US2706685A - 3-acylamido-5-(m-sulfobenzoyloxy) pyrazole coupler compounds - Google Patents

3-acylamido-5-(m-sulfobenzoyloxy) pyrazole coupler compounds Download PDF

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US2706685A
US2706685A US324153A US32415352A US2706685A US 2706685 A US2706685 A US 2706685A US 324153 A US324153 A US 324153A US 32415352 A US32415352 A US 32415352A US 2706685 A US2706685 A US 2706685A
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Ilmari F Salminen
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/36—Couplers containing compounds with active methylene groups
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings
    • 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

Definitions

  • solubilizing groups can be introduced into pyrazolone coupler molecules in an unexpected manner to facilitate incorporation of the couplers into aqueous systems and that the solubilizing groups of such couplers are readily eliminated during color development to yield relatively insoluble dye images and therefore improved image sharpness.
  • the coupling activity of the couplers is surprisingly great considering the manner of attachment of the solubilizing group to the pyrazolone coupler molecule.
  • similar coupler compounds containing the reactive methylene group and the same solubilizing group do not possess the increased coupler activity as will be explained more fully hereinafter.
  • One object of my invention is to provide coupler compounds containing alkali solubilizing groups, which groups are readily removable during color development. Another object is to provide coupler compounds which have increased coupling activity. Other objects will become apparent from consideration of the following description of my invention.
  • the coupler compounds of the invention are 5-pyrazole derivatives and possess the following structural formula:
  • N CNHC OR in which R represents a mononuclear aryl group of the benzene series substituted or not, such as phenyl, trichlorophenyl, etc., and R represents either a mononuclear aralkyl group of the benzene series, a mononuclear aryloxyalkyl group of the benzene series, or a mononuclear arylene group, such as a phenoxypropyl group or a phenoxyacetamidophenyl group.
  • R represents a mononuclear aryl group of the benzene series substituted or not, such as phenyl, trichlorophenyl, etc.
  • R represents either a mononuclear aralkyl group of the benzene series, a mononuclear aryloxyalkyl group of the benzene series, or a mononuclear arylene group, such as a phenoxypropy
  • the coupler compounds are prepared by reacting m-chlorosulfonyl benzoic acid with 3-acylamido-5-pyrazolones in the presence of pyridine. Surprisingly, the result is that the carboxyl group of the sulfonyl halide rather than the chlorosulfonyl group reacts with the enolized carbonyl group of the pyrazolone. Little is known of the reactions of m-chlorosulfonyl benzoic acid. However, the unexpected nature of this reaction is attested by the prior knowledge in a similar reaction (Sekera and Marvel, J. A. C. S.
  • Coupler 1 is prepared as follows: In a suitable 3-necked flask equipped with a thermometer, a coil condenser, a stirrer and stoppered with a calcium chloride tube, are placed volumes of pyridine and while stirring vigorously, 11.53 parts of m-chlorosulfonyl benzoic acid are added. A rise in temperature is noted from 29-52 C. and the solution turns yellow. Stirring is continued for 1 /2 hours and at this time there are added 34.5 parts of 1 (2,4,6-trichlorophenyl) 3 ⁇ m [oz-(2,4-di-tert-amy1- phenoxy)acetamidolbenzamido ⁇ 5 pyrazolone (U. S.
  • Patent 2,600,788, Example No. 7 The solution is complete within 30 minutes and a change of color to deep purple is evident. Stirring is continued overnight. The viscous resulting solution is poured with stirring upon 600 parts of ice in which 160 volumes of concentrated hydrochloric acid have been added. After one-half hour of stirring, the white product is filtered and washed well with several portions of Water and dried as much as possible upon the filter. The moist material is then dried at C. 41.5 parts of coupler are obtained which represents an 86.5 percent yield of the theoretical quantity of 48 parts.
  • Patent 2,600,788 except using aniline in place of 2,4,6-trichloroaniline).
  • the reaction mixture is stirred for one hour at ordinary temperature, added in a thin stream to 300 parts of ice containing 50 volumes of concentrated hydrochloric acid.
  • the solid which precipitates is filtered by suction, washed on the funnel with ice water in order to remove pyridine.
  • the product is air-dried, 7 parts being obtained.
  • Coupler 3 is prepared as follows: In a suitable flask is dissolved in 2.2 parts 1-[p-(p-tert-butylphenoxy)phenyl]-3-[a (p tert-butylphenoxy)propionamido1-5-pyrazolone by warming with 25 volumes of benzene. To the solution is added 1 part of m-chlorosulfonylbenzoic acid, followed by 1.2 parts of pyridine. The solution becomes turbid and is heated under reflux for three hours. On cooling, the benzene is removed and the residue triturated with petroleum ether to a white solid; it is filtered, washed on the funnel with petroleum ether and dried, 2.3 parts being obtained.
  • the pyrazolone coupler used in this synthesis is described in U. S. Patent 2,369,489, Example Coupler 4 is prepared as follows:
  • -(2,4-di-tert-amylphenoxy)butyric acid is first prepared as follows: In a suitable vessel provided with stirrer, thermometer, and coil condenser is placed 500 volumes of absolute methyl alcohol and 46 parts of sodium. To the sodium methoxide thus made is added 468 parts of 2,4-di-tcrt-amylphenol and stirred 15 minutes. Butyrolactone (198 parts) is added and the mixture refluxed 15 minutes. The condenser is inverted and the excess methyl alcohol distilled up to Concentrated hydrochloric acid (500 volumes) in 1400 volumes of distilled water is added continuously with stirring, and the acidic mixture poured into a glass tray to cool. The solid is washed and filtered, 650 parts being obtained. The
  • product is crystallized from 1500 volumes of ligroin, 300 grams of product melting at 98-100 being obtained.
  • -(2,4-di-tert-amylphenoxy)butyryl chloride is prepared as follows: In a suitable vessel, provided with a condenser, is placed 32 parts of y-(ZA-di-tert-amylphenoxy)butyric acid to which is added 22 volumes of thionyl chloride. The mixture is heated for 3 hours at 40; at the end of this time the excess thionyl chloride is removed under vacuum, the temperature being allowed to reach 55. The crude acid chloride is purified by distillation, B. P. 165166/ 1 mm.
  • l-phenyl-3- ⁇ 3-l'y-(2A di tert amylphenoxy)butyramido]-benzamido) ⁇ -5-pyrazolone is prepared as follows: In a suitable reaction vessel, provided with a stirrer, thermometer, and dropping funnel, is placed 100 volumes of glacial acetic acid and 5 volumes of water. To this mixture is added 2.83 parts of anhydrous sodium acetate which is allowed to dissolve with stirring. 1-phenyl-3- (3-aminobenzamido)-5-pyrazolone, 8.3 parts, is added, and stirring continued 15 minutes to assure homogeneous distribution.
  • the desired coupler 4 is then finally prepared as follows: In a suitable reaction vessel, provided with a stirrer and thermometer, is placed parts of m-chlorosulfonylbenzoic acid followed by 175 volumes of pyridine. A clear solution results, with a rise in temperature. Within a few minutes a yellow solid separates. When the mixture has cooled to room temperature, 35 parts of the pyrazolone, prepared directly above, is added. Again the temperature rises. The mixture is stirred for approximately one hour at ordinary temperature, then added with stirring to a mixture of 350 volumes of concentrated hydrochloric acid in 1000 parts of ice.
  • the pale yellow mixture is filtered and the solid washed on the funnel with 2000 volumes of water containing 70 volumes of hydrochloric acid and free ice. The solid is dried at room temperature.
  • Coupler 5 is prepared as follows: In a suitable 3-necked flask provided with a stirrer and a thermometer is placed 5 parts of m-chlorosulfonylbenzoic acid, followed by 25 volumes of pyridine. After 15 minutes, to this mixture is added 5 parts of the 1-(2,4,6-trichlorophenyl)-3- ⁇ a- ⁇ p-[a- (2,4-di-tert-amy1phenoxy)acetamido]-phenyl ⁇ acetamido ⁇ - 5-pyrazolone (U. S. Patent 2,600,788). The reaction mixture is stirred for one-half hour, drowned by stirring in 300 parts of crushed ice containing volumes of concentrated hydrochloric acid. The cream-colored mixture is filtered by suction, the product washed on the funnel with water in order to remove pyridine, and the product air-dried, 6.2 parts being obtained.
  • Coupler 6 is prepared as follows: In a suitable 3-necked flask provided with a stirrer and a thermometer is placed 6.6 parts of m-chlorosulfonylbenzoic acid, followed by SOaH-N prepared by reaction of m-chlorosulfonylbenzoic acid with the appropriate methylene coupler give very useful dye images upon development in the presence of exposed silver halide with a primary aromatic amino silver halide developing agent, apparently by the same mechanism pointed out above; however, the coupling rates of these methylene couplers are markedly lower than those of the pyrazole couplers described above.
  • the coupler compounds of the invention may be incorporated into silver halide emulsions in the desired amount by merely dispersing the couplers in water and adding to the aqueous emulsion.
  • Suitable silver halide emulsions are those well known in the art containing hydrophilic colloid vehicles such as gelatin, partially hydrolyzed cellulose esters, polyvinyl alcohol, etc.
  • the emulsions containing the couplers may be employed for the production of colored photographic images on various supports such as glass, cellulose ester, or non-transparent reflecting medium such as paper or an opaque cellulose ester support.
  • the emulsion containing the coupler compounds of the invention can be coated as one of several difierently sensitized silver halide emulsions on a support for the production of subtractively colored dye images, the emulsion containing the coupler of the invention pro viding the magenta dye image for the picture.
  • a suitable developer composition for use in development of exposed silver halide emulsions containing the coupler compounds of the invention is the following:
  • the coupling rate of the couplers is exceptionally high and can obviously be used to great advantage.
  • the aromatic amino developing agents used with the coupler compounds of our invention include the mono-, di-, and tri-amino aryl compounds and their derivatives formed by substitution in the amino group as Well as in the ring, such as alkyl, phenylene diamines and alkyl toluene diamines. These compounds are usually employed in the salt form, such as the hydrochloride or the sulfate which is more stable than the amines themselves. Suitable compounds are diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine sulfate, and 2 amino 5- diethylaminotoluene hydrochloride.
  • the p-aminophenols and their substitution products may also be used where the amino group is unsubstituted. All of these developing agents have an unsubstituted amino group to which the oxidation products of the developer couple with the colorforming compounds to form dye images.
  • the method of producing a colored photographic image in a silver halide emulsion layer which comprises incorporating into said layer a coupler compound selected from those set forth in claim 1, exposing the emulsion layer to light and developing the emulsion layer with a primary aromatic amino silver halide developing agent, thereby forming a dye in the exposed region of the layer the pyrazolone nucleus of which contains only a carbonyl group in the 5-position.

Description

United States Patent 0 3-ACYLAMIDO-S-(M-SULFOBENZOYLOXY) PYRAZOLE COUPLER COMPOUNDS llmari F. Salminen, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application December 4, 1952, Serial No. 324,153
9 Claims. (Cl. 95-6) No Drawing.
quirements of subtractive color photography, that is, dyes Y which are colored yellow, magenta or blue-green and many have been directed to methods for rendering the couplers non-diffusing in the silver halide emulsion. .A number of other patents pertain to providing coupler compounds with alkali solubilizing groups such as sulfonic acid groups which facilitate the incorporation of the coupler compounds into aqueous silver halide emulsions without destroying the non-diffusing properties of the couplers.
I have discovered that solubilizing groups can be introduced into pyrazolone coupler molecules in an unexpected manner to facilitate incorporation of the couplers into aqueous systems and that the solubilizing groups of such couplers are readily eliminated during color development to yield relatively insoluble dye images and therefore improved image sharpness. Moreover, the coupling activity of the couplers is surprisingly great considering the manner of attachment of the solubilizing group to the pyrazolone coupler molecule. In contrast to this behavior of the coupler compounds of the invcntion, similar coupler compounds containing the reactive methylene group and the same solubilizing group do not possess the increased coupler activity as will be explained more fully hereinafter.
One object of my invention is to provide coupler compounds containing alkali solubilizing groups, which groups are readily removable during color development. Another object is to provide coupler compounds which have increased coupling activity. Other objects will become apparent from consideration of the following description of my invention.
The coupler compounds of the invention are 5-pyrazole derivatives and possess the following structural formula:
N=CNHC OR in which R represents a mononuclear aryl group of the benzene series substituted or not, such as phenyl, trichlorophenyl, etc., and R represents either a mononuclear aralkyl group of the benzene series, a mononuclear aryloxyalkyl group of the benzene series, or a mononuclear arylene group, such as a phenoxypropyl group or a phenoxyacetamidophenyl group. The presence of the rn-sulfobenzoyl substituent in the 5-position of the pyrazole nucleus will be noted. It is believed that the presence of this group in the 5-position together with the acylamido group in the 3-position of the molecule is responsible for the improved coupling rates of the couplers compared to simple S-pyrazolone or 3-acyl amido-S-pyrazolone coupler compounds. The nature of the interactivity of the substituents in the 3- and 5-posi tions of the pyrazole coupler molecule is not understood.
The following examples illustrate the coupler compounds of my invention.
1 =0 NH0 0 s u NHO ocmo-Qmnm 1 c=on S OaH-N I 0 3 1- (2,4,6-trichlorophenyl;-3-{m- [a- 2,4-di-tert-amylphenoxv acetamidolbenzamido -5-m-sulfobenzoxy pyrazole pyridinium salt 1-phenyl-3-(m-[a- (2,4-di-tert-amylphenoxy) acetamido1benzamido}5-m-sulfobenzoxy pyrazole pyridinium salt NHCOCHlO-Q-Csliii SOsH-N l-[p (p tert butylphenoxy)phenyl]- 3-[a-(p-tert-butylph en 0x1; -propi0namido] -5-m-sulfobenzoxy pyrazole pyridinium sa 1-pl1enyl-3-m- ['y- (2,4-di-tert-amylphenoxy hutyramido 1 benzarn1do-5-m-su1f0benzoxy pyrazole pyridimum salt C=CH l-[p (p tert butylphenoxy)pheny1]-3- ['y-(2,4-di-tert-a mylphenoxl pbutyramido]-5-m-sulfobenzoxy pyrazole pyridinrum sa The coupler compounds of the invention are also unique, particularly in regard to their method of preparation. The coupler compounds are prepared by reacting m-chlorosulfonyl benzoic acid with 3-acylamido-5-pyrazolones in the presence of pyridine. Surprisingly, the result is that the carboxyl group of the sulfonyl halide rather than the chlorosulfonyl group reacts with the enolized carbonyl group of the pyrazolone. Little is known of the reactions of m-chlorosulfonyl benzoic acid. However, the unexpected nature of this reaction is attested by the prior knowledge in a similar reaction (Sekera and Marvel, J. A. C. S. 55, 345 (1933)) showing that aromatic sulfonyl halides'form esters with alcohols in the presence of pyridine. Also, Re, Annalen 233, 228, has shown that a similar compound, sulfophthalic acid reacts with ammonia at the sulfo group.
Coupler 1 is prepared as follows: In a suitable 3-necked flask equipped with a thermometer, a coil condenser, a stirrer and stoppered with a calcium chloride tube, are placed volumes of pyridine and while stirring vigorously, 11.53 parts of m-chlorosulfonyl benzoic acid are added. A rise in temperature is noted from 29-52 C. and the solution turns yellow. Stirring is continued for 1 /2 hours and at this time there are added 34.5 parts of 1 (2,4,6-trichlorophenyl) 3 {m [oz-(2,4-di-tert-amy1- phenoxy)acetamidolbenzamido} 5 pyrazolone (U. S. Patent 2,600,788, Example No. 7). The solution is complete within 30 minutes and a change of color to deep purple is evident. Stirring is continued overnight. The viscous resulting solution is poured with stirring upon 600 parts of ice in which 160 volumes of concentrated hydrochloric acid have been added. After one-half hour of stirring, the white product is filtered and washed well with several portions of Water and dried as much as possible upon the filter. The moist material is then dried at C. 41.5 parts of coupler are obtained which represents an 86.5 percent yield of the theoretical quantity of 48 parts.
Coupler 2 is prepared as follows: In a suitable 3- necked flask provided with a stirrer and thermometer is I NHC oomornomog-ctnn l s n N=(J-NHC oom-Qmao oomoQ-oaau C b ll placed 25 volumes of pyridine, to which is added 5 parts of m-chlorosulfonyl-benzoic acid. After 15 minutes, to the resulting mixture is added 5 parts of the pyrazolone, l phenyl 3 {m-[a-(2,4 di-tert-amylphenoxy)acetamido]benzarnido}-5-pyrazolone (prepared as Coupler No. 7 of U. S. Patent 2,600,788 except using aniline in place of 2,4,6-trichloroaniline). The reaction mixture is stirred for one hour at ordinary temperature, added in a thin stream to 300 parts of ice containing 50 volumes of concentrated hydrochloric acid. The solid which precipitates is filtered by suction, washed on the funnel with ice water in order to remove pyridine. The product is air-dried, 7 parts being obtained.
Coupler 3 is prepared as follows: In a suitable flask is dissolved in 2.2 parts 1-[p-(p-tert-butylphenoxy)phenyl]-3-[a (p tert-butylphenoxy)propionamido1-5-pyrazolone by warming with 25 volumes of benzene. To the solution is added 1 part of m-chlorosulfonylbenzoic acid, followed by 1.2 parts of pyridine. The solution becomes turbid and is heated under reflux for three hours. On cooling, the benzene is removed and the residue triturated with petroleum ether to a white solid; it is filtered, washed on the funnel with petroleum ether and dried, 2.3 parts being obtained. The pyrazolone coupler used in this synthesis is described in U. S. Patent 2,369,489, Example Coupler 4 is prepared as follows:
-(2,4-di-tert-amylphenoxy)butyric acid is first prepared as follows: In a suitable vessel provided with stirrer, thermometer, and coil condenser is placed 500 volumes of absolute methyl alcohol and 46 parts of sodium. To the sodium methoxide thus made is added 468 parts of 2,4-di-tcrt-amylphenol and stirred 15 minutes. Butyrolactone (198 parts) is added and the mixture refluxed 15 minutes. The condenser is inverted and the excess methyl alcohol distilled up to Concentrated hydrochloric acid (500 volumes) in 1400 volumes of distilled water is added continuously with stirring, and the acidic mixture poured into a glass tray to cool. The solid is washed and filtered, 650 parts being obtained. The
product is crystallized from 1500 volumes of ligroin, 300 grams of product melting at 98-100 being obtained.
-(2,4-di-tert-amylphenoxy)butyryl chloride is prepared as follows: In a suitable vessel, provided with a condenser, is placed 32 parts of y-(ZA-di-tert-amylphenoxy)butyric acid to which is added 22 volumes of thionyl chloride. The mixture is heated for 3 hours at 40; at the end of this time the excess thionyl chloride is removed under vacuum, the temperature being allowed to reach 55. The crude acid chloride is purified by distillation, B. P. 165166/ 1 mm.
l-phenyl-3-{3-l'y-(2A di tert amylphenoxy)butyramido]-benzamido)}-5-pyrazolone is prepared as follows: In a suitable reaction vessel, provided with a stirrer, thermometer, and dropping funnel, is placed 100 volumes of glacial acetic acid and 5 volumes of water. To this mixture is added 2.83 parts of anhydrous sodium acetate which is allowed to dissolve with stirring. 1-phenyl-3- (3-aminobenzamido)-5-pyrazolone, 8.3 parts, is added, and stirring continued 15 minutes to assure homogeneous distribution. After 15 minutes of stirring, 11.16 parts of -(2,4-di-tert-amylphenoxybutyryl) chloride is added in a slow stream in about 10 minutes with virgorous stirring. The mixture remains fluid for about 10 minutes after addition, and then sets up into a mush. It is allowed to stand 2 hours and then filtered free from the mother liquor, washed with 100 volumes of water to which 5 volumes of glacial acetic acid has been added, filtered and dried. The product is recrystallized from absolute alcohol; M. P. 218-220.
The desired coupler 4 is then finally prepared as follows: In a suitable reaction vessel, provided with a stirrer and thermometer, is placed parts of m-chlorosulfonylbenzoic acid followed by 175 volumes of pyridine. A clear solution results, with a rise in temperature. Within a few minutes a yellow solid separates. When the mixture has cooled to room temperature, 35 parts of the pyrazolone, prepared directly above, is added. Again the temperature rises. The mixture is stirred for approximately one hour at ordinary temperature, then added with stirring to a mixture of 350 volumes of concentrated hydrochloric acid in 1000 parts of ice.
The pale yellow mixture is filtered and the solid washed on the funnel with 2000 volumes of water containing 70 volumes of hydrochloric acid and free ice. The solid is dried at room temperature.
Coupler 5 is prepared as follows: In a suitable 3-necked flask provided with a stirrer and a thermometer is placed 5 parts of m-chlorosulfonylbenzoic acid, followed by 25 volumes of pyridine. After 15 minutes, to this mixture is added 5 parts of the 1-(2,4,6-trichlorophenyl)-3-{a-{p-[a- (2,4-di-tert-amy1phenoxy)acetamido]-phenyl}acetamido}- 5-pyrazolone (U. S. Patent 2,600,788). The reaction mixture is stirred for one-half hour, drowned by stirring in 300 parts of crushed ice containing volumes of concentrated hydrochloric acid. The cream-colored mixture is filtered by suction, the product washed on the funnel with water in order to remove pyridine, and the product air-dried, 6.2 parts being obtained.
Coupler 6 is prepared as follows: In a suitable 3-necked flask provided with a stirrer and a thermometer is placed 6.6 parts of m-chlorosulfonylbenzoic acid, followed by SOaH-N prepared by reaction of m-chlorosulfonylbenzoic acid with the appropriate methylene coupler give very useful dye images upon development in the presence of exposed silver halide with a primary aromatic amino silver halide developing agent, apparently by the same mechanism pointed out above; however, the coupling rates of these methylene couplers are markedly lower than those of the pyrazole couplers described above.
The coupler compounds of the invention may be incorporated into silver halide emulsions in the desired amount by merely dispersing the couplers in water and adding to the aqueous emulsion. Suitable silver halide emulsions are those well known in the art containing hydrophilic colloid vehicles such as gelatin, partially hydrolyzed cellulose esters, polyvinyl alcohol, etc. The emulsions containing the couplers may be employed for the production of colored photographic images on various supports such as glass, cellulose ester, or non-transparent reflecting medium such as paper or an opaque cellulose ester support. The emulsion containing the coupler compounds of the invention can be coated as one of several difierently sensitized silver halide emulsions on a support for the production of subtractively colored dye images, the emulsion containing the coupler of the invention pro viding the magenta dye image for the picture.
A suitable developer composition for use in development of exposed silver halide emulsions containing the coupler compounds of the invention is the following:
Grams 2-amino-5-diethyl-aminotoluene HCl 2 Sodium sulfite 5 Sodium carbonate 30 Water to 1 liter.
tioned, the coupling rate of the couplers is exceptionally high and can obviously be used to great advantage.
The aromatic amino developing agents used with the coupler compounds of our invention include the mono-, di-, and tri-amino aryl compounds and their derivatives formed by substitution in the amino group as Well as in the ring, such as alkyl, phenylene diamines and alkyl toluene diamines. These compounds are usually employed in the salt form, such as the hydrochloride or the sulfate which is more stable than the amines themselves. Suitable compounds are diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine sulfate, and 2 amino 5- diethylaminotoluene hydrochloride. The p-aminophenols and their substitution products may also be used where the amino group is unsubstituted. All of these developing agents have an unsubstituted amino group to which the oxidation products of the developer couple with the colorforming compounds to form dye images.
What I claim is:
1. A photographic silver halide emulsion containing as a color-forming coupler a compound having the general formula wherein R represents a mononuclear aryl group of the benzene series, and R represents a member of the group consisting of mononuclear aralkyl groups of the benzene series, mononuclear aryloxyalkyl groups of the benzene series, and mononuclear arylene groups of the benzene series.
2. A photographic silver halide emulsion containing as a color-forming coupler a compound having the general formula set forth in claim 1 wherein R represents a mononuclear aryl group of the benzene series and R represents a mononuclear arylene group of the benzene series.
3. A photographic silver halide emulsion containing as a color-forming coupler a compound having the general formula set forth in claim 1 wherein R and R each represent a mononuclear arylene group of the benzene series.
4. A photographic silver halide emulsion containing as a color-forming coupler the compound l-(2,4,6-trichloro phenyl) -3 -{moc- 2,4-di tert-amylphenoxy) -acetamido] benzamido}-S-m-sulfobenzoxy pyrazole pyridinium salt.
5. A photographic silver halide emulsion containing as a color-forming coupler the compound 1-phenyl-3-{m-[a- (2,4-di tert amylphenoxy)acetamido]benzamido}-5-m sulfobenzoxy pyrazole pyridinium salt.
6. A photographic silver halide emulsion containing as a color-forming coupler the compound l-lp-(p-tert-butylphenoxy)-phenyl]-3-[a-(p tert butylphenoxy) -propionamidol-S-m-sulfobenzoxy pyrazole pyridinium salt.
7. A photographic silver halide emulsion containing as a color-forming coupler the compound l-phenyl-3-{m-l'y- (2,4-di-tert amylphenoxy)butyramido]benzamido}-5-msulfobenzoxy pyrazole pyridinium salt.
8. A photographic silver halide emulsion containing as a color-forming coupler the compound 1-(2,4,6-trichlorophenyl)-3-{a-{p-[a-(2,4-di tert amylphenoxy)acetamido]phenyl}acetamido}-5-m sulfobenzoxy pyrazole pyridinium salt.
9. The method of producing a colored photographic image in a silver halide emulsion layer which comprises incorporating into said layer a coupler compound selected from those set forth in claim 1, exposing the emulsion layer to light and developing the emulsion layer with a primary aromatic amino silver halide developing agent, thereby forming a dye in the exposed region of the layer the pyrazolone nucleus of which contains only a carbonyl group in the 5-position.
References Cited in the file of this patent UNITED STATES PATENTS 2,369,489 Porter et al Feb. 13, 1945 2,436,130 Weissberger et al Feb. 17, 1948 2,476,986 Martin July 26, 1949 2,476,988 Martin July 26, 1949

Claims (1)

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING AS A COLOR-FORMING COUPLER A COMPOUND HAVING THE GENERAL FORMULA
US324153A 1952-12-04 1952-12-04 3-acylamido-5-(m-sulfobenzoyloxy) pyrazole coupler compounds Expired - Lifetime US2706685A (en)

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US324153A US2706685A (en) 1952-12-04 1952-12-04 3-acylamido-5-(m-sulfobenzoyloxy) pyrazole coupler compounds
FR1098055D FR1098055A (en) 1952-12-04 1953-12-03 New pyrazole compounds which can be used in particular for color photography and process for their preparation
GB33554/53A GB738957A (en) 1952-12-04 1953-12-03 Improvements in pyrazolone compounds and in colour couplers for use in colour photography

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1075431B (en) * 1957-09-04 1960-02-11 General Aniline &. Film Corporation, New York, N. Y. (V. St. A.) Photographic, in particular color photographic recording and copying material
US3271152A (en) * 1962-09-04 1966-09-06 Eastman Kodak Co Light-sensitive elements for color photography and process therefor
US3790388A (en) * 1971-09-13 1974-02-05 Fuji Photo Film Co Ltd Direct positive color photographic materials
US4275148A (en) * 1977-12-09 1981-06-23 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide color photographic materials
US4283472A (en) * 1980-02-26 1981-08-11 Eastman Kodak Company Silver halide elements containing blocked pyrazolone magenta dye-forming couplers
US4310618A (en) * 1980-05-30 1982-01-12 Eastman Kodak Company Silver halide photographic material and process utilizing blocked dye-forming couplers
EP0686873A1 (en) 1994-06-08 1995-12-13 Eastman Kodak Company Color photographic element containing new epoxy scavengers for residual magenta coupler

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2369489A (en) * 1941-09-25 1945-02-13 Eastman Kodak Co Acylated amino pyrazolone couplers
US2436130A (en) * 1944-11-25 1948-02-17 Eastman Kodak Co Acyl substituted reactive methylene color couplers
US2476986A (en) * 1949-07-26 Elmobe louis martin
US2476988A (en) * 1946-07-08 1949-07-26 Du Pont 5-acyloxypyrazole amidoacetals

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2476986A (en) * 1949-07-26 Elmobe louis martin
US2369489A (en) * 1941-09-25 1945-02-13 Eastman Kodak Co Acylated amino pyrazolone couplers
US2436130A (en) * 1944-11-25 1948-02-17 Eastman Kodak Co Acyl substituted reactive methylene color couplers
US2476988A (en) * 1946-07-08 1949-07-26 Du Pont 5-acyloxypyrazole amidoacetals

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1075431B (en) * 1957-09-04 1960-02-11 General Aniline &. Film Corporation, New York, N. Y. (V. St. A.) Photographic, in particular color photographic recording and copying material
US3271152A (en) * 1962-09-04 1966-09-06 Eastman Kodak Co Light-sensitive elements for color photography and process therefor
US3790388A (en) * 1971-09-13 1974-02-05 Fuji Photo Film Co Ltd Direct positive color photographic materials
US4275148A (en) * 1977-12-09 1981-06-23 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide color photographic materials
US4283472A (en) * 1980-02-26 1981-08-11 Eastman Kodak Company Silver halide elements containing blocked pyrazolone magenta dye-forming couplers
US4310618A (en) * 1980-05-30 1982-01-12 Eastman Kodak Company Silver halide photographic material and process utilizing blocked dye-forming couplers
EP0686873A1 (en) 1994-06-08 1995-12-13 Eastman Kodak Company Color photographic element containing new epoxy scavengers for residual magenta coupler

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GB738957A (en) 1955-10-19
FR1098055A (en) 1955-07-18

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