US2728658A - Benzoyl acetanilide couplers for color photography - Google Patents

Description

United States PatentO BENZOYL ACETANILIDE COUPLERS FOR COLOR PHUTOGRAPHY Fred C. McCrossen, Paul W. Vittum, and Arnold Weissberger, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y?., a corporation of New Jersey No Drawing. Application June 26, 1952, Serial No. 295,806

7 Claims. (Cl. 95-6) This invention relates to photographic emulsions containing coupler compounds for color photography and processes of color photography utilizing coupler compounds for the formation of photographic images. In

particular, our invention relates to couplercompounds for forming yellow dye images in color photography.

The formation of colored photographic images by coupling the development product of aromatic amino developing agents with color-forming or coupling compounds is well known. In these processes the subtractive ously known couplers in at least one important respect,

that is, the methylene group of the couplers is substituted with a chlorine atom with the result that the number of mols of silver halide required for the production of one mol of dye from the coupler is reduced from A to 2. The apparent advantage is that such couplers require less silver halide to produce a given amount of dye.

It has been found, however, that this advantage is often outweighted by the serious difliculty that these chlorinated couplers give rise to higher stain, that is, larger amounts of dye are formed in the unexposed area of the color developed image. This stain probably arises from one of two causes: (a) the coupler reacts directly with the unoxidized developer to form leuco dye which is later oxidized to the dye, or (b) the coupler, which contains an active chlorine atom, oxidizes the developer which then reacts withmore of the coupler in the normal way to produce dye stain. Whatever the mechanism, the formation of excessive dye stain has been a serious problem Whenever attempts have been made to realize the advantages of the chlorine-containing couplers.

When it is desired to utilize couplers, of the benzoyl acetanilide type, it has been found advisable to employ the o-alkoxy-benzoyl acetanilide couplers as described in the Weissberger et al. U. S. Patent 2,407,210 granted September 3, 1946, in order to obtain yellow dye images of color most suitable for use with the best cyan and magenta dyes of the subtractive color processes of color photography, and which couplers have less elfect upon the stability of the yellow dye images than do the unsubstituted benzoyl acetanilides. However, this o-alkoxy substitution appears to cut down the coupling ability of the coupler and to decrease the tinctorial power of the dye.

We have discovered that if we employ benzoyl acetanilide couplers in which the carbon atom of the active methylene group is substituted by a chlorine atom and at 2,728,658 1C6 rimmed Dec. 27, 1955 the same time the benzoyl group contains an o-alkoxy substituent, stain is reduced apparently by virtue of the presence of the o-alkoxy substituent, and the coupling ability is increased apparently by the presence of the chlorine substituent on the active methylene group. The two substituents thus compensate for the deleterious effects of each other. A particular advantage of our couplers compared to those of the Weissberger et al. patent above resides in the fact that it is considerably easier and accordingly less costly to produce the ,o-alkoxy and chlorine-substituted compounds than it is to produce the o-alkoxy and o-chloro or dichloro derivatives water.

of the patent. Furthermore, it was not known previous to our invention that the u-chlorine substituent would be satisfactory in itself to improve the coupling ability of the o-alkoxy ben'zoyl acetanilide couplers.

The coupler compounds of our invention have the following general formula: 0

I I OR:

'where R represents a mononuclear aryl group substituted EXAMPLE 1 4 (u-2-meth0xybenz0yl u chloroacetamido)-3"-(4'- tert. amylphenoxy) benzanilide I Q0 OZHQQNHONHG 0- o on. o

CrHu-t.

o-Methoxybenzoylacet-4-nitroanilide is prepared as follows:

In a 3-l. three-necked flask fitted with a stopper, stirrer, and a steam-jacketed column terminating in a partial condensing still heat containing alcohol (Org. Syn. 20, 27) which is connected to a water-cooled condenser set for distillation, are placed 222 g. (1.0 mole) of ethyl o-methoxybenzoyl acetate and 800 cc. of dry xylene. 2 g. of anhydrous sodium acetate are added and the mixture is heated to a boil. Heating is discontinued while one-half of 138 g. (1.0 mole) of p-nitroaniline is added. The flask is stoppered again and the mixture refluxed for 1 hour, a vapor temperature of 80-90 being maintained. After 30 min, the remaining half of the amine is added and reflux is continued for an additional 2.5 hours.

About 200*300 cc. of Xylene should be collected to ensure a complete reaction. The xylene solution is then chilled to 5, and the product is filtered, washed well with 500 cc. of pet. ether, and dried. The yield is 160-200 g. (51- 64%), M. P. -150. The crude material is recrystallized from 15 parts of ethyl alcohol in an 80-87% recovery of yellow-tan crystals which melt at 153-155". o-Methoxybenzoylacet-4-aminoanilide is prepared as follows:

In a 3-l. three-necked flask equipped with a stirrer, stopper, and reflux condenser is placed 62.8 g. (0.2 mole) of o-methoxybenzoylacet-4-nitroanilide, 300 ml. of ethyl alcohol, 300 ml. of glacial acetic acid, and 300 ml. of The reaction mixture is brought to a boil while stirring, and boiled for fiveminutes, heating is discontinned, and 63 g. of Plast iron powder is added. When the initial reaction subsides, the reaction mixture is refluxed for an additional ten minutes, filtered, and diluted with a solution of 300 ml. of cone. hydrochloric acid and 1 l. of water. The pale yellow solution is chilled to and the precipitate filtered, washed well with 1 l. of cold 3% hydrochloric acid, and dried. 57-582 g. (89-91%) of a pale yellow hydrochloride is obtained. This is mixed intimately with an equal weight of anhydrous sodium acetate and poured with vigorous stirring into 1 l. of ethyl alcohol. (Crystals can be obtained at this point M. P. 103-105 65% yield). After stirring minutes, the reaction mixture is diluted with 1 l. of water, stirred an additional five minutes, and chilled to 5. The precipitate is filtered, washed with 1 l. of cold 50% alcohol, and dried. The yield is 47 g. (83%) of tan crystals which melt at 90-92. A 90% recovery of material melting at 100-102 can be obtained by dissolving the material in 10 parts of ethyl alcohol and diluting with 5 parts of water.

In an alternate procedure o-methoxybenzoylacet-4- nitroanilide is reduced with hydrogen overRaney nickel. Crystallization from alcohol yields product sintering at 98 and melting 102-106 C. Recrystallization gives the amino compound melting 102l04 C.

4 (2 methoxybenzoylacetamido)-3"-(4-tert. amylphenoxy) benzanilide is prepared as follows:

In a 500 ml. three-necked flask equipped with a stirrer and stoppers, is placed 28.4 g. (0.1 mole) of o-methoxybenzoylacet-4-aminoanilide and 250 ml. of 5% sodium acetate-acetic acid solution. To the well-stirred suspension 30.3 g. (0.1 mole) of m-(p-tert. amylphenoxy) benzoyl chloride is added all at once. The suspension clears and the product begins to separate almost immediately. The mixture is stirred until stirring becomes impossible (ca. 1 hour) and then allowed to sit for an additional hour. The precipitate is filtered, washed with 500 ml. of 50% acetic acid, followed by 500 ml. of water, and dried. The yield is 50.5-52 g. (92-95%) of light yellow powder which melts at 143-145". Recrystallization from methanol and dioxane is assumed to yield polymorphs M. P. 147-149 C. and 163-165 C. respectively.

The desired product I was prepared as follows:

In a 1-1. three-necked flask equipped with a stirrer and dropping funnel, is placed 27.5 g. (0.05 mole) of 4-(2- methoxybenzoylacetamido)-3-(4 tert. amylphenoxy) benzanilideand 500 ml. of dry chloroform. 4.05 ml. (0.05 mole) of sulfuryl chloride is added rapidly with stirring and the reaction mixture is stirred until it sets to a thick paste. The reaction mixture is then heated until solution is complete, filtered, and allowed to cool slowly until crystallization is almost complete. It is then cooled to 5, filtered, washed with petroleum ether, and dried. The yield is 21.3-24.5 g. (73-80%) of a White powder which melts 163-165 EXAMPLE II 4-(a-Z'-methoxybenzoyl-a-chloroacetamido -2 ,4"-diterL-amylph enoxyacetanilide II Qooenoomr 0H3 C1 (nun-z.

4 (2 methoxybenzoylacetarnido)-2",4"-di-tert. amylphenoxyacetanilide is prepared as follows:

In a 1-liter flask equipped with a stirrer is placed 250 ml. of a 5% solution of anhydrous sodium acetate in glacial acetic acid and 28.4 g. (0.1 mole) of 4-(2-methoxybenzoylacetamido)-aniline. The slurry is stirred for ten minutes, and then 31.1 grams (0.1 mole) of (the acid chloride) 2,4-di-t. amylphenoxyacetyl chloride is added all at once. The reaction becomes clear and, after stirring ten minutes, sets to a heavy slurry. When stirring becomes impossible (after about five to ten minutes), the sludge is filtered, washed well with water, and dried. The yield of crude light yellow (or white if colorless acid chloride is used) product, M. P. 178-180", is 51 g., which is 91% of the theoretical 55.8 g. This is recrystallized from 70 parts of methyl alcohol to yield 33 g. (59%) of material which melts 188-190.

In an alternate procedure 2,4-di-t. amylphenoxy acetyl chloride is reacted with p-phenylene diamine and the product treated as follows:

A solution of 17 g. (0.0445 mole) of the product 4-amino-u-(2,4'-di-tert.-amylphenoxy)acetanilide in 200 cc. of histological xylene in a 500 cc. flask fitted with a steam-jacketed still head was heated to boiling. Then 9.9 g. (0.0445 mole) of ethyl o-methoxybenzoylacetatewas added in one portion. Refluxing was continued for one hour while 2.5 cc. of ethanol was collected. The xylene solution was filtered and chilled. The product was collected and washed with cc. of petroleum ether. The yield of white crystals, M. P. 190-192", was 18 g. (74%).

The desired product II is prepared as follows:

In a 1-liter flask equipped with stirrer is placed 37.5 g. (0.0672 mole) of 4- (2'- methoxybenzoylacetamido)- 2",4"-di-tert.-amylphenoxyacetanilide and 250 ml. of dry chloroform. The mixture is stirred ten minutes and then 5.45 ml. (0.0672 mole) of sulfuryl chloride is added all at once. The temperature rises from 23-30" and complete solution is obtained immediately. The reaction mixture is stirred two hours, then 500 ml. of dry ether is added with stirring and chilling. At 0-5 the product is filtered, washed with ether, and dried. 35 g. (89%) of yellow product is obtained which melts at -147. Upon crystallization from 30 parts of methyl alcohol, 28 g. (70%) of oft-white powder is obtained which melts at 153155. Recrystallization again from 15 parts of 3A alcohol produces 22 g. (55%), M. P. 154-15 6.

EXAMPLE III ot-o-Methoxybenzoyl-a-chloro-4- a (2,4-di-tert.-amylph n0xy)-n-butyramido1 acetanilide III Cl OCH; l

CxsHu t.

lr,H1 i..

a+(2,4di-tert. Amy1phenoxy)-n-butyryl chloride is prepared as follows:

In a 1-liter three-necked flask equipped with a stirrer, thermometer, and reflux condenser are placed 234 g. (1.0 mole) of diamylphenol, 40 g. (1.0 mole) of sodium hydroxide (pellets) in 100 ml. of water and 83 g. (0.5 mole) of a-brornobutyric acid. After stirring at reflux for 1.5 hours, the reaction mixture is diluted with 350 ml. of benzene and 500 ml. of water. The mixture is acidified with 110 ml. of concentrated hydrochloric acid and the benzene layer is washed with 2 x 500 ml. of water. The benzene is removed in vacuo and the syrupy residue is distilled. About 155 g. of diamylphenol (B. P. 106/ 1 mm.) and 25 g. of product (B. P. 152-158/1 mm.) are obtained.

The acid (25 g.) is refluxed one hour in five parts of thionyl chloride. The excess thionyl chloride is removed in vacuo and when the viscous residue reaches constant weight the acid chloride is ready for use. The yield is ca. 25% based on diamylphenol not recovered.

a-o-Methoxybenzoyl-4-l a (2,4-di-tert.-amylphenoxy) n-butyramidolacetanilide is prepared as follows:

In a 50 ml. three-necked flask equipped with a stirrer is placed 2.84 g. (0.01 mole) of o-methoxybenzoylacet-4- aminoanilide prepared above and 1.0 g. (0.01+ mole) of sodiumacetate in 25 ml. of glacial acetic acid. With rapidstirring, 3.4 g. (0.01 mole) of a-(2,4-di-tert.-amylphe'noxy)-n-butyryl chloride is added all at once. The

' longer.

7 reaction mixture becomes murky immediately and is stirred for three hours at room temperature. With goodstirring the reaction mixture is drowned in 300 ml. of

The desired product III is prepared as follows:

In a '500 ml. round bottom flask equipped with a stirrer is placed 35.5 g. (0.0605 mole) of a o-methoxy benzoyl-4-[a 2,4 di-tert.-amylphenoxy) -n-butyramido acetanilide in 200 ml. of dry chloroform, and 4.9 m1. (0.0605 mole) of sulfuryl chloride is added dropwise with stirring. The reaction mixture is stirred overnight. The chloroform is'rernoved invacuo and the oily residue is dissolved in 300 mlpof methanol. After cooling to -5, a white solid separates which is filtered, washed with 50 ml. of cold methanol, and dried. The crude product (26.1 g., 70%, M. P. 80-90") is recrystallized from parts of methanol to give 22 g. (59%) of material which melts at 88-90.

This coupler compound is outstanding among the other couplers contemplated by our invention because the three terminal alkyl groups apparently enhance its solubility in coupler solvents used for dispersing the coupler in gelatino-silver halide emulsions.

EXAMPLE IV The precipiof snow white solid which EXAMPLE V oi-(o-Methoxybehzoyl) cL-chlor -S-[u -(2,4 di tent-amylphenoxy)-n-butyramid0]acetanilide V eon. llrnoooncnzom is prepared by a procedure similar to Example III with the substitution of o-methoxy-benzoylacet-3-aminoanilide for o-methoxy-benzoylacet-4-aminoanilide as follows:

u- (2,4-Di-tert.-amylphen0xy -3-nitrobutyranilide Dimethyl 5-{4 (2,4-di-tert.-amylphenoxy) -3-{u-[4-(0t-0-. anisoyl-a-chloroacetamido) phenaxy] acetamidojibenzmcoooU-oooon.

amid0}is0phthalate IV Q4: OEHC ONHO-O omooNH- UsHu-t.

a (o Methoxybenzoyl)-4-{ [2 (2,4-di-tent.'-amylphenoxy) -5 3 5 -dicarbomethoxyp henylcarbamyl )phenylcarbamyl]methoxy}-acetanilide is prepared by first reacting 4-(2,4-di-tert.-amylphenoxy) 3 nitrobenzoyl chloride with 3,5-dicarbomethoxy aniline; reducing the nitro group of the product followed by reaction of the resultant amino group with 4-nitrophenoxyacetyl chloride. The nitro group of this product is then reduced and the product condensed at the resultant amino group with ethyl-omethoxybenzoyl acetate.

The desired product IV is obtained as follows:

Ten grams (0.0113 mole) of a-(o-methoxybenzoyD- [2-(2,4-di-tert.-amylphenoxy) 5 (3,5 dicarbomethoxy phenylcarbamyl)phenylcarbamyllmethoxy acetanilide is dissolved in 150 ml. of dry chloroform and cooled to 5 C. At this temperature there is added in 10 minutes 1.75 g. (0.0113 mole) of sulfuryl chloride dissolved in ml. of dry chloroform. The solution is stirred during the addition of the sulfuryl chloride and for one hour The reaction mixture is then heated to 50 C. for 5 minutes and the solvents removed under diminished pressure. The residue is crystallized from ethyl acetate, thus obtaining a good yield of white product, melting at 223-224 C.

An addditional recrystallization from cc. of alcohol gave 18 g. of White crystals, M. P. 84-86".

. Anal. -Calcd. for C2sH3sN204! N, 6.35; found: N, 6.4.

3-am inc-a (2,4 -di tert-amylph enoxy) butyrtm ilide ao-Methoxybenzoyl -3- ot-(2,4-di-tert-amylph enoxy butyramido acetanilide To a refluxing solution of 11.5 g. of 3-amino-a-(2,4 di-tert-amylphenoxy)butyranilide in 100 cc. of histological xylene was added 6.2 g. of ethyl o-methoxybenzoylacetate. The solution was refluxed for two hours in such a way that the ethanol distilled under reduced pressure.

The gummy residue was stirred under petroleum ether to give 13.5 g. of an amorphous solid melting above 60".

It was not obtained in a crystalline form.

The desired product V is obtained as follows;

To a solution of g. of e-(o-methoxybenzoyl)-3-[a- (2,4-di-tert-amylphenoxy)butyramido]acetanilide in cc. of chloroform was added 0.7 cc. of sulfuryl chloride dropwise with shaking. The solution was allowed to evaporate slowly at room temperature. The yellow gum was soluble in alcohol, benzene, acetonitrile, chloroform, and carbon tetrachloride. It was insoluble in water and petroleum ether. The material did not crystallize.

Compounds having the general formula given above in which R is an ortho-substituted phenyl group are not readily prepared by the methods of the preceding examples.

Coupler iV has the unusual property that the spectral absorption of theazomethine dyes made therefrom by color development, are particularly sharp, that is, the absorption in the blue region of the spectrum is confined to a relatively narrow range of wavelengths which is an effect long sought in dyes for color photography. The etiect is due, at least in part, to the alkoxy group in the p-position of acetanilide nucleus of the coupler.

This coupler is of particular value in those cases where it is desirable to incorporate a coupler into an emulsion by use of alkali rather than a coupler solvent. Accordingly, the ester groups of the above coupler are first hydrolyzed in alcoholic alkali in a well known manner, then the coupler is incorporated into an emulsion as the alkali metal salt.

All of the couplers of the invention may be incorporated into emulsion layers by the method of Fischer U. S.

Patent 1,055,155, or by means of coupler solvents by the methods of Mannes et al. U. S. Patent 2,304,940, granted December 15, 1942, and .lelley and Vittum U. S. Patent 2,322,027, granted June 15, 1943.

As is apparent, the couplers of the invention are primarily useful in multilayer color films and for that purpose the couplers are particularly efficacious since they show relatively little diffusion in gelatin emulsion layers especially when the substituent in the p-position of the acetanilide nucleus is sizeable.

In the development of exposed photographic silver halide emulsion layers using the couplers of our invention, any color-forming developer containing a primary amino group may be used. These include developers having two primary amino groups as well as those having one of the amino groups substituted or having substituents in the ring, such as the alkyl phenylene diamines. compounds are usually used in the salt form, such as the hydrochloride or the sulfate which are more stable than the amines themselves. The suitable compounds are diethyl-p-phenylenediamine hydrochloride, monomethyl-pphenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, and Z-amino-5-diethylaminotoluene hydrochloride. The p-amino phenols and their substitutionproducts may also be used where the amino group is unsubstituted. All of these developers have an unsubstituted amino group which enables the oxidation products of the developer to couple with the color-forming compounds to form a dye image.

Our development process may be employed for the pro- These mixture of silver halide and the coupler compound diduction of colored photographic images in layers of gelatin or other water-permeable colloidal carriers, such as albumin, collodion organic esters of cellulose, or synthetic resins. The carrier may be supported by a transparent medium such as glass, a cellulose ester or synthetic resin or a non-transparent reflecting medium such as paper or an opaque cellulose ester. The emulsion may be coated as a single layer on the supoprt or as one of a number of superposed layers on one or both sidesof'the support. The superposed layers may bedifferentially sensitized as is conventional in color photography.

What We claim is: p

.1. A photographic silver halide emulsion comprising a mixture of silver halide and a coupler compound of the class consisting of 4- ct-Z-methoxybenzoyl-a-chloroacetamido) -3"-(4-tert.

amylphenoxy) benzanilide 4 (a 2-methoxybenzoyl-a-chloroacetamido)-2", 4"-ditert. amylphenoxyacetanilide a 0 Methoxybenzoyl a-chloro-4-[a-(lA-di-terh-amylphenoxy -n-butyramido acetanilide Dimethyl 5 {4-(2,4-di-tert.-amylphenoxy) -3-{a- [4-( 01-0- anisoyl -u.- chloroacetamido) phenoxy] acetamido}-benzamido}isophthalate a (o Methoxybenzoyl)a-chloro-3-[a-(ZA-di-tert. amylphenoxy) -n-butyramido] acetanilide .mixtureof silver halide and the coupler compound 4-(oc- 2 methoxybenzoyl oz chloroacetamido)-2",4-di-tert.- amylphenoxyacetanilide.

4. A photographic silver halide emulsion comprising a mixture of silver halide and the coupler compound Ot-O- methoxybenzoyl on chloro 4 [a-(2,4-di-tert.-amylphenoxy -n-butyramido] -acetanilide.

5. A photographic silver halide emulsion comprising a methyl 5-{4- 2,4-di-tert.-amylphenoxy) -3-{cc- [4 a-o-anisoyl a chloroacetamido) phenoxy]acetarnido}benzamido}isophthalate.

6. A photographic silver halide emulsion comprising a mixture of silver halide and the coupler compound a-(omethoxybenzoyD-a chloro 3-[a-(2,4-di-tert.-amylphenoxy -n-butyramido] -acetanilide.

7.. A method of producing a colored photographic image in a silver halide emulsion layer, which comprises exposing said layer and developing it with a primary aromatic amino silver halide developing agent in the presence of a coupler compound designated in claim 1.

References Cited in the file of this patent

Claims (1)

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION COMPRISING A MIXTURE OF SILVER HALIDE AND A COUPLER COMPOUND OF THE CLASS CONSISTING OF 4-(A-2''-METHOXYBENZOYL-A-CHLOROACETAMIDO)-3"-(4''''''-TERT. AMYLPHENOXY) BENZANILIDE 4-(A-2''-METHOXYBENZOYL-A-CHLOROACETAMIDO)-2", 4"-DITERT. AMYLPHENOXYACETANILIDE A - O - METHOXYBENZOYL - A-CHLORO-4-(A-(2,4-DI-TERT-AMYLPHENOXY)-N-BUTYRAMIDO)ACETANILIDE DIMETHYL 5-(4-(2 4-DI-TERT-AMYLPHENOXY)-3-(A-(4-(A-OANISOYL -A-CHLOROACETAMIDO)PHENOXY)ACETAMIDO)-BENZAMIDO)ISOPHTHALATE A - -(O - METHOXYBENZOYL)A-CHLORO-3-(A-(2,4-DI-TERT. AMYLPHENOXY)-N-BUTYRAMIDO)ACETANILIDE.