US3183095A - Color couplers containing a tertiary amino group - Google Patents

Description

United States Patent s 183 09s COLOR COUPLERS ONTAlNlNG A TERTIARY AMINO GROUP Gunther H. Klinger, Binghamton, N.Y., assignor to General Aniline & Film Corporation, New York, N.Y., any

corporation of Delaware No Drawing. Filed July 1, 1960, Ser. No. 40,160 11v Claims. (Cl. 96-100) This invention relates to color photography and to couof this type the subtractive method of color formation is ordinarily employed with the result that the photographic images so obtained are composed of the subtractive primary colors, i.e., cyan, magenta, and yellow.

The color photographic materials in use today commonly employ phenol or naphthol as the couplers for the production of cyan images; couplers used for producing magenta dyes are commonly pyrazolones whereas open chain reactive methylene compounds serve as a source of the yellow dye images.

One of the most difficult obstacles confronting artisans in color photography is obtaining dyes of the required stability that go to make up the colored photographic images: Stability in this instance refers to the ability of a photographic dye image to resist breaking down or otherwise degrading under conditions of light, heat and excessive humidity. This latter is especially hard to overcome and very few photographic dyes are capable of retaining their tinctorial strength under conditions of humidity such as prevail in tropical climates.

It is, therefore, the primary object of this invention to provide a class of color forming components or couplers which on color development with a primary aromatic amino'developing agent yield dye images which are highly resistant when subjected to conditions of excess humidity.

It is also an object of this invention to provide light sensitive silver halide emulsions containing these couplers.

It is a still further object of the invention to provide a method for producing the couplers.

Other objects and purposes will become apparent as the description proceeds.

I have discovered that color couplers containing within their structure a tertiary amino group yield dye images on color development marked by excellent stability in the I presence of anenvironment of high humidity. The surprising feature of my discovery is a fact that the tertiary amino moiety is effective in producing the desired stability in all three types of couplers, i.e., naphthol or cyan couplers; reactive methylene or yellow couplers and pyrazolone or magenta couplers. It is, of course, not too unusual to uncover a moiety or type of a chemical grouping capable of conferring in a rather specific manner stability to a color forming component. However, the location of the stabilizing group is fairly critical and is commonly restricted to a certain location within the coupler structure. case. I have synthesized a large variety of color forming structures containing the above described tertiary amino substituent and have found such structures to yield dyes having excellent stability under conditions of excessive high humidity.

In the present instance, however, this is not the 2 The color couplers, as described herein, can be represented by the following general formulae:

decyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, etc.; R is hydrogen or alkyl as above; X is hydrogen, a sulfo group and the ammonium an alkali metal salts thereof; Z represents a non-metallic atom such as oxygen or carbon which when inserted in the formula produces a morpholine or piperidine ring; R represents a lower alkyl group, i.e.,

methyl, ethyl, propyl, butyl, etc.; A is hydrogen, an alkylamido group of at least 10 carbon atoms, e.g., undecylamido, lauramido, tridecamido, myristamido, pentadecanamido, palmitamido, stearamido, etc.; B represents a COOM group wherein M is ammonium, an alkali metal, i.e., sodium potassium lithium, etc.; an alkylamido group wherein R andM have the aforesaid values; Y represents hydrogeman alkylamido group for A as .above or the grouping: I

. 000M 0 R Ji-i:

. 00M whereinVR and M have thepreviously. assigned designations.

Examples of color former components falling'within the ambit of the above "formula include the following:

CYA IN COUPLERS wherein R is an alkyl group of at least 10 carbon atoms, 1.e., decyl, undecyl, dodecyl, tridecyl, tetradecyl, penta- 5 MAGENTA COUPLERS plated in the instant CONE N SOsNB j 12.58 g. (0.02 M) l-hydroxy-Z-(morpholinoj--stearamido-2-naphthanilide was dissolved in a mixture of ml. of carbon tetrachloride and 50 ml. of benzene and the water removed by azeotropic distillation witha moisture trap. The solution was cooled to C. and 1.3' ml. of chlorosulfonic acid was added dropwise. The solution was refluxed for 2 /2 hours and a solution of 1 .2 g; s'odi um chloride in 4 ml. of was added} followed by 150' ml. of acetone. -The mixture" was stirred at room tentperature for 2 hours, and: filteredorr a Biichner funnel. It was recrystallized from: 80% a'cet-ie acid-.- Yield 4- g. dec. 19s-200 c. y I

1 g. of the above col'or' former was dissolved in 20ml. of water and sutiicien't 2 N sodium" hydroxide. to bring the pH to 8.5-9. This solution was incorporatedinto 50- g. of a silver halide emulsion and coated. Upon develop ment with a color developer, containing' N e'thyl-N-B hydroxyethyl p-phenylenediam'ine as": the developing. agent. A cyan dye with an absorption at 690 mp.- was obtained. This image shows no loss uponalO dayhigh humidity fading test. V

The 1-hydrox-y-2'-(l-morpholino) 5' st'earamido 2- naphthanilide was preparedas -follows:

19.25 g. of S-amino-1-hydroxy-2#(.l -morpholino) 2 naphthanilide was dissolved in 200 ml. of-pyrid-ine. To this solution- 21.4 g. of steroyl chloride" was added in one portion. The reaction mixture was stored for 25 liours' at 3540 C. andthen poured into iceHgO (51 liter). The precipitate was filtered on 'a Biichnerfuntiel washedwith" water and dried over HSDn Itwas'recry'stallized from" a mixture of dimetliylfo'rm'amide and" methanol; yield-2'1 g.,M.P.155-157 c. p

The S'-amino-1-hydroxy'-*2:' 1-rnorpholino)-2-naphthanilide was prepared in thefollowing manner. m

43 g. of1hydroxy 2 mbrpliolino 5 nitioQ naplithanilide' was added gradually to at boiling. mixture" of 45 g; of

tered and acidified with 80% acetic-acid. It was recrystallized by dissolving in hot dimethylformamide and addition of methanol to thissolution; yield nearly quantitative; M.P. 192-194 C. v s

The 1 hydroxy-2'-morpholin6-5'-nitro was obtained as follows:

69 g. of 2-chlor"ol-hydroxy-5' and 450 m1. of morpholine (5 M) was refluxed for 3 hours. The solvent was then removed in vacuo, the residue dissolved in a mixture of methanol and 2 N sodium ,hydrox ide. This solution was filtered andacidified with acetic acid. The precipitate was filtered olf and washed on the funnel with water. It was pure enough for the next step; yield 75-80%; 'M.P. 244 C.

' The 2'-chloro-1-hydroxy-5'-nitro-2-naphthanilide was prepared in the following manner:

80 g. of 2-chloro-5-nitroaniline and hydroxy-2-naphthoate were co bottom flask and inserted i -nitro- 2-.naphthanilide g. of phenyl-lmbined in a 500 ml. round nto a metal bath, which. was heated for 1 hour at 160 C., 1 hour at C. and 1 hour at 140 C. During the last hour the flask was connected with a distilling head and a condenser and a vacuum of 1 -2 m Hg was applied.

The material was ground in a mechanical blender with 200 ml. of cold methanol, then filtered on a Biichner funnel and washed with cold methanol; M.P. 240 C. The compound was pure enoughfor the next step. It can be recrystallized from chlorobenzene.

Example II.1-hydr0xy-4'-(l-morpholino)-N-0ctadecyl- 2-naphthaniIide-4-sulf0nic acid sodium salt OK QQ 36 g. of 1 hydroxy-4'-(l-morpholino)-N-octadecyl-2- naphthanilide was dissolved in 300 ml. of benzene. The watef'was removed by azeotropic distillation with a moisture trap The solution was cooled to 24-30" C. and 5 ml. ofchlorosulfonic 'acid was added dropwise with rapid stirring" during 5 minutes. After another 5 minutes stirring at 24-30" C. the mixture was refluxed for 2 hours without stirring. It was cooledagain to 24-30 C. and 2' mlio't chlorosulfonic acid were added with rapid stirring. The mixture was refluxed again for 1 hour. Now 250' ml. acetone was added'and finally a solution of 3.6 g. of sodiumchloride in 20 ml. of H 0 was added. The mixture was stirred for 1 hour at roomtemperature, then cooledwith ice, filteredon a Biichner funnel and washed on the funnel with 100 ml. of cold acetone; yield 40 g. dec. 2l0'-220 C.

1g.- of the above color former was dissolved in 20 ml.

of H' O and sufiicient NaOH to bring the pH of the solution to 8-9. This solution was added to 50 g. of a silver halide fine grain emulsion and coated. Upon development with a color developer containing N-ethyl, N-p-hydroxyethyl-p-phenylenediamine, a cyan dye with an absor'ptionat 630 m was formed.

The- 1-liydro'xy-4'-( 1-morpholino)-N- than'ilide was obtained by the followin I 80 g. of 4-(l-morpholino)-N-octadecylaniline and 5.2 g. of phenyl-1'-hydroxy2-naphthoate were heated in a round bottom flask which was i The bath was he'ated2 hours at atmospheric pressure to -165" C. and-1 hour at a reduced pressureof approximately 0.1mm. Hg at 155-165 C. During the last hour the flask was' connected to a vacuum of 10. l m Hg.

The melt was Ieached Z t-imes with 20 ml. of methanol after cooling and'then dissolved ina small amount of acetone. The compound crystallized-from this solvent upon standing for about 20 hours in the refrigerator; yield 9.5 g.=73%; M.P. 61-62." C.

octadecyl-2-naphg synthetic route:

-2-naphthanilide mmersed in an oil bath.

The 4-(l-morpholino)-N-octadecylaniline was obtained as follows:

11.2 g. of 4-(l-morpholino)aniline, 7 g. of octadecylbromide and 150 ml. of ethanol (95%) were refluxed for 60 hours. A compound crystallized upon cooling and was collected on a Biichner funnel and washed with a small amount of ice cold methanol. It can be crystallized from methanol; yield 10 g.; M.P. 8385 C.

The 4(1-morpholino)aniline, used in the above reaction, was synthesized by refluxing, for 3 hours, 100 g. of p-nitrobromobenzene (0.5 M) and 250 ml. of morpholine. After distilling off the exces of morpholine in vacuo, the residue was washed with water and crystallized from methanol. The yield was 86 g.; M.P. 152-l56 C. Reduction of the nitro group with iron and hydrochloric acid yielded the desired 4-( l-morpholino)aniline.

Example III. 3'-N-(3,5-dicarboxyphenyl)-N-octadecyl- 1-hydr0xy-4'-(1morpholine)-2-naphthanilide sulfonic acid sodium salt CODE CnHu JOOH SO;Na

25.7 g. of 3-N-(3',5-dicarbomethoxyphenyl)-N-octadecyl carbamyl-l-hydroxy-4'-(1-rnorpholino)-2-naphthanilide was refluxed for /& hour in a solution of 3.2 g. of sodium hydroxide, 7 ml. of water and 68 ml. of methanol.

The solution was cooled to room temperature and acidified with 80% acetic acid. The precipitate was collected on a Biichner funnel, dried over calcium chloride in a desiccator and finally crystallized from 70% methanol; yield 75%. l g. of this color former was dissolved in 20 ml. of H 0 and sufficient 2 N NaOH to adjust the pH of the solution to 8-9. This solution was added to 50 g. of fine grain silver halide emulsion and coated in the usual manner. On development with a color developer, containing N-ethyl N-hydroxyethyl-p-phenylenediamine a cyan image was produced with an absorption at 685 mg. The blue transmission of this dye was exceptionally good, and its stability on high humidity treatment excellent.

The dimethyl ester of the above dicarboxy coupler was prepared as follows:

38 g. of -[5-amino-2-(l-morpholino)-N-octadecylbenzamido1isophthalic acid dimethyl ester and 14 g. of phenyl-l-hydroxy-Z-naphthoate were combined in a 500 ml. round bottom flask and inserted into a metal bath which was heated 4 hours at 150-160 C. During the last 2 hours a vacuum of about 0.1-1 mm. of Hg was applied to the flask. The reaction mixture was allowed to cool, then refluxed with 200 ml. of MeOH, in which it is only partly soluble. The material crystallizes upon standing overnight. It was filtered, washed with methanol and crystallized from isopropanol; yield 70%; M.P. 151- 152 C.

The above aminoisophthalic ester was obtained in the following manner:

70 g. of 5-[2-(1 morpholine) 5 nitro-N-octadecylbenzamido]isopht-halic acid were added .to a refluxing mixture of dimethyl ester, 45 g. of iron (40 mesh), 15 ml. of concentrated hydrochloric acid, 100 ml. of water and 400 ml. ethanol. The mixture was refluxed for 24 hours then filtered, cooled to room temperature and carefully neutralized with 2 N sodium carbonate solution. The iron carbonate was filtered off and the solution evaporated to dryness. The oily residue was dissolved in benzene, the benzene washed with water, to remove inorganic salts, dried with sodium sulfate and evaporated in vacuo. The oily compound was used as such in the preceding step.

The 5-[2-(1-morpholino) 5 nitro-N-octadecylbenzamidoJisophthalic ester was prepared as follows:

58 g. of 2-n1orpholino-5-nitrobenzoylchloride was dissolved in 125 ml. of dry benzene and added to a slurry of 99 g. of N-octadecylaminoisophthal-ic acid dimethyl ester in 35 ml. of pyridine kept at 37 C. for 24 hours. The solvents were removed in vacuo on a steam bath. The residue was washed several times with cold water. It crystallized and can be purified from ethanol; yield 146 g.=99% M.P. 87-88 C.

The acid chloride was obtained by refluxing for 1.5 hours 90.0 g. of 2-(l-morpholino)-5-nitrobenzoic acid with 250 ml. of thionyl chloride in the presence of 2 drops of pyridine. The excess of halogenating agent was removed by distillation in vacuo at 0.1 to 10 mm. The residue of crude acid chloride was used without further purification. I

The free acid was obtained by refluxing 40.6 g. of 2- chloro-S-nitrobenzoic acid and 200 m1. of morpholine for a period of three hours. The excess amine was removed in vacuo and the residue acidified with acetic acid. The crude product was collected on a Biichner funnel. The yield was almost theoretical; M.P. 166-167 C. The crude material which is sufliciently pure for the above use can be crystallized if desired from methanol.

Example I V.-3'-carboxy-2- (3-Iauramid0benzoyl) -4'- (I -m0rph0lin0 )acetanilide coon ooornc Orrin-Gr? o NII co (ClIfliuCH;

6 g. of the methyl ester of the above coupler carboxylic acid was refluxed for 25 minutes with a solution of 1.5 g. of sodium hydroxide, 5 ml. of water and 50 ml. of methanol. The mixture was acidified with 80% acetic acid and the solvents were removed in vacuo on a steam bath. The residue was crystallized from ethanol; yield 4.0 g. 1 g. of the above color former was dissolved in 20 ml. of H 0 and sufficient 2 N sodium hydroxide to bring the pH of the solution to 8-9. This solution was added to 50 g. of a silver halide fine grain emulsion and cooled. Upon development with a color developer containing N-ethyl-N-hydroxy-ethyl-p-phenylenediamine a yellow dye was formed which absorbs at 438 m The methyl ester of the above coupler was obtained as follows:

4.0 g. of 2-(S-aminobenzoyl)-3-carbomethoxy-4-(lmorpholino)-acetanilide was dissolved in 200 ml. of dry benzene. A solution of 4.5 g. of lauroyl chloride in ml. of dry benzene was added slowly at 30-35 C. to the amino compound. The combined solutions were stirred at 30-35 C. for 2 hours, then 40 m1. of pyridine were added and stirring was continued for another hour at 35 C. The solvents were removed in vacuo on a steam bath. The residue was dissolved in 200 ml. of benzene and chromatographed on aluminum oxide. A pale yellow syrup was isolated; yield 6.0 g.

The intermediate 2-(3-aminobenzoyl)-3'-carbomethoxy- 4'-(l-morpholino)acetanilide was produced from reduction of the corresponding nitro compound in the following manner:

4.2 g. of 3'-car-bomethoxy- 4-( l-morpholino)-2-(3-nitrobenzoyl)acetanilide was added to 100 ml. of pure dioxane containing 0.5 g. of Pd on charcoal (45% Pd). The mixture was hydrogenated at 40 p.s.i. at room temperature. After 2 hours the calculated hydrogen uptake was reached. The solution was filtered off from the catalyst and evaporated in vacuo. The material was obtained as a heavy, straw-colored syrup and was used as such in the preceding step.

I III.

The morpholinoanthranilic was obtained by reduction of the corresponding nitro derivative employing the following procedure: 7

73 g. of 2-(l-morpholino)-4-nitrobenzoic.acid methyl ester was gradually added to a refluxing mixture of 115 g. of iron powder (40 mesh), 40 m1. of concentrated hydrochlorie acid, 300 ml. of water and 1200 ml. of ethanol (95%). The mixture was stirred and refluxed for I hours and then cooled to room temperature and filtered.

The cold solution was carefully neutralized with aqueous 2O 2 N sodium carbonate and filtered again. The filtrate was distilled to dryness in vacuo and the residue recrystallized from methanol; yield 3 5 g.; M.P. 81-82 C.

The 2-(l-morpholino)-5-nitrobenzoic acid and acid chloride thereof was prepared as described above under 5 Example 111.

Example V.2-benz0yl-4'(I-morpholino)-3'-(N-ocladecyl) N-(3,5-dicarb0xyphenyl) carbamylacetanilide '80 g. of the dimethyl ester of the above couplerwas OOH relluxedfor hour with 9.8 g. of sodium hydroxide, 220

ml. of methanol and 22 ml. of water. Half of the solvent was removed in vacuo and the residue acidified with 80% acetic acid. The precipitate of sticky oil was washed several times with water and then dissolved in water and 2 N sodium hydroxide, adjusting the pH of the solution :to

about 7. This solution was extracted 3 times with (each time) 100 ml. of ether; The aqueous solution was aciditied with hydrochloric acid '(6 N) and extracted with 2 portions of 400 ml. of ether. This ether solution was extracted 2 times with 100 ml. of 6 N hydrochloric acid and then washed 3 times with saturated sodium chloride solution. The ether solution was then evaporated to dryness on a steam bath. The residue was finally recrystallized cfrom 70% methanol. 1 g. of the above color former was dissolved in 20 ml. of water and sufficient 2 N sodium hyby the following route:

'58 g. of 5-[5'-amino 2 l-morpholino-l-N-octadecflbenzamido] isopt-halic, acid dimethyl ester; 22 got ethylbenzoylacetate, 150 ml. of dry xylene and 1 ml. of piperidine were slowly heated until the distillate comes over at a temperature oil-3543 6 C. The rest of the xylene was a removed on a steam bath in vacuo. The residue was a light yellow syrup which-gave good analytical values but did not crystallize. I

The preparation of, the above'intermediate 5-[5'-amino- 2-(l-monpholino)-N-octadeeylbenzamido] isopthalie acid dimethyl esterhas been deseribedabove under Example 10 1 Example Vl.2benzoyl-5'-lauram ido-2-(I-morph0lin0) acetom'lide r rnoowimmom Ooocmc ONHQ 17 g. of 5'-amino-2-benzoyl-2'-(1-morpholino)acetanilide, 170 ml. of dry benzene, 11 g. of lauroyl chloride were mixed and then 5 ml. of dry pyridine were added to this slurry. It was kept at room temperature for 4 days. The solvents were removed in vacuo. 20 ml. of

water were added to the residue and removed again in vacuo. Finally the residue was crystallized from acetone; yield 18 g.; M.P. 125-126 C. 1g. of this color former was dissolved in 5 ml. of a mixture containing 50 parts of phenethyl alcohol, 40 parts of t-ricresyl phosphate and 10 parts of dibu-tyl phthalate. The solution was dispersed in 50 g. of silver halide fine grain emulsion and coated on paper base. U-pon development with a color developer containing vN,-N'-diethyl-p-aminotoluene as a color developer, a yellow dye image was formed with an absorption at 643 mu.

The above intermediate, '-amino-2-benzoyl-2-(1-mor-' pholino) acetanilide, was obtained by the following reaction:

3.6 g. of 2 benzoyl 2'-(1-morpholino)-5'-nitroacetanilide in 50 ml. of dry di-oxane in the presence of 0.1 g. of platinum oxide were hydrogenated at room temperature and 40 psi. The hydrogen uptake ceased afiter 2 hours. The solution was filtered and evaporated to dryness in vacuo on a steam bath. The residue was crystallized from acetone; yield M.P. 160 C.

The above nitroacetanilide was prepared by condensing 19.2 g. of benzoylacetic ester and 22.3 g. of Z-(I-morpholino)-5-nitroaniline in ml. of xylene using 2 ml. of piperidine as catalyst. The mixture was slowly heated until distillation occurred, and most of the xylene (about 50%) had slowly distilled oil. This required about 4 hours. The rest of the solvent was removed .on a steam bath in vacuo. The residue crystallized upon cooling. It is crystallized from methanol; yield 30 g.:=8-0%; M.P. 169-170" C.

The above intermediate 2-(l-morpholino)-5-nitroaniline was synthesized by refluxing 111 g. of Z-(I-morpholino)-5-nitroacetanilide with 111 g. of 2-m-or'pholino-5- nitroacetanilide refluxed ch'loric acid for 2 hours. The solution was cooled and brought to pH 8 with aqueous sodium carbonate and the precipitate collected on a Biichner funnel and dried. The crude product was crystallized from methanol; yield 82 g."=87%; M.P. -156 C.

The 2-morpholino-5-nitroacetanilide was obtained by refluxing 4.28 g. of 2-chloro-5-nitroacetani-lide for 3 hours 1 with 25 ml. of morpholine. The unreacted morpholine was removed in vacuo on a steam bath. The residue was washed with water on a Biichner funnel, dried and crystallized from methanol; yield nearly quantitative; M.P. 128-129 C.

The above intermediate, 2-chloro-5-nitroacetanilitie was produced as follows:

17.3 g. of Z-chioro-S-nitroaniline are added to a mixture of 20 ml. of dry pyridine, 20 ml. of aceticanhy'di ide and 50 ml; of benzene. The mixture was refluxed for 2 hours and after the solvent was removed in vacuo, cooled and filtered. The solid was washed on the funnel with water and then dried. It was crystallized from methanol; yield 19 g.; M.P. l63l64 C.

with l400 ml. of 15% hydro 10.5 g. of 3-I5-amino-2-(l-morpholino)benzamido1-lphenyl-Z-pyrnzolin-S-one was slurried with 50 ml. of dry benzene and after which a solution of 11.5 g. of a-pentadecylphenoxybutyryl chloride in 50 m]. of dry benzene was added. 20 ml. of pyridine was added and the solution kept at 37 C. for 15 hours. The solvent was removed in vacuo. 10 m1. of water was added to the residue and removed again in vacuo. The residue was dissolved in propanol and precipitated from this solution with methanol. 1 g. of this color former was dissolved in 5 m1. of a mixture, containing 50 parts phenethyl alcohol, 40 parts tricresyl phosphate and parts dibutyl phthalate. This solution was coated on film base. Upon development with a color developer containing N-ethyl-N- hydroxyethyl-p-phenylcnediamine, a magenta dye image was produced with an absorption at 540 me.

The above amino Z-pyrazoline-S-one was obtained by reduction of the corresponding nitro compound in the following manner:

26 g. of 3-[1-(morpholine)-5-nitrobenzamido]-2- pyrazoline-S-one was added in small portions to a boiling mixture of 27 g. of iron powder mesh), 60 ml. of water, 9 ml. of concentrated hydrochloric acid and 240 ml. of ethanol. After-addition of the nitro compound, refluxing and stirring was continued for 10 hours. The reaction mixture was rendered basic against phenolphthalein with 40% aqueous sodium hydroxide and filtered.

' The filtered solution was acidified with 80% acetic acid and the precipitate collected on a Biichner funnel. The compound was crystallized from a mixture of dimethylformamide and methanol; M.P. 279-280 C. (dcc.).

The nitro 2-pyrazoline-5-one intermediate employed in the above reaction was obtained as follows:

17.5 g. of 3-amino-2-pyrazoline-5-one was slurried in 500 ml. of dry benzene and a solution of 27.1 g. of 2-(l-morpholino)-5-nitrobenzoylchloride in 200 ml. dry benzene was added dropwise with stirring to this slurry. The temperature during the addition was maintained at 10-15 C. The mixture was kept at room temperature for 20 hours then 20 ml. pyridine was added and the mixture retained another 20 hours at 37 C. The precipitate was filtered ofi and dried. It was crystallized from a mixture of dimethylformamide and methanol; yield 26 g.; M.P. 237239 C.

The preparation of 2-(l-morpholino)-5-nitrobenzoyl chloride is described under Example III.

As indicated in the various examples the color-forming components contemplated herein can be incorporated in a gelatino silver halide photographic emulsion in the usual manner, i.e., by the dispersion method or dissolving the alkali metal salts directly in the aqueous gelatin carrier. The water immiscible high boiling oily solvents commonly used in preparing coupler dispersions include high boiling esters, alcohols, ketones, or mixtures thereof. The chemical literature and patents contain such listings of these solvents and it is not considered necessary to reproduce such information in the present specification.

Suitable developing agents include the various alkyl phenylenediamines as exemplified by the following: 4 aminoaniline, 4 ethylaminoaniline, 2 diethylaminoaniline, 4-dialkylaminoaniline, e.g., 4-dimethylaminoaniline, 4-diethylaminoaniline, 4-[N-(fi-hydroxyethyU-N- ethyl] aminoaniline, 4-amino-N-ethyl-N-(fi-methanesul- 12 fonamidoethyl)-2-methylaniline sulfate and the like. The above developing agents are preferably used in the form of their salts such as the hydrochloride or hydrosulfate as they are more soluble and stable than the free bases. All of these compounds have a primary amino group which enables the oxidation product of the developer to couple with the color compounds to form dye images. After removal of the silver image by bleaching and fixing, in a manner well known to the art, the color image remains in the emulsion. A suitable developing solution can be prepared as follows:

Water to make 1 liter.

The exposed silver halide emulsions containing the color formers are developed in the above solution in the usual manner.

My couplers may be incorporated in gelatino silver halide layers or in silver halide emulsions or other carriers such as organic acid esters of cellulose or synthetic resins. Typical supports are exemplified by brass, cellulose ester or poly terephthalic acid esters or a non-transparent reflecting medium such as paper or an opaque cellulose ester. The emulsions containing my color formers may be in the form of a single layer on a support or a superimposed layer which may be coated on one or both sides of the support. In the case of a multilayer photographic element, various layers may be differentially sensitized to various regions of the visible spectrum in a known manner.

I claim:

1. A photographic silver halide emulsion containing a color coupling compound selected from the class represented by the following general formulae:

on 0 R1 Y w A B {P-oocmoou- N wherein R is selected from the class consisting of an alkyl group of at least 10 carbon atoms; R; is selected from the class consisting of hydrogen and an alkyl group of at least 10 carbon atoms; X is selected from the class consisting of hydrogen, a sulfo group and the ammonium and alkali metal salts thereof; Z represents the non-metallic atoms necessary to complete a heterocyclic ring selected from the class consisting of morpholine and piperidine; R, represents a lower alkyl group; A is selected from the class consisting of hydrogen and an alkylamido group of at least 10 carbon atoms; B is selected from the class consisting of a -COOM group wherein M is selected from the class consisting of ammonium and alkali metal salts,

13 an alkylamido group at least 10 carbon atoms and the grouping x;

000M 9 L N wherein R and M have the aforesaid values; and Y is selected from the class consisting of hydrogen, an alkyl- 10 amido group of at least carbon atoms and the grouping 000M 0 R N I C-N sag wherein R is selected from the class consisting of hydrogen'and an alkyl group of at least 10 carbon atoms; X is selected from the class consisting of hydrogen, a suite group and the ammonium and alkali metal salts thereof; Z represents the non-metallic atoms necessary to complete a heterocyclic ring selected from the class consisting of 'morpholine and piperidine and Y is selected from the class consisting of hydrogen and an alkylamido group of at least 10 carbon atoms and the grouping:

Wherein R'is an alkyl group of at 16381210 carbon atoms and M is selected from the class consisting of ammonium and alkali metal salts, wherein at least one of said substituents R and Y contain an alkyl chain of at least 10 carbon atoms.

3. A photographic silver halide emulsion containing a color coupling compound represented by the following formula:

wherein R is an'falkyl group "of "at least 7 loxcarbon atoms,

R, is a lower 'alkyl group and Z represents the non-me'taillic atoms necessary to complete a heterocyclic ring selected from the class consisting of morpholine and piperidine. 4. A photographic silver halide emulsion containing a color" coupling compound represented by the following formula:

at n Q-co01hctm A v a z wherein A is selected from the class consisting of hydrogen and an alkylamido group of at least 10 carbon atoms; Z represents the non-metallic atoms, necessary to complete a heterocyclic ring selected from the class consisting of morpholine and piperidine; B is selected from theclass consisting of a COOM group wherein M is selected from the class consisting of; ammonium and alkali metal salts and analkylamido group of at least 10 carbon atoms and the grouping:

COOM

CO0M wherein R is an alkyl group of at least 10 carbon atoms. 5. A photographic silver halide emulsion containing the color coupling compound represented by the following formula:

0H NBC 0 Cam CONH 6. A photographic silver halide emulsion containing a color coupling compound represented by the following l ia at formula:

SO NE 7. A photographic silver halide emulsion containing a color coupling compound represented by the following formula:

X 81A pho'tograpliiesilven'hal'idta.emulsion containinga color coupling compound represented by the following formula:

15 16 9. A photographic silver halide emulsion containing a 11. A photographic silver halide emulsion containing color coupling compound represented by the following a color coupling compound represented by the following formula: formula:

coon o H O CnHu 5 g I g I N-C-OH| ..N 03H; E Ii i N $=O n 0- -c-N \N/ I OOH g COCH;CON N uHu N r 10 10. A photographic silver halide emulsion containing a color coupling compound represented by the following formula:

H 15 References Cited by the Examiner v H romotion- UNITED STATES PATENTS O 2,133,931 10/38 Middleton 96-100 x 2,408,421 was Grimmel et a1. 260-203 N 2,710,803 6/55 Salminen et al. 96-55 20 )2 1 NORMAN G. TORCHIN, Primary Examiner. 0 HAROLD N. BURSTEIN, Examiner.

Claims (1)

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING A COLOR COUPLING COMPOUND SELECTED FROM THE CLASS REPRESENTED BY THE FOLLOWING GENERAL FORMULAE: