US3822248A - 1-hydroxy-4-(pentafluorophenoxy)-n-(beta-(4-(alpha-(2,4-di-t-amylphenoxy)acetamido)phenyl)ethyl)-2-naphthamide - Google Patents

Abstract

COUPLERS CONTAINING AT LEAST ONE 4-HYDROXY-3-CARBAMYL-1-NAPHTHYL GROUP WHEREIN THE HYDROGEN ATOM OR THE ONE POSITION OF SAID NAPHTHYL GROUP HAS BEEN REPLACED WITH AN ARYLOXY GROUP ARE USED ADVANTAGEOUSLY IN COLOR PHOTOGRAPHY TO FORM CYAN DYE IMAGES. THE IMMEDIATE COUPLERS THAT ARE DIFFUSIBLE ARE USED TO ADVANTAGE IN CYAN COLOR DEVELOPER SOLUTIONS WHILE THE IMMEDIATE COUPLERS THAT ARE NON-DIFFUSIBLE ARE ADVANTAGEOUSLY INCORPORATED IN CYAN DYE-FORMING PHOTOGRAPHIC EMULSION LAYERS.

Description

United States Patent l-HYDROXY 4 (PENTAFLU0R0PHEN0XY)-N- {,8-{4-[a-(2,4 DI-t-AMYLPHENOXY) ACETAMIDO] PHENYL}ETHYL}-2-NAPHTHAMIDE Anthony Loria, Rochester, N. assignor to Eastman Kodak Company, Rochester, N.Y.

No Drawing. Continuation of abandoned application Ser. No. 798,228, Sept. 30, 1968, which is a division of application Ser. No. 483,807, Aug. 30, 1965, now Patent No. 3,476,563. This application Sept. 27, 1971, Ser.

Int. Cl. C07c 103/26 U.S. Cl. 260-207 4 Claims ABSTRACT OF THE DISCLOSURE Couplers containing at least one 4-hydroxy-3-carbamyl-l-naphthyl group wherein the hydrogen atom of the one position of said naphthyl group has been replaced with an aryloxy group are used advantageously in color photography to form cyan dye images. The immediate couplers that are diffusible are used to advantage in cyan color developer solutions while the immediate couplers that are non-difiusible are advantageously incorporated in cyan dye-forming photographic emulsion layers.

This is a continuation of application Ser. No. 798,228, filed September 30, 1968 (now abandoned) which was a division of application Ser. No. 438,807, filed Aug. 30, 1965 (now US. 3,476,563).

This invention relates to color photography and more particularly to new and improved cyan dye-forming coupler compounds for use in image-forming systems and processes utilizing such couplers for the formation of images. In a more specific aspect, my invention relates to two-equivalent coupler compounds for forming cyan dye images in color photography.

The formation of color photographic images by the imagewise coupling of oxidized aromatic primary amino developing agents with color-forming or coupling compounds to form indoaniline, indophenol, and azomethine dyes is well known. In these processes, the subtractive process of color formation is ordinarily used and the image dyes customarily formed are cyan, magenta, and yellow, the colors that are complementary to the primary colors, red, green, and blue, respectively. Usually phenol or naphthol couplers are used to form the cyan dye image; pyrazolone or cyanoacetyl derivative couplers are used to form the magenta dye image; and acylacetamide couplers are used to form the yellow dye image.

In these color photographic systems, the color-forming coupler may be either in the developer solution or incorporated in the light-sensitive photographic emulsion layer so that, during development, it is available in the emulsion layer to react with the color developing agent that is oxidized by silver image development. Diifusible couplers are used in color developer solutions. Nondiffusing couplers are incorporated in photographic emulsion layers.

Most of the couplers which have been used in the various color photographic systems described above are four-equivalent couplers, that is, they require reduction of 4 mols of silver halide for the formation of 1 mol of dye. Certain of the prior art couplers are two-equivalent couplers, i.e., they require reduction of only 2 mols of silver halide for the formation of 1 mol of dye. However, some of the prior art couplers exhibit serious disadvantages such as low reactivity, formation of an un-- acceptably high level of color fog, and other undersirable side reactions.

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It is an object of my invention to provide new and improved two-equivalent couplers capable of forming a dye on coupling with the oxidation product of an aromatic amino developing agent.

It is another object to provide new two-equivalent couplers having a materially reduced tendency to produce unwanted color density in the non-image areas.

It is another object of this invention to provide new two-equivalent couplers with greatly reduced propensity to unwanted side reactions and hence higher dye yield.

It is a further object of this invention to provide new and improved two-equivalent cyan couplers which have greatly increased reactivity, thereby obviating prolonged or forced development.

It is another object of my invention to provide improved color photographic image-forming layers containing my new two-equivalent couplers dispersed in a colloidal filmforming binder.

It is another object of my invention to provide a simple, economical, and reproducible process for preparing my novel couplers in high yield.

It is a further object to provide photographic silver halide-gelatin emulsion layers containing my new conplers for use in color photography.

It is another object of my invention to provide improved photographic cyan dye images by the use of these couplers.

These and other objects will appear from the following description of my invention.

These and other objects are accomplished according to my invention by the preparation and use of my 1- hydroxy-4-aryloxy-2-naphthamide two-equivalent couplers wherein the hydrogen atom of the coupling position (i.e., 4-position) in the naphthyl nucleus has been replaced with an aryloxy radical.

The couplers of my invention include those represented by the formula I:

R0 t wherein R represents a 4-hydroxy-3-carbamyl-l-naphthyl group and R represents an aryl or an arylene (i.e., a divalent organic aromatic radical) group. Although the effectiveness of my couplers as two-equivalent couplers is not dependent on the specific composition of R and R it will be understood that these radicals may contain various substitutent groups and that the character and the degree of substitution may be modified according to such requirements, e.g., spectral absorptivity, reactivity, and solubility, as may be imposed by the photographic system in which the coupler is to be used.

Accordingly, the couplers of my invention may be further represented by the following formula II:

(II) r l CON R (7l=1 or 2) groups, i.e., alkyl, aryl, and heterocyclic as defined above, may contain substituent groups such as halogen, nitro, hydroxyl, carboxyl (such that the coupler contains ballasting groups with at least 12 carbon atoms or equivalent in a non-coupling position) amino, an aryl, a substituted amino (e.g., alkylamino, dialkylamino, anilino, N-alkylanilino, etc.), a carboxyl ester (e.g., carboalkoxy, carboaryloxy, etc.), an amido (e.g., acetamido, butyramido, ethylsulfonamido, N-methylbenzamido, N-propylbenzamido, 4-t-butylbenzamido, etc.), a carbamyl (e.g., carbamyl, N-octadecylcarbamyl, N,N-dihexylcarbamyl, N-methyl-N-phenylcarbamyl, 3-pentadecylphenylcarbamyl, etc.), a sulfamyl (such that the coupler contains ballasting groups with at least 12 carbon atoms or equivalent in a non-coupling position) (e.g., N-propylsulfamyl, N-tolylsulfamyl, etc.), an alkoxy (e.g., ethoxy, octadecoxy, etc.), an aryloxy (e.g., phenoxy, tolyloxy, naphthyloxy, etc.), sulfo, such that the coupler contains ballasting groups with at least 12 carbon atoms or equivalent in a non-complexing position, a substituted sulfonyl (e.g., methylsulfonyl, octadecylsulfonylethoxysulfonyl, decoxysulfonyl, phenylsulfonyl, tolylsulfophenyl, phenoxysulfonyl, etc.), etc. R represents, when n represents the integer 1, an aryl group such as phenyl, naphthyl, pyridyl, quinolyl, etc., and when n represents the integer 2, R represents an arylene group such as 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,5-naphthylene, 2,5-pyridylene, ethylene bis(l,4-phenylene), 4,4'-diphenylene sulfone, etc. These groups, i.e., aryl and arylene, may also contain substituent groups (e.g., halogen, nitro, hydroxyl, carboxyl, amino, substituted amino, carboxyl esters, amido, carbamyl, sulfamyl, alkoxy, aryloxy, sulfo, sulfonyl, etc.) as defined for alkyl, aryl, and heterocyclic in R and R above and phenylazo and substituted phenylazo groups.

My novel couplers are characterized by having an aryloxy group on the coupling position of the coupler which gives them good coupling reactivity and other valuable properties. These couplers are particularly characterized by the low levels of unwanted color fog, high reactivity, and good stability. Excellent coupling reactivity is obtained with couplers of my invention when incorporated in emulsion layers without the use of highboiling coupler solvents. When high-boiling solvents are used to dipserse these couplers, high dye yield and low color fog are attained over a wide range of coupler-tosolvent ratios. When the diffusible couplers of my invention are used in color developing solution, excellent reactivity and good dye yield are achieved.

Included among my novel couplers are the following typical examples which are used to illustrate but not limit my invention.

Coupler 11-Hydroxy-4-(4-methylsulfonylphenoxy) 2- naphthamide Coupler 2l-Hydroxy-4 {4-[a-(3-pentadecylphenoxy) butyramido]phenoxy}-N-octadecyl 3',5'-dicarboxy-2- naphthanilide OH CgH31 (IJOOH CON 4 Coupler 3-l-Hhydroxy 4-(4-nitrophenoxy)-N-[it-(2,4-

di-t-amylphenoxy)butyl]-2-naphthamide coNn om ,o-@-otnu-t Coupler 4-1-Hhydroxy-4-(2,4-dinitrophenoxy)-N-ethyl- Z-naphthamide Coupler 5-1-Hydroxy-4-phenoxy-2' methoxy-Z-naphthanilide Coupler 61-Hydroxy-4-(4-nitrophenoxy)-N-(fi-phenylethyl) -2-naphthamide O ONHCHICH2 CoHs 5 Coupler 16-1-Hydroxy-4-phenoxy N-{p-{4-[2-(2,4-dit-amylphenoxy) 5-(3,5-disulfobenzamido)benzamido]-phenyl}ethyl}-2-naphthamide disodium salt ONHCH ClHQ-NHCO- O-C H SO Na SO Na csHn-t gHu-t Coupler l71-Hydroxy-4-[4-(4 sulfophenylazo)phen oxy]-4-(4-t-butylphenoxy)-2-naphthanilide sodium salt Coupler 18-1-Hydroxy-4-(4-sulfophenoxy)-N-octadecyl- 2-naphthamide sodium salt Coupler 19l-Hydroxy-4-phenoxy-2-naphthomorpholide CHr-CHI Coupler 20--1-Hydroxy-4-(4-nitrophenoxy)-N-cycloheXyI-Z-naphthamide Coupler 21-4,4'-Bis[4-hydroxy-3-(N-ethylcarbamyl)-1- naphthyloxy] diphenylsulfone C ONHCzHs C ONHO H;

Coupler 22l,4-Bis{4-hydroxy-3-[N-(Z-acetamidO- phenyl) carbamyl] -1-naphthyloxy}benzene Coupler 23-1-Hydroxy-4-(4-sulfophenoxy)-N-methyl-2- naphthanilide sodium salt Coupler 24lHydroxy-4-(4acetamidophenoxy)-N-octadecyl-3',5'-dicarboxy-2-naphthanilide (RH T3111 COOH Q OOH l THCOCHs Coupler 25-l-Hydroxy-4-(4-nitrophenoxy)-N-octadecyl- 3,5-disulfo-2-naphthanilide disodium salt Coupler 26-1-Hydroxy-4-phenoxy N (2-benzimidazolyl -2-naphthamide Coupler 27l-Hydroxy-4-(4-nitrophenoxy)-N-methyl-N- ethyl-2-naphthamide Coupler 28-l-Hydroxy-4-phenoxy N,N (dirnethyl)-2- naphthamide The couplers of my invention are distinguished by their high reactivity and the very low density of unwanted color fog. The aryloxy group provides a means of attaching other substituents to my couplers such as, for example, preformed dyes useful in color correction, dye transfer processes and the like. Additional ballasting groups can conveniently by introduced via the aryloxy group; these ballastiug groups are then eliminated during the coupling reaction with oxidized color developer which forms the image dyes.

The dilfusible couplers of my invention, such as Couplers 1, 4, 5, 6, 7, 19, 20, 23, 26, 27, and 28 are used to advantage in color developer solutions used to color develop light-sensitive elements used for color photography which do not contain the color-forming coupler. Any of the well-known primary aromatic amino color-forming silver halide developing agents such as the phenylenediamines, e.g., diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2 amino-S-(N-ethyl-N-laurylamino toluene, N-ethyl-N- (fi-methanesulfonamidoethyl)-3-methyl-4-aminoaniline, 4-[N-ethyl-N-(p hydroxyethyl)amino]aniline, etc., the p-aminophenols and their substitution products where the amino group is unsubstituted may be used in the alkaline developer solution with my couplers. Various other materials may be included in the developer solutions depending upon the particular requirements, for example, an alkali metal sulfite, carbonate, bisulfite, bromide, iodide, etc., and the thickening agents used in viscous developer compositions such as carboxymethyl cellulose, carboxyethyl cellulose, gelatin, etc. The following is a typical developer solution given to illustrate but not limit my invention.

G. 2-Amino-5-diethylaminotoluene HCl 2.0 Sodium sulfite (anhydrous) 2.0 Sodium carbonate monohydrate 20.0 Potassium bromide 1.0 Coupler 2.0

Water to 1000.0 ml.

The other coupler examples used to illustrate my in- 'vention are nondiifusing and are used to advantage in photographic emulsion layers. Couplers, such as 2, 12, 14, 15, 1-6, 17, 18, 24, and 25 illustrate those that are incorporated as Fischer-type couplers. The other nondiffusing couplers, e.g., 3, 8, 9, 10, 11, 13, 21, and 22, are

7 incorporated in emulsion layers by methods such as are described by Mannes et al., U.S. Pat. 2,304,939, issued Dec. 15, 1942, Jelley et a1. U.S. Pat. 2,322,027, issued June 15, 1943, etc., in which high-boiling organic solvents are used to dissolve the coupler, and by methods described in Vittum et al. U.S. Pat. 2,801,170, and Fierke et a1. U.S. Pat. 2,801,171, both issued July 30, 1957, and Julian U.S. Pat. 2,949,360, issued Aug. 16, 1960, in which lowboiling or water-soluble organic solvents are used with or in place of the high-boiling solvent. The use of such coupler dispersions permits thinner emulsion layers. These thinner layers are very desirable because they cause less light scattering, consequently they produce sharper images.

Coupler 17 contains a preformed dye attached to the coupler on the aryloxy group. This dye is eliminated on the coupling of the coupler with an oxidized color developer and diffuses out of the film. This coupler can be used as a yellow-colored coupler for the purpose of correcting for the unwanted blue absorption of the cyan image dyes, i.e., that formed from the coupler itself as well as that formed from other cyan couplers. Generally, such a coupler as this would be used in combination with another image-forming cyan coupler in the same layer.

My couplers are used to advantage in the color development of photographic hydrophilic colloid-silver halide emulsion layers of the developing-out type in the emulsion layer or a contiguous layer. The emulsions may contain silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc., as the light-sensitive material.

Any of the hydrophilic colloids used in photographic elements are used to advantage, including gelatin, colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound, etc.

The emulsions used in the photographic element of my invention can be chemically or optically sensitized.

The couplers of my invention may also be used to advantage in image-forming layers, either alone or with image-forming compounds other than silver halide, such as ZnO, ZnS, CdS, CdSe, NiS, etc., either with or without binders such as gelatin, polyvinyl alcohol, etc.

Usually my emulsions are coated on photographic supports in the form of multilayer color photographic elements wherein at least three difierently sensitized emulsion layers are coated over one another on the support. Usually the support is coated in succession with a redsensitive layer, a green-sensitive layer, and a blue-sensitive layer either with or without a Carey Lea silver yellow filter layer between the blue-sensitive and green-sensitive layers. The three diflFerently color sensitized layers may be arranged in any other order over one another that is desirable; however, the Carey Lea filter layer obviously would not be put over the blue-sensitive layer. Preferably, these light-sensitive layers are arranged on the same side of the support.

My invention is further illustrated by the following typical examples.

EXAMPLE 1 Samples of a single layer gelatin silver bromoiodide coating were exposed (i.e., for -second on a 1B intensity scale sensitometer). These strips were then processed to color positives by the following process; all process temperatures were 68.

8 Developer Formula Benzyl alcohol ml 4 Sodium hexametaphosphate g 0.5 Sodium sulfite desiccated g 2.0 Sodium Hydroxide g 0.16 Coupler* g 2.0 4 Amino 3-methyl-N-ethyl-N-[fi-methane-sulfonamido)ethyl]aniline sesquisulfate hydrate -g 5.0 Sodium carbonate monohydrate g 50.0 Sodium bromide g 0.2 Water liters to 1 pH to 10.75

*The couplers used in the above-mentioned developer formula were Couplers 1, 4, 5, 6, 7, 19, and 20 respectively.

Good cyan dye images were formed in each of the respective strips.

EXAMPLE 2 Single layer gelatin silver bromoiodide coatings were prepared containing Couplers 3, 8, 9, 10, 11, 13, 21, and 22, respectively. Each of these couplers were dispersed in said coatings in the form of a finely-dispersed solution of the coupler in coupler solvent, di-n-butylphthalate. These coatings contained 10 parts of gelatin, 5 parts of silver, 2 parts of coupler, and 1 part of coupler solvent. Samples of the above-mentioned coatings were given second exposure on a 1B intensity scale sensitometer and processed in a conventional manner to color negatives, respectively, using the following developer solution.

G. Sodium sulfite (anhydrous) 2.0 2-Amino-5-diethylaminotoluene HCl 2.0 Sodium carbonate monohydrate 20.0 Potassium bromide 2.0

Water to 1.0 liter.

pH to 10.86

Each of the processed strips contained high quality cyan dye images having good heat and light stability and low fog.

Similarly, other couplers of my invention are used to advantage in color photography as illustrated previously with representative couplers. Further, the couplers of my invention are valuable as cyan image-forming couplers in multilayer photographic color films containing other classes of couplers in the other layers of said film. Such other couplers are, for example, yellow image-forming couplers containing a methylene or substituted methylene group having two carbonyl groups directly attached thereto, and magenta image-forming couplers such as 5- pyrazolones, cyanoacetyl coumarones, etc.

In general, my couplers are the product of the reaction of a 1-hydroxy-4-aryloxy-2-naphthoyl chloride with the appropriately substituted amine.

Alternatively, my couplers may be prepared by reacting 1-hydroxy-4-acetoxy-2-naphthoyl chloride with an amine, converting the resultant 1-hydroxy-4-acetoxy-2- naphthamide to the 1-benzyloxy-4-acetoxy-2-naphthamide, hydrolyzing to the corresponding 4-hydroxy compound, the sodium salt of which is then reacted with the fluorobenzene. This 1 benzyloxy-4-aryloxy-2-naphthamide is then converted to the corresponding 1-hydroxy-4aryloxy- 2-naphthamide by hydrogenolysis of the l-benzyloxy group.

The following preparations will illustrate the various methods which were used to prepare my cyan-forming two-equivalent couplers.

Preparation of Coupler 2, 1-hydroxy-4-{4-[a-(3-pentadecylphenoxy)butyramido]phenoxy} N octadecyl- 3,5-dicarboxy-2-naphthanilide Intermediate I.--1 Hydroxy 4-(4-nitrophenoxy)-2- naphthoic acid: To a solution of 20 g. of 1,4-dihydroxy-2- naphthoic acid in ml. of dimethyl formamide was added 20 g. of aqueous 40% sodium hydroxide solution and 14 g. of 4-nitrofluorobenzene over a period of minutes with stirring under a nitrogen atmosphere. The reaction mixture was stirred for a total of 2 hours, after which time it was poured into dilute hydrochloric acid whereupon a solid separated, was collected, recrystallized twice from methyl alcohol, to yield the product.

Intermediate 2.1 Hydroxy 4-(4-nitrophenoxy)-2- naphthoyl chloride: A mixture of 3.25 g. of Intermediate 1 above in ml. of thionyl chloride was stirred at room temperature for 2 hours, during which time all of the acid dissolved and a yellow solid separated, was collected, and recrystallized from warm anhydrous acetonitrile to yield the product.

Intermediate 2.1 Hydroxy 4 (4-nitrophenoxy) -2- octadecyl-3,5'-dicarbomethoxy-Z-naphthanilide: To a solution of 2.4 g. of Intermediate 2 above in 100 ml. of anhydrous dioxane was added 3.4 g. of N-octadecyl-3,5- dicarbomethoxyaniline and 1 m1. of N,N-dimethylaniline. The clear reaction mixture was held at room temperature overnight, after which time it was poured into 500 ml. of cold water, whereupon an oil separated which solidified on additional water washing. The solid was collected and recrystallized twice from acetonitrile to yield the product.

Intermediate 4.1 Hydroxy 4-(4-aminophenoxy)- N-octadecyl-3',5-dicarbomethoxy-Z-naphthanilide: A solution of 1.6 g. of Intermediate 3 above in 100 ml. of absolute ethyl alcohol was reduced on the Parr hydrogenation apparatus using Raney nickel as the catalyst. After the reduction had been completed and the catalyst removed by filtration, the filtrate was concentrated in vacuo and the solid residue was recrystallized from acetonitrile to yield the product.

Intermediate 5 .-1-Hydroxy 4 {4-[a-(3-pentadecylphenoxy)butyramido]phenoxy} N octadecyl-3,5-dicarbomethoxy-Z-naphthanilide: To a solution of 3.5 g. of Intermediate 4 above and an excess of sodium acetate in 50 ml. of acetic acid was added to a solution of 2 g. of u-(3-pentadecylphenoxy)butyryl chloride in 25 ml. of acetic acid with stirring at room temperature. After stirring the reaction mixture for 1 hour, it was heated to 60 C. and held at room temperature overnight. The mixture was then poured into 500 ml. of cold water whereupon a solid separated, was collected and dried to yield the product.

Coupler 2Named above: To a solution of Intermediate 5 above in 250 ml. of absolute ethyl alcohol was added a solution of 6 g. of sodium hydroxide in 100 ml. of water over a period of 2 minutes with vigorous stirring. The mixture was stirred at 65 C. for 1 /2 hours, after which time it was poured into 1 liter of water contaiinng 25 ml. of concentrated hydrochloric acid. The solid which separated was collected, washed with cold water, dried and recrystallized twice from acetonitrile to yield the product.

Preparation of Coupler 3, 1-hydroxy-4-(4-nitrophenoxy)- N- [8- (2,4-di-t-amylphenoxy) butyl] -2-naphtharnide) To a solution of 17 g. of 6-(2,4di-t-amylphenoxy)- butylamine and 6 ml. of dimethylaniline in 200 ml. of anhydrous dioxane was added 18 g. of 1-hydroxy-4-(4- nitrophenox'y)-2- naphthoyl chloride (Intermediate 2, Coupler 2 above) with stirring. The reaction mixture was stirred overnight at room temperature, after which time it was poured into 1 liter of cold water containing 5 ml. of acetic acid whereupon a solid separated, was collected, washed with cold water, and dried. The solid was recrystallized from a mixture of hexane and benzene to yield the product.

Preparation of Coupler 24, l-hydroxy-4-(4-acetamidophenoxy)-N-octadecyl-3',5'-dicarboxy-Z-naphthanilide Intermediate-l-Hydroxy 4 (4-acetamidophenoxy)- N-octadecyl-3',5-dicarbomethoxy-Z-naphthanilide: To a solution of 9.6 g. of 1-hydroxy-4-(4-aminophenoxy)-N- octadecyl-3,5"-dicarbomethoxy 2 naphthanilide (Intermediate 4, Coupler 2 above) and 1.5 g. of anhydrous sodium acetate in ml. of acetic acid was added 1.1 g. of acetyl chloride with stirring. The reaction mixture was stirred at room temperature for 1 hour, after which time it was poured into 800 ml. of water whereupon a solid separated, was collected, and air dried. This solid was recrystallized from acetonitrile to yield the product.

Coupler 24--Named above: To a solution of 3 g. of the Intermediate above in 50 ml. of ethyl alcohol was added 2 ml. of aqueous 40% sodium hydroxide. An additional 5 ml. of water was added and the solution was stirred for 2 hours. The resultant solution was added to 200 ml. of 5% hydrochloric acid whereupon a solid separated, was collected, washed with water, and dried. This solid was recrystallized twice from acetonitrile to yield the product.

Preparation of Coupler 25, l-hydroxy 4 (4-nitrophenoxy) N octadecyl 3,5 disulfo 2 naphthanilide disodium salt Intermediate--1 Hydroxy 4 (4-nitrophenoxy)-N- octadecyl-3',5-dittiuorosulfonyl 2 naphthanilide: To a solution of 1.3 g. of l-hydroxy-4-(4-nitrophenoxy)-2- naphthoyl chloride (Intermediate 2, Coupler 2 above) and 10 drops of dimethylaniline in 20 ml. of anhydrous dioxane was added 1.4 g. of N-octadecyl-3,5-difluorosulfonylaniline with stirring. This mixture was stirred overnight at room temperature, after which time it was poured into ml. of dilute acetic acid whereupon a solid separated, was collected, and recrystallized twice from acetonitrile to yield the product.

Coupler 25-Named above: The Intermediate above was converted to the sodium salt in a manner similar to that used to prepare Coupler 24 above.

The other couplers of my invention were each prepared in accordance with the procedure used to prepare Coupler 3 using the respective intermediates given in the following table.

TABLE Coupler Acid chloride number intermediate Amine intermediate 1 1-hydroxy-4-(4 Ammonia;

methylsuli'onylphenoxy)-2- naphthoyl chloride.

4 1-l1ydroxy-4-(2,4- Ethylamine.

dinitrophenoxy)-2-naphthoyl chloride.

5 1-hydroxy-4 2methoxyaniline.

phenoxy-Z- naphthoyl chloride.

6 1-hydroxy-4-(4- Phenethylamine.

nitrophenoxy)- 2-nephth0yl chloride.

7 1-hydroxy4-(4- B-(Z-nitrophenyl)-ethylamine. (The ninitrophenoxy)- tro product was catalytically reduced 2-naphthoyl and the two amino groups were acetychloride. lgted iisigg acetic anhydride to yield oup er 8 l-hydroxy-d-(hex- B-(4-nitrophenyl)-ethylamine. (The niefiuorophentro intermediate was then catalyti oxy)-2-nephcally reduced and the resultant amino thoylchlorlde. compound was ecylated with a-(2,4-

di-t-amylphenoxy)acetyl chloride to yield Coupler 8.)

9 l-hydroxy-Ml- Dioctylamine.

naphthyloxy)-2- naphthoyl chloride.

10 1-hydroxy4- 4-(4-t-butylphenoxy)-aniline. (The inacetoxy-2- termediate, 1-hydroxy-4-acetoxy-4- naphthoyl (4-t-butylphenoxy) 2 naphthanilide chloride. was converted to the corresponding l-benzyloxy derivative, hydrolyzed to the corresponding 4-hydroxy derivative, converted to the 4-pyridyloxy derwetive (i.e., using i-fiuoropyridine), and then converted to Coupler 10 by the hydrogenolysis oi the l-benzyloxy group.)

11 Y Y Z-tetredeeyloxyaniline.

chloro-phenoxy)- 2-naphthoyl chloride.

TABLEContinued Coupler Acid chloride number intermediate Amine intermediate 12 1-hydroxy-4-[4- N-octadecyl-3,5-dicarbomethoxyaniline (N-methyl-N- (The ester intermediate was then propylsulhydrolyzed to yield Coupler 12.) iamyl)phenoxy]- 2,2-naphthoyl chloride.

13 1-hydroxy-4-[4-(4- B-nitroamllne. (The nitro intermediate hydroxyphenylwas catalytically reduced and acylsulionyDphenated with a-(3-pentadecylphenoxy)- oxy]-2-naphbutyryl chloride to yield Coupler thoyl chloride.

14 1-hydroxy-4-(4- N-octadccyl-4-sulioaniline sodium salt.

nitro-S-pentadecylphenoxy)- Z-naphthoyl chloride.

15 1-hydroxy-4-(3- N-octadecyl-3,5-dicarbomothoxyanlline.

nitrophenoxy)- (The ester intermediate was hydro- 2-naphthoyl lyzed to yield Coupler 15.) chloride.

16 1-hydroxy-4- -(4-nitrophenyl)-ethylamlne. (The phenoxy-2- nitro intermediate was catalytically naphthoyl reduced and acylated with 2-(2,4-d1 chloride. t-amylphenoxy)--nitrobenzoyl chloride. The second nitro intermediate was also catalytically reduced and acylated with 3,5-dichlorosulionyl benzoyl chloride. The chlorosuhonyl groups were hydrolyzed to the suli'onic acid sodium salts to yield Coupler 16.) l I 17 1-hydroxy-4- 4-(4-t-butylphenoxy)-anihne (The inacetoxy-2- termediate l-hydroxyi-aceto zyl naphthoyl (4-t-butylp enoxy)-2 naphthanihde, chloride. was converted to the corresponding l-benzyloxy derivative, hydrolyzed to the corresponding 4-hydroxy derivative, and converted to the 4-[4- (4-sulfophenylazo)phenoxy] derivative (i.e., using 4-(4-iluorophenyl azo)-benzene sulfonic acid), and then converted to Coupler 17 by the hydrogenolysis oi the l-benzyloxy group.)

18 1-hydroxy-4-(4- Octadecylamine. (The ohlorosulionyl chlorosulionylintermediate was converted to Couphenoxy)-2- pler 12 by alkaline hydrolysis). naphthoyl chloride.

19 1-hydroxy-4- Morphohne.

phenoxy-Z- naphthoyl chloride.

20 1-hydroxy-4-(4- Cyclohexylamine;

nitrophenoxy)- Z-naphthoyl chloride.

21... 4, 4'-bis(1-hy- Ethylamine. droxy-Z-chlorocarbonyl-4- naphthyloxy)- diphenylsulione.

22 1,4-bis(1-hydroxy- 2-nitroanihne. (The mtro intermediate 2-chlorocarwas catalytically reduced and acetybonyl-4-naphlated with acetic anhydnde to yield thyloxy)-ben- Coupler 22.) zone.

23 1-hydroxy-4-(4- N-methyl-aniline. (The intermediate chlorosulfonylcontaining the chlorosulfonyl group phenoxy)-2- was hydrolyzed (i.c., by alkaline naiphthoyl chlohydrolysis) to yield Coupler 23.)

26 l-hydroxyi- 2-eminobonzirm'dazole.

phenoxy-2 naphthoyl chloride.

27 1-hydroxy-4-(4- N-ethylmcthylemine.

nitrophenoxy)- 2-naphthoyl chloride.

28 1-hydroxy-4- Dimethylamine.

phenoxy-2- naphthoyl chloride.

The two-equivalent image-forming couplers of my invention are distinguished from other two-equivalent couplcrs by having an aryloxy group substituted on the coupling position of the coupler molecule. My couplers are characterized by not producing color fog, a problem with certain prior art two-equivalent couplers, and by having very good coupling reactivity. Further, my novel couplers form dye images which exhibit very good heat and light stability when they are incorporated into photographic coatings relative to that exhibited by many of the prior art couplers.

My couplers are dispersed readily in emulsion layers as a coupler solvent solution having a wide range of coupler-to-solvent ratios.

My couplers are not only valuable for the reasons cited, but because photographic emulsion layers color developed with them require only one-half the amount of silver halide required by four-equivalent couplers. Of particular value are certain of my nondifiusing couplers which have high coupling reactivity when dispersed in photographic emulsion layers without any high-boiling solvent. These couplers are coated to advantage in particularly thin layers that produce good sharp images. The couplers of my invention may be used in emulsion layers or color developer solutions either alone or admixed with other couplers, either fouror two-equivalent couplers, competing couplers, and the like.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

I claim:

1. l-Hydroxy-4-(4 acetamidophenoxy) N [cc-(2- acetamidophenyl ethyl] -2-naphth amide.

2. 1 Hydroxy-4- (4 chlorophenoxy)-2-tetradecyloxy- Z-naphthanilide.

3. l-Hydroxy 4 [4-(4-sulfophenylazo)phenoxy]-4'- (4-t-butylphenoxy)-2-naphthanilide sodium salt.

4. '1-Hydroxy-4(pentafluorophenoxy) N 3-{4-[a- (2,4 di t amylphenoxy)acetamido]phenyl}et hyl}-2- naphthamide.

References Cited UNITED STATES PATENTS 3,227,554 1/1966 Barr et a1. 96-55 FOREIGN PATENTS 625,137 3/1963 Belgium 260-559 1,147,843 11/1963 Germany 96-55 HARRY I. MOATZ, Primary Examiner US. Cl. X.R.

260202, 247.7 A, 287 R, 295 K, 305, 309.2, 507 R, 519, 520, 51 8 R, 543 R, 544 M, 556 AR, 559 S, 570.7, 571; PC, 91 R v UNITED STATES PATENTQOFFICEO CERTIFICATE OF CORRECTION Patent 3,822,248 Dated July 2, 1974 Inventor) Anthony Lo 1" 1a It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 9', line 14, "Intermediate 2" should read ---Intermediate 3---;

Column 9, line 14, "-2-" should read N- Signed and sealed this 29th day of October 1974.

(SEAL) Attest:

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting: Officer Commissioner of Patents