Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/04—Ortho-condensed systems
• • 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
  • 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
  • C07D209/52—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 condensed with a ring other than six-membered
• • 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
• • 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

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-ditfusibility, 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-diffusion and the solubilising group are introduced at separate stages and the colour couplers are often difiicult 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.
• the solubilising groups in the new colour couplers may be in a protected form which often facilitates the isolation and purification of the colour couplers.
• the solubilising groups are readily freed as the compounds are dissolved in alkali prior to addition to the photographic emulsion.
• A is a tetravalent radical selected from (where n is nought or one), where B is a colour coupler residue as hereinafter defined, R is an alkyl, aralkyl, cycloalkyl or aryl group, and Y is a direct linkage or a divalent group selected from NHCOCH and the related compounds of the Formulae H, III and IV OOOH
• colour coupler residue used to define the symbol B is meant a grouping such that the compound B-H (and therefore also the compound B.NH is a compound which will react with the oxidation products of N.N-diethyl p-phenylene diamine, formed during the development of a silver salt image with that compound, to yield a quinone-imine or azarnethine dyestuff.
• colour couplers of the foregoing general formulae wherein Y is a direct link are prepared by condensing a compound of the general Formula V:
• Colour couplers of Formula II may be obtained by treating couplers of Formulae I, III and IV with alkali, preferably in a solvent such as a lower alcohol, for example n-propanol, followed by acidification.
• Colour couplers of the general Formula IV where Y is a direct linkage may be obtained by first reacting a compound of general formula B-NH with a dianhydride of general Formula VI:
• divalent. group NHCOCH or colour couplers of the general Formula I are prepared by reacting an anhydride of general Formula V with either glycine or an amino'benzoic acid followed by conversion of the acids so obtained to acid chlorides by treatment with thionyl chloride and reaction of these products with compounds B-NH where B has the meaning assigned to it above.
• 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-ch1oro-5-methyl-2-aminophenol or the aminophenols described in British patent specifications Nos. 797,141, 754,306; l-amin-o-S-naphthol, N-(B- aminoethyl)-l-hydroxy-2-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. 757,368 and which give cyan dyestuffs on colour development with substituted pphenylene diamines.
• an amino group for example 4-ch1oro-5-methyl-2-aminophenol or the aminophenols described in British patent specifications Nos. 797,141, 754,306
• l-amin-o-S-naphthol N-(B- aminoethyl)
• 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 water-permeable 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 When Y is the 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 couplers 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. If a colour coupler of Formula I, III or IV is used, the alkali may cause the ring structure to break down yielding a product of Formula II.
• dilute alkali e.g. dilute sodium hydroxide
• the compounds may be dispersed, in a non-solvent medium, and the dispersion added to the photographic emulsion. Since in this case alkali is not used the products of Formula I remain with their ring structure intact, though they are possibly broken down by the effect of treatment of the emulsion with alkaline developers. It is to be observed that in the compounds of Formula I the potential solubilising 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.N-(4-d0decylphenyl) -N'-(1-phenyl-5- pyraz0l0nyl-3-) pyromellitic di-z'mide A mixture of 18.4 parts of N -(4-dodecylphenyl) pyromellitic mono-imide mono-anhydride, 7.0 parts of 1- phenyl-3-amino-5-pyrazolone and 50 parts of glacial acetic acid is heated under reflux for 2 hours. The solid reaction product formed is, after cooling, collected by filtration and recrystallised from 600 parts of n-butanol.
• N-(4-dodecylphenyl)-N'-( 1-phenyl-5- pyrazolony1-3-) pyromellitic di-imide are obtained as a yellow solid melting at 255-260 C. and on analysis it is found to contain 71.8% of carbon, 5.9% of hydrogen and 9.0% of nitrogen (C37H2gN4O5 requires 71.85% of carbon, 6.15% of hydrogen and 9.05% of nitrogen).
• N-(4-dodecylphenyl) pyromellitic mono-imide mono-anhydride used in the above example may be prepared as follows:
• the 4-(4-dodecylphenyl-amino carbonyl)-5-carboxyphthalic anhydride itself is prepared as follows:
• a photographic layer containing the colour coupler may be obtained in the following manner:
• reaction product formed is filtered ofl after cool- 1 ing, added to 220 parts of benzene and the mixture heated under gentle reflux for 15 minutes, the solid is filtered from the hot benzene and added to 225 parts of ethyl alcohol and again heated under gentle reflux for 15 minutes. The product is then collected by filtration from the cold ethyl alcohol.
• a photographic layer containing the colour coupler may be obtained in the following manner:
• a mixture of 2.43 parts of the colour coupler, 15 parts of n-propyl alcohol and 5.4 parts of 2N potassium hydroxide solution is heated until a solution is obtained and then diluted to 40 parts with distilled water.
• the solution so obtained is added to 500 parts of a red sensitised gelatino silver halide emulsion containing silver halide equivalent to 2.0 parts of silver and 3.5% of gelatin.
• the emulsion is then coated on a film base and the coated layer dried.
• the photographic layer is so obtained is exposed to red light, developed in a colour. developer containing 4 amino N ethyl-N-e-hydroxypentylaniline, bleached and fixed, a cyan image is obtained which has an absorption maximum at a wavelength of light at 650 millirnicrons.
• N (dodecylphenyl)-N-(2-hydroxy 4- methyl-S-ohlorophenyl)-pyromellitic di-imide is obtained as a yellow solid melting at 285-288 C.
• the compound is found to contain 71.8% of carbon, 5.9% of hydrogen and 9.0% of nitrogen.
• C37H3BN4O5 requires 71.8% of carbon, 6.15% of hydrogen and 9.05% of nitrogen.
• Example 5 N -n-0ctaa'ecyl-N 1 -ph enyl-S -pyrazolonyl-3-)pyr0mellitic di-imide
• a mixture of 14.0 parts of N-n-octadecylpyromellitic mono-imide mono-anhydride, 5.25 parts of 1-phenyl-3- amino-S-pyrazolone and 260 parts of glacial acetic acid is heated under reflux for 2 hours.
• the solid reaction product formed is, after cooling, collected by filtration and recrystallised from 400 parts n-butanol.
• N-n-octadecyl-N-(1-phenyl-5-pyrazolonyl-3-) pyromellitic di-imide are obtained as a solid melting at 218-220 C. and on analysis it is found to contain 71.1% of carbon, 7.7% of hydrogen and 8.9% of nitrogen (C H N O requires 70.9% of carbon, 7.35% of hydrogen and 8.9% of nitrogen).
• N-n-octadecyl pyromellitic mono-imide mono-anhydride used in the above example may be prepared as follows:
• the 5-n-octadecylaminocarbonyl-trimellitic acid itself is prepared as follows:
• a solution of 67 parts of n-octadecylarnine in 450 parts of dry ethyl acetate and 200 parts of glacial acetic acid is added dropwise over 30-40 minutes to a stirred solution of 77.5 parts of pyrornellitic dianyhydride in 800 parts of dry acetone and 540 parts of dry ethyl acetate at room temperature.
• the solution is screened immediately the addition is complete and then allowed to stand for 15 hours to crystallise.
• the colourless precipitate formed is filtered off, pressed dry and dissolved in 2000 parts of water at 40 C. by the addition of 2 N sodium hydroxide until alkaline.
• the solution, after screening, is acidified with 2 N hydrochloric acid solution to precipitate a colourless solid, which is collected by filtration and washed acid free.
• the 45.2 parts of -n-octadecylaminocarbonyl trimellitic acid are obtained as a white solid melting at a temperature higher than 300 C.
• a photographic emulsion layer containing 1.49 parts of the colour coupler formulated by the method of Example 1 gives a magenta dye image with light absorption maximum at 536 millimicrons.
• Example 6.4 [ti-(1 hydroxy 2 naphthamz'tioythylaminocarbonyl] -5-carb0xy-N-n-0ctadecylph thalimide
• the solid reaction product formed is filtered off after cooling, added to 270 parts of ethyl acetate and heated under gentle reflux for 30 minutes, cooled ample 3 gives a cyan dye image with light absorption maximum at 679 millimicrons.
• Example 7 N-[4-methoxy-3-(4-meth0xybenz0ylacetamido)phenyl]-N'-n-0ctadecylpyromellitic di-imide A mixture of 16.4 parts of N-n-octadecylpyromellitic mono-imide mono-anhydride, 11.0 parts of 4-methoxy-3- (4-methoxybenzoyl-acetamide) aniline in 310 parts of ethyl acetate is heated under reflux for 2 hours. The solid reaction product formed is, after cooling, filtered off and recrystallised from 400 parts of n-butanol.
• Example 8 -N-(4-w-cyanqacetylphenyl)-N- ('4-d0decylphenybpyromelletic di-imide
• a mixture of 4.0 parts of 4-w-cyanoacetylaniline, 11.6 parts of N-(4-dodecylphenyl)pyromelletic mono-imide mono-anhydride and 250 parts of glacial acetic acid is heated under reflux for 2 hours.
• the yellow reaction solid produced is, after cooling, filtered off and gently refluxed for minutes with 200 parts of ethyl acetate, cooled and filtered.
• N-(4-w-cyanacetylphenyl) -N'-(4-dodecylphenyl) pyromellitic di-irnide are obtained as yellow solid melting above 300 C. 011 analysis the compound is found to contain 73.0% of carbon, 6.0% of hydrogen and 7.0% of nitrogen.
• the coupler may be prepared in the following manner:
• N-(4-w-cyan-oacetylphenyl) pyromellitic mono-imide mono-anhydride A mixture of 12 parts of N-(4-w-cyan-oacetylphenyl) pyromellitic mono-imide mono-anhydride, 8.7 parts of 4-n-'dodecylaniline and 250 parts of glacial acetic acid is stirred and heated under reflux for /2 hr. during which time the product separates out. After cooling the coupler is filtered off, washed well with methanol and dried.
• the N-(4-w-cyanoacetylphenyl)pyromellitic mono-imid-e mono-anhydride itself may be prepared as follows:
• a solution of 16 parts of 4-w-cyanoacetylaniline in 200 parts of dry acetone is added over 20 minutes to a stirred solution of 22 parts of pyromellitic dianhydride in 400 parts of dry acetone at 20 C. and the solution stirred for a further 1% hr. before evaporating to dryness under reduced pressure keeping the temperature below 30 C.
• the gum so obtained is heated at 100 C. for 4 hr. with 75 parts of acetic anhydride when the hot mixture is filtered from a yellow precipitate and the filtrate cooled when the coupler anhydride crystallises out and is filtered off, washed with ether and dried.
• the coupler anhydride melts at 254 C.
• a photographic emulsion layer containing 1.44 parts of the colour coupler formulated by the method of Example 1 gives a magenta dye image with light absorption maximum at 507 millimicrons.
• a mixture of 4.4 parts of 1 phenyl-3-arnino-5-pyrazolone, 7.7 parts of N-benzylpyromellitic mono-imide and mono-anhydride and parts of glacial acetic acid is heated under reflux for 2 hours.
• the solid reaction product formed is filtered off and dissolved in a warm mixture of 150 parts of water and 150 parts of ethyl alcohol by the addition of 2 N sodium hydroxide solution.
• the solution obtained is acidified with 2 N hydrochloric acid solution after screening and the precipitate collected by filtration.
• N-benzylpyromellitic mono-imide mono-anhydride used in the above example may be prepared as follows:
• a mixture of 38 parts of 5-benZylaminocarbonyl-4- carb-oxy-phthalic anhydride, parts of benzene and 220 parts of acetyl chloride is heated under reflux for 2 hours.
• the crystalline precipitate obtained after cooling is filtered off and washed well with benzene.
• the 20 parts of product are extracted in a continuous extracter with 300 parts of ethyl acetate.
• the 13 parts on N-benzylpyromellitic mono-imide mono-anhydride are obtained as a colourless solid melting at 235238 C.
• S-benzylaminocarboxyl-4-carboxy-phth-alic anhydride itself may be prepared as follows:
• 7.85 parts of 4-methoxy-3-(4- methoxybenzoylacetamido)aniline 7.85 parts of 4-methoxy-3-(4- methoxybenzoylacetamido)aniline.
• the 7.4 parts of 2:5- 4 benylaminocarbonyl-N-[ i methoxy-3-(4-methoxybenzoylacetamido)phenyl]benzamide are obtained as a solid melting at 155-156 C. and on analysis is found to contain 61.5% of carbon, 4.8% of hydrogen and 6.4% of nitrogen. (C H N O H O requires 62.0% of carbon, 4.6% of hydrogen and 6.45% of nitrogen.)
• 1-phenyl-3-amino-5-pyrazolone of Example 9 5.75 parts of N-(fi-aminoethyl)-1-hydroxy-Z-naphthamide.
• the 7.5 parts of 2:5 dicarboxy-4-benzoylaminocarbonyl N [,8(1-hydroxy-2- naphthamido)ethyl]benzamide are obtained as a solid melting above 300 C. and on analysis is found to contain 62.6% of carbon, 4.8% of hydrogen and 7.3% of nitrogen. (C H N OH O requires 62.8% of carbon, 4.7% of hydrogen and 7.3% of nitrogen.)
• N-phenylpyromellitic mono-imide mono-anhydride used in the above example may be prepared as follows:
• a mixture of 40 parts of 5-phenylaminocarbonyl-4-carboxyphthalic anhydride, 250 parts of benzene and 250 parts of thionyl chloride is heated under reflux for 2 hours.
• the yellow reaction product formed is, after cooling, filtered olf and recrystallised from a mixture of 700 parts of toluene and 360 parts of ethyl acetate.
• the 12.8 parts of N-phenylpyromellitic mono-imide monoanhydride are obtained as a pale yellow solid melting at 284-286 C. and on analysis is found to contain 65.4% of carbon, 2.1% of hydrogen and 4.9% of nitrogen.
• the S-phenylaminocarbonyl-4-carboxy-phthalic anhydride its self may be prepared as follows:
• Example 1 3 .2 :5 -dicarboxy-4 phenylamz'nocarbonyl-N- [,8 (1 -hydroxy-2-naphthamido) ethyl] benzamz'de
• 1-phenyl-3-amino-5-pyrazolone of Example 9 5.75 parts of N-(B-aminoethyl)-1-hydroxy-2-naphtharnide and in place of the 7.7
• N-benzylpyromellitic mono-imide mono-anhydride 10 parts are used 7.3 parts of N-phenylpyromellitic monoimide mono-anhydride.
• the 3.0 parts of 2:5-dicarboxy- 4-phenylaminocarbonyl-N [B(-hydroxy-Z-naphthamidb) ethyl]benzamide are obtained as a solid melting above 300 C.
• Example 14.2 S-dicarboxy-4-cycl0l2exylaminocarbonyl- N- [6 (1-hydroxy-2-naphthamido) ethyl] benzamide
• 1-phenyl-3-amino-5-pyrazolone of Example 9 5.75 parts of N-(fi-amin'oethyl)-l-hydroxy-2-naphthamide and in place of the 7.7 parts of N-benzylpyromellitic mono-imide mono-anhy dride are used 7.5 parts of N-cyclohexylpyr'omellitic monoimide mono-anhydride.
• N-cyclohexylpyromellitic mono-imide mono-anhydride used in the above example may be prepared as follows:
• the 5-cyclohexylaminocarbonyl-4-carboxyphthalic an hydride itself may be obtained as follows: A solution of 25 parts of cyclohexylamine in 450 parts of dry ethyl acetate is added dropwise over 20 minutes to a stirred solution of 77 parts of pyromellitic dianhydride in 800 parts of dry acetone, at room temperature. The mixture obtained is screened immediately and allowed to stand 15 hours to crvstallise. The colourless precipitate formed is filtered off and dried at 40 C. The 38 parts of 5-cyclohexylaminocarbonyl-4-carboxyp'hth alic anhydride are obtained as a solid melting at 260-262 C.
• N-(4-dodecylphenyl)butane tetracarboxylic 1:2- imide, 3:4 anhydride used in the above example may be prepared as follows:
• the mono potassium salt of N-(4-dodecylpheny1) butane 122:3:4 tetracarboxylic acid 1:2-irnide itself may be prepared as follows:
• a mixture of 80 gm. of the mono-anhydride of butane 1:2:3:4 tetracarboxylic acid, 100 parts of p-dodecylaniline and 700 parts of glacial acetic acid is heated under reflux of 2 /2 hours then the solution screened hot and then evaporated to dryness in vacuo.
• the dark residue is dissolved in 1600 parts of ethyl alcohol by warming, the solution screened, then 60 parts of potassium acetate added to precipitate a pole brown solid which is collected by filtration and recrystallised first from a mixture of 500 parts of ethyl alcohol and 600 parts of water and then from 1000 parts of ethyl alcohol.
• 1-phenyl-3-amino-5- pyrazolone inExample 15 are used 5.75 parts of N-(B- aminoethyl)-hydroxy-2naphthamide.
• the residue on evaporating to dryness in Vacuo is stirred first with methanol, filtered off and recrystallised from 200 parts of n-propyl alcohol.
• a mixture of 7.85 parts of 4-methoxy-3-(4-methoxybenzoylacetamido)aniline, 13.5 parts of N-(4-dodecylphenyl)pyromellitic di-imido acetyl chloride and 250 parts of acetonitrile is' stirred under reflux for 2 hours.
• the solid reaction product formed is collected by filtration and recrystallised from 1250 parts of acetic acid.
• N-[4-methoxy-3-(4-methoxybenzoyl acetarnido)phenylaminocarbonylmethyl] N-(4-dodecylphenyl)pyromellitic di-imide are obtained in a yellow solid melting at 2l0212 C. and on analysis is found to contain 69.4% of carbon, 5.9% of hydrogen and 6.7% of nitrogen. (C H N O requires 69.3% of carbon, 6.1% of hydrogen and 6.9% of nitrogen.)
• N-(4-dodecylphenyl)pyromellitic di-imidoacetyl chloride used in the above is prepared as follows:
• N-(4-dodecylphenyl)pyromellitic di-imidoacetic acid itself may be prepared as follows:
• N-(4-dodecylphenyl)pyromellitic mono-imide mono-anydride 15 parts of aminoacetic acid and 1050 parts of glacial acetic acid is heated under reflux for 2 hours. After cooling the solid reaction product formed is filtered off and washed well with ethyl acetate. The parts of N-(4-dodecylphenyl) pyromellitic di-imidoacetic acid are obtained as a solid melting at 273-275" C. and on analysis is found to contain 69.7% of carbon, 6.1% of hydrogen and 5.3% of nitrogen. (C H N O requires 69.5% of carbon, 6.6% of hydrogen and 5.3% of nitrogen.)
• a photographic emulsion layer containing 5.64 parts of the colour coupler formulated by the method of Example 2 gives a yellow dye image with light absorption maximum at 428 millimicrons.
• Example 18 N-[,8(1-hydr0xy 2-naphthamido)ethylaminocarbonylmethyl] N (4-d0decylphenyl) pyromellitic di-imide In place of the 7.85 parts of 4-methoxy-3-(4-methoxybenzoylacetamido)aniline in Example 17 are used 5.75
• a photographic emulsion layer containing 2.63 parts of the colour coupler formulated by the method of Example 3 gives a cyan dye image with the light absorption maximum at 676 millimicrons.
• Example 19.N-3-[5-chl0r0-4-methyI-Z-hydroxyphenylaminocarbonyl] phenyl-N-(4 dodecylphenyl) pyromellitic di-imide A mixture of 6.9 parts of 5-met-hyl-4-chl-oro-2-(3- aminobenzoylamino) phenol, 11.5 parts of N-(4-dodecylphenyl)pyromellitic mono-imide mono-anhydride and 250 parts of acetic acid glacial is heated under reflux for 1 hour. After cooling the yellow reaction product formed is filtered off and washed well with ethyl acetate.
• Example 20 -N-(4-d0decylphenyl) N [1 (4-carb0- ethoxy)phenyl-5-pyraz0l0nyl-3-]pyr0mellitic di-imide
• 6.15 parts of 1-(4-canboethoxy)phenyl-3-amino-5-pyrazolone In place of 6.9 parts of 5-methyl-4-chloro-2-(3-aminobenzoylamino) phenol used in example 19, there are used 6.15 parts of 1-(4-canboethoxy)phenyl-3-amino-5-pyrazolone.
• Example 22 N-[3-(4 chloro 1 hydroxy 2 naphthamido)methyl]phenyl-N-(4 ddecylphenyl)pyr0mellitic di-imide
• 5-methyl-4-c-hloro-2-(3-arninobenzylamino)phenol used in Example 19 there are used 8.15 parts of 4-chloro-1-hydroxy-2-N-i('3aminobenzyl) naphthamide.
• the product obtained is recrystallised from 250 parts of glacial acetic acid.
• the 1-hydroxy-4-chloro-2-N (3 nitrobenzyDnaphthamide itself may be prepared as follows:
• a mixture of 15.2 parts of 3-nitrobenzylamine and 29.8 parts of phenyl-l-hydroxy-4-chloro-2-naphthoate is heated at 160170 C. at a pressure of 12 mm. and the phenol formed is distilled off. After cooling the reaction mixture is stirred with methanol, filtered and recrystallised by dissolving in 100 parts of Cellosolve adding 90 parts of ethanol and 50 parts of Water. The 15.8 parts of 4-chloro-1-hydroxy-2-N (3-nitrobenzyl)naphthamide are obtained as a solid melting at 192-194 C.
• Example 23 N-[4-(4 methoxybenzoylacetamido)-2.'5- diethoxyJpheriyl-N'M dodecylphenyl)pyromellitic diimide
• the 5-methyl-4-chloro-2- (3-aminobenzoylamino)phenol used in Example 19 there are used 9.3 parts of 4-(4-methoxybenzoylacetamido)- 2z5-di-ethoxyaniline.
• the product so obtained is recrystallised from 180 parts of glacial acetic acid.
• Example 24 N-4-(2:5 di carbomethoxyphenylaminocarb0nylacetyl)phenyl-N'- (4 dodecylphenyl) pyromellitic di-z'mide
• 5-methyl-4-chloro-2-(3- a-minobenzoylamino)phenol used in Example 19 there are used 9.25 parts of 4-aminobenzoylacetyl-(3 :S-di-carbomethoxy)ani-lide.
• Example 25 Example 25 .2 :5 -di-carboxy-4 (4-d0decylphenylamin0- carbonyl) -N-(I-phenyl-5-pyraz0lonyl-3-) benzamide
• the screened solution is cooled and acidified with 2 N hydrochloric acid solution, the pale yellow precipitate is filtered off and washed well with water.
• the 4-(4-methoxybenzoylacetamido)-2:5 di ethoxynitro benzene itself may be prepared as follows: A sobenzamide are obtained as a solid melting at 279-281 C. and on analysis is found to contain 66.0% of carbon, 6.4% of hydrogen and 8.3% of nitrogen. (C37H42N4OqH2O requires 66.0% of carbon, 6.4% of hydrogen and 8.3% of nitrogen.)
• Example 26 N-3 (l-hydroxy-Z-naphthamido) methyl] phenyl-N'-(4-d0decylphenyl)pyromellitic di-imiae
• 2-amino-4-chloro-5-methylphenol used in Example 4 there are used 8.75 parts of N(3-aminobenzyl)1-hydroxy-2-naphthamide.
• the coupler is filtered off from the reaction mixture and washedwith methanol.
• the coupler is obtained as colourless micro crystals melting above 300 C.
• the coupler is found to contain 75.2% of carbon, 6.0% of hydrogen and 5.5% of nitrogen. (C H O N requires 75.1% of car bon, 6.1% of hydrogen and 5.7 of nitrogen.) 1
• An emulsion layer containing the above coupler and a derived dye image may be obtained as described in Ex ample 3.
• the cyan dye image so obtained has an absorption maximum at 680 my.
• Example 27 (4-n-a'0d ecy lph enyl N ' ⁇ 4 [.J -phenyl-5 -pyrazolonyl-d aminoacetyl] phenyl ⁇ pyr0mellitic di-imide
• 2-amino-4-chloro-5-methylphenol used in Example 4 there are used 9.25 parts of lphenyl-3-(4 aminophenylacetylamino)5 pyrazolone the preparation of which is described in Example 26 of British patent specification No. 830,797.
• the coupler is filtered oil? from the reaction mixture and washed first with acetic acid and then with methanol.
• the coupler is obtained as cream colouredmicro crystals melting above 330 C. On analysis the coupler is found to contain 9.5% of nitrogen. (C H O N requires 9.3% of nitrogen.)
• An emulsion layer containing the above coupler and a derived dye image may be obtained as described in Ex- 15 ample 1.
• the magenta dye image so obtained has an absorption maximum at 526 m
• 8.8 parts of 1- phenyl-3-(3-aminobenzoylamino --pyrazolone The coupler is filtered off and washed with acetic acid and then methanol.
• the coupler is obtained as pale yellow micro crystals, melting above 330 C. On analysis the coupler is found to contain 70.9% of carbon, 5.8% of hydrogen and 9.7% of nitrogen. (C H O N requires 71.65% of carbon, 5.8% of hydrogen and 9.5 of nitrogen.)
• An emulsion layer containing the above coupler and a derived dye image may be obtained as described in Example 1. The magenta dye image so obtained has an aborption maximum at 518 m Example 29.
• 7.85 parts of 4-methoxy-3-(4-meth-oxybenzoylacetamido) aniline used in Example 2 there are used 10.1 parts of 1(2,4,6-trichlorophenyl)-3(2-chloro-4- aminoanilino)-5-pyrazol0ne, the preparation of which is described in Example '21 of British patent specification No. 956,261.
• the coupler After recrystallisation from n-propanol the coupler is obtained as pale yellow microcrystals M.P. 162-164 C. with decomposition. On analysis the coupler is found to contain 60.0% of carbon, 5.1% of hydrogen and 8.1% of nitrogen. (C H O N Cl requires 59.65% of carbon, 4.85% of hydrogen and 8.1% of nitrogen.)
• An emulsion layer containing the coupler and a derived dye image may be obtained as described in Example 1.
• the magenta dye image so obtained has an absorption maximum at 532 mu.
• Example 32 -5-carb0xy-4-[4- ⁇ B-(1-hydr0xy-2 naphthamido)ethyl ⁇ phenyl]aminocarbonyl N (4 dodecylphenyl)phthalimia'e 7.0 parts of N-(4-dodecylphenyl)pyromellitic monoimide mono-anhydride and 4.5 parts of 2-(p-amino-B- phenylethyl) 1 -hydroxynaphthamide as described in United States Patent specification 2,589,004 to Eastman Kodak Company are dissolved separately in the minimum quantity of boiling dry ethyl acetate. The solutions are filtered and then mixed whilst hot.
• the mixture r-apidly deposits a cream coloured precipitate.
• the mixture is kept at room temperature for 18 hours and then filtered.
• the product is washed with ethyl acetate and dried.
• the 8.5 parts of 5-carboxy-4-[4-fi-(l-hydroxy-Z-naphthamido) ethylphenyl] aminocarbonyl-N- (4-dodecylphenyl) phthalimide so obtained is a cream coloured solid which does not melt below 330 C. On analysis this compound is found to contain 73.5% of carbon, 6.6% of hydrogen and 5.6% of nitrogen.
• Example 33.5-carb0xy-4 [6-(1- hydr0xy 2 naphthamido) hexyl] aminocarbonyl-N-(4-dodecylphenyl) phthalimide 11.6 parts of N-(4-dodecylphenyl)pyromellitic monoimide mono-anhydride and 7.0 parts of l-(l-hydroxy-Z- naphthami-d o)-6-aminohexane are mixed in parts of dry ethyl acetate. The mixture is heated under reflux for one hour after which time it is cooled to room temperature. The product is filtered 01f.
• the product is purified by continuous extraction with ethyl acetate in a Soxhlet apparatus.
• the material which has separated in the reservoir is filtered oif and washed with ethyl acetate and dried.
• the 16.8 parts of 5 carboxy 4[6 (1 hydroxy-Z-naphthamido) hexyl]aminoc-arbony1-N-(4 dodecylphenyl) phthalimide so obtained is a solid melting at 223224 C. On analysis, this compound is found to contain 72.0% of carbon, 7.2% of hydrogen and 5.6% of nitrogen. (C45H53N30q requires 72.3% of carbon, 7.1% of hydrogen and 5.6% of nitrogen.)
• a photographic emulsion layer containing 2.7 parts of the colour coupler formulated by the method of Example 3 gives a cyan dye image with light absorption maximum at 684 mp.
• Example 34 -5 -carb0xy-4 [2- ⁇ 13-(1 -hydr0xy-2-naphthamido)ethyl ⁇ phenyl]amin0carb0nyl-N-(4 dodecylphenyl) phthalimide a pale yellow solid melting at 203 C. with decomposition.
• a photographic emulsion layer containing 2.76 parts of the colour coupler formulated by the method of Example 3 gives a cyan dye image with alight absorption maximum at 687 III/.4.
• Example 35 -carb03cy-4-(Z-hydroxy-S methylpheriyl) aminoca rbonyl-N-(4-d0decylphenyl) phtlmlimlde 11.5 parts of N-(4-dodecylpheny1)pyromellitie monoimide mono-anhydride and 3.1 parts of 2-methyl-6-aminophenol are mixed in 100 parts dry ethyl acetate. The mixture is heated under reflux for one hour which time it is cooled to room temperature. The product is filtered off and is purified by continuous extraction with ethyl acetate in a Soxhlet apparatus.
• Example 36 5-carb0xy-4-(2-hydroxy-4-methylphenyl) z'zminocarbonyl-N-(4-dodecylphenyl) phthalz'mide 11.5 parts of N-(4-dodecylphenyl)pyromellitic monoimide mono-anhydride and 3.5 parts of 3-methyl-6-aminophenol are mixed in 130 parts of dry ethyl acetate. The mixture is heated under reflux for one hour after which time it is cooled to room temperature.
• the product is filtered off and purified by continuous extraction with ethyl acetate in a Soxhlet apparatus.
• the mate-rial which has separated'in the reservoirv is filtered off, and the Soxhlet extraction repeated.
• the final product is filtered off, washed with ethyl acetate and dried.
• the 7.0 parts of 5-carboxy-4-(2- hydroxy 4 methylphenyl)aminocarbonyl N (4 dodecylphenyl)phthalimide so obtained is a yellow solid which does not melt below 300 C. On analysis, this compound contained 4.8% of nitrogen. (C H N O requires 4.8% of nitrogen.)
• a photographic emulsionlayer containing 1.83 parts of the colour coupler formulated by the method of Example 3 gives a cyan dye image.
• Example 37 5-carb0xy-4- [2- (1-hydr0xy-2-naphthamido)methyl]plzenylzrminocarbonyl N (4 dodecylphenyl) phthalimide.
• Example 38.1 4-(4-dodecylphenylaminocarbonyl)-5-car boxy-N-(4-w-cyanacetylphenyl) phthalimide A solution of 8.7 parts of 4-n-dodecylaniline in parts of dry acetone is added to a solution of 12 parts of N(4-w-cyanoacetylphenyl)pyromellitic mono imide mono anhydride, the preparation of which is given in Example 8, in 500 parts of .dry acetone and the solution heated under reflux for /2 hour. The solution is then evaporated to dryness and theresidue crystallised from acetone to give the coupler as pale yellow micro crystals melting above 300 C.
• a colour coupler which is a compound selected from the group consisting of compounds of the formula:
• A is tetravalent radical having linkages (a), (b), (c) and (d) selected from the group consisting of:
• n is selected from nought and one, R is selected from the group consisting of cyclohexyl,
• alkyl group contains about 12 to 18 carbon atoms
• Y is selected from the group consisting of the direct linkage, and the linkages -NHCOCH B is the residue of a color coupler compound BNH selected from the group consisting of compounds of the formula ('a):
• R is selected from the group consisting of phenyl, 2,4,6-trichlorophenyl and carboethoxyphenyl,
• X is hydrogen and Y is selected from the group consisting of -NH aminophenylacetylamino, aminobenzoylamino, Z-methoxy-S-aminoanilino and 2-chlor'o-4-amino'anilino, and

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