US3328419A - Colour couplers and their production and use in colour photography - Google Patents

Colour couplers and their production and use in colour photography Download PDF

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US3328419A
US3328419A US375308A US37530864A US3328419A US 3328419 A US3328419 A US 3328419A US 375308 A US375308 A US 375308A US 37530864 A US37530864 A US 37530864A US 3328419 A US3328419 A US 3328419A
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colour
sulphonamide
phenyl
nitrogen
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Anderson Brian
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Ilford Imaging UK Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/3212—Couplers characterised by a group not in coupling site, e.g. ballast group, as far as the coupling rest is not specific
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/52—Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3

Definitions

  • the colour coupler is incorporated in the photographic emulsion layer in which the image is ultimately to be formed, it is important that it should be non-diffusing in such layer, i.e. that it should neither diffuse away during the processing steps nor migrate from its layer to any adjacent layer.
  • Many attempts have been made to achieve this characteristic of non-diffusibility, i.e. to make the colour coupler substantive to the medium, usually gelatin, of the photographic emulsion.
  • the methods which have been employed consist generally in the use of colour couplers containing groups of substantial molecular size, e.g. long chain alkyl groups, and also solubilising groups.
  • Such colour couplers are often manufactured by a synthesis in which the group conferring non-difiusion and the solubilising group are introduced at separate stages and the colour couplers are often difficult to isolate and purify. It is one object of the present invention to provide a new class of colour couplers which are non-diffusing in photographic emulsion layers, and which may be manufactured by a simple synthetic process in which two solubilising groups and a group conferring non-diffusion are introduced simultaneously, and further the carboxylic acid group may be obtained in a protected form if so desired.
  • COOH I where the COOH group is ortho to the carbonylamino group
  • colour couplers of the foregoing general Formulas I and II are prepared by condensing a compound of the general Formula III o 0 III with a colour coupler of the general formula B-NH where B has the meaning assigned to it above.
  • a compound of the general Formula II is obtained if the ring structure of the compound of Formula III is retained; otherwise, if the ring opens, a product of Formula I is obtained.
  • the colour couplers containing an amino group which may be used in the process of the invention are for example:
  • Phenols and l-naphthols which contain an amino group, for example 4-chloro-5-1nethyl-2-aminophenol or the aminophenols described in British patent specification Nos. 797,141; 754,306; l-a-mino-S-naphthol, N(B-aminoethyl)-l-hydrOXy-Z-naphthamide or similar N-substituted naphthamides containing an amino group, as described in British patent specification No. 902,266 which may also be substituted in the 4-position, as described in British patent specification No. 757,3 68 and which give cyan dyestuffs on colour development with substituted p-phenylene diamines.
  • an amino group for example 4-chloro-5-1nethyl-2-aminophenol or the aminophenols described in British patent specification Nos. 797,141; 754,306; l-a-mino-S-naphthol,
  • the new colour couplers of the invention may be used in the developing solution or they may be included in a light-sensitive layer or in a non-light-sensitive layer adjacent to a sensitive layer or separated therefrom by a waterpermeable colloid layer.
  • the multilayer colour photographic material may be a natural order material in which the images are to be formed in colours complementary to those of the original object or one in which an unnatural order is used, for example one in which in the top layer there is formed a yellow image of the blue parts of the object, in one of the two layers there is formed a cyan image of the green parts of the object and in the other a magenta image of the red parts of the object.
  • the new colour coupler-s may be incorporated in the photographic emulsion layers by taking them up in dilute alkali, e.g. dilute sodium hydroxide, and adding the resulting solution to the emulsion.
  • dilute alkali e.g. dilute sodium hydroxide
  • the alkali may cause the ring structure to break down yielding a product of Formula 1.
  • the compounds may be dispersed, in a non-slovent medium, and the dispersion added to a photographic emulsion. Since in this case alkali is not used the products ofFormula II remain with their ring structure intact, though they are possibly broken down by the eflect of treatment of the emulsions with alkaline developers. 7
  • EXAMPLE 1 Z-carboxy-N- (1 -phenyl-pyraz0l0ny l-3 -benzam'ide- 4-N'- (4-d0decy lphenyl sulphonamide chloride obtained is removed by filtration. The solution is then evaporated to dryness in vacuo and the residue dissolved in 200 parts of water by the addition of 2 N sodium hydroxide solution. After filtering, the solution obtained is acidified with 2 N hydrochloric acid to precipitate the product which is collected by L-filtration and dried. The 7.1 parts of phthalic acid-4-N-(4-dodecylphenyl) sulphonamide are obtained as a colourless solid melting at 164-165 C.
  • a photographic layer containing the colour coupler may be obtained in the following manner:
  • a mixture of 1.54 parts of the col-our coupler and 12 parts of n-propyl alcohol is warmed to dissolve and 2.35 parts of 2 N potassium hydroxide then added.
  • the solution so obtained is diluted to 30 parts with distilled Water and added to 500 parts of a green sensitised gelatino silver halide emulsion containing silver halide equivalent to 2.5 parts of silver and 3.5% gelatin.
  • the emulsion is then coated on film base and the coated layer dried.
  • phthalic anhydride-4-N-(4-dodecylphenyl) sulphonamide used in the above example may be prepared as follows:
  • a mixture of 30 parts of phthalic acid-4-N-(4-dodecylphenyl)-sulphonamide and 300 parts of acetyl chloride is heated under reflux for 1 hour then evaporated to dryness in vacuo.
  • the solid residue is recrystallised from 400 parts of 60-80 grade petroleum ether.
  • the 12.5 parts of phthalic anhydride-4-N-(4-dodecylphenyl) sulphonamide are obtained as a colourless crystalline solid melting at 83 C.
  • the compound is found to contain 66.3% of carbon, 7.0% of hydrogen, 3.1% of nitrogen and 6.8% of sulphur. (C H 'NO S requires 66.3% of carbon, 7.0% of hydrogen, 3.0% of nitrogen and 6.8% of sulphur.)
  • the phthalic acid-4-N-(4-dodecylphenyl) sulphonamide itself may be prepared as follows:
  • a mixture of 5.3 parts of phthalic acid-4-sulphon.ch1o-; ride, 10.44 parts of p-dodecylaniline and '100 parts of ethyl acetate is heated under reflux for 12 hours, cooled to 20 C. and the precipitate of p-dodecylaniline hydro- COOH
  • a mixture of 7.85 parts of 4-methoxy-3-(4-methoxybenzoylacetamido)aniline, 11.75 parts of phthalie anhydride 4-N-(4-dodecylphenyl)sulphonamide and parts of ethyl acetate is heated at 50 C. for 1 hour, 500 parts of 60-80 grade petroleum ether are then added and the precipitate obtained filtered off, dried and recrystal-, lised from 1 20 parts of methanol.
  • a photographic layer containing the colour coupler may be obtained in the following manner:
  • a mixture of 3.8 parts of the colour coupler and 20 parts of n-propyl alcohol is warmed to dissolve and 3.5 parts of 2 N potassium hydroxide solution then added.
  • the solution so obtained is diluted to 70 parts with distilled water and added to 500 parts of a blue sensitised gelatino silver halide emulsion containing silver halide equivalent to 7.0 parts of silver and 4% gelatin.
  • the emulsion is then coated on film base and the coated layer dried.
  • EXAMPLE 5 EXAMPLE 3 5 Z-carboxy N 4-(3:5 dicarbomethoxyphenylaminocar- Z-carbOxy-N-[B(I-hydroxy-Z-naphthamido)ethyl]benzbonyl)acetyl]phenylb enzamide 4 N (4 dodecylamiae-4-N'-(4-d0decylphenyl)sulphonam ide phenyl)sulphonamide $OOCH3 Q-NHC O CHiC OQNHO (IQ-S OaNHQ-CnHzs (2000113 H006 CONH.CH2OH2NHOC-SO2-NHC:2H25
  • the product is obtained by evaporating the is added to 500 parts of a red sensitised gelatino silver reaction mixture to dryness in vacuo and recrystallising halide emulsion containing silver halide equivalent to 2.0 the residue from methanol.
  • the emulsion is then [4-.(4-methoxybenzoylacetamido) 2:5 diethoxyphenyl] coated on a paper base and the coated layer dried.
  • benzamide-4-N'-(4-dodecylphenyl)sulphonamide are obthe photographic layer so obtained is exposed to red light, tained as a solid melting at 94-96 C.
  • the 4 (4 methoxybenzoylacetamido)-2:S-di-ethoxyaniline used in the above example is prepared as follows EXAMPLE 4 A mixture of 40 parts of 4-(4-methoxybenzoylacet- 2-carb0xy-N-[fi(4-chlar 1 hydroxy 2 naphlhamido) amido)-2:5-di-ethoxy nitrobenzene, 800 parts of ethyl ethyl]benzamide-4-N'-(4 d0decylphenyl)sulphonamide alcohol and Raney nickel catalyst is heated'with hydro- OH V ,7 l
  • decylphenyl)sulphonamide are obtained as a colourless solid melting at 203204 C. and on analysis is found to The (4' y ynlcontain 64.0% of carbon, 6.0% of hydrogen and 5.5 of 75 trobenzene itself maybe prepared as follows:
  • the product is isolated by pouring 0f 4-(4-1'11ethoxybflflzoylacetamidonitl'obenzefle am into an excess of petroleurn'ether.
  • the 19.6 parts of 2- tained as a pale yellow needle crystal melting at 197- carboxy N- ⁇ 3-[(,5-ehlor-4-methyl-2-hydroxyphenyl) 198 C.
  • aminocar-bonyl]phenyl ⁇ benzamide -4-N (4 dodecyl
  • phenyl)sul phonamide are obtained as a solid melting at Z-carboxy-N-[4-(methoxyb enzoylacetam idoy) h l] 2l0213 C.
  • EXAMPLE 8 product is recrystallised from glacial acetic acid.
  • N-(4-methoxybenzoylacetamido)phenylphthalimide-4- 50 The 11.2 parts of N- ⁇ 4-[N-(l-phenyl-S-pyrazolonyl- N'-(4-d0decylphenyl)sulphrmamide 3-)aminoacetyl]phenyl ⁇ phthalimide-4 N (4 dodecyloo CHaO-COCHzCONH- 41 SOENEP-QCHHIS 1
  • a mixture of 9.94 parts of 4-(4-methoxybenzoylacetaphenyl)sulphonamide are obtained as a solid melting at mido)aniline, 16.45 parts of phthalic anhydride-4-N-(4- 6O 228231 C.
  • EXAMPLE 13 2-carboxy-N-[;8(I-hydroxyQ-rtaphthamido) ethyl] benzamide-4-N'n-0ctadecylsulphonamide o oNHomomNHoo-Q-somnmrm crystallised from ethyl acetate.
  • the 7.0 parts of 2- carboxy N [3(1 hydroxy-Z-naphthamido)ethyl]benzamide-4-n-octadecylsulphonamide are obtained as a colourless solid melting at 225-226 C. and on analysis is found to contain 66.1 of carbon, 8.6% of hydrogen and 4.1% of sulphur. (C39H55N3S07 requires 66.1% of carbon, 7.8% of hydrogen and 4.5% of sulphur.)
  • the phthalic anhydride 4-N-n-octadecylsulphonamide used in the above example may be prepared as follows: A mixture of 26.9 parts of n-octadecylamine, 29.2 parts of phthalic acid-4-sulphonyl chloride, 8.2 parts of anhydrous sodium acetate and 400 parts of ethyl acetate is heated under reflux for 12 hours then evaporated down to dryness. To the residue is added 600 parts of acetyl chloride and the mixture heated under reflux for /2 hour. After filtering hot the solution is cooled to crystallise, the product collected by filtration and recrystallised from ethyl acetate.
  • a color coupler which is a compound selected from the group consisting of compounds of the formula:
  • R is a. member selected from the group consist- EXAMPLE 17 ing of alkyl and Ialkyl substituted phenyl, wherein the alkyl radical, and the alkyl substituent contain from 12 2 -arb0xy-N-[Z- ⁇ fi-(4-Chl0r0 1 hydroxy 2 naphthto 18 carbon atoms, and B is the residue of a compound amid0)ethyl ⁇ phenyl]benzamide-4 N (4 dodecyl- BNH which is selected from the group consisting of phenyl)sulph0namide (I) Ho 0 c- SO;NH-C ,H
  • R is phenyl
  • one of X and Y is --NH and the other is H
  • X is NH and Y is anilino or X is H and Y is -NH aminophenylacetylamino, or (Z-methoxy- 5-amino)anilino.
  • B is the residue of a compound BNH which is selected from the group consisting of N-(fi-aminoethyl)-1-hydroxy-2- napthamide, N (B aminoethyl) 4 chloro 1 hydroxy 2 napthamide, 2 (o amino B phenylethyl)- 1 hydroxynaphthamide, 1 (1 hydroxy 2 naphthamide)-6-aminohexane, and 2-(o-amino-fi-phenylethyl)-1-hydroxy-4-chl0ronaphthamide.
  • BNH which is selected from the group consisting of N-(fi-aminoethyl)-1-hydroxy-2- napthamide, N (B aminoethyl) 4 chloro 1 hydroxy 2 napthamide, 2 (o amino B phenylethyl)- 1 hydroxynaphthamide, 1 (1 hydroxy 2 naphthamide)-6-aminohexane, and 2-(o-amino-fi-phen

Description

United States Patent Officev 3,328,419 Patented June 27, 1967 3,328,419 COLOUR COUPLERS AND THEIR PRODUCTION AND USE IN COLOUR PHOTOGRAPHY Brian Anderson, Marple, England, assignor to Ilford Limited, Essex, England, a British company No Drawing. Filed June 15, 1964, Ser. No. 375,308 Claims priority, application Great Britain, June 17, 1963, 24,027/ 63 6 Claims. (Cl. 260-310) This invention relates to colour couplers and to their production and use in colour photography.
Many modern processes of colour photography are based on the development of a developable silver salt photographic image by means of an aromatic primary amino compound, such as an N.N-diethyl p-phenylene diamine or a derivative thereof in the presence of a so-called colour coupler, this being a compound which will couple with the oxidation products of the developer to yield a dye image, usually an azamethine or quinone-im-ine dye image, in situ with the developed silver.
Where, as in many of the processes, the colour coupler is incorporated in the photographic emulsion layer in which the image is ultimately to be formed, it is important that it should be non-diffusing in such layer, i.e. that it should neither diffuse away during the processing steps nor migrate from its layer to any adjacent layer. Many attempts have been made to achieve this characteristic of non-diffusibility, i.e. to make the colour coupler substantive to the medium, usually gelatin, of the photographic emulsion. The methods which have been employed consist generally in the use of colour couplers containing groups of substantial molecular size, e.g. long chain alkyl groups, and also solubilising groups. Such colour couplers are often manufactured by a synthesis in which the group conferring non-difiusion and the solubilising group are introduced at separate stages and the colour couplers are often difficult to isolate and purify. It is one object of the present invention to provide a new class of colour couplers which are non-diffusing in photographic emulsion layers, and which may be manufactured by a simple synthetic process in which two solubilising groups and a group conferring non-diffusion are introduced simultaneously, and further the carboxylic acid group may be obtained in a protected form if so desired.
According to a first feature of the present invention there is provided, as a new class of colour couplers, compounds of the general Formula I BNH.COASO2NH.R
COOH I where the COOH group is ortho to the carbonylamino group, and the corresponding cyclised compounds of the general Formula II where A is a grouping selected from the groups and velopment of a silver salt image with that compound, to yield a quinone-irnine or azamethine dyestuff.
According to a further feature of the invention colour couplers of the foregoing general Formulas I and II are prepared by condensing a compound of the general Formula III o 0 III with a colour coupler of the general formula B-NH where B has the meaning assigned to it above. A compound of the general Formula II is obtained if the ring structure of the compound of Formula III is retained; otherwise, if the ring opens, a product of Formula I is obtained.
The colour couplers containing an amino group which may be used in the process of the invention are for example:
(l) Those which contain a COCH CO group, for example benzoyl-4-amino-Z-methoxyacetanilide, 4-methoxybenzoylacet-4-amino-Z-methoxyanilide, the 2-alkoxybenzoylacet-amino-anilides described in British patent specification No. 595,314 or the aminobenzoylacet-methoxy-anilides of British patent specification No. 800,108, and which give yellow dyestuffs on colour development with substituted p-phenylene diamines.
(2) Those which contain a cyanacetyl group or a pyrazolone ring for example 4-w-cyanacetylaniline, 1- methyl 3 amino-S-pyrazolone, 1 (18 hydroxyethyl)-3- amino-S-pyrazolone, 1-phenyl-3-an1ino-5-pyrazolone and substituted 1-aryl-3-amino-5-pyrazolones as described in British patent specification Nos. 547,064; 680,474; 680,- 488, the 1-heterocycle-3-amino-5-pyrazolones as described in British patent specification No. 599,919, the l-(aminoaryl)-3-coumarilylamino-S-pyrazolones of British patent specification No. 890,305, the l-alkyl-3-(aminophenoxyacetamido)-5-pyrazolones of British patent specification No. 865,720 or the 1-phenyl-3-amino-arylamino5-pyrazolones described in British patent specification No. 956,- 261 and which give magenta dyestuffs on colour development with substituted p-phenylene diamines.
(3) Phenols and l-naphthols, which contain an amino group, for example 4-chloro-5-1nethyl-2-aminophenol or the aminophenols described in British patent specification Nos. 797,141; 754,306; l-a-mino-S-naphthol, N(B-aminoethyl)-l-hydrOXy-Z-naphthamide or similar N-substituted naphthamides containing an amino group, as described in British patent specification No. 902,266 which may also be substituted in the 4-position, as described in British patent specification No. 757,3 68 and which give cyan dyestuffs on colour development with substituted p-phenylene diamines.
The new colour couplers of the invention may be used in the developing solution or they may be included in a light-sensitive layer or in a non-light-sensitive layer adjacent to a sensitive layer or separated therefrom by a waterpermeable colloid layer.
It is a preferred feature of the invention to include the new colour couplers of the invention in a light-sensitive gelatino or gelatino-substitute silver halide emulsion layer which forms part of a multilayer film or paper of the kind used for colour photography.
The multilayer colour photographic material may be a natural order material in which the images are to be formed in colours complementary to those of the original object or one in which an unnatural order is used, for example one in which in the top layer there is formed a yellow image of the blue parts of the object, in one of the two layers there is formed a cyan image of the green parts of the object and in the other a magenta image of the red parts of the object.
The new colour coupler-s may be incorporated in the photographic emulsion layers by taking them up in dilute alkali, e.g. dilute sodium hydroxide, and adding the resulting solution to the emulsion. I-f a colour coupler of Formula II is used the alkali may cause the ring structure to break down yielding a product of Formula 1.
Alternatively, the compounds may be dispersed, in a non-slovent medium, and the dispersion added to a photographic emulsion. Since in this case alkali is not used the products ofFormula II remain with their ring structure intact, though they are possibly broken down by the eflect of treatment of the emulsions with alkaline developers. 7
It is to be observed that in the compounds of Formula II the potential solu'bilising groups are protected in the form of the ring structure, so that the, compounds are more readily isolated and purified. Nevertheless, the solubilising groups are freed as the compounds are dissolved in alkali for addition to the photographic emulsion.
The following examples will serve to illustrate the invention:
EXAMPLE 1 Z-carboxy-N- (1 -phenyl-pyraz0l0ny l-3 -benzam'ide- 4-N'- (4-d0decy lphenyl sulphonamide chloride obtained is removed by filtration. The solution is then evaporated to dryness in vacuo and the residue dissolved in 200 parts of water by the addition of 2 N sodium hydroxide solution. After filtering, the solution obtained is acidified with 2 N hydrochloric acid to precipitate the product which is collected by L-filtration and dried. The 7.1 parts of phthalic acid-4-N-(4-dodecylphenyl) sulphonamide are obtained as a colourless solid melting at 164-165 C. On analysis the compound is found to con tain 64.0% of carbon, 7.0% ofhydrogen, 3.1% of nitrogen and 6.7% of sulphur. (C H NO S requires 63.8% of carbon, 7.2% of hydrogen, 2.9% of nitrogen and 6.5% of sulphur.)
A photographic layer containing the colour coupler may be obtained in the following manner:
A mixture of 1.54 parts of the col-our coupler and 12 parts of n-propyl alcohol is warmed to dissolve and 2.35 parts of 2 N potassium hydroxide then added. The solution so obtained is diluted to 30 parts with distilled Water and added to 500 parts of a green sensitised gelatino silver halide emulsion containing silver halide equivalent to 2.5 parts of silver and 3.5% gelatin. The emulsion is then coated on film base and the coated layer dried. When the photographic material so obtained is'exposed to green COOH A mixture of 11.75 parts of phthalic anhydride-4-N (4-dodecylphenyl) sulphonamide, 4.35 parts of l-phenyl- 3-amino-5-pyrazolone and 110 parts of ethyl acetate is heated under reflux for 2 hours. 200 parts of 6080 grade petroleum ether are then added and the precipitate obtained is filtered off, dried and recrystallised from 240 parts of methanol. The 8.5 parts of 2-carboxy-N-(1- phenyl-5-pyrazolonyl-3-) benzamide 4 N'-(4-dodecylphenyl) sulphonamide are obtained as a colourless solid light, developed in a colour developer containing 4-amino- N-ethyl-N-ehydroxypentylaniline, bleached and fixed, a magneta image is obtained which has an absorption maximum at a wavelength of light of 540 millimicrons. I
melting at 160-162 C. On analysis the compound is found to contain 64.3% of carbon, 6.0% of hydrogen, 8.4% of nitrogen and 4.4% of sulphur.
requires 64.3% of carbon, 6.8% of hydrogen, 8.35% of nitrogen and 4.4% of sulphur.)
The phthalic anhydride-4-N-(4-dodecylphenyl) sulphonamide used in the above example may be prepared as follows:
A mixture of 30 parts of phthalic acid-4-N-(4-dodecylphenyl)-sulphonamide and 300 parts of acetyl chloride is heated under reflux for 1 hour then evaporated to dryness in vacuo.
The solid residue is recrystallised from 400 parts of 60-80 grade petroleum ether. The 12.5 parts of phthalic anhydride-4-N-(4-dodecylphenyl) sulphonamide are obtained as a colourless crystalline solid melting at 83 C. On analysis the compound is found to contain 66.3% of carbon, 7.0% of hydrogen, 3.1% of nitrogen and 6.8% of sulphur. (C H 'NO S requires 66.3% of carbon, 7.0% of hydrogen, 3.0% of nitrogen and 6.8% of sulphur.)
The phthalic acid-4-N-(4-dodecylphenyl) sulphonamide itself may be prepared as follows:
A mixture of 5.3 parts of phthalic acid-4-sulphon.ch1o-; ride, 10.44 parts of p-dodecylaniline and '100 parts of ethyl acetate is heated under reflux for 12 hours, cooled to 20 C. and the precipitate of p-dodecylaniline hydro- COOH A mixture of 7.85 parts of 4-methoxy-3-(4-methoxybenzoylacetamido)aniline, 11.75 parts of phthalie anhydride 4-N-(4-dodecylphenyl)sulphonamide and parts of ethyl acetate is heated at 50 C. for 1 hour, 500 parts of 60-80 grade petroleum ether are then added and the precipitate obtained filtered off, dried and recrystal-, lised from 1 20 parts of methanol.
The 8.0 parts of 2-carboxy-N-[3- (4-methoxybenzoylacetamido)-4-methoxyphenyl]benzamide-4-N'-(4 dodecylphenyl)sulphonamide are obtained as a colourless solid melting at -137" C. On analysis the compound is found to contain 64.4% of carbon, 6.5% of hydrogen, 5.1% of nitrogen and 3.7% of sulphur.
requires 64.6% of carbon, 6.6% of hydrogen, 5.1% of nitrogen and 3.9% of sulphur.)
A photographic layer containing the colour coupler may be obtained in the following manner:
A mixture of 3.8 parts of the colour coupler and 20 parts of n-propyl alcohol is warmed to dissolve and 3.5 parts of 2 N potassium hydroxide solution then added. The solution so obtained is diluted to 70 parts with distilled water and added to 500 parts of a blue sensitised gelatino silver halide emulsion containing silver halide equivalent to 7.0 parts of silver and 4% gelatin. The emulsionis then coated on film base and the coated layer dried.
When the photographic materialso obtained is exposed.
to blue light, developed in a colour developer containing 3,328,419 6 4-amino-N-ethyl-N-e-hydroxypentylaniline, :bleached and nitrogen. (C H N O SCl requires 63.7% of carbon, fixed, a yellow image is obtained which has an absorption 6.3% of hydrogen and 5.7% of nitrogen.)
maximum at a wavelength of light of 440 millimicrons. EXAMPLE 5 EXAMPLE 3 5 Z-carboxy N 4-(3:5 dicarbomethoxyphenylaminocar- Z-carbOxy-N-[B(I-hydroxy-Z-naphthamido)ethyl]benzbonyl)acetyl]phenylb enzamide 4 N (4 dodecylamiae-4-N'-(4-d0decylphenyl)sulphonam ide phenyl)sulphonamide $OOCH3 Q-NHC O CHiC OQNHO (IQ-S OaNHQ-CnHzs (2000113 H006 CONH.CH2OH2NHOC-SO2-NHC:2H25
A mixture of 8.05 parts of N-(fi-aminoethyD-l-hy- In place of. the 8.05 parts of N-(fi-aminoethyDJ-hydroxy-Z-naphthamide, 16.45 parts of phthalic anhydridedroxy-Z-naphthamide used in Example 3 there are. used 4-N-(4-dodecylphenyl)-sulphonamide and 160 parts of 12.95 parts of 4 aminobenzoylacet-(3:S-di-carbomeethyl acetate is heated at 50 C. for 1 hour and then althoxy)anilide. The product is obtained by evaporating the lowed to stand until the product crystallises out. The 10.5 reaction mixture to dryness and crystallising the residue parts of 2-carboxy-N-[fi-(l-hydroxy 2 naphthamido) from methyl alcohol. The 3.5 parts of 2-carboxy-N-4- ethyl]benzamide-4-N (4 dodecylphenyl)sulphonamide [(325 di carbomethoxyphenylaminocarbonyl)acetyl] are obtained as a colourless solid melting at 178-179" C phenylbenzamide 4 N-(4-dodecylphenyl)sulphonamide On analysis the compound is found to contain 66.9% of are obtained as a solid melting at 128-131 C. carbon, 6.6% of hydrogen, 6.1% of nitrogen and 4.5% EXAMPLE 6 of sulphur. (C H N O S requires 66.9% of carbon, 6.7% I I of hydrogen, 6.0% of nitrogen and 4.6% of sulphur.) 2 carboxy-N-[4-(4-m-erhoxybenzoylacezlamido) 2:5-di- A photographic layer containing the colour coupler may ethoxyphenyl] benzam ide 4 N (4 dodecylphenyl) be obtained in the following manner: sulp'honamide v 50.11.
CH OCOCH:C0NHNHOCQSOzNH-CuHn I oogm OOH A mixture of 2.53 parts of the colour coupler, 12 parts ..-In place of the 8.05 parts of N-(fl-aminoethyh-l-hyof n-propyl alcohol and 3.6 parts of 2 N potassium hydroXy-Z-naphthamide used, in Example 3 there are used droxide solution is warmed to dissolve and then diluted 13.02 parts of 4-(4 methoxybenzoylacetamido)-2;5 dito 40 parts with distilled water. The solution so obtained ethoxyaniline. The product is obtained by evaporating the is added to 500 parts of a red sensitised gelatino silver reaction mixture to dryness in vacuo and recrystallising halide emulsion containing silver halide equivalent to 2.0 the residue from methanol. The'8.-4 parts of 2-carboXy-N- parts of silver and 3.5% gelatin. The emulsion is then [4-.(4-methoxybenzoylacetamido) 2:5 diethoxyphenyl] coated on a paper base and the coated layer dried. When benzamide-4-N'-(4-dodecylphenyl)sulphonamide are obthe photographic layer so obtained is exposed to red light, tained as a solid melting at 94-96 C. and on analysis developed in a coluor developer containing 4-amino-N- is found to contain 3.8% of sulphur. (C H N SO reethyl-N-e-hydroxypentyl-aniline, bleached and fixed, a qu'ires'3.8% of sulphur.) cyan image is obtained. The 4 (4 methoxybenzoylacetamido)-2:S-di-ethoxyaniline used in the above example is prepared as follows EXAMPLE 4 A mixture of 40 parts of 4-(4-methoxybenzoylacet- 2-carb0xy-N-[fi(4-chlar 1 hydroxy 2 naphlhamido) amido)-2:5-di-ethoxy nitrobenzene, 800 parts of ethyl ethyl]benzamide-4-N'-(4 d0decylphenyl)sulphonamide alcohol and Raney nickel catalyst is heated'with hydro- OH V ,7 l
c ONHCHzCHzNHO (IQ-S O2NHCnH25 7 $0011 7 In place of the 8.05 parts of N-(fi-aminoethyD-l-hygen at -80 C. under a pressureof atmospheres for dfoxy-z-naphthamide used in 5x31111316 there are used 15 hours. After cooling the product is filtered ofi? and re- 9.26 parts of N-(fiyn- 1 Y Y' 70 crystallised from'ethyl alcohol. The 28 parts of 4(4-me naphthamlde- The P F of f gf zg thoxybenzoylacetamido) 2:5 di ethoxyaniline are obhydroxy 2 naphthamldokthyl]benzamlde-ll- O- tained as fawn needle crystals melting at 154-155 C.
decylphenyl)sulphonamide are obtained as a colourless solid melting at 203204 C. and on analysis is found to The (4' y ynlcontain 64.0% of carbon, 6.0% of hydrogen and 5.5 of 75 trobenzene itself maybe prepared as follows:
3,328,419 a 7 '8 A solution of 45 parts of anisoylacetic ester in 70 parts v I EXAMPLE 9 of xylene is added over 30 minutes to a refluxing mixture of 30.7 parts of 4-nitro-2:S-di-ethoxyaniline, 350 parts of y-N-{ 4 yp y xylene and parts of pyridine. aminocarbonyl] phenyl}benzamide 4 N l-dodecyl- The' mixture is then distilled until .130 parts of distillate 5 phenyl)sulphonamide has been collected, the mixture is then refluxed fora fur- In place of the 8.05 parts of N-(fi-aminoethyD-l-hyther 4 hours. After standing for hours the mixture is 15 droxy-2-naphthamide used in Example 3 there are used diluted with 300 parts of methanol, cooled in ice and 9.65 parts of 3'-amino-N-(5-chloro-4-methyl-2-hydroxythe precipitaated solid collected by filtration. The 40 parts phenyl)benzamide. The product is isolated by pouring 0f 4-(4-1'11ethoxybflflzoylacetamidonitl'obenzefle am into an excess of petroleurn'ether. The 19.6 parts of 2- tained as a pale yellow needle crystal melting at 197- carboxy N-{3-[(,5-ehlor-4-methyl-2-hydroxyphenyl) 198 C. aminocar-bonyl]phenyl}benzamide -4-N (4 dodecyl EXAMPLE 7 phenyl)sul phonamide are obtained as a solid melting at Z-carboxy-N-[4-(methoxyb enzoylacetam idoy) h l] 2l0213 C. and on analysis is found to contain 63.7% benzamide-4-N'-(4-dodecy-lphengyl)sulphonumiae of carbon, 5.7% of hydrogen, 5.7% of nitrogen and omoQ-ooomo ONH-Q-NHOCQ-sOZNH-QCHHH I 7 11006 In place of the 8.05 parts of N-(fi-aminoethyD-l-hY- 4.4% of sulphur. (C H N SClO requires 64.3% of cardroxy-Z-naphthamide used in Example 3 there are used bon, 6.2% of hydrogen, 5.6% of nitrogen and 4.4% of 9.94 parts of 4-(4-methoxybenzoylacetamido) aniline. The sulphur.) productobtained is heated with 60 parts of methanol, cooled and filtered. The 11.9 parts of 2-carboxy-N-[4-(4- EXAMPLE 10 methoxybenzoylacetamido)phenyl1benzamide- 4 N' N-{4[N-(1-ph@n: yl-5 pyrazol0nyl-3-)aminoacetyl1phen- (4-dodecylphenyl)sulphonamide are obtained as a solid yl}phthalimide-4-N'-(4-d0decyl phenyDswlphonamide O=C C-NHCOCHzmelting at 189-490 C. and on analysis is found to con- In place of the 9.94 parts of '4-(4-methoxybenzoyltain 66.5% of carbon, 6.5% of hydrogen, 5.6% of nitroacetamido)aniline used in Example 8 there are used 10.8 8 and 43% 0f Sulphllf- 4z 49 s q es 66-55% parts of 1 phenyl 3 (4 aminophenylacetylamino)-5- of C 65% of hydrogen, of nitrogen a i pyrazolone, the preparation of which is described in Exof sulphur.) I ample 26 of British patent specification No. 830,797. The
EXAMPLE 8 product is recrystallised from glacial acetic acid. N-(4-methoxybenzoylacetamido)phenylphthalimide-4- 50 The 11.2 parts of N-{4-[N-(l-phenyl-S-pyrazolonyl- N'-(4-d0decylphenyl)sulphrmamide 3-)aminoacetyl]phenyl}phthalimide-4 N (4 dodecyloo CHaO-COCHzCONH- 41 SOENEP-QCHHIS 1 A mixture of 9.94 parts of 4-(4-methoxybenzoylacetaphenyl)sulphonamide are obtained as a solid melting at mido)aniline, 16.45 parts of phthalic anhydride-4-N-(4- 6O 228231 C. and on analysis is found to contain 67.4% dodecylphenyl)sulphonamide and 350 parts of glacial of carbon, 6.4% of hydrogen, 9.0% of nitrogen and 4.5% acetic acid is heated under reflux for 2 hours. After coolof sulphur. (C43H47N506S requires 67.8% of carbon, ing the solid is filtered off and recrystallised from 320 6.2% of hydrogen, 9.2% of nitrogen and 41% of 1. parts of ethyl alcohol. The 12.6 parts of N-(4-methoxyphur.) benzoylacetamido)phenylphthalimide-4-N'-(4 dodecylphenyl)sulphonamide are obtained as a solid melting at EXAMPLE 11 170l74 C. and on analysis is found to contain 68.4% 2-ca rb0 xy-N-[4-(3 phenylamin0-5-pyrazol0nyl-1-) phenof carbon, 6.6% of hydrogen and 5.7% of nitrogen. ylbenzamide-4-N'-(4-d0decylphenyDsulpIwnamid I u O=C 000E G (C42H4I7O7N3S' requires 68.4% of carbon, 6.4% of by In place of the 8.05 parts of N-(B-aminoethyD-l-hydrogen and 7.5% of nltrogen.) -dIoxy-2-napthamide used in Example 3 there are used EXAMPLE 12 2-carboxy-N-[4-methoxy-3-(1 -phenyl 5 pyrazlonyl-3-) aminophenyl] benzamide 4 N (4 dodecylphenyl) sulphonamide In place of the 8.05 parts of N-(B-aminoethyD-l-hydroxy-Z-naphthamide used in Example 3 there are used 10.36 parts of 1-phenyl-3-(5-amino-2-methoxy)anilino-5- pyrazolone. The 11.2 parts of 2-carboxy-N-[3-methoxy- 4(1-phenyl 5 -pyrazolonyl-3-) aminophenyl1benzamide- 4-N'-(4-dodecylphenyl)sulphonamide are obtained as a solid melting at 216-219 C. and" on analysis is found to contain 65.2% of carbon, 6.1% of hydrogen, 9.1% of nitrogen and 4.6% of sulphur. (C42H49N5O7 requires 65.7% of carbon, 6.4% of hydrogen, 9.1% of nitrogen and 4.2% of sulphur.) v
The preparation of 1-phenyl-3-(5-amino-2-methoxy) anilino-S-pyrazolone used in the above example is described in Example 32 of British Specification No. 956,- 261.
EXAMPLE 13 2-carboxy-N-[;8(I-hydroxyQ-rtaphthamido) ethyl] benzamide-4-N'n-0ctadecylsulphonamide o oNHomomNHoo-Q-somnmrm crystallised from ethyl acetate. The 7.0 parts of 2- carboxy N [3(1 hydroxy-Z-naphthamido)ethyl]benzamide-4-n-octadecylsulphonamide are obtained as a colourless solid melting at 225-226 C. and on analysis is found to contain 66.1 of carbon, 8.6% of hydrogen and 4.1% of sulphur. (C39H55N3S07 requires 66.1% of carbon, 7.8% of hydrogen and 4.5% of sulphur.)
The phthalic anhydride 4-N-n-octadecylsulphonamide used in the above example may be prepared as follows: A mixture of 26.9 parts of n-octadecylamine, 29.2 parts of phthalic acid-4-sulphonyl chloride, 8.2 parts of anhydrous sodium acetate and 400 parts of ethyl acetate is heated under reflux for 12 hours then evaporated down to dryness. To the residue is added 600 parts of acetyl chloride and the mixture heated under reflux for /2 hour. After filtering hot the solution is cooled to crystallise, the product collected by filtration and recrystallised from ethyl acetate. The 19 parts of phathalic anhydride-4-N-n-octadecylsulphonamide is obtained as a colourless solid melting at 128-132 C. and on analysis is found to contain 63.8% of carbon, 8.5% of hydrogen and 3.1% of nitrogen. (C H NSO requires 65.1% of carbon, 8.6% of hydrogen and 2.9% of nitrogen.)
EXAMPLE 14 Z-Carboxy-N (5 -chlor0-4-methyl-2-hyaroxyphenyl) benzamide-4-N'- (4-doaecylphenyl) sulphonamide on HOOC soiNH-oum5 NHC 0 01 9.14 parts of phthalic anhydride-4-N-(4dodecylphenyl) sulphonamide, 2.8 parts of 2-amino-4-chl0ro-5 methylphenol and 100 parts by volume of dry ethyl acetate are heated at 60- for 0.75 hour. The mixture is cooled and then evaporated to a low bulk. The residue is taken up in methanol, and the insoluble material is filtered off. The methanol solution is evaporated at low temperature and the residue dissolved in sodium carbonate solution. The solution is filtered and the filtrate acidified with hydrochloric acid. The precipitate is filtered ofi, washed with water and dried at room temperature. The 8.8 parts of 2- carboxy-N-(5=ch1oro-4-methyl 2 hydroxyphenyl)benz amide-4-N'-(4-dodecylphenyl)sulphonamide are obtained as a solid melting at 145-148 C. On analysis, this com- I pound is found to contain 4.3% of nitrogen and 4.7% of sulphur. (C H C1N O S requires 4.6% of nitrogen and 5.1% of sulphur.)
EXAMPLE 15 Z- carboxy-N-[Z-{B-(I-hydroxy 2 naphthamz'do) ethyl} phenyl]benzarriide-4-N"- (4 d0decylphenyl)sulph0namide no 0 o somrrQ-mrm r zrroo OCONHCEHCEU I 9.14 parts of phthalic anhydride-4-N-(4-dodecylphenyl) sulphonamide, 6.2 parts of 2-(o-amino-B-phenylethyl)'-1- hydroxynaphtharnide as described in United States patent specification 3,002,836 to Eastman Kodak Company, and parts by volume of dry ethyl acetate are heated at 60 for 0.75 hour. The mixture is cooled and evaporated to dryness at low temperature. The product is dissolved out of the residue with methanol insoluble material being filtered off. The filtrate is evaporated to dryness and the residue dissolved in the theoretical quantity of sodium carbonate solution. This solution is filtered hot and after cooling, the colour coupler is obtained by acidifying with hydrochloric acid. The solid is filtered ofl and washed with water and dried at room temperature. i
The 10.1 parts of 2-carboxy-N-[2-{;9-( l-hydroxy 2- with decomposition. Onanalysisit is found to contain naphthamido)ethyl}phenyl]benZamide-4-N'-(4 dodecyl- 4.6% of chlorine, 4.9% of nitrogen and.4.2% ofsulphur. phenyl)sulphonamide so obtained melted at 118-.l20. (C H ClN O S requires 4.4% of chlorine, 5.2% of nitro- On analysis, this compound is found to contain 68.0% gen and 3.9% of sulphur.) I of carbon, 6.2% of hydrogen, 5.5% of nitrogen and 3.9% 5 A photographic emulsion layer containing 2.93 parts of of sulphur; (C H N O S1equi1es 689% of b 65% the colour coupler formulated by the method of Example of hydrogen, 5.4% of nitrogen and 4.1% of sulphur.) 3 gives a y y image With light absorption maximum Ahtoahi ml' 1 in.2 31 n- P 0 gr p C 6 llSlOIl ayer CO1! am g p EXAMPLE 18 of the colour coupler formulated by the method of Example 3 givesa cyan dye image with light absorption 0 2-carboxy-N-[3-(4-mlethoxybenzoylacetamido)-4-methmaximum at 690 III 1.. v oxyphenyl]benzwm ide-4-N'4t-0ctadecylsulphonamide ontoo 0 011,0 ONE-Q NHOC-SO1NELC1BHU HOOC EXAMPLE 16 20 In place of the 8.05 parts of N-(5-aminoethyl)-lhy droxy-2-naphthamide used in Example 13 there are used Z-carboxy-N-[6-(l-hy yp exyllbenz- 10.85 parts of 4-meth0xy-3-(4 methoxybenzoyl acetamid y l p amid0)-aniline. The product is recrystallised from 140 parts of ethyl alcohol. The Z-carboxy-N-[3-(4-methoxy- OH H006 benzoylacetamido)-4-methoxyphenyl]benzamide 4 N'- n-octadecylsulphonamide is obtained as a solid melting O at C- I claim as my invention: 1. A color coupler which is a compound selected from the group consisting of compounds of the formula:
6.5 parts of phthalic anhydride-4-N-(4-dodecylphenyl) C O OH sulphonamide, 5.0 parts of 1-(l-hydroxy-Z-naphthamide)- 6-aminohexane and 100 parts by volume of dry ethyl ace- B-NHC tate are heated under reflux for 0.75 hour. The solution is 5 evaporated to dryness at a low temperature and then dis- 1 solved in 2 normal sodium carbonate solution. Any insoluble material is filtered oil and the filtrate is acidified S|O2NHR with hydrochloric acid. The precipitated solid is filtered Washed with Water and dried at room temperature 4 and corresponding cyclised compounds of the formula:
The 6.0parts0f 2-carboxy-N-[6-(l-hydroxy-Z-naphthvamido)hexyl] benzamide-4 N (4 dodecylphenyl)sulc phonamide so obtained is a solid melting at 117-120". -S()2NHR On analysis this compound is found to contain 67.0% of p B-N carbon, 6.9% of hydrogen, 5.6% of nitrogen and 3.9% of sulphur. (C43H55N3O'7S requires 68.2% of carbon, 7.3% Go of hydrogen, 5.6% of nitrogen and 4.2% of sulphur.)
wherein R is a. member selected from the group consist- EXAMPLE 17 ing of alkyl and Ialkyl substituted phenyl, wherein the alkyl radical, and the alkyl substituent contain from 12 2 -arb0xy-N-[Z-{fi-(4-Chl0r0 1 hydroxy 2 naphthto 18 carbon atoms, and B is the residue of a compound amid0)ethyl}phenyl]benzamide-4 N (4 dodecyl- BNH which is selected from the group consisting of phenyl)sulph0namide (I) Ho 0 c- SO;NH-C ,H
o ONHC H1011 $1 8.0 parts of phthalic anhydride-4-N-(4-dodecylphenyl) 2 sulphonamide, 5.95 parts of 2-(o-amino-B-phenylethyl)-1- I ll hydroxy-4-chloronaphthamide and 100 parts of dry ethyl 0:0
acetate are heated under reflux for 0.75 hour. The mix- CH1 ture is cooled and any precipitated material is filtered oil? and (3) primary amino com Ound s select d f and the filtrate evaporated to dryness. The residue 1s disgroup consisting of N-( g i {;f f
solved in sodium carbonate solution and the solution is thamide,N ami filtered. The filtrate is made acid with hydrochloric acid naphthamidef 3amihtlfifi -clilofii ineihyl h ox and the product filtered off, washed with water and then phenyl)-benzamide, 2-amino-4-chloro-5 methylph nol drled. The 6.7 parts of 2-carboxy-N-[2-{B-(4-chloro-l-hy- (oamino [5' phenylethyl) 1 hydroxynaphthamide droxy-Z-naphthamrdo)ethyl}phenyl]benzamide-4-N' (4-- 1-(l-hydroxy-Z-naphthamide)-6-aminohexane and 2-(o dodecylphenyl)sulphonamide so obtained melted at 186 amino-fl-phenylethyl)-1-hydroxy-4-chloronaplithamide wherein R and R are independently selected from the group consisting of phenyl, methoxyphenyl, dicarbomethoxyphenyl, and diethoxyphenyl,
R is phenyl,
one of X and Y is --NH and the other is H,
X is NH and Y is anilino or X is H and Y is -NH aminophenylacetylamino, or (Z-methoxy- 5-amino)anilino.
2. A compound according to claim 1 wherein R represents dodecyl phenyl.
3. A compound according to claim 1 wherein R represents stearyl.
4. A compound according to claim 1 wherein B represents l-phenyl-S-pyrazolonyl-1.
5. A compound according to claim 1 wherein B is the residue of a compound BNH which is selected from the group consisting of N-(fi-aminoethyl)-1-hydroxy-2- napthamide, N (B aminoethyl) 4 chloro 1 hydroxy 2 napthamide, 2 (o amino B phenylethyl)- 1 hydroxynaphthamide, 1 (1 hydroxy 2 naphthamide)-6-aminohexane, and 2-(o-amino-fi-phenylethyl)-1-hydroxy-4-chl0ronaphthamide.
6. A compound according to claim 1 wherein B represents paramethoxy benzoyl acet.
References Cited UNITED STATES PATENTS 2,083,216 6/1937 Benade et a1. 260-310 2,710,803 6/1955 Salminen et al. 260 3l0 2,837,557 6/1958 Lynn 260465.4 2,878,263 5/ 1959 Oroshnik 260-310 2,905,694 9/1959 Pinson 260 -310 2,933,391 4/1960 Feniak et a1. 96100 2,983,608 5/1961 Beavers 96-100 3,034,891 5/1962 Burgardt et a1. 260465 3,148,178 9/1964 Wallace et a1. 260326 OTHER REFERENCES Cram et al.: Organic Chemistry, McGraw-Hill Book Co., Inc., New York, 1959, p. 384.
ALEX MAZEL, Primary Examiner.
NORMAN G. TORCHIN, HENRY R. JILES,
NICHOLAS S. RIZZO, Examiners.
M. OBRIEN, J. T. BROWN, Assistant Examiners.

Claims (2)

1. A COLOR COUPLER WHICH IS A COMPOUND SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS OF THE FORMULA:
4. A COMPOUND ACCORDING TO CHAIN 1 WHEREIN B REPRESENTS 1-PHENYL-5-PYRAZOLONYL-1.
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US3547944A (en) * 1964-02-20 1970-12-15 Ilford Ltd Colour photography utilizing colour couplers which yield quinone imine or azamethine dye images
US3711286A (en) * 1968-02-07 1973-01-16 Konishiroku Photo Ind Light-sensitive silver halide color photographic emulsion
US3973968A (en) * 1971-04-26 1976-08-10 Konishiroku Photo Industry Co., Ltd. Photographic acyl acetanilide color couplers with 2,5-dioxo-1-imidazolidinyl coupling off groups
US4106940A (en) * 1974-10-03 1978-08-15 Agfa-Gevaert, A.G. Light-sensitive material containing emulsified substances
US4269936A (en) * 1971-12-28 1981-05-26 Fuji Photo Film Co., Ltd. Process of forming yellow photographic images
US4404274A (en) * 1971-03-20 1983-09-13 Fuji Photo Film Co., Ltd. Photographic light sensitive element containing yellow color coupler and method for forming yellow photographic images
US4835094A (en) * 1986-10-01 1989-05-30 Agfa-Gevaert Aktiengesellschaft Color photographic recording material containing a color coupler of the pyrazoloazole series

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US2933391A (en) * 1956-09-06 1960-04-19 Eastman Kodak Co Photographic emulsions containing 5-pyrazolone coupler compounds
US2983608A (en) * 1958-10-06 1961-05-09 Eastman Kodak Co Yellow-colored magenta-forming couplers
US3034891A (en) * 1958-07-31 1962-05-15 Gen Aniline & Film Corp Procedure for the production of yellow dye images by color development
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US2905694A (en) * 1959-09-22 Certain esters of i
US2083216A (en) * 1934-06-20 1937-06-08 Gen Aniline Works Inc Monoazo dyes
US2710803A (en) * 1953-03-26 1955-06-14 Eastman Kodak Co Color couplers containing hydroxyalkyl groups
US2837557A (en) * 1953-04-22 1958-06-03 Union Carbide Corp Esters of n, nu-bis(2-cyanoethyl) carboxamic acids
US2933391A (en) * 1956-09-06 1960-04-19 Eastman Kodak Co Photographic emulsions containing 5-pyrazolone coupler compounds
US2878263A (en) * 1958-02-14 1959-03-17 Ortho Pharma Corp 4-methyl-4-phenyl-5-pyrazolone
US3034891A (en) * 1958-07-31 1962-05-15 Gen Aniline & Film Corp Procedure for the production of yellow dye images by color development
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US3148178A (en) * 1962-11-07 1964-09-08 Eastman Kodak Co Azo compounds containing a dicarboximido radical

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3547944A (en) * 1964-02-20 1970-12-15 Ilford Ltd Colour photography utilizing colour couplers which yield quinone imine or azamethine dye images
US3711286A (en) * 1968-02-07 1973-01-16 Konishiroku Photo Ind Light-sensitive silver halide color photographic emulsion
US4404274A (en) * 1971-03-20 1983-09-13 Fuji Photo Film Co., Ltd. Photographic light sensitive element containing yellow color coupler and method for forming yellow photographic images
US3973968A (en) * 1971-04-26 1976-08-10 Konishiroku Photo Industry Co., Ltd. Photographic acyl acetanilide color couplers with 2,5-dioxo-1-imidazolidinyl coupling off groups
US4269936A (en) * 1971-12-28 1981-05-26 Fuji Photo Film Co., Ltd. Process of forming yellow photographic images
US4106940A (en) * 1974-10-03 1978-08-15 Agfa-Gevaert, A.G. Light-sensitive material containing emulsified substances
US4835094A (en) * 1986-10-01 1989-05-30 Agfa-Gevaert Aktiengesellschaft Color photographic recording material containing a color coupler of the pyrazoloazole series

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