DE885197C - Process for the production of purple photographic images in halogen-gelatin emulsion layers by color-forming development - Google Patents

Description

The invention relates to the production of colored photographic images by color development and in particular to substituted and unsubstituted bis (pyrazolones) as new color-forming agents Coupling components for this process.

The formation of colored photographic images by coupling the development product of a aromatic amine developer with color-forming and coupling compounds is called color-forming development known. These methods commonly use the subtractive method of color formation applied, the image dyes having the complementary primary colors cyan, purple and should have yellow. The coupling components, through which purple dyes are obtained, are usually pyrazolone or cyanoacetyl compounds. The dyes formed during the coupling are azomethines, indamines or indophenols, depending on the composition of the coupling component and the developer. The coupling component or the color former can be the emulsion or also be incorporated into the developer solution and then couples with the during development Oxidation product of the aromatic amine developer with the formation of a dyestuff image in the emulsion. The developed emulsion can then be bleached to remove the silver image, leaving the color image remains in the emulsion

It has now been found that substituted and unsubstituted Bis- (pyrazolone) particularly valuable

Color couplers are those with the oxidation product an aromatic primary amine developer to form a magenta dye image in the Emulsion react. The substituted and unsubstituted bis (pyrazolones) are for blue light rays permeable and have a high permeability, so that when developing "the coupling component obtain a color with good properties for the subtractive color synthesis process will.

The new color couplers, which in color development coincide with the photographic ones The photographic developer solutions can provide images with stable purple dye images or incorporated into the emulsions, they can be given by the following structural formula:

R-C-

CO OC

-C-R

Il

R ₁ R ₁

are represented in which R is hydrogen, an alkyl group, e.g. B. methyl, ethyl, propyl, butyl, octyl, decyl, heptadecyl, octadecyl, stearyl or any other alkyl group with up to 24 carbon atoms, a carbalkoxy-alkyl group, e.g. B. the ethyl acetate residue, etc., an alkyl carboxy group, e.g. B. carbethoxy, carbmethoxy, carbpropoxy, etc., aryl groups, e.g. Phenyl, naphthyl, anthranyl, diphenyl, etc., aralkyl groups, e.g. B. benzyl, methylbenzyl, ethyl-benzyl u. Ä., Alkylaminogmppen, z. B. Amylamino radicals, among others, Aiylamino groups, for example aniline and anisylamino radicals and the like. B. acetanilido, acetanisido, acetdimethylanilido, acetnaphthylamino, etc. or the sulfamylphenylamine, etc., and R _{1 is} either hydrogen, alkyl, aryl or aralkyl of the same meaning as R or a heterocyclic radical, ζ. B. the thiazolyl, benzothiazolyl, quinolyl, pyridyl, naphthothiazolyl, and other similar groups. The alkyl, aryl and aralkyl groups mentioned for R and R ₁ can also be replaced by halogens such as chlorine, bromine or iodine, acetamino groups, imino groups, nitro groups,

Alkoxy groups, such as methoxy, ethoxy, propoxy, Butoxy radicals etc., amino groups, ζ. Β. primary amino, secondary amino, such as methylamino, Phenylamino and similar groups, or tertiary amino radicals, such as dimethylamine, diphenylamino and similar groups, sulfoamino radicals or groups that increase solubility, such as sulfonic acid or carboxylic acid groups. ■ compounds that fall under this general classification are, for example, the following: 4, 4'-bis (i-phenyl-3-methyl-pyrazolon-5), 4,4'-bis (i-p-nitrophenyl-3-methyl-pyrazolon-5), 4,4'-bis (i-a-naphthyl-3-methyl-pyrazolon-5), 4,4'-bis (i-p-bromophenyl-3-methyl-pyrazolon-5), 4,4'-bis (pyrazolon-5) (unsubstituted), 4,4'-bis (3-phenyl-pyrazolone-5), 4,4'-bis (1-phenyl-pyrazolone- (5) -3-acetic acid ethyl ester),

4,4'-bis (i-phenyl-3-acetanilido-pyrazolone-5), 4,4'-bis (i-phenyl-3-p-chloro-acetanilido-pyrazolone-5) ₎ 4,4 ' -Bis- (i-phenyl-3-acet-a-naphthylamido-pyrazolon-5), 7 "4,4'-bis (i - ^ - naphthyl-pyrazolone- (5) -3-acetic acid ethyl ester),

4, 4'-bis (i- / S-naphthyl-3-acet-o-anisido-pyrazOlon-5), 4,4'-bis (i-phenyl-3-acet-a-naphthylamido-pyrazolon-5), 4,4'-bis (i-p-tolyl-3- (acet-2, 4-dimethylanilido) -pyrazolon-5),

4,4'-bis (3-anilino-pyrazolon-5),
4,4'-bis (i-acetyl-3-anilino-pyrazolone-5), 4,4'-bis (3-a-naphthylamino-pyrazolone-5), 4,4'-bis (3- o-bromanilino-pyrazolone-5), 4, 4'-bis (3-n-amylamino-pyrazolone-5), 4, 4'-bis (i-benzoyl-3-anilino-pyrazolone-5), 4 , 4'-bis (i-phenyl-3-anilino-pyrazolone-5), 4, 4'-bis (i-phenyl-3-p-anisyl-aminopyrazolone-5), 4, 4'- Bis- (i -phenyl-3-p- sulfamylphenyl-amino-pyr-

azolon-5),
4,4'-bis (i-phenyl-3-p- (p-tert-amyl-phenoxy) -phenyl-

amino-pyrazolone-5),
4,4'-bis (i- (3-carboxyphenyl) -3-heptadecylpyrazolon-5),

4,4'-bis (i- (phenyl-4'-sulfonic acid) -3-heptadecyl-

pyrazolone-5),
4,4'-bis (i- (phenyl-3'-sulfonic acid) -3-heptadecyl-

pyrazolone-5),
4,4'-bis (i- (phenyl-3'-carboxylic acid) -3-undecyl-

pyrazolone-5),
4,4'-bis (i- (ethane sulfonic acid) -3-p-nitrophenylpyrazolon-5),

4,4'-bis (i- (ethane-sulfonic acid) -3-methyl-pyrazolon-5), 4,4'-bis- (i- (ethane-sulfonic acid) -3-heptadecylpyrazolone-5),

4, 4 ^/ bis (i- (4'-phenyl-ethoxy) -3-methyl-pyrazolone-5), 4, 4'-bis (1 - (4'-nitrophenyl) -3-methyl-pyrazolone -5), 4,4'-bis (i- (4'-sulfo-a-naphthyl) -3-methyl-pyrazolon-5), 4, 4 ^/ -Bis- (i- (4'-sulfophenyl) -3-methyl-pyrazolone-5), ^{4,4'-bis (i- (2 /} -benzothiazolyl-3-anilino-pyrazolone-5) _> ^{4,4 /} -bis- (ia-quinolyl-3-anilino -pyrazolon-5), 4, 4'-bis (ia-pyridyl-3-anilino-pyrazolon-5), 4, 4'-bis (3-methyl-pyrazolon-5),

4,4'-bis (i, 3-di-phenyl-pyrazolone-5), 4,4'-bis (ip-tolyl-3-methyl-pyrazolone-5), 4,4'-bis ( i- (2 ^/ -methyl-5'-sulfo-phenyl) -3-heptadecyl-

pyr azolon-5),
4,4'-bis (1- (2'-methoxy-5'-sulfophenyl) -3- (3'-stearylamino-phenyl) -pyrazolon-5),

4,4'-bis (1- (2'-phenoxy-5'-sulfophenyl) -3 -heptadecyl-

pyrazolone-5) sodium salt,
4,4'-bis (i- (3-carboxyphenyl) -3-heptadecyl-

pyrazolone-5),
4,4'-bis (i-phenyl-3- (heptadecyl-4'-sulfonic acid) -pyrazolon-5) and

4,4'-bis (r-phenyl-3- (undecyl-3'-carboxylic acid) pyrazolone-5).

In general, the coupling components of the present invention that lack solubility Carrying promoting groups, insoluble in water. she

however, can be made water soluble by adding in the general formula given above substituents denoted by R are suitable solubility-increasing groups, e.g. B. sulfonic acid or carboxylic acid groups.

The condensation is carried out by adding a substituted or unsubstituted pyrazolone in The presence of phenylhydrazine is heated under reflux in a manner known per se. The substituted ones

ίο pyrazolones can be prepared by the US in the patent specifications 2200306, 2265221, 2334495, ² 343 7 ° 3 ^an d R ^e procedure described 22,329 are prepared. These substituted pyrazolones have an active methylene group in position 4 and correspond to the general formula

R-C:

sCO

N "

in which R and R _{1 have} the same meaning as above.

Those in the description and in the above

Substituted pyrazolones cited in patents are only examples, and they can also contain other substituents and also contain the substituents listed for the above formula.

It has been found that the nature of the substituents for R and R _{1 is} insignificant, since any substituted or unsubstituted pyrazolone with an active methylene group in the 4-position can condense in the presence of phenylhydrazine to give the corresponding symmetrical bis (pyrazolone) and that all of these products can be used as color formers.

The color formers or color couplers can be added to the developer if they are not in gelatin are diffusion-resistant, or the halogen silver emulsion in the form of a solution or suspension in a suitable Solvents such as B. 1 η-alcoholic sodium or potassium hydroxide solution, acetone, ethyl alcohol, isopropyl alcohol etc. For the preparation of the developers or the halide silver emulsions to be incorporated Suspensions of the water-insoluble color couplers can also contain dispersants, such as isopropylnaphthalene sulf acid or any of the dispersants mentioned in U.S. Patent 2,186,717 to be used. Instead of gelatin, the color couplers can also contain other colloids, such as organic ones Cellulose esters, super polyamides, polyesters or synthetic resins can be added. The emulsion can on a transparent material as a layer support, such as on cellulose esters, super polyamides, synthetic resins, or painted on an opaque, reflective material such as paper or opaque cellulose esters will. The emulsion can be applied to the substrate as a single layer, or it may be superimposed layers containing the coupling components on one or both Sides of the substrate are arranged. The superimposed layers can be in a known Be sensitized to different wavelengths.

If the color couplers are incorporated into the photographic silver halide emulsions, the substituents R in the above formula must be selected so that they prevent the color couplers from diffusing from one layer to another, since color shifts otherwise occur during color development. In order to prevent the color couplers from migrating out of the halogen silver emulsion layers and to make them diffusion-resistant, various methods have already been proposed. So z. B. the i- and / or 3-position of the pyrazolone nucleus can be substituted by suitable groups that give the color couplers substantive properties so that they really absorb the gelatin and the other colloids of the halogen silver emulsions, or the substituent of the color coupler can be a long-chain one Alkyl radical can be extended, which prevents the color coupler from diffusing out of the gelatin or the other colloids. Examples of methods of making color couplers diffusion-resistant by imparting substantive properties to them are given in US Pat. No. 2,179,228. Examples of color couplers which are made diffusion-resistant by lengthening the substituents (R and / or R ₁ ) are given in American patents 2175 512, 2 179 238/9, 2 179 234, 2 178 612, 2 179 344, 2179 244, 2 186 719, 2 186 851/2, 2 186 732/3/4, 2 186 849, 2 186 045, 2 200 306, 2 280 722, 2 292 575, 2 303 928 and 2 307 399 are given. According to the latter patents, the color couplers are by incorporating radicals from synthetic resins, polypeptides, hydrogenated ring systems, carbohydrates and. long aliphatic chains and by allowing the substituting radical to appear multiple times in the final molecule. The substituent groups of the color couplers of the present invention also contain, in addition to the above-mentioned substantivating groups or the molecule-enlarging radicals, in order to make the bis- (pvrazolones) diffusion-resistant.

Suitable aromatic primary amine developers to be used with the color couplers of the present invention are for example: p-phenylenediamine, Mono-ethyl-p-phenylene-diamine, diethyl-ophenylene - diamine, 4, 4 '- diamino - diphenylamine, ρ - amino -dialkyl- aniline, ζ. Β. ρ-amino-dimethylaniline and p-amino-diethylaniline. -These developers are expedient in the form of their salts, e.g. B. as hydrochloride, used because they are so more soluble and are more stable than in the form of the free base. They contain a free or primary amino group in the phenyl nucleus, which enables the oxidation product of the developer to work with the color couplers to form a To couple the dye image in the emulsion in register with the individual silver particles of the silver image. The silver image can then be removed by bleaching according to known methods, the Color image remains in the emulsion alone.

A suitable developer can be prepared as follows will:

p-amino-diethyl-aniline HCl 2.0 g

Sodium carbonate (anhydrous) 5 ° j ° 8

Sodium sulfite (anhydrous) 2.0 g

Potassium bromide 0.2 g

Water made up to 1 1

The exposed silver halide emulsions are developed with the above solution in the usual manner. A solution or suspension of the color coupler is only added to the developer if if the color coupler is not already in the Halogensüb it contains emulsion.

The invention is illustrated in more detail by the following examples.

Example I.

4,4'-bis (i-phenyl-3-methyl-pyrazolon-5)

HH

H ₃ C

CH ₃

This connection was named after Ann. 238 167 and Ber. 17.2044 prepared by adding 5 g of i-phenyl-3-methylpyrazolon-5 were refluxed with 15 ecm phenylhydrazine for 1 hour. After the The resulting precipitate was filtered off in the reaction mixture and recrystallized from ethyl alcohol.

ι g of this product was dissolved in 20 ecm of ethanol and 2 ecm of the solution were then added to the developer and exposed to develop one Halogen silver emulsion used. Coinciding with the silver picture, there became a purple picture obtain.

Example II

4,4'-bis (3-methyl-pyrazolone-5)
HH

H ₈ CC-

Il

CO OC

-C-CH ₃

Il

N
H

^N N
H

This connection was made according to the method of MaxEdam, Diss. Jena, 1893, pp. 16 and 29, by refluxing 5 g of 3-methyl-pyrazolone-5 with 20 ecm of phenylhydrazine for ι hour. After the reaction mixture had cooled, the resulting precipitate was filtered off and extracted from ethyl alcohol recrystallized.

ι g of this product was dissolved in 20 ecm of ethanol and 2 cc of the solution were then added to the developer liquid and used to develop a exposed silver halide emulsion used. It became, coinciding with the Süberbild, Got purple image.

4,

—C-

Example III:, 3 "diphenyl-pyrazolone-5) H H

p p

N CO OC N

a

According to the information in Ber. 20, p. 2548, prepared by adding 5 g of i, 3-diphenyl-pyrazolon-5 were refluxed with 20 ecm phenylhydrazine for 1 hour. After the reaction mixture had cooled, the resulting precipitate was separated off and recrystallized from ethyl alcohol.

ι g of this product was in 20 ecm of ethanol dissolved and 2 ecm of the solution was added to the developer liquid and to develop a exposed silver halide emulsion used. Coinciding with the Süberbild, it became a Got purple image.

Example IV

4,4'-bis (i-p-tolyl-3-methyl-pyrazolon-5) H H

H ₃ CC-

N CO OC

-C-CH ₃

CH ₃

CHo

This connection was established according to the information provided by C. T. Sprague, Diss. Göttingen, 1890, p. 46 (It can also be presented according to the method of W. Hippmeir, Diss. Jena, 1894, p. 17 be) by adding 5 g of i-p-tolyl-3 ~ methyl-pyrazolon-5 with 15 ecm phenylhydrazine under reflux for 2 hours were heated. After the re-

action mixture became the excreted product filtered off and recrystallized from ethyl alcohol.

ι g of this product was in 20 ecm of ethanol dissolved and 2 ecm of the solution was added to the developer liquid and to develop a exposed silver halide emulsion. Coinciding with the silver picture, it became purple Image received.

Example V

4,4'-bis (i- (4'-ethoxyphenyl) -3-methyl-pyrazolon-5) H H

H ₃ CC-

-C-CO ₃

N CO OC N

[i

OC ₉ H ₁ -.

H ₅ C ₂ O

This connection was made according to the method of J. Grenzfelder, Diss. Jena, 1894, p. 17, by refluxing 5 g of i- (4'-ethoxyphenyl) -3-methyl-pyrazolon-5 with 20 ecm of phenylhydrazine for 2 hours were heated. After the reaction mixture had cooled, the precipitate was separated off and out Recrystallized ethyl alcohol.

ig of this product was in 20 ecm ethanol dissolved and 2 ecm of the solution became the developer liquid added and used to develop an exposed silver halide emulsion. It was, coinciding with the silver picture, a purple picture is obtained.

Example VI
4,4'-bis (i- (4'-nitrophenyl) -3-methyl-pyrazolon-5)

-C-

H
-C-

CO OC

-C-CH ₃

NO ₂

NOo

This compound was prepared according to the procedure mentioned in Example V by adding 5 g of 1- (4'-nitrophenyl-3-methyl-pyrazolone-5) were heated under reflux for 2 hours with 20 ecm phenylhvdrazine.

After the reaction mixture had cooled, the resulting precipitate was separated off and taken from ethanol recrystallized.

ι g of this product was in 20 ecm ethyl alcohol solved; 2 ecm of the solution were added to the developer liquid and an exposed one was used to develop Halogen silver emulsion used. It became a purple in accordance with the silver image Image received.

Example VII 4,4'-bis (i- (4'-sulfo-a-naphthyl) -3-methyl-pyrazolone-5)

-C-CH ₃

CO OC

SO ₃ H

SO ₃ H

This connection was made according to the information provided by M. Müller, Diss. Jena, 1892, p. 22, prepared by adding 5 g of i- (4'-sulfo-a-naphthyl) -3-methyl-pyrazolon-5 with 15 ecm phenylhydrazine were heated under reflux for 2 hours. After the reaction mixture had cooled, the precipitate was filtered off and removed Recrystallized ethanol.

1.8 g of the above-mentioned color coupler were dissolved in 2 ecm ι η-alcoholic potassium hydroxide solution and taken under good mixing to 100 ecm of a gelatin silver bromide iodide emulsion admitted. After applying the emulsion containing the color coupler to a suitable one Backing and, after drying, the film was exposed and developed, creating coverage a purple image was obtained with the silver image.

Example VIII 4,4 ^/ -Bis- (i- (4'-sulfophenyl) -3-methyl-pyrazolone-5)

H H

-C- C-CH ₃ U ₅

N CO OC N

SO ₃ H SO ₃ H

This compound was prepared according to the procedure given in Example VII by adding 5 g of i- (4'-sul - fophenyl) -3-methyl-pyrazolon-5 with 15 ecm phenyl hydrazine were refluxed for 2 hours. After the reaction mixture had cooled, the Filtered off precipitate and redissolved from ethanol.

1.8 g of the color coupler became n-alcoholic in 2.0 ecm 1 Potassium hydroxide solution and, with thorough mixing, to 100 ecm of a gelatin-silver bromide-iodide emulsion added. After moving from the emulsion to a had prepared a layer on a suitable film base and dried it, the film was exposed and developed, whereby it had a magenta-colored image in register with the silver image.

Example IX-4,4'-bis (i-phenyl-3-heptadecyl-pyrazolone-5)

H ₃₅ C ₁₇ C

C-C ₁₇ H ₃

This compound was prepared by adding 5 g of i-phenyl-3-heptadecyl-pyrazolone-5 with 20 ecm of phenylhydrazine Was refluxed for 2 hours. The reaction mixture was allowed to cool and the precipitate is filtered off and recrystallized from ethyl alcohol.

1.8 g of the compound obtained were in 2 ecm Dissolved water and the solution to 100 ecm of a gelatine-silver bromide-iodide emulsion admitted. The emulsion was poured onto a support made of cellulose acetate and dried. The movie was then exposed and developed, an image being more splendid in accordance with the silver image Purple color was obtained.

Example X

4,4'-bis (i- (4 ^/ -sulfophenyl) -3-heptadecyl-pyrazolone-5) HH

H ₃₅ C ₁₇ -C-

CO OG

-C — C ₁₇ H ₃₅ N

SOoH

SO ₅ H

This connection was obtained by the connection of Example IX was sulfurized with 30% fuming sulfuric acid with cooling.

After recrystallization from water, 1.8 g of the product obtained were dissolved in 2 ecm of water dissolved and the solution 100 ecm of a gelatin-silver bromide-iodide emulsion added. The emulsion was painted onto a cellulose acetate film base and dried. After exposure and development, the emulsion became a dye image Obtained of excellent purple color.

Example XI

4,4'-bis- (i-phenyl-pyrazolon- (5) -3-acetic acid ethyl ester) HH

I I

H ₅ CaO-OC-H ₂ CC-CC C-CH ₂ -CO-OC ₂ H ₅

Il Il Il

N CO OC N

'5g i-phenyl-pyrazolone- (5) -3-acetic acid ethyl ester, produced according to example 1 of the American patent 334 495, 2 hours with 20 ecm Phenylhydrazine heated to reflux. After the reaction mixture had cooled, the precipitate became separated and recrystallized from ethanol. 1.8 g of the above color coupler were in

ecm ι η-alcoholic potassium hydroxide solution and under iac thorough mixing to 100 ecm gelatin-silver bromide-iodide emulsion admitted. After applying the emulsion to a suitable substrate and drying, the film was exposed and developed, in accordance with that Silberbild a purple-colored picture was created.

Cl-

Example XII

4,4'-bis (i-yS-naphthyl-3-p-chloroacetanilido-pyrazolone-5) H H

• _NH —CO —CH ₂ —C C — CH ₂ —CO —HN

> —Cl

5 g i-ß-naphthyl-s-p-chloroacetanilido-pyrazolon-s, prepared according to Example 8 of American patent specification 2,334,495, phenylhydrazine were used with 20 ecm Heated under reflux for 2 hours. After the reaction mixture had cooled, the precipitate became separated and the ethanol recrystallized.

1.8 g of the product formed were in 2 ecm Dissolved water, and the solution was added to 100 ecm of a gelatin-silver bromide-iodide emulsion. the Emulsion was coated on a cellulose acetate film support and dried. After exposure and During development, a dye image with an excellent purple color resulted in the emulsion.

Example XIII 4, 4'-bis (i-phenyl-3-acet-a-naphthylamido-pyrazolone-5)

NH-CO-CH "-C C-CHo-CO-HN

5 g of i-phenyl ^ -acet-a-naphthylamido-pyrazolon-s (produced according to example 6 of American patent 2 334 495) were 2 hours with 20 ecm Phenylhydrazine heated to reflux. After the reaction mixture had cooled down, the was obtained Filtered off precipitate and recrystallized from ethanol.

1.8 g of the product formed were in 2 ecm Dissolved water and the solution with 100 ecm a Gelatin silver bromide iodide emulsion mixed. the Emulsion was painted on a cellulose acetate film support and dried. After exposure and development, a dye image with an excellent purple color resulted in the emulsion.

Example XIV

4,4'-bis (3-anilino-pyrazolone-5)
HH

5 g of 3-ani] ino-pyrazolones (manufactured according to American patent Re 22329) were refluxed for ι hour with 15 ecm phenylhydrazine. After the reaction mixture had cooled, the resulting precipitate was filtered off and removed Recrystallized ethyl alcohol. "

i, 8 g of the product obtained were in 2 ecm Dissolved water, and the solution was mixed with 100 ecm of a gelatin-silver bromide-iodide emulsion. The emulsion was coated on a cellulose acetate support and dried. After exposure and development became a picture; Obtained in an excellent purple color.

Example XV 4,4'-bis (i ~ phenyl-3-p-anisyl-aminopyrazolone-5)

H H

ΗΧΟ

OCH,

5 g of i-phenyl-s-p-anisyl-amino-pyrazolone-s (prepared according to the American patent specification 2343703) were refluxed with 20 ecm phenylhydrazine for 2 hours. After the reaction mixture had cooled, the precipitate was separated off and out Recrystallized ethanol.

1.8 g of the above color coupler were in 2 ecm ι η-alcoholic potassium hydroxide solution and the solution became 100 ecm of a gelatin-silver bromide-iodide emulsion with thorough mixing added. After the emulsion with the color coupler to a suitable Film base had been poured on and dried, the film was exposed and developed, wherein . a purple image was obtained in accordance with the silver image.

Example XVI 4,4'-bis (i- (3-carbQxyphenyl) -3-heptadecyl-pyrazolone-5)

5 S i- (3-carboxyphenyl) -3-heptadecyl-pyrazolone-5 (prepared according to Example I of American Patent 2 200 306) were refluxed with 20 ecm of phenylhydrazine for 2 hours. After the reaction mixture had cooled, the precipitate was filtered off and recrystallized from ethanol. 1.8 g of the above color coupler were dissolved in 2 ecm COOH

ι η-alcoholic potassium hydroxide solution and under good iao Mix to 100 ecm of a gelatin silver bromide iodide emulsion given. After pouring the emulsion with the color coupler onto a suitable film base and drying, the film was exposed and developed, in accordance with that Silver image a purple image was obtained.

Example XVII
4,4'-bis (i- (a-cb.inolyl) -3-anilino-pjrazolon-5)

N CO OC N

5 g of i- (a-quinolyl) -3-anilino-pyrazolon-5), which is in the The usual way were prepared with 20 ecm phenylhydrazine for 2 hours under reflux heated. After the reaction mixture had cooled, the precipitate was filtered off and extracted from ethyl alcohol recrystallized.

1.8 g of the color coupler became more n-alcoholic in 2 ecm 1 Dissolved potassium hydroxide solution and, with thorough mixing, 100 ecm of a gelatin-silver bromide-iodide emulsion added. After spreading the emulsion with the color coupler onto a suitable film substrate and drying, the film was exposed and developed, being in accordance with the silver image a purple colored image was obtained.

Example XVIII

4,4'-bis- (i-sulfonyl-ethyl-3-methyl-pyrazolon-5)
HH

JdLoU — O ——— ν

N CO OC N

HO ₃ SH ₂ CH ₂ C

CH ₂ CH ₂ SO ₃ H

5 g of i-sulfonyl-ethyl-s-methyl-pyrazolone-s (prepared according to example 2 of the American patent specification 2 265 221) with 20 ecm phenylhydrazine were 2 hours heated to reflux. After the reaction mixture had cooled, the precipitate was filtered off and recrystallized from ethanol.

1.8 g of the color coupler became more n-alcoholic in 2 ecm 1 Potassium hydroxide solution and, with thorough mixing, to 100 ecm of a gelatin-silver bromide-iodide emulsion added. After spreading the emulsion with the color coupler onto a suitable film substrate and drying, the film was exposed and developed, being in accordance with the silver image a purple image was obtained.

Claims (6)

Patent claims: i. Process for the preparation of purple photographic images in halosilver gelatin emulsion layers characterized by color-forming development with the use of aromatic primary amines as developers through the use of coupling components of the general formula: H H R-C- CO OC C-R R ₁ R ₁ ^{1 Χ} in which R is hydrogen, alkyl, aryl, arylamino, acetarylamido or aralkyl groups and R _{1 is} hydrogen, alkyl, aryl, aralkyl or heterocyclic groups. 2. The method according to claim 1, characterized in that that the coupling component is added to the developer. 3. The method according to claim 1, characterized in that that the coupling component is added to the halosilver gelatin emulsion layer will. 4. The method according to claim 1 to 3, characterized in that that 4,4'-bis (i- (4'-sulfo-a-naphthyl) -3-methyl-pyrazolon-5) is used as a coupling component. 5. The method according to claims 1 to 3, characterized in that that 4,4'-bis (i- (4'-sulfophenyl) -3-methyl-pyrazolon-5) is used as a coupling component. 6. The method according to claim 1 to 3, characterized in that 4,4'-bis (i-phenyl-3-heptadecyl-pyrazolone-5) is used as a coupling component. Referred publications: British Patent No. 513 596, © 5294 7.53