DE1927924A1 - Color photographic material - Google Patents

Description

AGFA-GEVAERT "~ ²ⁿⁿ

PATENT DEPARTMENT

Leverkusen May 30, 1969 Hs / tfs

garbphotographlschea material

The invention relates to new 2- ^ yrazolin-5-one couplers and a Photographic light-sensitive material containing such couplers to form a magenta image.

It is known for the production of color photographic photosensitive silver halide emulsion layers Exposure to develop in the presence of color-forming couplers with a color developing agent. In the eubtractive Tricolor photography is usually used with a multilayer photographic light-sensitive material one red-sensitized, one green-sensitized and a blue-sensitive silver halide emulsion layer wherein on development in the presence of suitable color couplers a blue-green, a purple bsw. a yellow picture emerges.

90988B / 1708

With many of the known 1-aryl-2-pyrazolin-5-one purple couplers the aryl group in the 1-position represents a benzene ring with Substituents such as halogen, alkyl groups, alkoxy groups, Alkylthio groups or alkylsulfonyl groups.

These 1-aryl-2-pyrazolin-5-one couplers contain a group in the 3-position which mainly serves as a ballast group and the tendency of the couplers to diffuse in the photographic colloid layers is reduced. However, you can also Diffusible couplers are prepared by suitable choice of the substituent in the 3-position, for example by a Low molecular weight substituents. As substituents in the 3-position of l-aryl-2-pyrazolin-5-one purple couplers For example, alkylamino, arylamino, acylamino, and also urethane or urea groups are suitable. Examples of this can be found in the literature, e.g. in English patents 909,318 and 1,069,534; in U.S. Pat. Patents 2,369,489, 3,325,482, 3,330,660, and 3,393,071, in Japanese patent specification 7039/57 and in German patent specification 1,176,479

New 2-pyrazolin-5-one purple couplers have now been developed which contain a phenyl ring in the 1-position, with at least one haloalkoxy group, haloalkylthio group or haloalkylsulfonyl group, preferably a Cl ₂ HC-SO ₂ -, a ClHgC-SOg-, a RCP ₂ O-, an RCP ₂ S or an RCFgSOg group, where R stands for hydrogen, fluorine or polyhaloalkyl, for example for -CHF ₂ , -CHFCl, -CHFBr, -CFCl ₂ , -CCl ₅₁ -CHF-CF ₅ and the same.

The color couplers of the present invention are represented by the following general formula I:

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where mean:

Q = haloalkoxy, haloalkylthio or halogenalkylsulfonyl, sB Cl ₂ HC-SO ₂ -, ClH ₂ C-SO ₂ -, RCFgO-, HCFgS- or RCFgSOg-, where R has the meaning given above,

Z = hydrogen, halogen such as chlorine, alkyl, alkoxy, alkylthio, Alkyleulfonyi or the groups Q and defined above

R ₁ = an alkyl group, an ary! Group, an acyl group, sB one which is derived from aliphatic, araliphatic or aromatic carboxylic acids or sulfonic acids, a carbamyl group, sB alkylcarbamyl, aralkylcarbamyl or arylcarbanyl, or an oxycarbonyl group, sB alkoxy carbonyl, aroxycarbonyl or aralkoxy carbonyl; the group R ₁ can also contain substituents which are suitable for influencing the physical, spectral and / or sensitometric properties of the color couplers and the dyes formed from them, for example halogen, selfo, carboxyl, alkoxy or phenoxy, which in turn are substituted in can, sB by halogen, sulfo, carboxyl or alkyl.

The color couplers of the previous charge differ Sound the well-known 2-fyrasolin-S-OB "tarhkuppl © rn by the fact that they in the 1-Fosltion of the 2- ^ rrasolia- = 5-one * I @ rn a benxolring old at least one haloalkoxy group, a halo-alkylthio group or a haloall ^ isulphonyl group. the Erfiadunegeaäflen color couplers are d @ & äekasmten suppliers Superior to similar structure in several respects. It proves to be extremely advantageous, for example, that the must have favorable spectral and sensitometric properties for them during development, E.B. they have a less broad spectral absorption curve and so there is little absorption of life in the undesired ones Areas of the spectrum. Another advantage is that they have improved stability against moisture and have light.

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In the manufacture of suitable photographic multilayer materials bit color couplers to form the one Partial images in the differently sensitized silver halide emulsion layers, the color couplers in diffusion-proof form in the hydrophilic silver halide emulsions * layers or stored in water-permeable neighboring layers. *

In order to reduce the tendency of the color couplers according to the invention to diffuse in the photographic colloid layers, they can, for example, be provided with a ballast group in the 3-position of the 2-pyrazolin-5-one ring. The group R ₁ can, for example, represent or contain a substituent of the formula -ZD, where D represents an acyclic aliphatic hydrocarbon radical with 5-20 carbon atoms and X represents a chemical bond, oxygen, sulfur, sulfonyl, -CONH-, -NHCO-, -SO ₂ N (R ₂ ) - with R ₂ = H or alkyl, -NHSO ₂ - or - »(alkyl) -.

Another interesting method is the color couplers according to the invention in a diffusion-proof manner in photographic colloid layers storage consists in using them in polymeric form, e.g. by copolymerizing monomeric color couplers according to the present invention, which in the 3-position a Ethylenic group, e.g. the group

T

-IfHCO-C = CH ₂

where T is hydrogen, halogen, a short-chain alkyl radical, Aralkyl or aryl means, bit one or more non-color-forming monomers, the at least one .äthylenische Group included.

The present invention therefore furthermore relates to both monomeric 2-pyrazolin-5-one color couplers corresponding to the general formula I, where R _{1 is} an acyl group

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formula

Y -CO-C = CH ₂

stands, in which T is defined as above, as well as polymeric color couplers which contain recurring units of the following general JSbrmel II:

H ^CH 2 C-HHCO-CY

wherein Z, Q and Y are as defined above.

The following couplers serve to illustrate the present invention, which, however, are not specifically pointed to Coupler should be limited.

1. · SO ₂ -CHF ₂

O = C Ν "

HC- C-NHCO- <^ 2> -0- (CH ₂ ) ₁₅ -

O = CN SO ₃ H
HpC C-NHCO-CH- (CH ₂ )

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SO ₂ -CHF ₂

O = C N ι II

H-C C-NHCO-

SO ₃ H

-0 (CH

O = C N

H ₂ C C -NHCO- (CH ₂ ) ₁₄ -CH ₃

SO ₂ -CHF ₂

O = CNI II H ₂ C —C-NHCONH- (CH) _1? -CH

SO ₂ CF ₃

O = C N ι π

H ₂ C C -NHCONH- (CH ₃ ) _1? -

9885/1708

SO ₂ -CF ₂ -CHFCl

T-

O = C N

H _? C C -C -NHCO- (CH ₂ ) ₁₄ "" ^CH 3

β.

SO ₂ -CF ₂ -CHFCl

O = C N

<(I
H ₀ C C-NHCO-

10.

-S-CHF.

N. -. -C-NHCO- (CH ₂ ) ₁₄ -CH ₃

I] -O-CF ₂ -CHFCl

O = C N-

C-NHCO-

C. C-—

?> -Q- (CH ₂ )

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O = C

-Lnh-U

COOH

12th

MO-CF ₀ -CHFCl

O = CN
I Il

H ₂ C ---C-NHCO- (CH ₂ )

13th

0-CF ₂ -CHFCl

O = C N

H ₂ C C -C NHSO ₂ - (CH ₂ ) ₁₅ -CH ₃

14th

0-CF ₂ -CHFCl

O = C N CH.

i I »I ³

H-C C -C -NHCO-C = CH.

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SO ₀ -CP ₉ -CHFCl

0-CN (CH ₀ K ₁ , -CH, i3

-Cl

CH

16,

^ S-SO ^ -CH.-Cl

O = C N H ^ C- C-NH-CO-O-CH ^ -

₂ -CH ₂ -O

-Cl

17. ^C1 * Cl '

O = C N

_? C -, - C-NHCO-O-CH ₂ -CH ₂ -O - <> ^

-Cl

18th

^ -SO ₂ -CH ₂ -Cl

c ' ^N

I II CCH ₂ ) ₁₃ -CH ₃

-NH-CO-O-

¹⁹ *

O = C'N H ^ CC-NH-CO-O-CH ₀ -CH ₀ -O ^w "2 X =

A-S 508

20th

-SO ₂ -CH '

O = C N (CH) -CH.

1 ti ι 2 13 3

V - ^C - ^NH -C0-0- ^

The inventive diffusion-resistant couplers with a ballast group in the 3-position can according to any of the known methods incorporated into the photographic dilution will. Water-soluble color couplers, «. B. those that one or contain several sulfo or carboxyl groups, can corresponding semolina solutions are prepared from aqueous solution, optionally in the presence of alkali. BIe in water Poorly soluble or insoluble color couplers are in a suitable water-miscible or not with water Miscible high-boiling or low-boiling organic solvent or solvent mixture dissolved and the so obtained solution is optionally in the presence of a let- or dispersant in a hydrophilic colloid mixture the dispersed, all or part of the binder of the Colloid layer forms. The hydrophilic colloid mixture can of course also contain all of the usual ingredients contain.

"The polymeric color couplers can be added to the photographic colloid mixtures can be added by any of the methods known for this purpose. For example, they can be dissolved in water or in water-miscible or immiscible solvents or solvent mixtures, whereupon the resultant Solution optionally dissolved in the presence of a hardening or dispersing agent in a hydrophilic colloid mixture or is dispersed. The polymeric color couplers can also have hydrophilic colloid layers in the form of latex trains « are set.

Ag 508 - 10 -

The solutions of the monomeric or polymeric color couplers as well as the corresponding color coupler latices do not necessarily need to be observed directly in the casting solutions. They can also advantageously first be dissolved or dispersed in an aqueous non-photosensitive hydrophilic colloid solution, whereupon the resulting mixture, if appropriate after removal of any organic solvents used, of the photosensitive silver halide emulsion or another hydrophilic casting solution immediately before the Potting is added.

Useful methods lur incorporation ballast group carrying a diffusion-resistant color couplers in hydrophilic colloid layers described in one of a in the following patents: in the British patent specifications 7911219t 1,098,594 _f 1,099,414, 1,099,415, 1,099,416 and 1,099,417, in French Patent 1,555,665, U.S. Patent 2,304,940 and in Belgian Patent 722,026.

Details of the synthesis of polymeres? Color coupler as well as the Production of latices from it, as well as the incorporation of the named polymeric color couplers in photographic Colloid mixtures can be found, for example, in Belgian patent specification 669,971 or English patent specification 1,130,581 can be removed.

The color couplers of the present invention can be used in conjunction with a wide variety of photographic emulsions be used. All photosensitive substances come in general the most varied of silver salts are in question ".3. Silver chloride, silver bromide or mixtures thereof, the optionally contain up to 10 Kol-ji silver iodide. the Color couplers can, for example, be used with emulsions in which the latent image mainly arises on the surface of the silver halide grain or with such emulsions in which the latent image occurs predominantly in the interior of the silver halide crystal.

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As a hydrophilic binder for the photosensitive silver halide For example, gelatin, colloidal albumin, zein, casein, a cellulose derivative, a synthetic one come into question hydrophilic colloid such as polyvinyl alcohol, poly-N-vinyl pyrrolidone and the like. Mixtures can optionally also be used of two or more of these colloids can be used.

The photosensitive silver halide emulsions of the present invention can be chemically or spectrally sensitized. the chemical sensitization can for example be achieved by ripening in the presence of small amounts of sulfur-containing compounds such as allyl thiocyanate ^ allyl thiourea, Sodium thiosulfate, etc. The emulsions can also be sensitized by using reducing agents, e.g. tin compounds as described in French Patent 1,146,955 and in Belgian patent 568,687, by pormamidinesulfinic acid derivatives as described in English Patent 789,823 and small amounts of noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or Rhodium compounds. Spectral sensitization can by using cyanine and herocyanine dyes.

The emulsions mentioned can also be development accelerators contain, e.g., compounds of the polyoxyalkylene type, e.g., alkylene oxide condensation products such as those described are in American patents 2,531,832, 2,533,990, 3,210,191 and 3,158,484, in English patents 920,637 and 991,608 and in Belgian patent specification 648,710 or onium compounds of amino-N-oxides such as described in English patent specification 1,121,696. The emulsions can also be stabilized with heterocyclic ones nitrogen-containing thio compounds such as benzothiazoline-2-thione or 1-phenyl-2-tetrazoline-5-thione or compounds of the hydroxy-triazolo-pyrimidine type. The stabilization can also can be achieved by mercury compounds as they are

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games are described in the Belgian patents 524,121, 677,337 and 707,386 and in the American U.S. Patent 3,179,500.

The photosensitive emulsions can also include any other Types of ingredients include such as "B. Plasticizers, hardeners, wetting agents, etc.

The magenta couplers according to the invention are preferably accommodated in the green-sensitized silver halide emulsion layer of a multilayer color photographic material. Such fairphotograph multilayer materials generally consist of a support, a red-sensitized silver halide emulsion layer with a cyan coupler, a green-sensitive silver halide emulsion layer with a purple rappler and a blue-sensitive silver halide emulsion layer with a yellow coupler. But there are also other combinations, especially others

The erfindunggg®MäS © a Emulsioa @ a kösm @ n on the various staa photographic.Sehicattragem Y © rgoss @ n. Typical substrates are b © ispi @ lsw © i © © lilac® aua callulose ester, polyvinyl acetate, polystyrene l @ ljätfefl © nt ^r @ ^ © phthalate and similar layer-forming materials ₉ as mu & h paper and glass.

In order to produce photographic color images in accordance with the invention, bright silver halide emulsion layers are developed in the presence of color couplers according to the invention, preferably with a developer substance containing aromatic primary amino groups. Suitable developer substances are aromatic compounds such as p-phenylenediamine, N, N ¹ -dialkyl-p-phenylenediamine, aB N, N-diethyl-p-phenylenediamine and their derivatives such as ^ N-dialkyl-IP-sulfomethyl-p-phenylenediamine and N, N-dialkyl-N-carboatymethy 1-p-phenylenediamine.

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909 68 5/1 7 0 P.

The l-aryl-2-pyr * ssolin-5-one color couplers of the general formula I, in which R _{1 is} an aryl group, an acyl group, a carbamyl group, tine Alkojycarbony! Group, an aroxycarbonyl group or an aralkoxycarbonyl group, can be prepared, for example, by Use one of the methods as described in English patents 909,318 and 1,069,534-, in American patents 2,369,489, 3,325,482, 3,330,660 and 3,393,071 and in German patent 1,176,479, where the corresponding l-aryl-3-amino-2 » pyraz © - lin-5-on connection is assumed.

The required 3-amino compounds can according to known Methods are produced by ringing a suitable substituted pheny! Hydrazine, b @ ispielsw @ i @ e with ß-Iaiao = · ß-ethoxy-propionic acid-ethy ester.

The following describes the synthesis of the l-aryl-O-aaino ^ -pyrazolin-5-one compounds as well as the color coupler according to Arfindusags are explained with a few examples.

A. Synthesis of the l-Aryl-S-aminq -ff ^ p yrmzolin-S-one compounds

Synthesis 1: l-p-Trifluorometh. ¥ lsulfonylphen.Yl-3-amino-2-pyra- zolin-5-one

22 g of p-trifluoromethylsulfonylphenylhydrazine, prepared according to the specification in Bull.Soc.Chim.BeIg. 2 £ _s 270 (1965) and 18 g of beta-imino-.beta.-ethoxy-propionic acid äthylesterhydrochlorid are heated in 50 ml of pyridine for 1 hour at 40 ⁰ G «The reaction mixture becomes solid and acetonitrile is" added The white precipitate is filtered off with suction.

22 g of the precipitate are mixed with 20 ml of setramethylguanidine added and heated for 30 minutes on a boiling water bath. The mixture is then diluted with water and the formed solution acidified by adding 2 η hydrochloric acid. The lower

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shock is suctioned off and recrystallized from toluene with the addition of a little acetonitrile ..
Fixed point: 188 ⁰ C.

Synthesis 2; l ~ p-J) ifluoromethylsulfonylphenyl-3-ainlno-2-pyrazolin-5-one

222 g of p-difluoromethylsulfonylphenylhydrazine, prepared according to the specification in Bull.Soc.Chim.Belg. J ±, 270 (1965), 200 g of .beta.-ethoxy-.beta.-imino-propionBäure-äthylesterhydroehlorid and 4 ml of acetic acid are melted on -this water bath at 90 ⁰ C. It resultant homogeneous melt is gertihrt one hour at 40 ⁰ C, wherein the ethanol formed is sucked off by a water jet pump.

A solution of 46 g Hatrium in 700 ml of methanol is added and the mixture heated for 30 min. At 50 ⁰ C. It is diluted with water, acidified and the precipitate formed is filtered off with suction. The precipitate is washed with water and recrystallized from ethylene glycol monome thy lather. Fixed point: 219 ⁰ C

Synthesis 3: lp- (l _t 1,2-Trlfluor ^ -chloräthoacy) -phenyl-3-amino-

a) 113 gp (l, 1,2-trifluoro-2-chlDratshoacy) aniline are added to 200 ml of concentrated hydrochloric acid and 75 ml of water. A white precipitate forms. It is cooled to 5 ^° C. and diazotized at this temperature by adding a solution of 35 g of sodium nitrite in 175 ml of water. Then we stir for 30 minutes.

The cold Diazoniumlßsung is added at 1O ⁰ C to a solution of 337.5 g of SnCl ₂ .2HgO in 350 ml of concentrated hydrochloric acid. One stirred for 2 hours at 10 Carry ⁰ C and then gradually heated to a Wasaerbad to 60 ⁰ C. The mixture is filtered hot and the precipitate with a 60 ⁰ C hot saturated sodium chloride solution. Then Aa 508 - 15 -

0 0 9885/1708

the precipitate is suspended in a 10 η sodium hydroxide solution and extracted with benzene. The benzene solution is dried over magnesium sulfate and distilled under reduced pressure. Boiling point: 120 ° C / lmm.

b) 72 g of the product obtained under a), 60 g of ß-ethoxy-ßimino-propionic acid ethyl ester and 1.8 ml of acetic acid are mixed and 30 Hin. left to stand for a long time at room temperature. The mixture is then ^{stirred for 1 hour at 50 °} C., the ethanol formed being sucked off with the aid of a water jet pump.

A solution of 14 g of sodium in 250 ml of ethanol is added and the mixture is left to stand for 1 hour at room temperature. It is diluted with water and acidified with acetic acid. The precipitate formed is recrystallized from methanol. Fixed point: 158 ⁰ C.

Synthesis 4: l-o- (1 «1.2-trifluoro-2-chloroethoxy) -phenyl-3-amlno-2-pyrazolln-5-one

a) 900 g of o- (1,1,2-trifluoro-2-chloroethoxy) aniline (Bull.Soc.Chim. France 1957, 581) were dissolved in 2.4 1 5 η hydrochloric acid at 5 ⁰ C diazotized with a solution of 280 g of sodium nitrite in 600 ml of water. After filtering, the solution is added to a solution of 2080 g of SnCl ₂ .2HgO in 2080 ml of concentrated hydrochloric acid. The mixture is stirred for one hour and the precipitate is filtered off with suction. The precipitate is washed with a 20 # aqueous sodium chloride solution.

Suspending the precipitate in a mixture of 4 1 of water and 4 1 2 1 10 are benzene η sodium hydroxide solution added and the mixture heated with stirring to 60 ⁰ C. The benzene layer is separated and the aqueous layer extracted with benzene. The combined benzene solutions are dried over magnesium sulfate, concentrated in vacuo and distilled under reduced pressure. Boiling point 120 - 125 ⁰ C / lmm.

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b) 48 g of the hydrazine obtained under a), 40 g of ß-ethoxy-ßimino-propionic acid ether and 1.2 ml of acetic acid are stirred for 90 minutes. A solution of 9.2 g of sodium in methanol is added, whereupon the temperature rises to 30 ^° C. It is cooled to room temperature and stirred for 2 hours. After evaporating the alcohol, the mixture is dissolved in water and acidified. The precipitate is filtered off with suction and recrystallized from acetonitrile.
Fixed point: 168 ⁰ C.

Synthesis jäs lo ° BifluormethvltMophenyl- ^ -amlno ° 2-pyi ⁱ azolin-5- one

a) 320 g of aluminum hydroxide are dissolved in 800 ml of diethylene glycol dimer and 150 ml of water while stirring. The solution v / ground 125 g Q-liaimo ^ thi © phenol was added, and the solution at 40 ⁰ C. erwärat initiates uad 2 hours Difluorchiormethan. Here, the temperature rises to 60 to 65 ⁰ C. Wtnn forms a precipitate is sugegeben water. The organic layer is separated off and the aqueous layer is washed with ether. The ether is evaporated off under pressure and the residue is acidified with 6% hydrochloric acid. The crystalline precipitate was filtered, washed with xther and recrystallized from acetic acid

Fixed point 180 ⁰ C (sublimation).

b) 120 ml of 5 η hydrochloric acid and 160 ml of water are placed in a 1 liter three-necked flask equipped with a stirrer, thermometer and dropping funnel. With stirring, 63 adds "g under a obtained o-Difluormethylthioanilinhydrochlorids added. The product is diasotiert at 51 ⁰ C by dropwise addition of a solution of 22.8 g of sodium nitrite in 60 ml water. The mixture is stirred until everything has dissolved. The solution is Filtered and ^{cooled to 0} ° C., whereupon a solution of 187.5 g of sodium sulfite in 225 ml of water is added as quickly as possible. The mixture is heated to 70 ^° C., during which the precipitate formed dissolves. It is then concentrated with 25 ml Acidified with salt acid and the re-

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Action mixture held at 65-7O ⁰ C for 4 hours. Allow to cool overnight. The precipitate formed is filtered off and dissolved in water. The solution is neutralized by adding 2 η sodium hydroxide solution, whereupon it is extracted three times with ether. The collected ether extracts are concentrated. The residue is distilled under reduced pressure. Boiling point: 120 ° C / 1.5 mm.

c) The hydrazine obtained under b) is usually processed further. The corresponding 3- * amino ~ 2-pyrazolin-5-one is isolated as a monohydrate and recrystallized from Mithanoi. Plague point: 60 ⁰ C.

Synthesis 6: lp- (l.1,2-trifluoro-2-chloroethylphenyl) -phenyl-

a) 117 g of p- (l, l »2-trifluoro-2-chloroethylsilfoml) = chlorobenzene are dissolved in 175 ml of ethanol and gel for 16 hours in the presence of 64 g of anhydrous hydrazine. The reaction mixture is concentrated and treated with water. The precipitate formed is filtered off with suction and recrystallized from ethanol.

Plague point: 102 ⁰ C..

b) The hydrazine obtained is usually processed further, The corresponding 3-amino-2-pyrazolin-5-one is recrystallized from ethanol.

Fixed point: 168 ⁰ C.

Synthesis 7: l- (2-chloro-5-chloromethylsulfonylphenyl) - 3-amino-2 · - pyrazolin-5-one

a) 4-chloro-3-nitrophenyl-chlormethyl®ulfon are added to a 70 ⁰ C hot solution of 1140 g SnCIg in 1800 ml of concentrated hydrochloric acid was added so that the temperature slowly rises to 100 ⁰ C. The solution is kept at this temperature by adding more sulfon and after adding a total of

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/ (9

192792 /,

stirred 10O ⁰ C '- together with 410 g of sulfone further 30 min at 95..

It is allowed to cool and decanted from the precipitate, which is then washed twice with 2 liters of 20% hydrochloric acid. It is suctioned off and the moist filter cake is treated with water until the hydrochloride has been completely converted into the free amine.
Melting point: 89-93 ° C

b) 140 g of the aniline obtained under a) are dissolved in 570 ml of glacial acetic acid while warming on a water bath. The solution is filtered and 1750 ml of concentrated hydrochloric acid are added. By adding a solution of 42 g sodium nitrite in 100 ml of water is diazotised at -20 to -5 ⁰ C. The mixture is stirred for 1 hour at -5 ⁰ C, then filtered and stored at -20 ⁰ C in a solution of SnCl ₂ .2H ₂ O 280 g were stirred in 300 ml of water. After addition of 700 ml water, the mixture is stirred for a further 2 hours at -20 ⁰ C. The mixture is left overnight at -20 ⁰ C are filtered off and the residue is dissolved in water. The aqueous solution is neutralized with ammonia and the precipitate formed is filtered off with suction, dried and recrystallized from 600 ml of ethanol.
Plague point: 100-105 ⁰ C.

c) The corresponding 3-amino-2-pyrazolln-one compound is made in the usual way.

Fixed point 193 - 195 ° C.

Synthesis 8; lm-dichloromethyl8 ^ 1fonylphenyl-3-amino-2-pyrazolin- 5-one

a) 112 g dichlonaethylphenylsulfone, produced according to the Brugnatell method; L, J.Prakt.Chem. 2.40, 541, are dissolved in 140 ml of sulfuric acid, whereupon at 20 ⁰ C 50 ml nitric acid (d: 1.52) are added dropwise, by cooling with ice water maintaining the temperature at 20-25 ⁰ C * is then stirred 2 hours at room temperature

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door and pour in 5 l of ice water. The deposited precipitate is filtered off with suction and washed neutral with water. Plague point: 90 - 100 ⁰ C.

b) 128 g of Fitroverbindung obtained under a) are added portionwise with stirring at 80 ⁰ C to a solution of 410 g SnCl ,,. 2H ₂ O in 612 ml concentrated hydrochloric acid gegebeti. The temperature rises to 105 ^° C. during this process. The mixture was stirred for 45 min at 95-100 ⁰ C and then cooled to room temperature. The precipitate formed is filtered off with suction and the filter cake is treated with water. The free amine separates out of the clear solution.

Plague point: 150 - 155 ⁰ C

c) 51.5 g of dissolved are diazotized at 0 ~ 5 ⁰ C with a solution of 15 g sodium nitrite in 43 ml Waeser in 322 ml of 2 η hydrochloric acid and 155 Ql water under b) obtained anilines. The mixture is subsequently stirred for 30 minutes and filtered. The filtrate is added all at once to a sulfite solution which has been prepared by introducing SO g into a solution of 43 g of sodium hydroxide in 345 ml of water. The mixture is heated to 80 ^° C. for 15 minutes and stirred for 40 minutes at this temperature. The pH is 7.3 - 7.5 maintained, then the mixture is acidified with 170 ml concentrated hydrochloric acid and 3 hours heated to 80 - 90 ⁰ C. The warm solution is filtered off, 100 ml of concentrated hydrochloric acid are added and the mixture is concentrated under reduced pressure, the hydrazine hydrochloride separating out.

d) The hydrasin hydrochloride obtained under c) is converted in the customary manner into the corresponding 3-amino-2-pyrazolin-5-one compound.
Fixed point: 260 - 27O ⁰ C.

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B. Synthesis of the color couplers Synthesis 9: compound 4

In a three- necked flask equipped with a stirrer, thermometer, reflux condenser and Tsoektn tube, 26.7 g of anhydrous aluminum chloride and 28 g of lp-difluoromethylsulfonylphenyl-3-amino-2-pyrazolin-5-one are dissolved in 70 ml of nitrobenaol. Then 27 »5 g Palmitoy chloride added dropwise, wherein the mixture at 40 - 45 ⁰ C is maintained.

If hydrogen chloride escapes. The mixture is stirred for 1 hour and then poured into 100 ml of concentrated hydrochloric acid and 500 ml of ice. The precipitate formed is filtered off with suction, taken up in acetonitrile, cooled to room temperature and recrystallized from ethylene glycol monomethyl ether. ! Fixed point s 178 ⁰ G

Synthesis of IQs compound 6

In © ijj, @ a B3? @ Inalskorhea, which is provided with a stirrer, thermometer and air cooler with 20 g of anhydrous alurainium chloride and 15.35 g! ■ = p-Triflu © 3PEiethylaulfonylphenyl-3-amino-2-pyragoline-5 ~ oa is. 100 ml of substance © b @ as0l dissolved. 15 g of octadecyl isocyanate are tropf®aw i © © e hiasugegQbe ^ s where di © temperature to 50 ⁰ C increases. AaeenlieSend is stirred for 3 hours.

The precipitate which forms when the reaction mixture is stirred into 200 ml of 2 η hydrochloric acid is treated with water and the nitrobenzene which precipitates is separated off. When pouring into methanol, a white precipitate forms, which is filtered off and recrystallized from ethanol. Fixed point 210 ⁰ C.

Synthesis 11: compound 9 .

22g l-Q-DifluQrmethyathiophenyl ^ -amino ^ -pyrazolin-S-one hydrate are added by adding benzene and evaporating the azeo-

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9 0 8 O 8 5/1 7 0'8

dehydrated tropical mixture of water and benzene. After addition of 21.2 g of palmitoyl chloride 2 hours, refluxed. One gives. Add acetonitrile and cook for another 2 hours. The mixture is concentrated to half sur and made alkaline with 2 η sodium hydroxide solution. After heating to 40 ^° C. for 30 minutes, it is acidified with acetic acid. An oil separates out, which gradually solidifies and is recrystallized from acetonitrile.
Fixed point: 78 ⁰ C.

Synthesis 12: compound 10

15.4 g of lo- (l, l, 3-trifluoro-2-chloroetho3E ^) - phenyl-3-amino-2-pyrazolin-5-one are added to a solution of 13.4 g of aluminum chloride in 100 ml of pyridine. After stirring for 20 minutes, 19 g of p-hexadeeyloxybenzoyl chloride are added at room temperature. It is stirred for 15 'minutes' after keeping tersisf the reaction mixture for 3 hours at 40 to 46 ⁰ C. It is said to dryness and taken up in warm
on. When 250 ml of concentrated hydrochloric acid are added, an oil separates out that is handled with ice. The precipitate formed is filtered off with suction and removed with a warning and then washed with cold water.

The crude product is dissolved in warm methanol, the solution is rendered alkaline by adding 1 η sodium hydroxide solution _9, diluted with fefaiser and acidified with acetic acid. The precipitate is sucked in, _{dried twice with warm water 9} and then from methanol recrystallized. Plague point 88 ⁰ C.

Synthesis 13: Compound 11

A solution of 28.9 g (0 _t l mol) of l ~ p-difluoromethyisulfonylphenyl-3-amino-2-pyrazolin-5-one and 41 »7 g of 2-hexad © eyloxg? - ~ 5-carboxy-aniline hydrochloride in 200 ml of glacial acetic acid is boiled for 2 hours and then poured into water. The precipitate formed is filtered off, washed with water, boiled in acetonitrile and filtered while warm. Compartment for drying AG 508 - 22 -

909885/1708

is recrystallized from ethylene glycol monomethyl ether. Fixed point 193 ⁰ C.

Synthesis 14; Connection 12

15.4 g of lo-Cljl ^ -Irifluar-α-chloroethoxy) -phenyl-3-amino-2-pyrazolin-5-one are taken up in a suspension of 13.4 g of anhydrous aluminum chloride in 100 ml of yridine and the mixture is stirred At least 16.5 g of arachidoyl chloride are added at room temperature and the mixture is then heated to 40-45% for 3 hours. It is concentrated to dryness under reduced pressure and the residue is dissolved in ethylene glycol monomethyl ether and 250 ml of concentrated hydrochloric acid. When ice is added, the oil solidifies and is suctioned off and washed first with warm and then with cold water. The crude product is taken up in methanol, made alkaline with 1 η sodium hydroxide solution, diluted with water and acidified with acetic acid. An oil forms that solidifies when standing. It is washed with water, dried and recrystallized from methanol. Fixed point: 72 ⁰ C

Synthesis 15t compound 13

24-25 g are added to a solution of 15.4 g of lp- (l, l, 2-trifluoro-2-chloroethoxy) -phenyl-3-amino-2-pyrazolin-5-one in 12 ml of pyridine and 88 ml of acetonitrile Hexadecylsulfonylchloride added. The mixture is stirred for 16 hours and the precipitate formed is filtered off and dissolved in alkaline ethanol. It is filtered again and the filtrate is neutralized by adding acetic acid. The precipitate is dried and repeatedly recrystallized from ethanol. Fixed point: 166 ⁰ C.

Syη thesis 16 ϊ compound 14

A solution of 30.75 g of l-p- (l, l, 2-trifluoro-2-chloroethoxy) -phenyl-3-amino-2-pyraeolin-5-one. and 10.5 g methacryloyl chloride

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9 0 9885/1 70S

in 50 ml of acetonitrile is boiled for 4 hours. The solution is diluted with water and the precipitate is filtered off and purified by recrystallization from acetonitrile.
Fixed point: 190 ⁰ C.

Synthesis 17; Copolymer of methyl acrylate and l-p- ^ 1,1,2-trifluoro-2-chloroethoxy) -phenyl-3-methacryloylamino-2-pyrazolin-5-one

Put 185 ml of distilled water, 2.4 g of the sodium salt of oleyl methyl tauride, 15.65 g of lp- <l, l, 2-trifluoro-2-chloroethoxy) into a 500 ml flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and gas inlet tube. -phenyl-3-methacryloyl-amino-2-pyrazolin-5-one and 32.3 g methyl acrylate. The suspension is stirred for 20 minutes and then heated to the reflux temperature under a nitrogen atmosphere. The polymerization is stopped by adding 2.4 ml of a 5.8 jijgen aqueous solution of 4,4-azobis (4-cyanovaleric acid) started and for 2 hours at 80 - 90 ⁰ C held in transition. The latex formed is cooled and filtered. Yield: 180 ml of latex.

Concentration of solids per 100 ml of latex: 20.3 g. Equivalent molecular weight (i.e. the number of grams of polymer in which contain 1 mole of polymerized monomeric color coupler is): 1418.

Synthesis 18: compound 15

37 g of anhydrous aluminum chloride are suspended in 180 ml of ethylene chloride and 550 ml of pyridine are added all at once. At 4O ⁰ C is added to the clear solution obtained 110 g of lp (l, l, 2-Triflucr-2-chloräthylsulfonylphenya) -3-amino-2-pyrazolin-5-on, and then 175 g of chloroformic acid ß (2 -Tetradecyl-4-chloro-5-methylphenoxy) ethyl ester. The mixture is stirred for 40 min at 50 -. 60 ⁰ C and then poured into a mixture of 0.8 1 concentrated SaIz- AG 508 * 24 -

909885/17 ÜB

acid 1 1 methanol and 1 1 ethyl acetate. After thorough mixing, 3 liters of water are added and the ethyl acetate solution is separated off. It is treated with dilute hydrochloric acid and then washed neutral with water. The solvent is evaporated under reduced pressure and the residue is dissolved in petroleum ether. 125 g of coupler precipitate from the solution on standing overnight. Plague point: 107 - 112 ⁰ C.

Synthesis 19 ; Connection 16

To a suspension of 22 g of anhydrous aluminum chloride in 70 ml of ethylene chloride, 320 ml of dry pyridine are added while stirring and cooling with ice water. 66 g of 1- (2-chloro-5-chloromethylsulfonyl) -3-amino-2-pyrazolin-5-one are added to the hot solution. The mixture is stirred at about 40 ⁰ C, whereupon 100 g of chloroformic acid ß (2-tetradecyl-4-chlorophenoxy) ethyl esters are htnzugefügt *. The mixture is stirred for 1 hour at 50 - 60 ⁰ C and poured into a mixture of 400 ml of concentrated hydrochloric acid 500 ml of methanol and 500 ml of ethyl acetate. The further work-up takes place as described for synthesis 18. Plague point: 80 - 83 ⁰ C

Synthesis 20: compound 17

160 ml of dry pyridine are added to a slurry of 11 g of anhydrous aluminum chloride in 50 ml of ethylene chloride while stirring and cooling with ice water. 32 g of 1-m-dichloromethylsulfonylphenyl-3-amino-2-pyrazolin-5-one are added in ^{portions at 20 ° C. to the clear solution.} When everything is dissolved, 46 g Chlorameiseneäure-.beta. (2-tetradecyl-4-chlorophenoxy) ethyl ester are added at once at 35 ⁰ C. The mixture warms to 50 ^° C. and is kept at this temperature for 40 minutes, whereupon it is stirred into a mixture of 200 ml of concentrated hydrochloric acid, 250 ml of methanol and 250 ml of ethyl acetate. The work-up is carried out as described for synthesis 18. Plague point-.50 - 59 ⁰ C

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The use of the magenta couplers according to the invention is intended to be described in the following application examples.

example 1

117 g of a silver bromide;) odidemuleion (2.3 mol- # iodide), the equivalent amount of 47 g silver nitrate and 73.4 g gelatine per kg are diluted with 192.3 g of a 7.5 # aqueous gelatin solution and 200 g distilled water. To the emulsion thus obtained, an emulsifier is added, which is obtained by dissolving 0.006 ml of the color coupler No. 12 in 14 ml of ethyl acetate, dispersing the solution in 100 ml of a 5 # gelatin solution with the help of an ultrasonic generator and removal of the ethyl acetate by evaporation under reduced pressure. After neutralizing the emulsion and adding the usual additives such as stabilizers, wetting agents and hardeners is made up to 720 g with distilled water.

The emulsion obtained is poured onto a cellulose triacetate carrier with an application of 125 g / m 2. the The emulsion layer is dried and coated with a protective gelatin layer.

After drying, the material is exposed for 1/20 second behind a gradient wedge with a constant 0.3 and then 8 back. developed at 20 ^° C. in a developer bath with the following composition:

Ν, Ν-diethyl p-phenylenediamine sulfate

Hydroxylamine sulfate Sodium hexametaphosphate

anhydrous sodium sulfite anhydrous potassium carbonate

Potassium bromide

Water on

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2, 75 G 1, 2 G 4th β 2 G 75 G 2, 5 G 1 liter

C treated in an intermediate bath of 30 g of sodium sulfate in 1 l of water.

The developed material is 2 min. At 18-20 ⁰ C in one

The material is watered for 15 minutes and then in one Treated bleach bath of the following composition:

Borax 20 g

anhydrous potassium bromide 15 g

anhydrous sodium bisulfite 4.2 g

Ealium hexacyanoferrate (III) 100 g Water on. 1 liter After bleaching, the material is soaked in water for 5 minutes and in

an aqueous solution of 200 g of sodium thiosulfate per liter fixed.

After the 15 minute final soak, the material will

dried.

A purple wedge with an absorption maximum of 534 mn is obtained.

If color coupler 2 or color coupler 10 is used instead of color coupler no. 12, purple wedges are also obtained with the same absorption maximum of 534 nm.

Example 2

117 g of a silver bromide iodide emulsion (2.3 mol Water. A solution of the color coupler 8, which was obtained at 55 ^° C., is added by dissolving 0.006 mol of the coupler in 44 ml of ethanol, 6 ml of 2 n sodium hydroxide solution and 32 ml of distilled water. After neutralizing and adding the usual emulsion additives wi; Stabilizers, wetting agents and hardeners are made up to 720 g with distilled water.

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90988 b / 170 8

fills, whereupon the emulsion is poured onto a cellulose triacetate carrier with an application of 125 g per m. The emulsion layer is dried and covered with a protective gelatin layer.

Exposure and processing are carried out as in Example 1

described.

A purple wedge is obtained with an absorption maximum of

538 nm.

By replacing in Example 2, the color coupler 8 by 0.006 Hol one of color coupler 1, 3, _f 4, 5 or 7, we obtain magenta wedge with absorption maxima at 538 nm, 544 nm, 538 nm, 542 nm and 540 nm.

Example 3

10 g of the color coupler 15 are dissolved in 30 ml of ethyl acetate and the solution is dispersed in 160 ml of a 5% aqueous gelatin solution. The ethyl acetate is dispersed, whereupon the emulsifier containing the color coupler 15 is admixed with a conventional green-unsensitized silver halide emulsion.

It is poured onto a cellulose triacetate support and, after drying, covered with a protective gelatin layer.

After exposure and processing in the manner indicated in Example 1, a transparent purple image of high quality is obtained Color density and only low secondary absorption in blue and red spectral region. The absorption maximum is at 545 nm.

If, in Example 3, the color coupler 15 is replaced by color coupler 16 or 17, then purple images are also obtained with absorption maxima at 544 nm and 535 nm, respectively.

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Claims (8)

1. Color coupler of the 2-pyrazolin-5-one. Series, which is capable of forming a purple azomethine dye upon reaction with an oxidized developer substance containing aromatic primary amino groups, characterized in that the 1-position is substituted with a phenyl group which carries at least one haloalkoxy, haloalkylthio or haloalkylsulfony group. 2. Color coupler according to claim 1, of the following formula: where mean: Q = haloalkoxy, haloalkylthio or haloalkylsulfonyl, Z = hydrogen, halogen, alkyl, alkoxy, alkylthio, alkyl sulfonyl, or the group -Q, and R ₁ = an alkyl group, an aryl group, an acyl group, a carbamyl group or an acyloxy group. 3. Color coupler according to claim 2, wherein the substituent R ₁ contains a group which makes the color coupler diffusion-resistant in the photographic colloid layers and which corresponds to the formula -XI), wherein D is an acyclic aliphatic hydrocarbon freet having 5-20 carbon atoms and X is a chemical bond , Oxygen, sulfur, sulfonyl, -COIIH-, -NHCO-, -SO ₂ I (R ₂ ) - with R ₂ = water off or alkyl, -NHSO ₂ - or -N (alkyl) - mean. 4. Color coupler according to claim 2, wherein R _{1 is} an acyl group of the following formula: Y
-CO-C-CH ₂ - 29 - 909885/17 08 where Y is hydrogen, halogen, a short-chain alkyl radical, aralkyl or aryl. 5. Color coupler according to claim 1, characterized by the content of recurring units of the following formula: O = C N CH ₂ H ₂ C C-HHCO-CY wherein Z and Q have the same meaning as in claim 2 and wherein Y has the same meaning as in claim 4 6. Color coupler according to claims 1 to 5 »wherein said haloalkoxy» haloalkylthio or haloalkylsulfonyl group represents the group RCF ₂ O-, RCF ₂ S- or RCF ₂ SO ₂ -, where R is hydrogen, fluorine or polyhaloalkyl. 7. color coupler according to claim 1 to 5 "wherein said haloalkylsulfonyl Cl ₂ HCSO ₂ - or ClH ₂ CSO ₂ -. 8. Light- sensitive color photographic material with at least one halide emulsion layer, characterized by the content of a color coupler according to Claims 1 to 7. 9 «Process for the production of color photographic images, by Development of a photographic material that image-wise Exposed silver halide tnttaält with a developer, the oxidation products of which are capable of forming an asoaethine dye on reaction with color couplers, characterized in that the development in the presence of one Color coupler according to claims 1 to 7 takes place. A-G 508 - 30 - 909885/1708