulphone and quaternary salt obtained from 22 grams of a -bromopropiophenone and 12,5 grams of quinoline; (29) 2- amino- 41- methyldiphenylsulphone- 4-sulphonic acid and 1-(41- phenoxy- 31-sulphonyl) - 3-heptadecyl- 4-methylpyrazolone-5; (30) 3- aminobenzonitrile and 1-(41-phenoxy-31-sulphophenyl) - 3-heptadecyl- 4-methylpyrazolone-5; (31) 31- carboxy- 41-hydroxy- 2-amino- 5 -acetaminodiphenylsulphone and 1-(41- phenoxy- 31- sulphophenyl) - 3-heptadecyl-4-methylpyrazolone-5; (32) tetrazotized 1, 2-di-(41- amino- 11- sulphophenyl)- ethane with cyclohexanoneo-oxyalylic acid ethyl ester.  Specifications 524,555, 541,589, 599,377, 617,247, 674,103, 689,023, 698,046, 739,913 and 834,082 are referred to.