US3312715A - Colour couplers and their production and use in colour photography - Google Patents

Description

United States Patent Office 3 312,715 COLOUR COUPLERS AND THEIR PRODUCTION AND USE IN COLOUR PHOTOGRAPHY Brian Anderson, Marple, and Colin William Greenhalgh, Manchester, England, assignors to Ilford Limited,

Essex, England, a British company No Drawing. Filed June 15, 1964, Ser. No. 375,380 Claims priority, application Great Britain, June 17, 1963,

24,026/ 63 7 Claims. (Cl. 260-326) 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 socalled 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 quinoneimine 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-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.

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:

where 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 By the term 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.

, According to a further feature of this invention, colour couplers of the foregoing general formulae wherein Y is a direct link are prepared by condensing a compound of the general Formula V:

00 oo (V) with a compound of the general formula B-NH where B has the meaning assigned to it above at a temperature above C. and preferably in a solvent such as acetic acid at the boil. -If the condensation is carried out at a lower temperature, for example in boiling ethyl acetate, then the part ring opened structure III is obtained.

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:

agent such as thionyl chloride and reaction of the anhy-. dride so obtained with a compound R-NH' where R Patented Apr. 4, 1967 has the meaning assigned to it above. 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.

To obtain compounds of the general Formula I where Y is the divalent radical an anhydride of general Formula V is reacted with a nitroaniline and the product reduced to the corresponding amine and converted to the isocyanate derivative which is then reacted with a compound 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:

(1) Those which contain a COCH COgroup, for example benzoyl 4 amino 2 methoxyacetanilide, 4'- methoxybenzoylacet 4 amino 2-methoxyanilide the 2- alkoxybenzoylacet-amino-anilides described in British patent specification No. 595,314 or the aminobenzoylacetmethoxy-anilides of British patent specification No. 800,108, and which give yellow dyestufis on colour de velopment 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 5-pyrazolone, l-(fi-hydroxyethyD-B- amino-S-pyrazolone, 1-phenyl-3-amino-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-heterocyclo-3-amino-5-pyrazolones as described in British patent specification No. 599,919; the 1 (aminoaryl) 3 coumarilylamino S-pyrazolones of British patent specification No. 890,305; the 1-alkyl-3- (aminophenoxyacetamido) 5 pyrazolones of British patent specification No. 865,720 or the 1-phenyl-3-aminoarylamino-S-pyrazolones which give magenta dyestuffs on colour development with substituted p-phenylene diamines (cgmpare British Patent No. 956,261).

(3) 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.

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.

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 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.

Alternatively, 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. The 6.5 parts of 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).

The N-(4-dodecylphenyl) pyromellitic mono-imide mono-anhydride used in the above example may be prepared as follows:

A mixture of parts of 4-(4-dodecylphenyl-aminocarbonyl)-5-carboxy-phthalic anhydride, 880 parts of benzene and 460 parts of thionyl chloride is heated under reflux for 2 hours, cooled and allowed to stand for 12 hours. The yellow reaction product is filtered ofi, washed with 100 parts of benzene and recrystaHised from 1,350 parts of ethyl acetate. The 70 parts of N-(4-dodecylphenyl)-pyromellitic mono-imide mono-anhydride is ob tained as pale yellow plate crystals melting at 196% 197 C. and on analysis is found to contain 73.0% of carbon, 6.5% of hydrogen and 3.1% of nitrogen (C H NO requires 72.9% of carbon, 6.7% of hydrogen and 3.0% of nitrogen).

The 4-(4-dodecylphenyl-amino carbonyl)-5-carboxyphthalic anhydride itself is prepared as follows:

A solution of 100 parts of p-dodecylaniline in 600 parts of dry acetone is added drop-wise over 1 hour to a stirred solution of 116 parts of pyromellitic dianhydride in 1200 parts of dry acetone. When the addition is complete the mixture is filtered immediately and the filtrates are allowed to stand for 15 hours to crystallise. The colourless precipitate formed is collected by filtration and dried at 40 C. in vacuo. 116 parts of 4-(4-dodecylphenyl-amino-carbonyl) 5 carboxy-phthalic anhydride are so obtained.

3.6 parts of 2 N potassium hydroxide solution are added to a suspension of 1.47 parts of the colour coupler in 12 parts of n-propyl alcohol and the mixture heated at 95 C. for 5 minutes. The solution so obtained is then diluted to 30 parts with distilled water. The colour coupler solution is added to 500 parts of a green sensitised gelatino silver halide emulsion containing silver halide equivalent to 2.5 parts of silver and 5% gelatin. The emulsion is then coated on paper base and the coated layer dried. When the photographic material so obtained is exposed to green light, developed in a colour developer containing 4-amino-Nethyl-N-e-hydroxypentylaniline, bleached and fixed, a bright magenta dye image is obtained.

Example 2.4-[4-methoxy 3 (4-methoxybenz0ylacelamido) phenylaminocarbonyl]-5-carboxy-N-(4 dodecylphenyl) phthalimide eon. on oooorno ONHQ o on A solution of 1 1.5 parts of N-(4-dodecylphenyl) pyromellitic mono-imide mono-anhydride in 180' parts of ethyl acetate is added to a solution of 7.85 parts of 4- methoxy-3-(4-methoxybenzoylacetarnido)-ani1ine in 135 parts of ethyl acetate and the mixture heated at 60 C.

for 1 /2 hours. The yellow reaction solid produced is, after cooling, filtered off and gently refluxed for 15 minutes with 400 parts of ethyl alcohol, cooled and filtered. The 10.5 parts of 4-[4-methoxy-3-(4-methoxybenzoylacetamido)phenylaminocarbonyl] carboxy-N-(4-dodecylphenyl) phthalimide so obtained is a pale yellow solid melting above 300 C. On analysis the compound is found to contain 69.9% of carbon, 6.1% of hydrogen and 5.5% of nitrogen (C H N O requires 69.7% of carbon, 6.3% of hydrogen and 5.4% of nitrogen).

A photographic layer containing the colour coupler may be obtained in the following manner:

10.4 parts of 2 N potassium hydroxide solution are added to a suspension of 5.36 parts of the colour coupler in 200 parts of n-propyl alcohol and the mixture heated at 95 C. for 5-10 minutes until a solution is obtained, which is then diluted to 100 parts with distilled water. The colour coupler solution is added to 500 parts of a blue sensitive silver halide emulsion containing silver halide equivalent to 10.0 parts of silver and 5% gelatin. The emulsion is then coated on paper base and the coated layer dried. When the photographic material so obtained is exposed to blue light, developed in a colour developer containing 4-amino-N-ethyl-N-s-hydroxypentyh aniline. bleached and fixed, a yellow image is obtained.

Example 3.N- [18(1 -hydr0xy-2-naphthamid0) ethyl] -N (4-d0decylphenyl) pyromellitic di-imiae aminoethyl)-1-hydroxy-2-naphthamide and 200 parts of glacial acetic acid is heated under reflux for 1 hour. The

yellow 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.

The 12.0 parts of N-[,8(l-hydroxy-Z-naphthamido) ethyl]-N'-(4 dodecylphenyl)pyrornellitic di-imide so obtained is a yellow solid melting at 304-306 C. On analysis the compound is found to contain 73.1% of carbon, 6.0% of hydrogen and 6.3% of nitrogen (C H U O carbon,

. 6 requires 73.1% of carbon, 6.4% of hydrogen and 6.2% of nitrogen).

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. When 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.

CO H Example 4. N (4-a0decylphenyl) N 2-hydr0xy-4- methyl-S-chlorophenyDpyromelliric di-imide A solution of 4.75 parts of 2-amino-4-chlor-5-methylphenol in parts of glacial acetic acid is added to a solution of 13.86 parts of N-(4-dodecylphenyl) pyromellitic mono-imide mono-anhydride in 150 parts of glacial acetic acid and the mixture is refluxed for 1 hour. The yellow reaction product formed is filtered 01f after cooling and recrystallised from 480 parts of n-butyl alcohol. The 13.0 parts of N (dodecylphenyl)-N-(2-hydroxy 4- methyl-S-ohlorophenyl)-pyromellitic di-imide is obtained as a yellow solid melting at 285-288 C. On analysis 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. The 10.0 parts of 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).

The N-n-octadecyl pyromellitic mono-imide mono-anhydride used in the above example may be prepared as follows:

A mixture of 45 parts of 5-noctadecylaminocarbonyltrimellitic acid, 200 parts of benzene and 250 parts of acetyl chloride is heated under reflux for 2 hours. The colourless reaction product is, after cooling, filtered off and recrystallised from 650 parts of petroleum ether. The 28.2 parts of N-n-actadecyl pyromellitic mono-imide mono-anhydride is obtained as a white solid melting at 84-85 C. and on analysis is found to contain 71.5% of 8.3% of hydrogen and 3.2% of nitrogen (C H NO requires 71.6% of carbon, 8.3% of hydrogen and 3.0% of nitrogen).

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 A mixture of 11.75 parts of N -n-octadecylpyromellitic mono-imide mono-anhydride, 5.75 parts of N-(B-aminoethyl)-1-hydroxy-2-naphthamide, 270 parts of ethyl acetate and 5 parts of glacial acetic acid is heated under reflux for 1 hour. 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. The 20.0 parts of N-[4methoxy-3-(4-methoxybenzoylacetamide)phenyl]-N-n-octadecylpyromellitic di-imide so obtained is a yellow solid melting at 149-152 C. On analysis the compound is found to contain 70.3% of carbon, 7.4% of hydrogen and 5.4% of nitrogen. (C H N O requires 70.5% of carbon, 7.2% of hydrogen and 5.5% of nitrogen.)

A photographic emulsion layer containing 5.42 parts of the colour coupler formulated by the method of EX- ample 2 gives a yellow dye image with light absorption maximum at 426 millimicrons.

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. The 13.3 parts of 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.

8 (C -7H N O requires 73.6% of carbon, 6.1% of hydrogen and 7.0% of nitrogen.)

Alternatively, the coupler may be prepared in the following manner:

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. with decomposition and is found to have .an equivalent weight of 91.4 in aqueous pyridine, by the addition of excess sodium hydroxide solution and back titrating with hydrochloric acid, 4-w-cyanoacetylphenyl pyromellitic mono-imide mono-anhydride has an equivalent weight of 90-.

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.

Example 9.2:5-dicarboxy-4-benzylaminocarbonyLN- (1-phenyl-5-pyraz0lonyl-3-) benzamide 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. After cooling, 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. The 7.7 parts of 2:5- dicarboxy 4 benzylaminocarbonyl N (l p'henyl 5- pyrazolonyl-3-)benzamide are obtained as a solid melting at 272-274 C. and on analysis is found to contain 62.1% of carbon, 4.1% of hydrogen and 10.8% of nitrogen. (C26H20N4O7 requires 62.4% of carbon, 4.0% of hydrogen and 11.2% of nitrogen.)

The 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.

The S-benzylaminocarboxyl-4-carboxy-phth-alic anhydride itself may be prepared as follows:

A solution of 27 parts of benzylamine 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 immediately screened then allowed to stand for 15 hours to crystallise. The colourless precipitate formed is collected by filtration and dried in vacuo at 40 C. The 51 parts of 5-benzylaminocarbonyl-4- carboxy-phthalic anhydride are. obtained as a white solid Example 10.2:5-dicarb0xy-4 benzylaminocarbonyl-N- [methoxy-3- (4-meth0xy benzoylacetamide phenyl] benzamide In place of the 4.4 parts of l-phenyl-3-amino-5-pyrazolone in Example 9 are used 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.)

Example 11.2:5-dicarb0xy-4 benzylaminocarbonyl-N- [5(1-hydr0xy-2-naphthamido)ethyl] benzamide In place of the 4.4 parts of 1-phenyl-3-amino-5-pyrazolone of Example 9 are used 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.)

Example I2.2:5-a'z'carb0xy-4 phenylaminocarbonyl-N- [4-methoxy-3 (4 methoxybenzoylacetamido)phenyl] benzamide In place of the 4.4 parts of 1-phenyl-3-amino-5-pyrazolone of Example 9 are used 7.85 parts of 4-methoxy-3- (4-rnethoxybenzoylacetamido)aniline and in place of the 7.7 parts of N-benzylpyromellitic mono-imide mono-anhydride are used 7.3 parts of N-phenylpyromellitic monoimide mono-anhydride. The 3.5 parts of 2:5-dicarboxy- 4-phenylaminocarbonyl N [4 methoxy-3-4-methoxy-3- (4-methoxybenzoylac-etamido)phenyl]benzamide are obtained as a solid melting at 290 C. and on analysis is found to contain 60.6% of carbon, 4.2% of hydrogen and 6.7% of nitrogen. (C H O N 1 A2H O requires 60.6% of carbon, 4.6% of hydrogen and 6.45 of nitrogen.)

The 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:

A solution of 23 parts of aniline in 450 parts of ethyl acetate is added dropwise over 30 minutes to a stirred solution of 77 parts of pyromellitic dianhydride in 800 parts of acetone, at room temperature. The mixture obtained is immediately screened and allowed to stand hrs. to crystallise. The colourless precipitate formed is collected by filtration and dried in vacuo at 40 C. to give 40 parts of S-phenylaminocarbonyl-4-carboxy-phthalic anhydride. On titration with alkali the compound is found to have an equivalent weight of 106 (C H NO requires equivalent weight of 103.3).

Example 1 3 .2 :5 -dicarboxy-4 phenylamz'nocarbonyl-N- [,8 (1 -hydroxy-2-naphthamido) ethyl] benzamz'de In place of the 4.4 parts of 1-phenyl-3-amino-5-pyrazolone of Example 9 are used 5.75 parts of N-(B-aminoethyl)-1-hydroxy-2-naphtharnide and in place of the 7.7

10 parts of N-benzylpyromellitic mono-imide mono-anhydride 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 In place of the 4.4 parts of 1-phenyl-3-amino-5-pyrazolone of Example 9 are used 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. The 9.0 parts of 2:5-dicarboxy- 4-cyclohexylaminocarbonyl N [5(1-hydroxy-2-naphthamido)ethyl]benzamide are obtained as a solid melting above 300 C. and on analysis is found to contain 62.9% of carbon, 5.4% of hydrogen and 7.6% of nitrogen. (C H O N /2H O requires 62.7% of carbon, 5.4% of hydrogen and 7.6% of nitrogen.)

The N-cyclohexylpyromellitic mono-imide mono-anhydride used in the above example may be prepared as follows:

A mixture of 13.8 parts of 5-cyclohexylaminocarbonyl- 4-carboxyphthalic anhydride and 120 parts of acetic anhydride is heated under reflux for 2 hours. The solid reaction product formed is, after cooling, filtered off and washed Well with ethyl acetate. The 8.5 parts of N-cyclohexylpyromellitic mono-imide mono-anhydride are obtained as a solid melting at 245247 C. and on analysis is found to contain 4.6% of nitrogen. (C H NO requires 4.7% of nitrogen.)

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.

Example 15.N-(4-dodecylphenyl)-N'-(]-phenyl-5-pyrazolonyl-3)-butane tetracarboxylic acid 1:2, 3:4 di-imide requires 66.3% of carbon, 7.8% of hydrogen.)

The N-(4-dodecylphenyl)butane tetracarboxylic 1:2- imide, 3:4 anhydride used in the above example may be prepared as follows:

A mixture of parts of the mono potassium salt N-(4-dodecylphenyl)butane 1:2:3:4 tetracarboxylic acid 1:2 imide and 100 parts of acetyl chloride is heated under reflux for 2 hours and then the solution is evaporated down to dryness in vacuo. The residue so obtained is recrystallised from 840 parts 60-80 grade petroleum ether to give 69 parts of N-(4-dodecylphenyl)butane tetracarboxylic 1:2-imide, 3:3 anhydride as a colourless solid melting at 136-139 C.

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. The 48.0 parts of the mono potassium salt N-(4-dodecylphenyl)butane 122:3:4 tetracarboxylic acid 1:2 monoimine are obtained as a colourless solid melting at 226-230 C. with decomposition and on analysis is found to contain 62.4% of carbon, 8.0% of hydrogen and 2.8% of nitrogen. (C H NO K requires 62.8% of carbon, 7.2% of hydrogen and 2.8% of nitrogen.)

Example 16.N-(4-dodecylphenyl)-N'-[fi(1-hydr0xy-2- naphthamido)ethyl] butane tetracarboxylic acid 1:2:3:4 di-imide In place of the 4.4 parts of 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. The 4.0 parts of N-(4-dodecylphenyl)-N[fi(1-hydroxy-2-naphthamido) ethyl] butane tetracarboxylic acid 122:3:4 di-imide are obtained as a solid melting at 176180 C. and on analysis is found to contain 6.1% of nitrogen. (C H N O requires 6.4%

of nitrogen.)

Example 17.-N-[4-methoxy-3-(4-meth0xybenz0ylacetamido)phenylaminocarbonylmethyl] N (4 dodecylphenyl)pyromellitic di-imide 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. The 16.0 parts of 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.)

The N-(4-dodecylphenyl)pyromellitic di-imidoacetyl chloride used in the above is prepared as follows:

A mixture of 100 parts of N-(4-dodecylphenyl)pyromelliticdi-imidoacetic acid and 1600 parts of thionyl chloride is heated under reflux for 6 hours. After cooling the yellow solid is filtered off and recrystallized from 4000 parts of benzene. The 62 parts of N-(4-dodecy1pheny1)pyromellitic di-imidoacetyl chloride are obtained as a yellow solid melting at 315-317 C. and on analysis is found to contain 67.5% of carbon, 5.7% of hydrogen, 5.6% of nitrogen and 6.4% of chlorine. (C H N O Cl requires 67.1% of carbon, 6.15% of hydrogen, 5.2% of nitrogen and 6.6% of chlorine.)

The N-(4-dodecylphenyl)pyromellitic di-imidoacetic acid itself may be prepared as follows:

A mixture of 92 parts of 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

gm. of N-(B-aminoethyl) l-hydroxy 2-na-phthamide,

The product is heated in 1500 parts of acetic acid cooled and filtered off. The 15.75 parts of N-[flU-hydroxy-Z- naphthamido ethyl aminocarbonylmethyl] -N' (4-dodecylphenyl)pyromellitic di-imide are obtained as a solid melting at 256258 C. and on analysis is found to contain 70.4% of carbon, 6.3% of hydrogen and 7.5%

of nitrogen. (C H N O requires 70.7% of carbon,

6.3% of hydrogen and 7.7% of nitrogen.)

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. The 14.5 parts of N-3-[5 chloro-4-methyl-2-hydroxyphenylaminocar-bonyHphenyl-N' (4 dodecylpheny1)pyromellitic di-imide are obtained as a yellow solid melting at 312-314 C. On analysis the compound is found to contain 69.7% of carbon, 5.5% of hydrogen and 4.8% of chlorine. (C H N O Cl requires 70.05% of carbon, 5.8% of hydrogen and 4.9% of chlorine.)

The preparation of 5-methyl-4-chloro-2-(3-aminobenzoylamino) phenol is described in British patent specification 791,219.

Example 20.-N-(4-d0decylphenyl) N [1 (4-carb0- ethoxy)phenyl-5-pyraz0l0nyl-3-]pyr0mellitic di-imide 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. The 12.1 parts of N-(4-dodecylphenyl)-N'-[1-(4- carboethoxy)phenyl 5 pyrazolonyl-3]pyromellitic diimide are obtained as a solid melting at 296-298 C. and on analysis is found to contain 69.4% of carbon, 5.9% ofhydrogen and 7.8% of nitrogen. (C H N O- requires 69.6% of carbon, 6.1% of hydrogen and 7.8% of nitrogen.) The 1-(4-car-boethoxy)phenyl-3-amino-5- pyrazolone used in the above example is prepared by the method of Example 18 of British patent specification Example 21.-N-[4-(4-meth0xybenz0ylacetamido) phenyl]-N-(4-d0decylphenyl)pyromellitic di-imide O Q /O O CH.O @GOOH..ONH N C O C O A mixture of 7.1 parts of 4-(4-methoxybenzoylacetamido)aniline, 11.5 parts of N-(4-dodecy1pheny-l)pyromellitic mono-imide mono-anhydride and 400 parts of ethyl acetate is heated under reflux for 1 hour. After cooling, the solid reaction product formed is filtered off and heated under reflux in 750 parts of glacial acetic acid for 30 minutes. The 1:1.9 parts of N-[4-(4-met-hoxybenzoylacetamido)phenyl]-N' (4 dodecylphenyl)pyromellitic di-imide are obtained as a yellow solid melting above 320 C. and on analysis is found to contain 72.5% of carbon, 5.7% of hydrogen and 5.5% of nitrogen. (C H N O requires 72.6% of carbon, 6.2% of hydrogen and 5.8% of nitrogen.)

Example 22.N-[3-(4 chloro 1 hydroxy 2 naphthamido)methyl]phenyl-N-(4 ddecylphenyl)pyr0mellitic di-imide In place of 6.9 parts of 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 10.5 parts of N-[3-(4-chloro-1-hydroxy-2 naphthamido)methyl]phenyl-N'-(4-dodecylphenyl)pyromellitic di-imide are obtained as a solid melting at 162-164 C.

' The 4-chloro-1-hydroxy-2-N-( 3 aminobenzyl)naphthamide used in the above example may be prepared as follows:

A mixture of parts of 1-hydroxy-4-chloro-2-N-(3- nitrobenzyl)naphthamide, 80 parts of ethyl alcohol and 20 parts of hydrazine hydrate is heated under reflux and Raney nickel catalyst added. After the vigorousreaction has subsided, the Raney nickel is filtered 01f and the filtrates evaporated in vacuo, the residue is then recrystallised from methyl alcohol containing a little sodium dithionite. The 4-chloro-1-hydroxy-2-N-( 3-aminobenzyl) napthamide is obtained as pale fawn crystals melting at 162-164 C.

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 In place of the 6.9 parts'of 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. The

12.0 parts of N'-[4-(4-methoxybenzoylacetamido)-2:S-diethoxy] phenyl-N- (4-dodecylphenyl) pyromellitic di-imide are obtained as a solid melting at 20l203 C. and on analysis is found to contain 5.1% of nitrogen.

(C H N O requires 5.2% of nitrogen.)

' The 4-(4-methoxybenzoylacetamido)-2:5 di ethoxyaniline used in the above example is prepared as follows:

A mixture of 40 parts of 4-(4-methoxybenzoyl-acetamido)- 2:5-di-ethoxy nitrobenzene, 800 parts of ethyl alcohol and Raney nickel catalyst is treated with hydrogen at lution of parts of anisoylaceti-c ester in 70 parts of xylene is added over 30 min. to a refluid'n-g mixture of 30.7 parts of nitro-2:S-diethoxyanilino, 350 parts of xylene and 10 parts of pyridine. The mixture is then distilled until 130 parts of distillate has been collected, the mixture is then refluxed for a further 4 hours. After standing for 15 hours, the mixture is diluted with 300 parts of methanol, cooled in ice and the precipitated solid collected by filtration. The 40 parts of 4-(4-methoxy- 'benzoylacetamido)-2:S-diethoxynitrobenzene are obtained as pale yellow needle crystals melting at 197298 C.

Example 24.N-4-(2:5 di carbomethoxyphenylaminocarb0nylacetyl)phenyl-N'- (4 dodecylphenyl) pyromellitic di-z'mide In place of the 6.9 parts of 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. The 17.5 parts of N-4-(2z5-di-carbomethoxyphenylamino carbonylacetyl)phenyl-N'- (4-dodecylphenyDpyromellitic di-imide are obtained as a solid melting above 300 C. and on analysis is found to contain 70.1% of carbon, 5.8% of hydrogen and 4.9% of nitrogen. (C47H47N3010 requires 69.4% of carbon, 5.8%

of hydrogen and 4.9% of nitrogen.)

Example 25 .2 :5 -di-carboxy-4 (4-d0decylphenylamin0- carbonyl) -N-(I-phenyl-5-pyraz0lonyl-3-) benzamide A mixture of 6.18 parts of N-(4-dodecylphenyl)-N'-(1- phenyl-S-pyrazolonyl-S-)pyromellitic di-imide, prepared in Example 1, 50 parts of n-propyl alcohol and 15 parts of 2 N potassium hydroxide solution is heated until a solution is obtained. 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 6.2 parts of 2:5-di-carboxy-4-(4-dodecylphenylaminocarbonyl)-N-( l-phenyl 5 pyrazolonyl 3-) -80 C. under a pressure of 100 atmospheres for 15 hours. After cooling the product is filtered off and recrystallised from ethyl alcohol. The 28 parts of 4-(4- methoxybenzylaoetamido)-2:5-di -ethoxyani'line are obtained as fawn needle crystals melting at 154-155 C.

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 In place of the 4.75 parts of 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. On analysis 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 .N (4-n-a'0d ecy lph enyl N '{4 [.J -phenyl-5 -pyrazolonyl-d aminoacetyl] phenyl}pyr0mellitic di-imide In place of the 4.75 parts of 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 Example 28.N(4-n-dodecylphenyl)N{3 [N(1-phenyl-5- pyrazl0nyl-3-)aminoearbonyl]phenyl}pyr0mellitic diimide In place of the 4.75 parts of 2-amino-4-chloro-5-methylphenol used in Example 4 there are used 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. -N(4-n-dodecylphenyl)N'{4-meth0xy-3[N- (1-phenyl-5-pyraz0l0nyl 3)amin0] phenyl}pyromellitic di-imide In place of the 4.75 parts of 2-amino-4-chloro-5-methylphenol used in Example 4 there are used 8.9 parts of l-phenyl-3(2-methoxy-5-aminoanilino)5-pyrazolone. The coupler is recrystallised from a mixture of acetic acid and xylene and then extracted with boiling n-butylacetate and is obtained as a pale yellow solid M.P. 253 C. On analysis the coupler is found to contain 71.3% of carbon,

5.9% of hydrogen and 10.1% of nitrogen. (C H O N requires 71.45% of carbon, 6.1% of hydrogen and 9.5%

of nitrogen.)

The preparation of the 1-pheny1-3(2-methoxy-5-aminoanilino)5-pyrazolone used in the above example is described in Example 32 of British specification No. 956,261.

Example 30.4[3-chl0r0-4-{N[1 (2,4,6 trichlorophenyl) S-pyrazolonyl 3]amin0}phenylamin0carb0nyl]5 carboxy-N-(4-n-dodecylphenyl)phthalimide In place of the 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. 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 31.5-carb0xy-4[2-{;8-(1-hydr0xy-4-chl0r0 2- naphthamido)ethyl}phenyl]aminocarbonyl-N (4 d0- decylphenyl)phthalimide.

9.0 parts of N-(4-dodecylpheny1)pyromellitic monoimide mono-anhydride and 6.8 parts of 2(-o-amino-,8- phenylethyl)-1-hydroxy-4-chloronaphthamide are mixed in 150 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 is purified by continuous extraction with ethyl acetate in a Soxhlet apparatus. When the extraction is complete, the material which has separated in the reservoir is filtered off, washed With ethyl acetate and dried. The 12.0 parts of 5 -carboxy-4- [2-13- 1-hyd'roxy-4-chloro-2-naphthamido) ethyl phenyl1aminocarbonyl N (4 dodecyl phenyl) phthalimide so obtained is a pale yellow solid melting at 222-224 C. On analysis, this compound is found to contain 70.1% of carbon, 6.0% of hydrogen, 4.5% of chlorine and 5.1% of nitrogen. (C H N 0 Cl requires 70.3% of carbon, 6.0% of hydrogen, 4.4% of chlorine and 5.2% of nitrogen.) A photographic emulsion layer containing 2.89 parts of the colour coupler formulated by the method of Example 3 gives a cyan dye image with light absorption maximum at 680 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. (C4qH4 N3O7 requires 73.5 of carbon, 6.4% of hydrogen and 5.5% of nitrogen.) A photographic emulsion layer containing 2.76 pa-rts of the colour coupler formulated by the method of Example 3 gives a cyan dye with light absorption maximum at 668 III/1..

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. Because of its relatively poor solubility in ethyl acetate, the product is purified by continuous extraction with ethyl acetate in a Soxhlet apparatus. When the extraction is complete, 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.

On analysis this compound is found to contain 73.7% of carbon, 5.9% of hydrogen and 5.4% of nitrogen. (C H N O requires 73.5% of carbon, 6.4% of hydrogen and 5.5 of nitrogen.)

' 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. When the extraction is complete, the material'which has separated in the reservoir is filtered ofi, washed with ethyl acetate and dried. The 10.5 parts of 5-carboxy-4-(2 hydroxy 3- methylphenyl)aminocarbonyl-N-(4-dodecylphenyl) phthalimide so obtained is a solid which does not melt below 320 C. On analysis this compound is found to contain 5.5% of nitrogen. (C H N O requires 5.5 of nitrogen.)

-A photographic emulsion layer containing 1.83 parts o fthe colour coupler formulated by the method of Example 3 gives a cyan dye image with light absorption maximum at 630 m 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. When theextraction is complete, 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.

7.0 parts of N-(4-dodecylphenyl)pyromellitic monoimide mono-anhydride and 4.3 parts of 2(2-aminobenzyl)-1-hydroxynaphthamide are each dissolved in the minimum quantity of boiling dry ethyl acetate. The solutions are filtered and then mixed whilst hot. The mixture is then boiled under reflux for a short time. After cooling to room temperature, the solid which separates is filtered off, washed with ethyl acetate and then dried. The 9.8 parts of 5-carboxy-4-[2-(1-hydroxy-2-naphthamido) methyl]phenylaminocarbonyl N (4 dodecylphenyl) phthalimide so obtained is a pale yellow solid melting at 190 C. with decomposition. On analysis, this compound is found to contain 73.4% of carbon, 6.0% of hydrogen and 5.7% of nitrogen. (C H N O requires 73.4% of carbon, 6.25% of hydrogen and 5.6% of nitrogen.) A photographic emulsion layer containing 2.72 parts of the colour coupler formulated by the methtod of Example 3 gives a cyan dye image with a light absorption maximum of 689 m 1 8 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.

On analysis the coupler is found to contain 72.2% of carbon, 6.3% of hydrogen and 6.9% of nitrogen. (C37H39O5N3 requires 71.5% of carbon, 6.3% of hydrogen and 6.75% of nitrogen.) N

We claim as our invention:

1. A colour coupler which is a compound selected from the group consisting of compounds of the formula:

where A is tetravalent radical having linkages (a), (b), (c) and (d) selected from the group consisting of:

and

(b)-oHNHo OI l'H-OH(c) (a)CH2 OH2(d) and related compounds of the formulae:

BY-NHOC|:aAc]-COOH wherein n is selected from nought and one, R is selected from the group consisting of cyclohexyl,

benzyl, phenyl, alkyl and alkyl phenyl,

wherein the 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):

X[-R COCH -CO-NHR ]Y wherein R and R are independently selected from the group consisting of phenyl, methoxyphenyl, diethoxyphenyl and dicarbomethoxy phenyl, one of X and Y is NH and the other H, compounds of the formula (b):

wherein 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

(c) compounds selected from the group consisting of 2-(o-amino-fi-phenylethyl) -1-hydroxynaphtl1amide, 2-methyl-6-aminophenol, 3-methyl-6-aminophenol and 2 (Z-aminobenzyl) -1-hydroxynaphthamide. 2. The colour coupler claimed in claim 1 wherein R is dodecylphenyl.

3. The colour coupler as claimed in claim 1 wherein R is N-octadecyl.

4. The colour coupler as claimed in claim 1 wherein B is 1-phenyl-3-amino-5-pyrazolone.

5. The colour coupler as claimed in claim 1 wherein B is 4-methoxy-3-(4-methoxy benzoyl acetamido)-aniline. 6. The colour coupler as claimed in claim 1 wherein B is N-(fi-aminoethyl)-) l-hydroxy-Z-naphthamide.

7. The colour coupler as claimed in claim 1 wherein B is 4-wcyanoacetylaniline.

References Cited by the Examiner UNITED STATES PATENTS 2,710,803 6/1955 Salrninen et al 260-310 2,837,557 6/1958 Lynn 260-46 5.4 2,878,263 5/1959 Oroshnik 260310 2,905,694 9/1959 Pinson 160-3 10 2,933,391 4/1960 Feniak et al. 96100 2,983,608 5/1961 Beavers 96100 3,014,033 12/1961 Jansen et al 260326 3,148,178 9/1964 Wallace et al 260-326 OTHER REFERENCES Cram et a1., Organic Chemistry, McGraw-Hill Book Company, Inc., New York, 1959, pages 75-76 and 384.

Fieser et 211., Advanced Organic Chemistry, Reinhold Publishing Corp, New York, 1961, p. 720.

Porai-Koshits, Chemical Abstracts, vol. 31, 1937, page Royals, Advanced Organic Chemistry, Prentice-Hall, Inc., New Jersey, 1956, pages 621-622.

ALEX MAZEL, Primary Examiner.

NORMAN L. TORCHIN, HENRY R. JILES,

Examiners.

MA RY OBRIEN, J. T. BROWN, Assistant Examiners.

Claims (1)

1. A COLOUR COUPLER WHICH IS A COMPOUND SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS OF THE FORMULA: