US3583971A - 1-hydroxy-4-(alkoxycarbonylphenylazo) 2-(n-naphthyl)naphthamides - Google Patents

Abstract

WHEREIN R REPRESENTS A SUBSTITUTED OR UNSUBSTITUTED NAPHTHALENE RING RESIDUAL GROUP, SAID GROUP BEING BONDED TO THE AMIDO GROUP AT THE A-POSITION, AND X REPRESENTS AN ARYL GROUP HAVING AT LEAST ONE ALKOXYCARBONYL GROUP.

2-(R-NH-CO-),4-(X-N=N-)-NAPHTH-1-OL

MAGENTA-COLORED CYAN COUPLER HAVING A REMARKABLE AUTO-MASKING ACTION FOR CORRECTING DEFICIENCIES OF REGENERATION OF COLOR PHOTOGRAPHIC MATERIAL, HAVING A HIGH COUPLING ACTIVITY, HAVING THE GENERAL FORMULA;

Description

United States Patent Int. C1. (3091 29/50; G03c 1/40 U.S. Cl. 260-202 8 Claims ABSTRACT OF THE DISCLOSURE Magenta-colored cyan coupler having a remarkable auto-masking action for correcting deficiencies of regeneration of color photographic material, having a high coupling activity, having the general formula;

CONHR I I=NX wherein R represents a substituted or unsubstituted naphthalene ring residual group, said group being bonded to the amido group at the tat-position, and X represents an aryl group having at least one alkoxycarbonyl group.

BACKGROUND OF THE INVENTION 1) Field of the invention The present invention relates to mouoazo color couplers and photographic materials containing the same and is concerned with a cyan coupler having an auto-masking action for correcting deficiencies of color regeneration of color photographic sensitive materials, said cyan coupler being used as a solution in an organic solvent.

(2) Description of the prior art Almost all of the cyan couplers used as color formers for color photography are l-naphthol-Z-carboxylic acid derivatives or aminophenol derivatives. When these conplers are used in photographic emulsions, a long chain alkyl group or a dialkylphenoxy group is introduced into the molecule of the coupler to endow a diffusion-fast property to the coupler in order to prevent the coupler from diffusing out of a layer in which it has beein incorporated.

In U.S. patent specification No. 2,449,966 and 2,455,- 169, there are described couplers having an auto-masking action for correcting deficiencies of color regeneration of color photographic materials.

In U.S. patent specification No. 2,521,908 there are described l-hydroxy-Z-naphthamide colored coupler compounds having the formula:

PII=NR1 in which X is hydrogen or alkyl group, Y is a mononuclear aryl group, or an aralkyl group and R is a mononuclear aryl group. In U.S. patent specification No. 2,706,- 684 there are described 1-hydroxy-2-naphthanilide colored coupler compounds having the above formula in which X is hydrogen, Y is a mononuclear aryl group which is 3,583,971 Patented June 8, 1971 "ice substituted, in a position ortho to the amide group, with either halogen, alkoxy or mononuclear aryloxy groups and R is a mononuclear aryl group.

In U.S. patent specification No. 3,034,892 there are de scribed l-hydroxy-Z-naphthamide compounds having the general formulae;

in which x is 0 or a positive integer from 1 to 4, y is 0 or 1; R is a phenyl group, an alkyl group having from 6 to 15 carbon atoms, an alkyl-substituted phenyl group, or an alkyl substituted phenoxy phenyl group; and R is an alkyl group having from 1-4 carbon atoms.

In order for these couplers to exhibit a sufficient automasking effect, it is necessary that the ratio of green absorption to blue absorption be large and in the course of color development, the coupler must cause rapid coupling with the oxidation product of a p-phenylenediamine series color developer to form a positive cyan image. That is, for the desired purpose, a magenta-colored coupler having a large coupling activity is required. However, although an orangeor orange-red-colored cyan coupler can be easily obtained, the preparation of a magentacolored cyan coupler is difficult.

It is, therefore, an object of the present invention to provide magenta-colored cyan couplers which will make it possible to correct for the color deficiencies in the cyan dye produced upon color development. A further object is to provide magenta-colored cyan couplers which demonstrate large bathochromic shifts that are unexpected in view of the small chemical differences from other couplers. A further object is to provide nonxliifusing magentacolored cyan couplers which can be used in combination with uncolored cyan couplers in photographic silver halide emulsions. A still further object is to provide magenta colored cyan couplers which have a large coupling activity. Other objects will appear from the following description and claims.

SUMMARY OF THE INVENTION The foregoing and other objects are accomplished by means of this invention by using magenta-colored cyan couplers which we have discovered. In these couplers a naphthalene ring is linked to the naphthol nucleus at the 2 position via an amido group, and at least one alkoxycarbonyl group is introduced into the aryl azo residual group at the 4 position.

According to the present invention there is provided a coupler for a color photographic material, having the structural formula:

CONHR wherein R represents a substituted or unsubstituted naphthyl group having up to 16 carbon atoms bonded to the amido group at the a-position and X represents an aryl group having at least one alkoxycarbonyl group.

A known coupler having the above-mentioned general formula but in which group R is a mononuclear aryl group has a considerably longer Wave length absorption maximum. However, the coupler of this invention having the same general formula wherein group R is a substituted or unsubstituted naphthyl group has a longer wave length absorption maximum. Also, the molecular extinction coefiicient of the coupler of this invention, at its absorption maximum, is higher than that of the known coupler. This eifect is particularly remarkable in the coupler wherein group R is bonded to the amido group at the u-position, but in a coupler wherein group R is bonded to the amido group at the B-position, the effect is almost the same as that of the known group, wherein group R is a mononuclear aryl group.

Furthermore, the coupling activity of the coupler of this invention is, unexpectedly, higher than that of the known coupler wherein group R is a mononuclear aryl group. These properties of the coupler are desirable for conducting effective auto-masking to correct color deficiencies.

BRIEF DESCRIPTION OF THE DRAWING FIG. 1 is a graph showing the spectral absorption curves of solutions of a coupler of this invention (II), and

known couplers, (a) and (b); and

FIG. 2 is a graph showing the densities of images obtained using a coupler of this invention.

DETAILED DESCRIPTION OF THE INVENTION As the couplers used in this invention, there are i1- lustrated as follows: In the following formulae, symbol sec indicates secondary.

(I) on I l N U-COOCpHza I l N.-

CaHs coo omcHoiH,

(III) COOCH (')HO H CoHia I i NQoooomonoan CgHs cllgHu See ii I C O O 0 H;

(VII) OH O Husee Q3CONHQNHCOCHN-Q-CaHm-sm The structural formulas of the known control couplers used in the following examples for comparing the coupler of this invention are as follows:

OH OCH:

C ONHCH2CHC4H9 The maximum absorption wave lengths of positive images of photographic light-sensitive color films prepared by using the couplers of this invention or the control couplers are shown in Table 1. Coupler (II) of this invention and known control couplers (a) and (b) were dissolved in tricresyl phosphate respectively and the spectral absorption curves of these solutions are shown in FIG. 1 of the accompanying drawings. As is clear from these results, the coupler of this invention has excellent color hue as compared with those of known couplers.

The examples of the preparation of the couplers of this invention are illustrated below:

EXAMPLE 1 1-hydroxy-4- O- (Z-ethylhexyloxycarbonyl -phenylazo) 2-(N- l-naphthyl) -naphthamide (Formula (H) (l-a): Preparation of l-hydroxy-2-(N-(l-naphthyl))- naphthamide.A mixture of 53 g. of l-hydroxynaphthoic acid phenylester and 29 g. of u-naphthylamine was heated to 160 C., for one hour. The solid product thus obtained was dissolved in acetone by heating and cooled to deposit crystals, which were recovered by filtration and washed with acetone to provide 39 g. of the above-mentioned compound having a melting point of 160-161 C. The yield of the product was 62%.

(1-b): Preparation of 2-ethylhexyl O aminobenzoate.-Ethyl-O-aminobenzoate was ,mixed with 2-ethylhexanol in an amount of 1.5 times the theoretical amount and the mixture was heated to 160 C. with stirring after the addition of butyl titanate as a catalyst to conduct the ester exchanging reaction while removing ethanol formed by distillation. Thereafter, by removing excessive 2-ethylhexanol by distillation under a reduced pressure, the oily objective material was obtained. (1-c): Preparation of l-hydroxy 4 (O)-2-ethylhexyloxycar-bonyl) phenylazo 2 (N-(I-naphthyID-naphthamide.--Into 100 ml. of methanol was dissolved 15 g. of the Z-ethyl-hexyl O aminobenzoate prepared in step (l-b). The solution was cooled to a temperature below 5 C., and subjected to diazotation under stirring by adding 16 ml. of concentrated hydrochloric acid and 30 ml. of water and further 5 g. of sodium nitrite dissolved into ml. of water. Apart from this, g. of the l-hydroxy-2-(N-(1-naphthyl))-naphthamide obtained in step (1a) was dissolved into 400 ml. of pyridine and into the solution was added dropwise the above-prepared solution of the diazonium salt at a temperature below 5 C., under stirring to form a crystal which was collected by filtration and recrystallized from acetone after water washing to provide 19 g. (yield 69%) of the objective material having a melting point of 139-l41 C., and nitrogen analysis value of 7.11% (calculated 7.33%).

EXAMPLE 2 1-hydroxy-4- (O(2-hexyldecyloxycarbonyl) -pheny1azo) 2-(N-( l-naphthyl) )-naphthamide (Formula (11)) The same procedure as in step (1-b) in the aforesaid example was repeated using 2-hexyldecyl alcohol instead of 2-ethylhexanol to provide oily Z-hexyldecyl-O-aminobenzoate. Then, the same procedure as in step (1-c) of the above example was repeated using 2-hexyldecyl-O- aminobenzoate instead of Z-ethylhexyl-O-aminobenzoate to provide the desired material with a yield of 63%. The melting point of the product was 111113 C., and the nitrogen analysis value was 6.08% (calculated 6.14%

EXAMPLE 3 l-hydroxy 4 (O-ethyloxycarbonylphenylazo) 2 (N- (1-(4 (2,5 disecondary-amylphenoxyacetoamido))- naphthyl))-naphthamide (Formula (VI)) (3a): Preparation of l-hydroxy 2-(N-(1-(4-nitro)- naphthyl) )-naphthamide.-A mixture of 38 g. of 4-nitrol-naphthylamine and 53 g. of l-hydroxynaphthoic acid phenylester was added to 500 ml. of xylene and the resulting solution was heated for 3 hours under refluxing. The solution was then cooled by ice and the crystal thus deposited Was collected by filtration to provide 40 g. (yield 55%) of the objective material having a melting point of 240242 C. (decomposed).

(3-b): Preparation of l-hydroxy-2-(N-(1-(4-amino)- naphthyl))-naphthamide.Into 300 ml. of dimethylformamide was dissolved 30 g. of the nitro-compound obtained in step (3-a) and the system was subjected to a catalytic reduction by using as the catalyst Raney nickel in a one liter autoclave. After removing the catalyst by filtration, the filtrate was concentrated and cooled to deposit a crystal, which was collected by filtration and washed with methanol to provide 16 g. (yield 58%) of the objective material having a melting point of 222- 225 C.

(3-c): Preparation of 1-hydroxy-2-(N-(1-(4-(2,4-disecondary amylphenoxyacetoamido) naphthyl) )-naphthamide.-To 200 ml. of acetonitrile was added 15 g. of the amine obtained in step -(3b) and the system was heated under refluxing. Then, a solution of 15 g. of 2,4-disecondary-amylphenoxy acetyl chloride in 50 ml. of acetonitrile was added dropwise into the system. After further adding 10 g. of triethylamine, the system was heated under refluxing for one hour. Then, after removing by distillation about 200 ml. of acetonitrile, the reaction mixture was poured into one liter of ice water to deposit a crystal, which was recovered by filtration and recrystallized with ethanol to provide 18 g. (yield 65%) of the objective material having a melting point of l78-180 C.

(3d): Preparation of 1-hydroxy-4-(O-ethyloxycarbonyl-phenylazo) 2 (N-(l-(4-(2,4-di-secondary-amylphenoxyacetamido)-naphthyl)) naphthamide.A mixture of 50 ml. of water and 10 ml. of concentrated hydrochloric acid was cooled to 5 C., and 4 g. of O-aminobenzoate was added into the mixture with stirring. Thereafter the system was subjected to diazotization by adding dropwise 2 g. of sodium nitrite in 5 ml. of Water. Apart from this, 12 g. of the 1-hydroxy-2-(N-(l-(4-(2,4- di secondary amylphenoxyacetamido)) naphthyl))- naphthamide was dissolved into 300 ml. of pyridine followed by ice-cooling. Into the pyridine solution was added dropwise the above-prepared solution of the diazonium salt with stirring at a temperature lower than 5 C. A red crystal thus precipitated was recovered by filtration, washed with water and recrystallized from ethyl acetate to provide 119 g. (yield 70%) of the objective material having a melting point of l98199 C. and a nitrogen analysis value of 7.03% (calculated 7.20%).

The present invention is further illustrated in the following examples:

EXAMPLE 4 Into 10 parts of tricresyl phosphate was dissolved 1.5 parts of the colored cyan coupler of this invention with stirring at about C., and the solution was mixed with 100 parts of a 10% gelatin solution wihch had been heated to 60 C. and, after the addition of 2 parts of an aqueous 10% solution of sodium alkylbenzene sulfonate, the system was stirred for 5 minutes at about 60 C., by means of a high speed rotary mixer to disperse the solution followed by one-minute stop. By repeating the procedure five times a dispersion of the colored couier was obtained.

On the other hand, the same procedure as above was repeated using 2.9 parts of the cyan coupler having the following structural formula to provide a dispersion of the cyan coupler:

ONE-CroHaa Into 100 parts of a gelatino silver iodobromide emnlsion containing a red-sensitive dye was added parts of each of the above prepared emulsions at 35 C., with stirring and, after further adding a hardening agent and a wetting agent, the resulting emulsion was applied to a film and dried to provide a photographic red-sensitive color film.

The above photographic light-sensitive color film was exposed to red light through an optical Wedge and developed in a developer having the following composition in a usual manner.

Color developer: G. N,N-diethyl-p-aminoaniline sulfate 2.0 Sodium sulfite 2.0

Sodium carbonate (monohydrate) 50.0 Hydroxylamine hydrochloride 1.5 Potassium bromide 1.0 Water to make 1 liter.

Thereafter, thus developed photographic film was bleached and fixed by using the bleaching solution and the fixing solution having the following compositions respectively to remove undeveloped silver halide and the reduced silver formed by the development.

Thus, there were obtained a positive magenta image by the colored coupler, remaining in the film, and a negative cyan image formed by coupling. About the results of measuring the densities of the images obtained by using the coupler I of this invention, the relations of the green filter density D and the blue filter density D of the positive magenta image to the red filter density D are shown in FIG. 2 of the accompanying drawings, from which it will be understood that a good masking effect was obtained by using the colored cyan coupler of this invention.

Then, the maximum absorption wave length of the positive magenta image in each case is shown in the following table.

8 TABLE 1 Colored coupler used: Maximum absorption Formulaswave length, m (a) Control 514 (b) Control 516 519 (II) 520 (III) 520 (IV) 524 (V) 520 (VI) 520 (VII) 521 The results show that in the case of using the colored cyan coupler used in the present invention, a positive image having a deeper color was obtained than the case of using control coupler (a) or (b).

What we claim is:

1. A compound represented by the formula wherein R represents an aromatic group selected from the group consisting of naphthyl and lsHn-Sec said aromatic group being bonded to the amido group at the -position of the naphthyl ring, and X represents a phenyl group having one or two alkoxycarbonyl groups, said alkoxycarbonyl groups having up to sixteen carbon atoms in the alkoxy portion of the group.

2. A compound as claimed in claim 1 which has the formula:

1 ii I C() O C H25 C 00 CHZCHCJHB 4. A compound as claimed in claim 1, which has the 7. A compound as claimed in claim 1 which has the V formula: formula:

01H l I @woomm COOCHzCHCaHfl 5. A compound as claimed in cla m 1 which has the 8. A compound as claimed in claim 1 which has the formula: formula:

OH OH I 1% N \OOOK'JHQCHCAH {a 03H; I 6. A compound as claimed in claim 1 which has the O formula: 2115 OH References Cited l UNITED STATES PATENTS 2,019,914 11/1935 Kracker 260-202 2,706,684 4/1955 Graham et a1 260-202X 2,750,378 6/1956 Fischer 260202 l 2,888,452 5/1959 Schmid et al 260--202X F 3,034,892 5/1962 Gledhill et a1 260202X by 3,113,938 12/1963 Nakaten et a1. 260-202X O00 CHz HC4 1 FLOYD D. I-IIGEL, Primary Examiner 0 H molflcmcooo 2 5 US. Cl. X.R.

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