US3619189A

US3619189A - Color photographic developing process

Info

Publication number: US3619189A
Application number: US4660A
Authority: US
Inventors: Makoto Yoshida; Momotoshi Tsuda; Isao Shimamura
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1969-01-22
Filing date: 1970-01-21
Publication date: 1971-11-09
Anticipated expiration: 1988-11-09
Also published as: GB1288733A; CA925749A; CH530657A; DE2002378A1; JPS4815873B1

Abstract

WHEREIN R and R'' may be the same or different and each represents an alkyl group having one to three carbon atoms and X represents an alkyl group, an aryl group, or a substituted aryl group.

A color photographic developer and process utilizing same employing particular yellow couplers represented by the formula

Description

United States Patent Inventors Makoto Yoshlda;

Momotoshl Tsuda; lsao Shlmamura, all of Minaml Ashlgara-Machl, Japan Appl. No. 4,660 Filed Jan. 21, 1970 Patented Nov. 9, 1971 Assignee Fuji Photo Film Co., Ltd.

Kanagawa, Japan Priority Jan. 22, 1969 Japan 44/4579 COLOR PHOTOGRAPHIC DEVELOPING PROEESS 12 Claims, 1 Drawing Fig.

Primary Examiner-J. Travis Brown Attorney-Sughruc, Rothwell, Mion, Zinn & Macpeak ABSTRACT: A color photographic developer and process utilizing same employing particular yellow couplers represented by the formula Rb xnsmx I OR wherein R and R may be the same or different and each represents an alkyl group having one to three carbon atoms and X represents an alkyl group, an aryl group, or a substituted aryl group.

PAIENTEDnnv 9 I91:

WAVE LENGTH INVENTORS MAKOTO YOSHIDA MOMOTOSHI TSUDA ISAO SHIMAMURA ATTORNEYS COLOR PHOTOGRAPHIC DEVELOPING PROCESS BACKGROUND OF THE INVENTION 1 Field of the Invention The present invention relates to color photography and, more particularly, to a color photographic developing process using a color developer containing an improved yellow coupler.

2. Description of the Prior Art In color photographic development, it is known to use couplers which form colored images by reaction with the oxidation products of aromatic primary amine developing agents.

These couplers react with the oxidation products of aromatic primary amines to form dyes which are insoluble in water or ordinary processing solutions, whereby. colored images are formed which remain in the photographic emulsion layers. Such couplers may be incorporated in a developing solution or in a photographic emulsion layer prior to exposure. The improved coupler of the present invention is of a type which is incorporated in a developing solution.

Color photographic development of the type wherein couplers are incorporated into the developer is usually conducted by a subtractive color process and the couplers form cyan, magenta, and yellow dyes in the process.

It is necessary, in general, that the coupler useful for color photography form a dye having particular desired spectral absorption characteristics.

Among the couplers to be used for color photography, a yellow coupler is theoretically required which would form a dye which completely absorbs blue light and completely transmits green and red light. However, many yellow couplers which have hitherto been used are not sufficiently effective with regard to these characteristics. Furthermore, the yellow dye or color image is formed by subjecting the blue-sensitive layer, after black and white development, to a reversal blue exposure and then subjecting the layer to a yellow color development, bleaching and fixing. it frequently occurs that the oxidation of developed silver is delayed by the bleaching process, thus leaving reduced silver. Further, the silver is often not completely removed by the fixing process, thus leaving the silver in the yellow (this phenomenon is called weak silver removing property). The occurrence of a weak silver removing property severely degrades the transparency of the yellow image.

An object of the present invention is to provide a color photographic developing process resulting in an ideal yellow image.

Another object of the present invention is to provide a color photographic developing process for forming a yellow dye having excellent spectral absorption characteristics and possessing a good silver removing property.

SUMMARY OF THE INVENTION These objects of the present invention can be achieved by incorporating in a color developer the yellow coupler represented by general formula RO NHSO X wherein R and R, which may be the same of different, each represents an alkyl group having one to three carbon atoms and X represents an alkyl group, an aryl group or a substituted aryl group.

It is well known that benzoylacetanilide is useful as a yellow coupler, but the dye image obtained by using such a yellow coupler is low in silver removing property and is inferior in spectral absorption characteristics.

It is also known that by introducing a substituent having an intramolecular hydrogen bonding function, such as a methoxy group, to the ortho position of the anilide nucleus of the benzoylacetanilide, the color hue of the yellow dye image is improved (cf.; Mees & James; The Theory of the Photographic Process"; 3rd edition, page 385). The compound, benzoylaceto(2-methoxy)anilide is considered to be the best yellow coupler at present but it has the disadvantage that the silver removing property is poor and the yellow image thus formed has reduced transparency. When -NHSO X, wherein X is the groups described above, is introduced to the anilide nucleus of benzoylacetanilide, the silver removing property and the water-solubility of the yellow coupler may be improved, but the color hue of the yellow image formed becomes reddish. Accordingly, for improving the color hue, a methoxy group may be introduced at the ortho position simultaneously. However, even if, for example, benzoylaceto[2-methoxy-4-(4- toluenesulfonamido)]anilide is employed, the yellow image formed is still reddish.

As another means of improving the color hue, the substitution of the benzoyl nucleus of benzoylacetanilide can be considered. Thus, when an alkoxy group is introduced to the ortho position of the benzoyl nucleus of benzoylacetanilide, the absorption maximum (Amax) shifts to a shorter wavelength to provide a desired color hue, but the coupling property of the coupler is reduced and the water solubility of the coupler is severely lowered. Moreover, when an alkoxy group is introduced to the paraposition of the benzoyl nucleus, the coupling property of the coupler may be improved, but the silver removing property is diminished and the water solubility of the coupler is also severely reduced. Furthermore, in the case of introducing a methoxy group at the anilide nucleus, for example, in the case of using 4-ethoxybenzoylaceto-(2- methoxy)anilide, the silver removing property is low and the water solubility of the coupler is poor. Also, 2-methoxybenzoylaceto[4-(4-toluenesulfonamido)]anilide having a -NHS0 X group, wherein X represents the groups described above, at the anilide nucleus and at the same time an alkoxy group at the benzoyl nucleus has the disadvantage that the color hue of the image becomes reddish. Still further, a coupler formed by introducing a chlorine atom to the ortho-position of the anilide nucleus of the latter, i.e., 2-methoxybenzoylaceto[2-chloro-4(4-toluenesulfonamide)lanilide also gives a reddish yellow image.

On the other hand, it has been found that when an alkoxy group is introduced at the ortho-position of the anilide nucleus of benzoylacetanilide, a -NHSO X, wherein X represents the groups described above, is introduced to the 4- or S-position thereof and, simultaneously, an alkoxy group is introduced to the 2- or 4-position of benzoyl group, unexpectedly better results are obtained. That is, the silver removing property is improved, the water solubility of the coupler is improved, the absorption maximum of the dye image is shifted to a shorter wavelength to provide a desirable color hue, and the coupler exhibits excellent coupling properties.

ln the accompanying drawing, there are shown l the spectral absorption curve A of color image (A) formed by the coupling of a typical coupler used in the present invention, 4- ethoyxbenzoylacetol24-(4-toluenesulfonamido)]- anilide, and the oxidation product of a color developer, 4- N ,N-diethylaminoaniline, (2) the spectral absorption curve B of color image (B) formed by the coupling of a control coupler, benzoylacetanilide, and the oxidation product of the aforesaid color developer, and (3) the spectral absorption curve C of color image (C) formed by the coupling of another control coupler, benzoylaceto-(Z-methoxy) anilide and the oxidation product of the aforesaid color developer.

From the results shown in the graph, it will be understood that the color image obtained by using the yellow coupler of the present invention has less undesirable absorptions in the green region and has very excellent absorption characteristics.

Further, it has been confirmed that the coupler of the present invention has preferable silver removing properties.

That is, the silver removing property is shown by the ratio of the silver image density measured by using a red filter to the sum of the densities of dye image and silver image measured by using a blue filter; thus, it is shown by lied dvu ii v l)r Blue density (Db Nurm-ricul value 0,, 0.5 L 2.0 Color Image E 0.l l 0.06 0.04

color images obtained by using the couplers of the present invention From the above, it will be understood that couplers of the present invention are excellent in silver removing properties. It is also clear that the excellent silver removing properties gives a color image having good transparency and is very profitable for the reproduction of color photography.

The reason that the color images obtained from the couplers of the present invention have excellent spectral absorption characteristics and that the coupler provides excellent silver removing properties is believed to be found in the specific chemical structure, that is, the presence of an alkoxy group at the 2- or 4- position of the benzoyl nucleus as well as an alkoxy group at the 2-position of the anilide'nucleus and a sulfonamido group at the 4- or position of the anilide nucleus of the benzoylacetonanilide.

The coupler of the present invention is used not only for natural color photography, but also may be employed in monochromatic or dichromatic photography.

Examples of the yellow couplers which may be employed in the process of the present invention are shown below:

Coupler 1 OCH:

Coupler 2 O C H3 Coupler 3 OCH;

Coupler ti Coupler 7 OCH:

Coupler Juno-Z s-cocmconrw ()Cail:

Coupler 8 O CzHs Coupler 10 1TH S 0 2C H; CEHtlOQC o c1120 OHN l O CH;

Coupler 11 OCH;

Coupler 12 cum-Q-o 0 01120 OHN lTlHS O2CH3 OCH:

('OIl[)l(l' 13 K -vot'niconx -wusocm fi ()(IIJ ()(lli Coupler 14 (roc11:c ou\' NlISOz- Coupler 15 @wocmcoars-@xnsm-Q-cm Cork OCH:

Coupler 16 ITHSOzCi-I;

-cocH-conN- 0011. cm Coupler 17 THS()Z -cocH:r'on.\'-

ocm 0cm Coupler 18 I O C 11; 0 CH3 Coupler 1'.)

O CZH 0 C2115 Coupler 20 OCH,"-

Several illustrative examples of preparing the yellow couplers of the present invention are shownbelow:

PREPARATION l l-a); Preparation of 4-methoxybenzoylaceto( 2-methoxy-4 -nitro)anilide:

Into a l-liter three-necked flash were charged 222 g. of ethyI-4-methoxybenzoyl acetate, l68 g. of 2-methoxy-4- nitroaniline and 250 ml. of xylol. The flask was equipped with a stirrer, a thermometer and a pipe for distilling out ethanol. The mixture was heated to l40-l50 Clin an oil bath with stirring and ethanol byproduct was distilled off. After 1 hour, 85% of the ethanol was distilled away. The reaction was stopped and 500 ml. of methanol was added to the product to precipitate yellow crystals, which were recovered by filtration and washed with 300 ml. of methanol to provide 300 g. of pure crystals of the above compound having a melting point of l83l 85 C. with a yield of 87%.

(l-b): Preparation of 4-methoxybenzoylaceto(2-methoxy-4 -amino)anilide hydrochloride:

In a 2-liter three-necked flash were charged 300 g. of the 4 methoxybenzoylaceto(2-methoxy-4-nitro)anilide prepared by preparation (l-a) and 200 ml. of dimethylformamide. The flask was equipped with a stirrer, a condenser, and a dropping funnel and heated on a water bath to dissolve the aforesaid compound into the solvent. Thereafter, 500 ml. of ethanol and 300 g. of iron powder were added to the solution and, while adding 300 ml. of concentrated hydrochloric acid through the dropping funnel, the reduction was conducted. The reduction product was filtered. the filtrate cooled and after adding 500 ml. of concentrated hydrochloric acid thereto. was further cooled, whereby the above hydrochloride was precipitated. The crystals were recovered by filtration and washed with 300 ml. of 10% hydrochloric acid to provide 230 g. of crystals of the above compound having a decomposition point of 2 l5-2 1 8 C. with a yield of 74%.

' (l-c): Preparation of Yellow compound I. 4-methoxybenzoylaceto(2-methoxy-4-methanesulfonamido)anilide:

In a 500 ml. three-necked flask were charged 35 g. of the amino compound prepared by preparation (l-b) and 300 ml. of pyridine and the mixture was stirred to dissolve the amino compound. Thereafter, 1 L2 g. of methanesulfonylchloride was gradually added to the solution while maintaining the temperature at 4045 C. Thereafter, the system was reacted for l hour at 5060 C. After cooling, the product was added to ice water acidified with hydrochloric acid to form crystals, which were filtered, washed with water, dried and recrystallized from acetonitrile to provide 21 g. of the coupler having a melting point of l9l-l92 C., with a yield of48%.

PREPARATION 2 Preparation of Yellow coupler 2, 4-methoxybenzoylaceto(2-methoxy-4-benzenesulfonamido)anilide:

The same procedure as in preparation (l-c) was followed using 35 g. of the amino compound obtained by preparation (l-b) and 200 ml. of pyridine, and also 18 g. of benzenesulfonyI chloride instead of the methanesulfonyl chloride used in l-c) to provide 23 g. of the yellow coupler having a melting point of 180 C. with a yield of 50%.

PREPARATION 3 Preparation of Yellow coupler 3, 4-methoxybenzoylaceto [2-methoxy-4-(4-toluenesulfonamido)lanilide:

The same procedure as l-c) was followed using 35 g. of the amino compound obtained in (l-b) and 200 ml. of pyridine, and also 23 g. of p-toluenesulfonyl chloride instead of the methanesulfonyl chloride in (l-c) to provide 27 g. of the yellow coupler having a melting point of 205-206 C. with a yield of 58%.

PREPARATION 4 (4-a): Preparation of 4-ethoxybenzoylaceto(2-methoxy-4- nitro)anilide:

The above compound was prepared by repeating the procedure of preparation l-a) using 236 g. of ethyl-4-ethoxybenzoyl acetate instead of the ethyl-4-methoxybenzoyl acetate used in (l-a) and using 168 g. of 2-methoxy-4- nitroaniline and 250 ml. of xylol to provide 304 g. of the above compound having a melting point of 175 C. with a yield of (4-b): Preparation of 4-ethoxybenzoylaceto)2-methoxy-4- amino)anilide hydrochloride:

The same procedure as preparation l-b) was followed with the exception that 304 g. of the 4-ethoxybenzoylaceto(2- methoxy-4-nitro)anilide prepared above was used instead of the 4-methoxybenzoylaceto)2-methoxy-4-nitro)anilide used in preparation l-b) to provide I g. of the above mentioned compound having a decomposition point of 209 C. with a yield of62.5%.

(4-c): Preparation of Yellow coupler 5, 4-ethoxybenzoy|aceto-( 2-methoxy-4-methanesulfonamido )anilide:

The same procedure as preparation (l-c) was followed using 58 g. of the amino compound prepared in (4-b), 200 ml. of pyridine, and 18 g. of methanesulfonyl chloride to provide 37 g. of the above-mentioned yellow coupler having a melting point of 189C. with a yield of57.5%.

PREPARATION 5 Preparation of Yellow coupler 6, 4-ethoxybenzoylaceto(2- methoxy-4benzenesulfonamido)anilide:

The same procedure as preparation l-c) was followed using 36.4 g. of the amino compound prepared (4-b), 200 ml. of pyridine, and 18 g. of benzenesulfonyl chloride to provide 30 g. of the aforesaid coupler having a melting point of 169 C. with a yield of 64%.

PREPARATION 6 Preparation of Yellow coupler 7, 4-ethoxybenzoylacetol2- methoxy-4-(4-toluenesulfonamido)lanilide:

The same procedure as preparation (l-c) was followed using 36.4 g. of the amino compound obtained in (4-b), 200 m1. of pyridine, and 19 g. of p-toluenesulfonyl chloride to provide 23 g. of the coupler melting point of 187 C. with a yield of 48%.

PREPARATION 7 (7-a): Preparation of 4-ethoxybenzoylaceto(2-methoxy-5- nitro)anilide:

The same procedure as preparation (l-a) was followed using 236 g. of ethyl-4-ethoxybenzoyl acetate and 168 g. of 2- methoxy-S-nitroaniline instead of the ethyl-4-methoxybenzoyl acetate and 2-methoxy-4-nitroaniline used in l-a) to provide 304 g. of the aforesaid compound compound having a melting point 205-206 C. with a yield of85%.

(7-b): Preparation of 4-ethoxybenzoylaceto(Z-methoxy-S- amino) anilide hydrochloride:

Into a 3-liter three-necked flask were charged 154 g. of the nitro compound obtained by (7-a) and 600 ml. of dimethyl formamide. After equipping the flask with a stirrer, a condenser, and a dropping funnel, the system was heated on a water bath with stirring to dissolve the nitro compound. After further adding 500 ml. of ethanol, 154 g. of iron powder, and then adding 300 ml. of hydrochloric acid gradually, the resultant mixture was boiled for minutes to effect the reduction. While the system was hot, the excess iron powder was filtered off and the filtrate was mixed with 500 ml. of hydrochloric acid followed by cooling. The white crystals thus formed were recovered by filtration, washed with water acidified with hydrochloric acid and then washed with acetonitrile to provide 100 g. of the above compound having a decomposition point of 202 C. with a yield of 64%.

(7-c): Preparation of Yellow coupler 10, 4-ethoxybenzoylaceto)2-methoxy-5-methanesulfonamido)anilide:

The same procedure as preparation (l-c) was repeated using 55 g. of the amino compound prepared by (7-b), 2g. of methanesulfonyl chloride, and 200 ml. of pyridine to provide 27 g. of the yellow coupler having a melting point of 207 C. with a yield of44.5%.

Preparation 8 Preparation of Yellow coupler l 1, 4-ethoxybenzoylaceto( 2- methoxy-S-benzenesulfonamido)anilide:

The same procedure as preparation (1-c) was followed using 25 g. of the amino compound obtained by (7c), 12 g. of benzenesulfonyl chloride and 150 ml. of pyridine to provide 12 g. of the yellow coupler having a melting point of 191 C. with a yield of46%.

Preparation 9 Preparation of Yellow coupler 12, 4-ethoxybenzoylaceto[2- methoxy-5-(4-toluenesulfonamido)]anilide:

The same procedure as preparation (l-c) was repeated using 55 g. of the amino compound prepared by (7-b), 29 g. of p-toluenesulfonyl chloride and 200 ml. of pyridine to provide g. of the yellow coupler having a melting point of 201-202 C. with a yield of48.5%.

Preparation 10 (10-a): Preparation of 2-methoxybenzoylaceto( 2-methoxy- 4-nitro)anilide:

The procedure of preparation (l-a) was followed with the exception that ethyl-Z-methoxybenzoyl acetate was used instead of the ethyl-4-methoxybenzoyl acetate used in (l-a) to provide 310 g. of the above compound having a melting point of l70-l72C. with a yield of l0-b): Preparation of 2-methoxybenzoylaceto(2-methoxy- 4-amino)anilide hydrochloride:

The same procedure as in preparation (l-b) was applied using 310 g. of the nitro compound obtained by (10-1), 210 ml. of dimethyl-formamide, 550 ml. of ethanol, 310 g. of iron powder and 550 ml. of cone. hydrochloric acid to provide 250 g. of the above compound having a decomposition point of C. with a yield of 79%.

IO-c): Preparation of Yellow coupler l3, Z-methoxybenzoylaceto-(2-methoxy-4-methanesulfonamido)anilide:

The procedure of preparation (l-c) was followed using 35 g. of the amino compound obtained by (IO-b}, 200 ml. of pyridine and l 1.4 g. of methanesulfonylchloride to provide 21 g. of the yellow coupler having a melting point of 172 C. with a yield of54%.

Preparation l 1 Preparation of Yellow coupler l4, Z-methoxybenzoylaceto(2-methoxy-4-benzenesulfonamido)anilide:

The procedure of preparation l-c) was followed using 35 g. of the amino compound obtained by (lO-b), 200 ml. of pyridine, and 18 g. of benzenesulfonylchloride to provide 25 g. of the yellow coupler having a melting point of 181 C. with a yield of55%.

Preparation 12 PREPARATION 13 13-a): Preparation of 2-methoxybenzoylaceto(2-methoyx- 5-nitro)anilide:

The procedure of preparation l-a) was repeated using ethyl-Z-methoxybenzoyl acetate and 2-methoxy-5-nitroaniline instead of the ethyl-4-methoxybenzoyl acetate and 2-methoxy-4-nitroaniline used in (l-a) to provide 237 g. of the above compound having a melting point of 163-l64 C. with a yield of 79%.

(l3-b): Preparation of 2-methylxybenzoylaceto(2-methoxy-5-amino)anilide hydrochloride:

The procedure of preparation (1-b) was applied using 237 g. of the nitro compound obtained by (l3-a), 150 m1. of dimethyl formamide, 400 ml. of ethanol, 237 g. of iron powder and 400 ml. ofconc. hydrochloric acid to provide 212 g. of the above compound having a decomposition point of 191 C. with a yield of 75%.

(13-0): Preparation of Yellow coupler l6, Z-methoxybenzoyl-aceto(2-methoxy-5-methanesulfonamido)anilide:

The procedure of preparation (l-c) was followed using 35 g. of the amino compound prepared in (13-b), 200 ml. of

pyridine, and 11.4 g. of methanesulfonylchloride to provide 28 g. of the yellow coupler having a melting point of C. with a yield of57%.

PREPARATION 14 The invention will be further illustrated by the following ex amples.

used in the example 1. a positive absorption maximum at 442 my. and very good transparency was obtained.

EXAMPLE I EXAMPLE 4 A gelatlno silver iodobromlde emulsion which had not been subjected to color sensitization (a blue-sensitive emulsion for By repeating the procedure of example 1. but using 2- color photographic elements of [he [ype developed in methoxybenzoylaceto(2-methoxy-4-benzenesulfonamtdo )amdevelopers containing couplers) was applied to a cellulose (Yellow F p l4) l ofthe Coupler used exam" acetate film. After subjecting the light-sensitive film to a P a Posnwe Yellow dye Image havmg ubsorpllfm wedge exposure by means f a sa sensimmeler the mum at 428 my and very good transparency was obtained. film was sub'ected to the followin hoto ra hic rocessin s:

1 5 g p P 8 EXAMPLE 5 Black a. white dB\e|UpmCl1l 14C 5 By repeating the procedure of example I, but using 2- fl l5 methoxy-benzoylaceto(Z-methoxy-S-methanesul- $t il: t t: t: :d c ::fien! s CMSI fonamido)anilide (Yellow coupler 16) instead of the coupler wmmashing in example 1, a positive yellow dye image having an absorp- Bleaching 2' tion maximum at 428mg. and very good transparency was ob- Water washing 2' i i Fixing 2' Water washing 2' 20 EXAMPLE 6 The compositions of the processing solutions used above The procedure of example 1 was followed by using a yellow were as follows: color developer having the following composition:

Black 6: White Developer Yellow color developer N-Methyl-p-aminophenol sulfite 20 g. ig g s s i ur fiii mide I. Sodium sulfite 90 g. Sodium sum 5 Potassium iodide (0.1% aq, 50in.) 16 ml. Sodium carbonate monohydrar: 52.5 g. sodium hydroxidc 0% q min.) 28 ml. Potassium bromide 5.0 g. Hexylcne glycol 20 ml Pomssmm '0 4-Eihoxyhcnzoylaceto(2'mclhoxywaer make S- enzcnesulfonamido)anilide Yellow Color Developer (Yellow coupler I I) L5 4-N.N-Diethylaminoiiniline sulfite 3 g. 4-N,N-Diethylaminoaniline sulfitc 3.0 g. pl 5- sodium Sun-"e 5D Water to make 1.000 ml. Potassium bromide 1.0 g. Potassium iodide (01% aq. soln.) 51) ml. S dium sulfate 20.0 g. :Ehoxybcnmymm l2 mflhxy By the procedure above, a positive yellow dye image having 4-(4-toluenesulfonamide)] anilide 1.0 g. 40 an absorption maximum at 442 mg and very good trans- (Yellow Coupler 1 parency was obtained. Sodium hydroxide 2.5 g. Water to make I-000 EXAMPLE 7 Bleaching Solution By repeating the procedure of example 1, but using 4-ethoxy-benzoylaceto(2-methoxy-4-benzenesulfonamido)anilide Poussin", femcyanide I00 (Yellow coupler 6) as the coupler in the color developer, a Potassium bromide 20 3. positive yellow dye image having an absorption maximum at g F is 441 my. and very good transparency was obtained.

orrc cl g. I Water to make 1.000 ml. What Is clalmed Fixing Solution l. A color photographic developer comprising an aromattc primary amino developing agent and a coupler having the for- Sodium thiosulfate 150 g. Sodium sulfitc 10 g. Water to make 1.000 ml. R0 NHS 02X @cocmc 0HN By this procedure, a positive image of yellow dye having an absorption maximum at 438 my and very good transparency was obtained. The spectral absorption curve of the color' wherein R and R may be the same or different and each is an image is shown in the accompanying r ing as curve as alkyl group having one to three carbon atoms and X is aC,-C,, mentioned before. alkyl group, a phenyl group, a methylphenylene group, a dimethyl phenylene group or an ethylphenylene group, EXAMPLE 2 wherein the OR group is in the 2- or 4-position and the NH- By repeating the procedure of example 1, with the excep- 2 P m the or -P tion that 4-ethoxybenzoylaceto(2-methoxy-4-methanesul- 2. The color photographic developer of claim 1 wherein the fonamido)anilide (Yellow coupler 5) was used instead of the coupler has the formula: coupler used in example 1, a positive yellow dye image having an absorption maximum at 441 my and very good trans- O R parency was obtained. l

-C EXAMPLE 3 Q OCHZCOHN NHS 02X By repeating the procedure of example 1, except that 4- methoxybenzoylaceto [2-methoxy-4-toluenesulfonamido)]- anilide (Yellow coupler 3) was used instead of the coupler wherein R, R and X are as set forth in claim 1.

yellow dye image having an wherein R, R and X are as set forth in claim 1.

4. The color photographic developer of claim 1 wherein the coupler has the formula:

ITIHS 02X I cocmcormwherein R, R and X are as set forth in claim I.

5. The color photographic developer of claim 1 wherein the coupler has the formula:

wherein R, R and X are as set forth in claim 1 6. The color photographic developer of claim 1 wherein the coupler is selected from the group consisting of 4-methoxybenzoylaceto-(2-methoxy-4-methanesulfonamido)anilide, 4 methoxy-benzoylaceto-(2-methoxy-4-benzenesulfonamido)anilide, 4-methoxy-benzoylaceto [2-methoxy-4-(4- toluenesulfonamido)lanilide, 4-methoxybenzoylaceto- [2 methoxy-5-( 4-toluenesulfonamido lanilide, 4-ethoxybenzoylaceto(2-methoxy-4-methanesulfonamido)anilide, 4- ethoxybenzoylaceto(2-methoxy-40benzenesulfonamido)anilide, 4-ethoxybenzoylaceto [2-methoxy-4( 4-toluenesulfonamido)]anilide, 4-ethoxybenzoylaceto [2-ethoxy-4-(3,4- xylenesulfonamide)]anilide, 4-ethoxybenzoylaceto [2- propoxy-4- (4-ethylbenzenesulfonamido)lanilide, 4-ethoxybenzoylaceto(2-methoxy-S-methanesulfonamido)anilide, 4- ethoxybenzoylaceto(Z-methoxy-S-benzenesulfonamido)anilide, 4-ethoxybenzoylaceto [2-methoxy-5-(4-toulenesulfonamido)]anilide, 2-methoxybenzoylaceto(2-methoxy-4- methanesulfonamido )anilide, 2-methoxybenzoylaceto( 2- methoxy-4-benzenesulfonamido)anilide, 2-methoxybenzoylaceto [2-methoxy-4-(4-toulenesulfonamido)]anilide, 2-methoxybenzoylaceto(-methoxy-5-methanesulfonamido) anilide, 2-methoxybenzoylaceto( 2-methoxy-5-benzenesulfonamido)anilide, Z-methoxybenzoylaceto [2-methoxy-5-(4- toulenesulfonamido)Ianilide, l-ethoxybenzoylaceto [2-ethoxy-4-(4-toluenesulfonamido)]anilide, and 4-propoxybenzoylaceto(2-methoxy-4-benzenesulfonamido)anilide.

7. A color developing process which comprises developing an exposed silver halide photographic emulsion layer with an aromatic primary amino developing agent in the presence of a coupler having the formula:

R0 NHSOzX wherein R and R may be the same or different and each is an alkyl group having one and three carbon atoms and X is a C C alkyl group, a phenyl group, a methylphenylene group, a dimethyl phenylene group or an ethylphenylene group, wherein the -OR group is in the 2- or 4-position and the NH- SQ X group is in the 4- or 5-position.

8. The color developing process of claim 7 wherein the coupler has the formula:

(')R COCH2COHN-/ NllS 01X wherein R, R and X are as set forth in claim 7.

9. The color developing process of claim 7 wherein the coupler has the formula:

wherein R, R and X are as set forth in claim 7.

10. The color developing process of claim 7 wherein the coupler has the formula:

(I)R IfHSOzX coupler has the formula:

NHS 02X wherein R, R and X are as set forth in claim 7.

12. The color developing process of claim 7 wherein the coupler is selected from the group consisting of 4-methoxybenzoylaceto(2-methoxy-4-methanesulfonamido)anilide, 4-benzoylacet0-(2-methoxy-4-benzenesulfonamido)anilide. 4-methoxybenzoylaceto[2-methoxy-4-(4-toluenesulfonamido) ]anilide, 4-methoxybenzoylaceto- [2-methoxy-5- (4-toluenesulfonamido)lanilide, 4-ethoxybenzoylaceto- (2- methoxy-4-methanesulfonamido)anilide, 4-ethoxybenzolaceto(2-methoxy-4-benzenesulfonamiod)anilide, 4- ethoxybenzoyla-ceto[2-methoxy-4-(4-toluenesulfonamido)1- anilide, 4-ethoxybenzoylaceto[2-ethoxy-4-(3,4-xylenesulfonamido)]anilide, 4-ethoxybenzoylaceto[2-xylenesulfonamido)]-4-(4-ethylbenzenesulfonamidolanilide, 4-ethoxybenzoylaceto (2-methoxy-5-methanesulfonamido)anilide,4- ethoxybenzoylaceto(2-methoxy-5-benzenesulfonamido)anilide, 4-ethoxybenzoylaceto[2-methoxy-5benzenesulfonamido)anilide, 4-ethoxybenzoylaceto[2-methoxy-5-(4- toluenesulfonamido)lanilide, 2-methoxybenzoylaceto(2- methoxy-4-methanesulfonamido)anilicle, 2-methoxybenzoylaceto(2-methoxy-4benzenesulfonamido)anilide, 2- methoxybenzoylacetol2e-methoxy-4-(4-toluenesulfonamido)] anilide, 2-methoxybenzoylaceto(Z-methoxy-S-methanesulfonamido)anilide,2-methoxybenzoylaceto(2-methoxy- 5- 'methanesulfonamido)anilide, 2-methoxybenzoylaceto(2 methoxy-S-benzenesulfonamido)anilide,2-methoxybenzoylaceto[ 2-methoxy-5-( 4-toluenesulfonamido ]anilide, 2-ethoxyben2olylaceto[2-ethoxy-4-( 4-toluenesulfonamido anilide, and 4-propoxybenzoylaceto(2-methoxy-4- benzenesulfonamido)anilide.

Claims

2. The color photographic developer of claim 1 wherein the coupler has the formula:
3. The color photographic developer of claim 1 wherein the coupler has the formula:
4. The color photographic developer of claim 1 wherein the coupler has the formula:
5. The color photographic developer of claim 1 wherein the coupler has the formula:
6. The color photographic developer of claim 1 wherein the coupler is selected from the group consisting of 4-methoxybenzoylaceto-(2-methoxy-4-methanesulfonamido)anilide, 4-methoxy-benzoylaceto-(2-methoxy-4-benzenesulfonamido)anilide, 4-methoxy-benzoylaceto (2-methoxy-4-(4-toluenesulfonamido))anilide, 4-methoxybenzoylaceto- (2 -methoxy-5-(4-toluenesulfonamido))anilide, 4-ethoxybenzoylaceto(2-methoxy-4-methanesulfonamido)anilide, 4-ethoxybenzoylaceto(2-methoxy-40benzenesulfonamido)anilide, 4-ethoxybenzoylaceto (2-methoxy-4(4-toluenesulfonamido))anilide, 4-ethoxybenzoylaceto (2-ethoxy-4-(3,4-xylenesulfonamide))anilide, 4-ethoxybenzoylaceto (2-propoxy-4- (4-ethylbenzenesulfonamido))anilide, 4-ethoxybenzoylaceto(2-methoxy-5-methanesulfonamido)anilide, 4-ethoxybenzoylaceto(2-methoxy-5-benzenesulfonamido)anilide, 4-ethoxybenzoylaceto (2-methoxy-5-(4-toulenesulfonamido))anilide, 2-methoxybenzoylaceto(2-methoxy-4-methanesulfonamido)anilide, 2-methoxybenzoylaceto(2-methoxy-4-benzenesulfonamido)anilide, 2-methoxybenzoylaceto (2-methoxy-4-(4-toulenesulfonamido))anilide, 2-methoxybenzoylaceto(2-methoxy-5-methanesulfonamido) anilide, 2-methoxybenzoylaceto(2-methoxy-5-benzenesulfonamido)anilide, 2-methoxybenzoylaceto (2-methoxy-5-(4-toulenesulfonamido))anilide, 1-ethoxybenzoylaceto (2-ethoxy-4-(4-toluenesulfonamido))anilide, and 4-propoxybenzoylaceto(2-methoxy-4-benzenesulfonamido)anilide.
7. A color developing process which comprises developing an exposed silver halide photographic emulsion layer with an aromatic primary amino developing agent in the presence of a coupler having the formula:
8. The color developing process of claim 7 wherein the coupler has the formula:
9. The color developing process of claim 7 wherein the coupler has the formula:
10. The color developing process of claim 7 wherein the coupler has the formula:
11. The color developing process of claim 7 wherein the coupler has the formula:
12. The color developing process of claim 7 wherein the coupler is selected from the group consisting of 4-methoxybenzoyl-aceto(2-methoxy-4-methanesulfonamido)anilide, 4-benzoylaceto-(2-methoxy-4-benzenesulfonamido)anilide, 4-methoxybenzoylaceto(2-methoxy-4-(4-toluenesulfonamido) )anilide, 4-methoxybenzoylaceto-(2-methoxy-5-(4-toluenesulfonamido))anilide, 4-ethoxybenzoylaceto- (2-methoxy-4-methanesulfonamido)anilide, 4-ethoxybenzolaceto(2-methoxy-4-benzenesulfonamiod)anilide, 4-ethoxybenzoyla-ceto(2-methoxy-4-(4-toluenesulfonamido))-anilide, 4-ethoxybenzoylaceto(2-ethoxy-4-(3,4-xyleNesulfonamido))anilide, 4-ethoxybenzoylaceto(2-xylenesulfonamido))-4-(4 -ethylbenzenesulfonamido)anilide, 4-ethoxybenzoylaceto (2-methoxy-5-methanesulfonamido)anilide,4-ethoxybenzoylaceto(2-methoxy-5 -benzenesulfonamido)anilide, 4-ethoxybenzoylaceto(2-methoxy-5benzenesulfonamido)anilide, 4-ethoxybenzoylaceto(2-methoxy-5-(4-toluenesulfonamido))anilide, 2-methoxybenzoylaceto(2-methoxy-4-methanesulfonamido)anilide, 2-methoxybenzoylaceto(2-methoxy-4benzenesulfonamido)anilide, 2-methoxybenzoylaceto(2-methoxy-4-(4-toluenesulfonamido))anilide, 2-methoxybenzoylaceto(2-methoxy-5-methanesulfonamido)anilide,2 -methoxybenzoylaceto(2-methoxy- 5-methanesulfonamido)anilide, 2-methoxybenzoylaceto(2-methoxy-5-benzenesulfonamido)anilide,2 -methoxybenzoylaceto(2-methoxy-5-(4-toluenesulfonamido))anilide, 2-ethoxybenzolylaceto(2-ethoxy-4-(4-toluenesulfonamido))anilide, and 4-propoxybenzoylaceto(2-methoxy-4-benzenesulfonamido)anilide.