US3476563A - Photographic silver halide elements containing two equivalent cyan couplers - Google Patents

Description

United States Patent 3,476,563 PHOTOGRAPHIC SILVER HALIDE ELEMENTS CONTAINING TWO EQUIVALENT CYAN COUPLERS Anthony Loria, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New .lersey No Drawing. Filed Aug. 30, 1965, Ser. No. 483,807 Int. Cl. G03c 1/40, 7/34 US. Cl. 96-100 9 Claims ABSTRACT OF THE DISCLOSURE Couplers containing at least one 4-hydroxy-3-carbamyll-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 nondiffusible are advantageously incorporated in cyan dye-forming photographic emulsion layers.

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 orcyanoacetyl 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 couplers 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. Ditfusible 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 fourequivalent couplers, that is, they require reduction of 4 mols of silver halide for the formation of 1 molof 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 unacceptably high level of color fog, and other undesirable side reactions.

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 Patented Nov. 4, 1969 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 film-forming 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 couplers 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 l-hydroxy- 4-ary1oxy-2-naphtharnide 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:

wherein R represents a 4-hydroXy-3carbamyl-l-naphthyl group and R represents an aryl or an arylene (i.e., a divalent organic aromatic radical) group. Although the elfectiveness of my couplers as two-equivalent couplers is not dependent on the specific composititon of R and R it will be understood that these radicals may contain various substituent 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:

wherein n represents an integer of from 1 to 2, R and R represent any combination of hydrogen, an alkyl radical, either straight or branched chain of from 1 to 30 carbon atoms, a monoor bicyclic alkyl radical such as cyclohexyl, terpenyl, e.g., a norbornyl radical, etc., an aryl radical such as phenyl, naphthyl, etc., a heterocyclic radical such as benzimidazolyl, benzothiazolyl, etc., or the non-metallic atoms necessary to complete a heterocyclic ring such as morpholine, pyridine, etc. These 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-coupling 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 (1,4-pheny1ene), 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 high-boiling coupler solvents. When high-boiling solvents are used to disperse these couplers, high dye yield and low color fog are attained over a wide range of coupler-to-solvent ratios. When the difiusible 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 1--1-hydroxy-4-(4 methylsulfonylphenoxy)-2 naphthamide Coupler 2--1-hydroxy-4-{4-[a (3 pentadecylphenoxy) butyramido]-phenoxy}-N-octadecyl-3',5' dicarboxy-Z- naphthanilide H C H37 $003:

CON

OOH

l O i l CaHs NHCOCHO l CONHCH tJH -Q-NHC 0G 4 Coupler 3-1-hydr0Xy-4-(4-nitrophenoxy)-N-[6-(2,4 dit-amylphenoxy butyl] -2-naphthamide I No:

Coupler 41-hydroxy-4-(2,4-dinitrophenoxy)-N-ethyl-2- naphthamide Coupler 51-hydroxy-4-phenoxy-2'-methoxy-2-naphthanilide Coupler 6-1-hydroxy-4-(4-nitrophenoxy)-N-(fi-phenylethyl) -2-nalphthamide O ONHCHzCHaCaHn I NO:

Coupler 7--l-hydroxy 4 (4-acetamidophenoxy)-N-[B- 2-acetamidophenyl)ethyl] -2-naphthamide Coupler 81-hydroxy 4 (pentafluorophenoxy) N {fl- {4-[a-(2,4 di t amylphenoxy)acetamidoJphenyl} ethyl}-2-naphthamide Coupler 9-l-hydroxy-4-(1 naphthyloXy)-N,N-dioctyl- 2-naphthamide Coupler 101-hydroxy-4-(4 pyridyloxy)-4'-(4-t-butylphenoxy)-2-naphthanilide Coupler 11--1-hydroxy 4 (4-chlorophenoxy)-2'-tetradecyloxy-Z-naphthanilide Coupler l2-1-hydroxy 4 [4-(N-methyl-N-propylsulfamy1)phenoxy]-N-octadecyl- 3,5' dicarboxy-Z-naphthanilide Coupler 131-hydroxy 4 [4-(4 hydroxyphenylsulfonyl)phenoxy] 3' [oc-(3-pentadecylphenoxy)butyramido]-2-naphthanilide Coupler 14-1-hydroxy 4 (4 nitro-3-pentadecylphenoxy)-N-octadecyl-4'-sulfo-2-naphthanilide sodium salt Coupler 15-1-hydroxy 4 (3 nitrophenoXy)-N-octadecy-l-3',5'-dicarboxy-2-naphthanilide Coupler 161-hydroxy 4 phenoXy-N-{fl-{4-[2-(2A- di-t-amylphenoxy) 5 (3,5 disulfobenzamido)benzamido] -phenyl}ethyl}-2-naphthamide disodium salt NHC'O SOaNa CsHu-t Coupler 17-1-hydroxy 4 [4-(4-sulfophenylazo)phenoxy]-4' (4-t-butylphenoxy)-2-naphthanilide sodium salt Coupler 18-1-hydroxy 4 (4 sulfophenoxy)-N-octadecyl-2naphthamide sodium salt Coupler 19-1-hydroxy-4-phenoxy-2-naphthomorpholide Coupler 20-1-hydroXy 4 (4-nitrophenoxy)-N-cyclohexyl-2-naphthamide Coupler 21--4,4-bis[4 hydroxy-3-(N-ethylcarbamyl)- l-n aphthvloxy] diphenylsulfone on @goonnoim Coupler 22-1,4-bis{4 hydroxy-3-[N-(2-acetamidophenyl) carbamyl]-1-naphthyloxy}benzene Coupler 231-hydroxy-4 (4 sulfophenoXy)-N-methyl- Z-naphthanilide sodium salt Coupler 241-hydroxy 4 (4 acetamidophenoXy)-N octadecyl-3',5-dicarboxy-2-naphthanilide T811211 COOH OH I GON I (ilOOH I IHCOCHa 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 be introduced via the aryloxy group; these ballasting groups are then eliminated during the coupling reaction with oxidized color developer which forms the image dyes.

The difiusible 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 colorforming silver halide developing agents such as the phenylenediamines, e.g., diethyl p phenylenediamine hydrov chloride, dimethyl-p-phenylenediamine hydrochloride, 2-

amino-S-diethylaminotoluene hydrochloride, Z-amino-S- (N-ethyl-N-laurylamino)toluene, N-ethyl-N-(B-methanesulfonamidoethyl) -3-methyl-4-aminoaniline, 4- [N-ethyl- N 3 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.

2-amino-S-diethylaminotoluene HCl 2.0 g Sodium sulfite (anhydrous) 2.0 g Sodium carbonate monohydrate 20.0 g Potassium bromide 1.0 g Coupler nnnnn M 2.0 g

Water to 1000 ml.

The other coupler examples used to illustrate my invention are nondiifusing and are used to advantage in photographic emulsion layers. Couplers, such as 2, 12, 14, 15, 16, 17, 18, 24, and 25 illustrate those that are incorporated as Fischer-type couplers. The other nondiifusing couplers, e.g., 3, 8, 9, 10, 11, 13, 21, and 22, are incorporated in emulsion layers by methods such as are described by Mannes et al., US. Patent 2,304,939, issued December 15, 1942, Jelley et al. US. Patent 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. US. Patent 2,801,170, and Fierke et al. US. Patent 2,801,171, both issued July 30, 1957, and Julian U.S. Patent 2,949,360, issued Aug. 16, 1960, in which low-boiling 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, silverbromide, silver iodide, silver chlorobromide, silver bromoiodide, silver ehlorobromoiodide, 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 differently 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 differently 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 relatin silver bromo-iodide 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 6 8".

4 amino 3 methyl N ethyl N [6 methanesulfonamido)ethyl] aniline sesquisulfate hydrate g 5.0 Sodium carbonate monohydrate g 50.0 Sodium bromide g 0.2 Water to 1 liter. pH to 10.75.

The couplers used in the above-mentioned developer frmula 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 from 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 3 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 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 S-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-4- aryloxy-Z-naphthamide by hydrogenolysis of the l-benzyloxy group.

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

Preparation of Coupler 2, 1-hydroxy-4-{4-[a-(3-pentadecylphenoxy) butyramido] phenoxy}-N-octadecyl-3,5'- dicarboxy-Z-naphthanilide Intermediate 1--1-hydroxy 4 (4-nitrophenoxy)-2- naphthoic acid: To a solution of 20 g. of 1,4-dihydroxy- Z-naphthoic acid in 150 ml. of dimethyl formamide was added 20 g. of aqueous 40% sodium hydroxide solution and 14 g. of 4-nitrofluorobenzene over a period of 5 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 21-hydroxy 4 (4-nitrophenoxy)-2- naphthoyl chloride: A mixture of 3.25 g. of Intermediate 1 above in 10 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 col lected, and recrystallized from warm anhydrous acetonitrile to yield the product.

Intermediate 31-hydroxy-4-(4-nitrophenoxy)-N-octadecyl-3,5-dicarbomethoxy-2-naphthanilide2 To a solution of 2.4 g. of Intermediate 2 above in ml. of anhydrous dioxane was added 3.4 g. of N-octadecyl-3,5- dicarbomethoxyaniline and 1 ml. 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-2-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-ctadecyl 3',5' disolution 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 100 ml. of acetic acid was added 1.1 g. of acetyl chloride with stirring. The reaction mixture was carbomethoxy-Z-naphthanilidez To a solution of 3.5 g. of stirred at room temperature for 1 hour, after which time Intermediate 4 above and an excess of sodium acetate it was poured into 800 ml. of water whereupon a solid in 50 ml. of acetic acid was added a solution of 2 g. of separated, was collected, and air dried. This solid was re a-(3-pentadecylphenoxy)butyryl chloride in 25 m1. of crystallized from acetonitrile to yield the product. acetic acid with stirring at room temperature. After stir- Coupler 24-Named above: To a solution of 3 g. of the ring the reaction mixture for 1 hour, it was heated to 60 Intermediate above in 50 ml. of ethyl alcohol was added C. and held at room temperature overnight. The mixture 2 ml. of aqueous 40% sodium hydroxide. An additional 5 was then poured into 500 ml. of cold water whereupon ml. of water was added and the solution was stirred for 2 a solid separated, was collected and dried to yield the hours. The resultant solution was added to 200 m1. of 5% rodu t, hydrochloric acid whereupon a solid separated, was col- Coupler 2Named above: To a solution of Intermedilected, washed with water, and dried. This solid was reate 5 above in 250 ml. of absolute ethyl alcohol was added crystallized twice from acetonitrile to yield the product. a solution of 6 g. of sodium hydroxide in 100 ml. of water over a period of 2 minutes with vigorous stirring. The Prepafatlon P Y Y- P y)'- mixture was stirred at 65 C. for 1 /2 hours, after which N-octadecyl-3',5"di5\11f2'11aPhthahilide disodillm Salt time it was poured into 1 liter of water containing ml. of concentrated hydrochloric acid. The solid which sepalntermedl?te lhydmxy 4 'PP Y)- rated was collected, washed with cold water dried, and decyl-3',5'-difluorosulfonyl-Z-naphthanrhde: To a solution recrystallized twice from acetonitrile to yield the product. of of Y' P Y 25 chloride (Intermediate 2, Coupler 2 above) and 10 drops Preparation of Co p y y- P Y of dimethylaniline in 20 ml. of anhydrous dioxane was N[5'(z4'dltamylphenoxy)butyl]'z'naphthamlde) added 1.4 g. of N-octadecyl-3,5-difiuorosulfonylaniline To a solution of 17 g. of 8-(2,4-di-t-amylphenoxy)- With stirring. This mixture was stirred overnight at room b l i d 6 1 of di h l ili i 200 1 f temperature, after which time it was poured into 150 ml. hydrous dioxane was added 18 g. of 1-hydroxy-4-(4-nitr0- of dilute acetic acid whereupon a solid separated, was colphenoxy)-2-naphthoyl chloride (Intermediate 2, Coupler lected, and recrystallized twice from acetonitrile to yield 2 above) with stirring. The reaction mixture was stirred the Product overnight at room temperature, after which time it was Coupler 25-Named above: T e Intermediate above poured into 1 liter of cold water containing 5 ml. of acetic was Converted to the Sodium S in a manner similar to acid whereupon a solid separated, was collected, washed 5 that used to Prepare Coupler 24 with cold water, and dried. The solid was recrystallized The other pl rs of my ention were each prepared f a i t f hexane d benzene t i ld th in accordance with the procedure used to prepare Coud g pler 3 using the respective intermediates given in the fol.-

lowing table. Preparation of Coupler 24, 1-hydroxy-4-(4-acetam1dophenoxy) -N-octadecyl-3,5 -dicarb oxy-2-naphthanilide Intermediate-1 hydroxy 4 (4-acetamidophenoxy)- N-octadecyl-3,5'-dicarbomethoxy-Z-naphthanilide: To 21 TABLE Acid Chloride Intermediate Amine Intermediate Coupler No.:

1 l-hydrosy-4-(i-methylsulionylphenoxy)-2-naphthoyl chloride Ammonia. 4 l-hydroxy-i-(2,4-dinitrophenoxy)2-naphthoyl chloride.-- Ethylamine. 5 l-hydroxy-d-phenoxy-Z-naphthoyl chloride 2-methoxyaniline. 6 l-hydroxy-4-(4-nitrophenoxy)-2-naphthoyl chloride. Phenethylamfne. 7..- do B-(Z-nitrophenyD-ethylamine. 8 1-hydroxy-4-(pentafluorophenoxy)-2-naphthoyl chloride- B-(4-nitropheny1)-ethylamine.

l-hydroxy-4-phenoxy-2-naphthoyl chloride l-hydroxy-4-(l-naphthyloxy)-2-naphthoyl chl0r1de l-hydroxy-d-acetoxy-Z-naphthoyl chloride l-hydroxy-k( i-chlorophenoxy)-2-naphthoyl chloride. 1-hydroxy-4-[4-(N-methyl-N-propylsuliamyl)phenoxy1-2-naphthoyl chloride) 1-hydroxy-4-[4-(i-hydroxyphenylsultonyl)phenoxy1-2-naphthoyl chloride.-. 1-hydroxy-4- (4-nitro-3-pentadecylphenoxy)-2-naphthoyl chloride. l-hydroxyt-(3-nitrophenoxy)-2-naphthoyl chloride 1-hydroxy-4-phenoxy-2-naphthoyl chloride 1-hydroxy-4-acetoxy-Z-naphthoyl chloride 1-hydroxy-4-(4-chlorosulionylphenoxy)-2-naphthoyl chloride l-hydroxy-4-( i-nitrophenoxy)-2-naphthoyl chloride 4,4-b1s(1-hydroxy-2-chlorocarbonyl-i-naphthyloxy)-diphenylsu lione 1,4-bis(1-hydroxy-2-chlorocarbonyl-i-naphthyloxy)-benzene 1hydroxy-4-(4-ch1orosulionylphenoxy)-2-naphthoyl chloride Dioctylamine. 4-(4-t-butylphenoxy)-aniline.

-- 2-tetradecyloxyaniline.

N-o ctadecyl-3,5-dicarbomethoxyaniline. 3-mtroaniline.

N-octadecyl-4-Su1ioaniline sodium salt. N-octadecyl-3,5-dicarbomethoxyaniline. B-(4-nitrophenyl)-ethylemine! 4-(4-t-butylphenoxy)-aniline. Octadecylamine.

Morpholine.

Cyclohexylamine.

Ethylamine.

2-nitroaniline.

...... N-methyl-aniline.

6 l-hydroxy-QphenoxyJ-naphthoyl chloride 2-aminobenzimidazo1e, 27 1-hydroxy-4-(4-n1trophenoxy)-2-naphthoyl chloride N-ethylmethylamine, 28 l-hydroxy-4-phenoxy-2-naphthoyl chloride Dimethylamine.

The nitro product was catalytically reduced and the two amino groups were acetylated using acetic anhydride to yield Coupler 7.

2 The nitro intermediate was then catalytically reduced and the resultant amino compound was acylated with a-(2,4-di-t-amylphenoxy)- acetyl chloride to yield Coupler 8.

3 The intermediate, 1-hydroxy-4-acetoxy-4-(4-t-butylphenoxy)-2rnephthanilide was converted to the corresponding l-benzyloxy derivative, hydrolyzed to the corresponding t-hydroxy derivative, converted to the kpyridyloxy derivative (i.e., using t-tiuoropyridine), and then converted to Coupler 10 by the hydrogenolysis oi the l-benzyloxy group.

4 The ester intermediate was then hydrolyzed to yield Coupler 12.-

t The nitro intermediate was catalytically reduced and aeylated with a-(3-pentadecylphenoxy)-butyryl chloride to yield Coupler 13.

t The ester intermediate was hydrolyzed to yield Coupler 15.

7 The nitro intermediate was catalytically reduced and acylated with 2-(2,4-dit-amylphenoxy)-5-nitrobenzoyl chloride. The second nitro intermediate was also catalytically reduced and acylated with 3,5-di chlorosultonylbenzoyl chloride. The chlorosulionyl groups were hydro lyzed to the sulfonic acid sodium salts to yield Coupler 16.

B The intermediate, 1-hydroxy-4-acetoxy-4-(4-t-butylphenoxy)-2-naphthanilide, was converted to the corresponding l-benzyloxy derivative, hydrolyzed to the corresponding 4'hyd1'oxy derivative, and converted to the 4-[4-( t-sulfophenylazolphenoxy] derivative (i.e., using 4-(4-fluoropheny1azo)-benzene sulioruc acid), and then converted to Coupler 17 by the hydrogenolysis of the i-benzyloxy group.

9 The chlorosulionyl intermediate was converted. to Coupler 12 by alkaline hydrolysis.

The nitro intermediate was catalytically reduced and ecetylated with acetic anhydride to yield Coupler 22.

The intermediate containing the chlorosulfonyll group was hydrolyzed (1.e., by alkaline hydrolysis) to yield Coupler 23.

The two-equivalent image-forming couplers of my invention are distinguished from other two-equivalent couplers 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 couplerto-solvent ratios.

My couplers are not only valuable for the reasons cited, but because photographic emulsion layers coor developed with them require only one-half the amount of siver halide required by four-equivalent couplers. Of particular value are certain of my nondiffusing 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 cou' plers, 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. An image-forming layer containing silver halide and a coupler of the formula:

R go ON K/ wherein n represents an integer of from 1 to 2; R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl radical, an aryl radical, a heterocyclic radical, and, together, the nonmetallic atoms necessary to complete a heterocyclic ring; R represents an aryl group selected from the class consisting of a phenyl group, a naphthyl group, a pyridyl group, a quinolyl group, a phenylene group, a naphthylene group, a pyridylene group and a quinolylene group such that when n represents the integer 1, R represents an aryl group selected from the class consisting of a phenyl group, a naphthyl group, a pyridyl group and a quinolyl group in which a carbon atom in a ring of said aryl group is attached directly to the oxygen atom attached to the 4 carbon atom of the 1-hydroxy-2-naphthamide ring shown inside the brackets of said formula, and and such that when n represents the integer 2, R represents an aryl group selected from the class consisting of a phenylene group, a naphthylene group, a pyridylene group and a quinolylene group in which one carbon atom in a ring of said aryl group is attached directly to the oxygen atom attached to the 4 carbon atom of one of the l-hydroxy-Z-naphthamide rings shown inside the brackets of said formula and in which another carbon atom in a ring of said aryl group is attached directly to the oxygen atom attached to the 4 carbon atom in the other l-hydroXy-Z-naphthamide ring shown inside the brackets of said formula.

2. In a multilayer multicolor element containing silver halide and incorporated color-forming couplers, the 1mprovement wherein at least one such coupler comprises a cyan-dye-forming coupler which is capable of forming a cyan dye on coupling with the oxidation product of an aromatic amino developing agent, said cyan-dye-forming coupler being selected from those having the formula:

wherein R represents a 4-hydroxy-3-carbamyl-1-naphthyl group; n represents an integer of from 1 to 2; and R represents an aryl group selected from the class consisting of a phenyl group, a naphthyl group, a pyridyl group, a quinolyl group, a phenylene group, a naphthy-.

lene group, a pyridylene group and a quinolylene group, such that when n represents the integer l, R represents an aryl group selected from the class consisting of a phenyl group, a naphthyl group, a pyridyl group and a quinolyl group, in which a carbon atom in a ring of said aryl group is attached directly to the oxygen atom in said formula, and such that when n represents the integer 2, R represents an aryl group selected from the class consisting of a phenylene group, a naphthylene group, a pyridylene group and a quinolylene group in which one carbon atom in a ring of said aryl group is attached directly to one of the oxygen atoms of said formula and in which another carbon atom in a ring of said aryl group is attached directly to the other oxygen atom of said formula.

3. In a multilayer multicolor element containing silver halide and incorporated color formers, the improvement wherein at least one such color former comprises a cyan-dye-forming coupler of the formula:

wherein n represents an integer of from 1 to 2; R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl radical, an aryl radical, a heterocyclic radical, and, together, the nonmetallic atoms necessary to complete a heterocyclic ring; R represents an aryl group selected from the class consisting of a phenyl group, a naphthyl group, a pyridyl group, a quinolyl group, a phenylene group, a naphthylene group, a pyridylene group and a quinolylene group such that when n represents the integer 1, R represents an aryl group selected from the class consisting of a phenyl group, a naphthyl group, a pyridyl group and a quinolyl group in which a carbon atom in a ring of said aryl group is attached directly to the oxygen atom attached to the 4 carbon atom of the 1-hydroxy-2-naphthamide ring shown inside the brackets of said formula, and such that when n represents the integer 2, R represents an aryl group selected from the class consisting of a phenylene group, a naphthylene group, a pyridylene group and a quinolylene group in which one carbon atom in a ring of said aryl group is attached directly to the oxygen atom attached to the 4 carbon atom of one of the 1-hydroxy-2-naphthamide rings shown inside the brackets of said formula and in which another carbon atom in a ring of said aryl group is attached directly to the oxygen atom attached to the 4 carbon atom in the other 1-hydroxy-2-naphthamide ring shown inside the brackets of said formula.

4. In an image-forming layer containing silver halide and a cyan-dye-forming coupler that is capable of forming a cyan dye on coupling with the oxidation product of an aromatic amino developing agent, the improvement wherein said coupler is selected from those having the formula:

[BO-hR wherein R represents a 4-hydroxy-3-carbamyl-1-naphthyl group; n represents an integer of from 1 to 2; and R represents an aryl group selected from the class consisting of a phenyl group, a naphthyl group, a pyridyl group, a quinolyl group, a phenylene group, a naphthylene group, a pyridylene group and a quinolylene group, such that when n represents the integer l, R represents an aryl group selected from the class consisting of a phenyl group, a naphthyl group, a pyridyl group and a quinolyl group, in which a carbon atom in a ring of said aryl group is attached directly to the oxygen atom in said formula, and such that when n represents the integer 2, R represents an aryl group selected from the class consisting of a phenylene group, a naphthylene group, a pyridylene group and a quinolylene group in which one carbon atom in a ring of said aryl group is attached directly to one of the oxygen atoms of said formula and in which another carbon atom in a ring of said aryl group is attached directly to the other oxygen atom of said formula.

5. In an image-forming layer containing silver halideand a cyan-dye-forming coupler, the improvement wherein the said coupler comprises a coupler of the formula:

CON

wherein n represents an integer of from 1 to 2; R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl radical, and aryl radical, a heterocyclic radical, and, together, the nonmetallic atoms necessary to complete a heterocyclic ring; R represents an aryl group selected from the class consisting of a phenyl group, a naphthyl group, a pyridyl group, a quinolyl group, a phenylene group, a naphthylene group, a pyridylene group and a quinolylene group such that when n represents the integer l, R represents an aryl group selected from the class consisting of a phenyl group, a naphthyl group, a pyridyl group and a quinolyl group in which a carbon atom in a ring of said aryl group is attached directly to the oxygen atom attached to the 4 carbon atom of the l-hydroxy-Z-naphthamide ring shown inside the brackets of said formula, and such that when n represents the integer 2, R represents an aryl group selected from the class consisting of a phenylene group, a naphthylene group, a pyridylene group and a quinolylene group in which one carbon atom in a ring of said aryl group is attached directly to the oxygen atom attached to the 4 carbon atom of one of the l-hydroxy-Z-naphthamide rings shown inside the brackets of said formula and in which another carbon atom in a ring of said aryl group is attached directly to the oxygen atom attached to the 4 carbon atom in the other 1-hydroxy-2-naphthamide ring shown inside the brackets of said formula.

6. A light-sensitive hydrophilic colloid silver halide emulsion containing 1-hydroxy-4-(l-naphthyloxy)-N,N- dioctyl-Z-naphthamide.

7. A light-sensitive hydrophilic colloid-silver halide emulsion containing 1-hydroxy-4-(pentafluorophenoxy)- N-{p {4 [a-(2,4-di-t-amylphenoxy) acetamido]phenyl} ethyl}-2-naphthamide.

8. A light-sensitive hydrophilic colloid-silver halide emulsion layer containing 1-hydroxy-4-(4-nitrophenoxy)- N- [6-2,4-di-t-amylphenoxy butyl] -2-naphthamide.

9. A light-sensitive hydrophilic colloid-silver halide emulsion containing 1-hydr0xy-4-(4-chlorophenoxy)-2'- tetradecyloxy-Z-naphthanilide.

References Cited UNITED STATES PATENTS 3,227,551 1/1966 Barr et a1. 96-100 J. TRAVIS BROWN, Primary Examiner US. Cl. X.R. 96-55, 74