DE1644046A1 - Process for producing color photographic images - Google Patents

Description

AGFA-GEVAERTAG

PATENT DEPARTMENT

LEVERKUSEN 1644046

Gs / Schü

Jan 17th, 1367

Process for producing color photographic images

The invention relates generally to a process for producing color photographic images, and more particularly the color correction by means of an integral masking process.

It is known that the dearest color densities of the image dyes those involved in photographic chromogenic development Materials are created by eliminating masking processes.

After the method described in the American patent specification 2,860,974, the mask dye is in the color photographic material. A colored Fprbkuppler is used for this, the light in the range of Partial absorption of the dye is absorbed which is formed during the color development with the above-mentioned color coupler will.

Another method is the color coupler, which is produced after the imagewise exposure and the first color development the silver halide emulsion in the not

10981B / 1978

exposed parts of the layer is oxidative -.-. converted into a mask dye. This procedure is described in British patents 880,862,975,930 975 932, 975,939 and 975,940.

According to British patent specification 975,932 it is known to perform color correction in photographic layers to achieve that the exposed and color developed Layer with an oxidizing solution, such as a photographic bleach bath, in the presence of a compound treated, the oxidative with the remaining color coupler. '.: able to couple, whereby a second color image is created, the gradation of which runs counter to that of the first color image.

A disadvantage of these known processes is that they do not compensate for the red component of the purple is possible.

The object of the invention is in a photographic Element having at least one silver halide emulsion layer produces a magenta image by color development to produce and the unused color coupler to be converted into a dye, primarily in the red Area of the spectrum absorbed.

According to the invention, this object is achieved by a process according to which a dye is formed by oxidative coupling which absorbs essentially in the red region of the visible spectrum and is characterized in that

A-G 204 - 2 -

10 9 816/1976

that a color coupler of the · pyrazolone type with a colorless compound couples that of the general formula

^ N-A-MH-IU

corresponds to, in the

IL is hydrogen or a monovalent organic group such as alkyl, aralkyl or aryl or a divalent one means organic group which is an ortho atom of the one represented by A, optionally substituted aromatic group is bonded;

R ₂ denotes a monovalent organic radical such as alkyl, aralkyl or aryl or a divalent organic radical which is bonded to an ortho atom of the optionally substituted aromatic group represented by A;

R stands for ¥ hydrogen or a substituent which is split off in the oxidative coupling and

A means an aromatic group which is in the p-position to the

■ a / N- group substituted by a -HH-R, group

JtIp O

and in the o-position with respect to the -NH-R, group carries a substituent by which the -NH-R, group is sterically hindered. A can also be one on top of the other Yeise represent substituted aromatic group.

AG 204 - 3 -

109816 / 1P7R

Steric hindrance reduces the ability to reduce aromatic phenyldendiamine derivatives to the extent that they are useful for developing exposed silver halides are no longer usable. As a substituent, the one can cause such steric hindrance the following mentioned: halogen atoms, e.g. chlorine or bromine, alkyl, e.g. methyl, alkoxy, e.g. methoxy or ithoxy, Acyl, an amino group substituted by acyl, sulfamyl Sulfonylalkyl, sulfonylaryl, a sulfo or carboxyl group.

When R_ substituents which can be split off by the oxidative coupling may be mentioned: a SuIfonylalkyl group, a sulfonylaryl group ⁿ der.der alkyl and aryl may be further substituted, a sulfo group, a carbamyl group, halogen, a Sulfomethylene group or a carboxymethylene group.

The aromatic group represented by A can be further substituted, for example with halogen, cyano, Sulfamyl, carboxyl, sulfo, alkyl, aryl, aralkyl or with a cycloaliphatic group. In addition, A can be a part of a ring system, the condensed rings from the Represents group of aromatic, alicyclic or heterocyclic rings, which can be further substituted.

The compounds preferably used for the masking method according to the invention correspond to the following

- 4 AG 204

10 9 816/1 976

16 A A O 4

general formula: *

Bf - // VV- NH

here means

R. hydrogen or an organic radical, for example alkyl, aralkyl or aryl including the corresponding substituted groups; -

Rp is an organic radical, e.g., alkyl, aralkyl or aryl including these groups in substituted form, or

RJ and R ₂ together form a nitrogen-containing ring, for example a piperdine-j morpholine _T piperazine or pyrazole ring, each of which may be optionally substituted;

R, and R represent a substituent which _{brings about a steric hindrance of the -NH 2} group, for example a halogen atom such as a chlorine atom, an alkyl, alkoxy, cyano, acyl, an amino group substituted by acyl, a sulfamyl -, sulfonylalkyl, sulfonylaryl, sulfo or carboxyl group;

R _c and R / - stand for a hydrogen atom or for a ρ ο

Substituents, for example a halogen atom, a cyano, sulfamyl, carbamyl, acyl, sulfo, carboxyl, alkoxy or alkyl radical, an alicyclic, an aralkyl or aryl group, these: groups optionally in substituted form or Rc together with R, and / or Rg together with R. stand for an aromatic, a partially hydrogenated aromatic AG 204 - 5 -

1 0981 6/1 P. 7S

or a heterocyclic fused core, all optionally in substituted form or R, - together with R ^ forms a condensed nitrogenous heterocyclic optionally, substituted, ring or

R _c together with R ₀ represents a condensed nitrogen ίο C.

containing heterocyclic optionally substituted Core.

The compounds mentioned preferably contain a substituent which they use in photographic colloids makes diffusion-proof.

The following describes the manufacture of a number of coupling components described which are particularly suitable for the masking method according to the invention.

Connection 1

2,6-Dimethyl-4-N "-n -hexadecyl-N- {p-N '- (methylsulfonyl-aminoj ethylaniline

GH,

CH, SO _? NHCH GH _? [ ³

-NH ₂

GH ₃ - (GH ₂ )

CH ₃

12.1 g (0.01 mol) 3,5-methylaniline, prepared according to A. van loon, Rec.Tr.Ch.Pays-Bas 7-9 (1960) 986, and 7 cnr 98% formic acid for 30 minutes heated on the reflux condenser. The resulting water is distilled off under reduced pressure on an oil bath of 100 ^{0 G.} J) s residue is recrystallized from gasoline. COPY yield: 10.8 g of 3,5-dimethylformanilide. AG- 204 - 6 -

1 098 1 B / 1 976

Melting point: 74 ° C.

10.8 g (0.072 mol) of the formanilide and 22.2 g (0.072 mol) n-Hexadecyl bromide are dissolved in 100 cm of ethanol. To this Solution a solution of 4.1 g (0.072 mol) of potassium hydroxide in 100 cm of ethanol is added. The mixture is 12 hours heated to reflux. The potassium bromide formed is sucked off and the piltrate evaporates under reduced pressure Dry up. The dry residue is heated in 50 cnr hydrochloric acid for one hour to remove the formyfemino bond to hydrolyze.

After cooling, the precipitate is recrystallized from acetonitrile.

Yield: 10 g of 3, δ-dimethyl-Nn-hexadecylaniline hydrochloride. Melting point: 105 ^° C

3 »31 g (O) O ¹ mol) of this aniline are dissolved together with 2.34 g (0.01 mol) ß-methylsulfonylamino-ethyl bromide in 100 cm ^{3 of} ethanol and heated for 15 hours with 1.7 g (0.03 mol ) Sodium carbonate on the reflux condenser. Then evaporated to dryness, the residue is wiped with ^V: ater and methanol and crystallized from η-hexane.

Yield: 2.3 g of 3,5-dimethyl-IT-n-hexadecyl-N- (β-methylsulfonylamino) ethylaniline. Melting point: 67 ° C

To a cooled to 5 ⁰ C solution of 5 mHol 2,5-Dichlorphenyldiazonium chloride is added one of the aforesaid compound, 2.2 g (4.75 mmol) in 20 cnr ⁵ acetic acid.

AG 204 - 7 -

1 η: i a 1R / 14 7 h

M-.n now adjust the pH of the mixture with sodium acetate to about

to 5 and stir for half an hour. Dsnn you pour them

Mix on ice, suck off the resulting precipitate, wash with water, dry and crystallize twice from gasoline

Yield: 2 g of 4-, N-n-hexadecyl-N- (β-methylsulfonylamino) -ethyl J-aminophenyl-azo-2 ·, 5'-dichlorobenzene.

Melting point: about 100 ⁰ C.

10 g of this azo compound are dissolved in 100 cnr acetic acid
reduced under hydrogen with Raney nickel. After filtration, the filtrate is poured onto ice and made alkaline with ammonium hydroxide. The resulting precipitate is sucked off,
washes with vaseer and recrystallized from acetonitrile.
Yield: 5.5 g of 2,6-dimethyl-4-Nn-hexadecyl-N- (β-methylsulfonylamino) ethylaniline.
Melting point: 70 ⁰ C.

Connection 2

2,6 ~ methyl-3-chloro-4-n-hexadecylaminoaniline ~ hydrochloride

Cl CH,

H ₅ C- (CH ₂ ) ₁₅ -NH - (S NX -NH ₂ .HCl

CH ₃

AG 204 - 8 -

10981 R / 1976

24.9 g (0.15 mol) 2,4-dimethyl-6-nitroaniline, prepared according to A. van loon, Rec.Tr.Chim. Pays-Bas 79, (1960) 986, are dissolved in 120 cm of hydrochloric acid and, after adding a solution of 12 g of sodium nitrite in 120 cm of water, diazotized ^{at 0 ° C.} The solution is brought to 25 ⁰ C and a copper (I) chloride solution (freshly prepared from 52 g waasserhaltigem copper sulfate), poured into 250 cnr hydrochloric acid. The resulting precipitate is isolated and recrystallized from η-hexane. Yield: 17 g, 2-chloro-3,5-dimethylnitrobenzene. Melting point: 50 ⁰ O. Λ

12.5 g of this nitro compound are reduced in 150 cnr ethanol under hydrogen with Raney nickel. It is then filtered and the filtrate is evaporated to dryness. The residue is mixed to 45 cnr 98 $ formic acid and heated for one hour in the oil bath at 120 ⁰ C. The mixture is then evaporated under reduced pressure and recrystallized from benzine. This gives 12 g of 2-chloro-3,5-dimethyl-formanilide having a melting point of 119 ⁰ C.

To a solution of 15.7 g (0.085 mol) of this fromanilide and 26 g (0.085 mol) of n-hexadecyl bromide in 100 cm of anhydrous Ethanol, a solution of 4.8 g of potassium hydroxide is added in 150 cm of anhydrous ethanol. The mixture is heated on a reflux cooler for 5 hours. After evaporation to dryness the mixture is heated in 100 cm hydrochloric acid for one hour to hydrolyze the formylamino bond. Then one lets the solution cool, the crystals formed are filtered off with suction and recrystallized from acetonitrile.

AG 204 - 9 -

10981R / 1P.76

16AA0A6 ti

Yield: 16.5 g of 2-chloro-3,5r-dimethyl-Nn-hexadecylaniline hydrochloride. With ammonium hydroxide, the corresponding base is produced from this, which is then recrystallized from methanol.
Yield: 10.3 g. Melting point: 53 ⁰ O.

To a 5 ⁰ C cooled solution of 2,5-dichlorophenyl-diazonium chloride (0.021 mol) is added solution of 8.7 g (0.021 mol) of the above hydrochloride in 100 cnr acetic acid. The pH of the mixture is adjusted to 5 with sodium acetate. It is allowed to the reaction mixture at 2O ⁰ C for 12 hours and then pour it into Kasser. The precipitate formed is recrystallized from isopropyl alcohol and gasoline. Yield: 5.4 g of 2,6-dimethyl-3-chloro-4-n-hexadecylaminophenyl-azo-2 ', 5'-dichlorobenzene. Melting point: 79 ⁰ C.

5 g of this azo compound with Raney nickel in 150 cur Acetic acid reduced under hydrogen. Then you filter the reaction mixture and pour the piltrate into a mixture

3 3

of 150 cm of concentrated hydrochloric acid and 20 cnr of Yasser. Of the The resulting precipitate is isolated and recrystallized from ethanol.

Yield: 3 g of 2,6-dimethyl-3-chloro-4-n-hexadecylaminoaniline hydrochloride. Melting point: about 124 ⁰ C.

Connection 3

2,3,5,6- {cetramethyl-4-n-decylamino-aniline dihydrochloride

-. 2HCl

A-G 204

- ■ 10981R / 1976

A mixture of 3.88 g (0.02 mol) of nitroaminoduren (prepared according to C. Ingham, J. Chem. Soc. (1939) 984, or according to G. Illuminati, J. Am. Chem. Soc. 74. (1952 ) 4952) and 30 evr 98% formic acid are refluxed for 1 hour. The excess formic acid is distilled off under reduced pressure. The residue is recrystallized from ethanol and xylene. Yield: 3 g of nitroformylamino acids. Melting point: 227 ° 6.

3 g of this nitro compound are reduced in 100 cur ethanol under hydrogen with Raney nickel. ITach filtration and cooling to 1.6 g of crystalline Aminoformylaniino- Λ receives duren. Melting point: 264 ^° C. (with decomposition).

A mixture of 1.92 g (0.01 mol) of the aforesaid compound, 2.42 g (0.011 mol) of n-decyl bromide, 1.06 g (0.01 mol) sodium carbonate and 50 cm ethylene glycol monomethyl ether are refluxed for 48 hours. After filtration and concentration of the filtrate, 1.9 g of the crystalline are obtained Reaction product which is then recrystallized from acetonitrile.

Yield: 1.05 g of n-decylamino-formylaminoduren. I.

Melting point: 135 ⁰ C.

2.5 g (0.075 mol) of this compound are obtained through 1 hour Hydrolyzed by boiling in 15 cm of concentrated hydrochloric acid. Afterward the reaction mixture is cooled and filtered off with suction. The crystals thus obtained are recrystallized from ethanol / hydrochloric acid.

Yield: 2.2 g of 2,3,5,6-tetramethyl-4-n-decylaminoanline dihydrochloride.

AG 204 - 11 -

109816/1 976

16U046

Connection 4 2-Bromo-4-n-hexadecylamino-6-methoxyajiline hydrochloride

^ S -NH ₂ .

34 g (0.2 MoI) of 2-methoxy-4-nitroaniline dissolved in .350 cm ³ of acetic acid are brominated by dropwise addition of 11 cm (0.2 mol) of bromine is below 2O ⁰ C. The reaction mixture is then poured onto ice, the precipitate obtained is filtered off with suction and recrystallized from xylene. Yield: 32.2 g of 2-methoxy-4-nitro-6-bromaniline. Melting point: 140 ⁰ C.

14.82 g of aniline are dissolved in a mixture of 200 cnr acetic acid, 40 cm 5 r hydrochloric acid and 10 cnr sulfuric acid and diazotized at 5 ⁰ C and a solution of 4.2 g of sodium nitrite in 20 cnr "water. Then they are 66 g 40 #ige hypophosphorous acid to which is cooled to below 5 ⁰ C. it is now the temperature allowed the reaction mixture slowly to 20 ⁰ C rise, and this temperature is maintained for 12 hours. the precipitate formed is filtered off with suction and introduced into 1 η hydrochloric acid, so that The precipitate is isolated from this suspension by steam distillation.

Yield: 11 g of 3-bromo-5-methoxy-nitrobenzene. Melting point: 85 ⁰ C.

AG 204 - 12 -

10 981R / 137 6

35 g (0.15 mol) of this nitro compound are heated in a mixture of 200 cnr acetic acid, 100 cm strong hydrochloric acid and HO g of crystalline tin (II j chloride for 12 hours at 120 C. The reaction mixture is then made alkaline with ammonium hydroxide and then subjected to steam distillation.
Yield: 24.7 g of 3-bromo-5-methoxyaniline. Melting point: 51 ^° C

The aniline thus prepared is heated for one hour at 120 ⁰ C in 50 cnr 98 #iger formic acid. Then the mixture is evaporated, the Reaktionsgemiseh under reduced pressure to dryness, M the residue is washed with water, dried and crystallized from xylene to.

Yield: 25.6 g of 3-ΒΓθΐη-5-πιβΐ] ιο ^ -ΐοΏη3ηί1ίά. Melting point: 125 ⁰ O.

^{A solution of 1.5 g of potassium hydroxide (25.8 mmol) in 100 cm 5 of} ethanol is added to 5.4 g (23.5 mmol) of this formanilide and 7.3 g (23.5 mmol) of n-hexadecyl bromide in 80 cnr of ethanol . The reaction mixture is refluxed for 2 hours. Then evaporated to the ethyl alcohol under reduced I pressure, sets 80 cm of concentrated hydrochloric acid, and hydrolyzing the iOrmylamino binding by half-hour heating the Reaktionsgemsitrhes to 120 ⁰ C. After cooling, the precipitate is filtered off with suction, washed with 5 r hydrochloric acid and acetonitrile which contains some hydrogen chloride, recrystallized Yield: 3.4 g of 3-bromo-5-methoxy-Nn-hexadecylaniline hydrochloride Melting point: 74 ⁰ C. Melting point of the free base: 48 ⁰ C.

AG 204 - 13 -

1098 1 R / 1976

Γοη To a solution 3.4 g (7.35 mmol) of the aforementioned compound in 40 cnr acetic acid is added a solution of 7.4 mmol 2,5-Dichlorphenyldiazoniumchlorid below 5 ⁰ C. Then the pH of the solution is adjusted to 5 with sodium acetate. The reaction mixture is then stirred for 3 hours without cooling, so that the temperature rises slowly to 20 ^° C. The mixture is then poured into water, the resulting lump is washed with water and recrystallized twice from ethylene glycol methyl ether.

Yield: 3.1 g of 2-bromo-4-n-hexadecylamino-6- methoxyphenyl azo-2 ', 5'-dichlorobenzene.
Melting point: 91 ⁰ C

The Aeo-compound thus obtained is dissolved in 35 cm warm acetic acid and a solution of 3.5 g crystalline tin (II) chloride in 10 cm acetic acid and 15 cm ethanolic hydrochloric acid is added. The reaction mixture is poured onto ice, the precipitate is filtered off with suction and recrystallized successively from acetonitrile and from acetic acid, which contains some ethanolic hydrochloric acid.

Yield: 1.2 g of 2-bromo-4-n-hexadecylamino-6-methoxyaniline- hydrochloride.

Melting point: approximately 100 ⁰ C.

AG 204 -H-

10 981R / 1976

Connection 5

2-chloro-6-methyl-4- (N-n-hexadecyl-N- 2f -sulfopropyl) -amino aniline hydrochloride

207 g (1.11 mol) of 2-methyl-4-chloro-6-nitroaniline (prepared according to A. Claus, Ann. 274 (1893) 297) dissolved in a mixture

5 liters of acetic acid, 1 liter hydrochloric acid and 200 η 5 cnr strong sulfuric acid are diazotized with a solution of 78 g sodium nitrite in 250 cm ³ of water at 5 ⁰ C. For sets to "at 2 ⁰ C. 1220 g of 40 #ige hypophosphorous acid to. The mixture is allowed now 12 hours at 20 ⁰ C and are then poured from 7 kg of ice. The resulting KMerschlag is suction filtered, washed with water and from its Solution in 1 η hydrochloric acid is distilled off with steam.

Yield: 94.5 g of 3-chloro-5-methylnitrolbenzene. Melting point: 56 ⁰ C.

0.552 mol of this nitro compound is heated in a mixture of 600 cm acetic acid, 400 cm strong hydrochloric acid and 510 <2.22 mol) hydrous tin (II) chloride for 12 hours at 120 ^° C. After addition of ammonium hydroxide and steam distillation , one obtains 70 g of 3-chloro-5-methylaniline. The product is ^{heated in 700 cm 5 of} formic acid for 1 hour, the reaction mixture is then evaporated to dryness and the residue is recrystallized from gasoline.

AG 204 - 15 -

109816/1976

164404

Yield: 70 g of 4-chloro-5-methylformanilide. Melting point: 94 ⁰ C

A solution of 3.25 g of potassium hydroxide in 100 cm of ethanol is added to a solution of 8.48 g (0.05 mol) of this compound and 15.75 g of n-hexadecyl bromide in 100 cm of anhydrous ethanol. The mixture is refluxed for 2 hours and then evaporated to dryness under reduced pressure. The formylamino bond is hydrolyzed by boiling the residue in 100 cnr hydrochloric acid for 1 hour. The crystals formed on cooling are suctioned off and recrystallized from ethanol / hydrochloric acid. The hydrochloride produced in this way is by dissolving in ethanol and through

the
Addition of ammonium hydroxide converted into the corresponding base.

The resulting precipitate is crystallized from methanol

Yield: 8.6 g of 3-chloro-5-methyl-Nn-hexadecylanine. Melting point: 28 ⁰ C.

7.31 g of OBEM said base are heated to 140 ⁰ C together with 3 g propanesultone 12 hours. The one with it

■ z

The resulting viscous mass is dissolved in 30 cm acetic acid and added to an aqueous solution of 2,5-dichlorophenyl-diazonium chloride. The pH of the mixture is adjusted to 4 with sodium acetate. After stirring for 3 hours at 2O ⁰ C, the reaction mixture is poured onto ice. 75 g of potassium hydroxide are then added. The songs strike formed is drained, with Vas s he washed sequentially au · dimethyl

AG 204 - 16 -

109816 / 197R

formamide and n-butyl acetate recrystallized. Yield: 4 g 2-chloro-6-methyl-4- (Nn-hexadecyl-NV-sulfobutyl) amino-azo-2 ^T _t 5'-dichlorobenzene. This azo compound is dissolved at 80 ⁰ C in 30 cnr acetic acid and reduced by adding a solution of 5 g of hydrous tin (II) chloride in 25 cm ethanolic hydrochloric acid at 75 C.

The resulting precipitate is dissolved in n-butyl acetate. The precipitate quickly settles out again and is then recrystallized from a mixture of 15 cm 5% salic acid and 15 cm ethanol and converted into the hydrochloride in the process. Yield: 2.2 g of 2-chloro-6-methyl-4- (Nn-hexadecyl-N-2f-sulfopropyl) aminoaniline hydrochloride.
Melting point: about 115 ⁰ C.

Connection 6

ff _s 6- 'methyl — 4— (N-η — hexadecyl — Ν— ) £ - sulfopropyl — amino— aniline hydrochloride

Br

HO ₅ S- (OH ₂ ), __

^ N -ζ / V ^ -NH ₂ .HCl Ä

225 g (1.21 mol) of J-bromo-S-methylaniline, prepared according to C. Glbßon, J. Chem. Soc. (1929) 1229, 380 cm are ⁵ formic acid heated for one hour em reflux. After adding να »/ easer, the precipitate formed is removed, washed with water, dried and recrystallized from xylene. Yield: 215 g of 3-bromo -5-methylformanilide. Melting point: 98 °.

A- & 204 - 17 -

10-9015 / 1 97 6

214 g (1 mol) of the above formanilide are dissolved together with 305 g (ΙΜ0Ι) n-hexadecyibromide in 3 liters of anhydrous ethanol. A solution of 57 g of potassium hydroxide in 3.8 liters of anhydrous ethanol is added to this solution. The mixture is refluxed for 2 hours. Subsequently, the ethyl alcohol and hydrolyzed -verdampft Fromylamino the binding by adding 3 liters of hydrochloric acid and by heating the mixture for 30 minutes at 120 ⁰ C on the oil bath. After cooling, the resulting precipitate is filtered off with suction, washed with 5 η hydrochloric acid and recrystallized from ethanol, which contains little hydrogen chloride. Yield: 315 g of 3-bromo-5-methyl-Nn-hexadecylaniline hydrochloride. Melting point j 100 ^° C. (with decomposition).

16.4 g (0.04 mol) of the läse ^{corresponding to the abovementioned hydrochloride are heated to 140 °} C. for 12 hours together with 6 g (0.048 mol) of propane sultone. The dabeir-vikose resulting mass is dissolved in 60 cm of acetic acid and, at about 5 ⁰ C to a solution of 2,5-wäisrigen Dichlorphenyldiaeoniumchlorid. The pH of the solution is adjusted to about 4 with sodium acetate. After the solution has been stirred for about 50 minutes at 20 ° C., it is poured onto ice and mixed with 150 g of potassium hydroxide. The resulting precipitate is filtered off with suction, washed with water and recrystallized twice from acetic acid.

Yield: 11 g of 2-bromo-6-methyl-4- (Nn-hexadecyl-N-1-1-sulfobutyl) -amino-azo-2 ^f , 5'-dichlorobenzene.
Melting point: about 200 ⁰ C.

10.5 g (0.015 mol) of the azo compound just mentioned

at 80 ° O in 60 cm ^{5 of} acetic acid and at the same temperature

AS 204 - 18 -

10 9816/1976

door through. Addition of a solution of 12 g of crystalline Zlnn (II) chloride reduced in 30 em of ethanolic hydrochloric acid. After the solution has been stirred for 10 minutes, it is poured put them on hold. The resulting precipitate is filtered off with suction, washed with water and successively from acetonitrile and from a mixture equal to parts of ethanol and 5 η hydrochloric acid recrystallized.

Yield: 4 _t 5 g of 2-bromo-6-methyl-4 ~ (Nn-hexadecyl-N - # '- BUlfopropyl) aminoaniline hydrochloride.
Melting point: about 120 ° C.

Connection 7

2,6-dibromo-4 ~ (N-n-hexadecyl-N-2f-sulfo-propyl-aminoaniline hydrochloride

Br

HO ₃ S- (OH ₂ ),

F - <y ^ \ - NIL, .HCl

Br

20 g (0.008 mol) of 3,5-dibromaniline are ^{heated to 120 ° C. in 75 cm 5 of} 98% formic acid for 1 hour. The solution is then evaporated to dryness and the residue is recrystallized from acetonitrile.

Yield: 19 g of 3,5-dibromoformanilide.

Melting point: 198 ° C.

The pormaanilide (0.0068 moles) and 20.74 g (0.068 moles) of n-hexadecyl bromide are dissolved in 170 cnr ethanol. A solution of 4 g of potassium hydroxide is added to this solution 170 cm of ethanol and cooks the whole thing for three hours Reflux. The resulting potassium bromide is sucked off.

AG 204 - 19 -.

10981fi / 1.976

16UQ46

The piltrate is evaporated to dryness and hydrolyzed

Residue by boiling in 150 cm ^{5 of} hydrochloric acid for one hour.

The solution is then allowed to cool and the crystallized hydrochloride is filtered off with suction. By loosening the hydrochloride in 30 cnr Ethanol and addition of 20 cnr ammonium hydroxide arrives one to the free base. After adding 100 cnr ice water the precipitate formed is filtered off with suction and recrystallized from methanol.

Yield 9 g of 3,5-dibromo-N-n-hexadecylaniline.

Melting point: 53 ⁰ C.

4.75 g (0.01 mol) of aniline and 4 g (0.02 mol) of propanesultone is heated to 140 ⁰ C. 12 S./tunden. The resulting viscous liquid is dissolved in 40 cm of acetic acid and added to a cooled solution of 2,5-dichlorophenyl-diazonium chloride. The pH of the mixture is adjusted to 4 with sodium acetate and a solution of 50 g of potassium hydroxide in 100 ml of water is then gradually added to ^{it below 10 0 O over the course of 2 hours.} The mixture is then poured into water, the precipitate formed is filtered off with suction, washed with sodium chloride solution and finally recrystallized from n-butanol.

Yield: 3 g of 2,6-dibromo-4- (Nn-hexadecyl-N-3 £ -sulfopropyl) aminophenyl-azo-2 ', 5'-dichlorobenzene. Fuzzy melting point: 205 ⁰ C.

25 g of this azo-7 compound are dissolved in 150 cnr acetic acid. To the solution is added dropwise at 30 ⁰ C a solution of 40 g of crystalline tin (II) chloride in 150 enr ethanolic hydrochloric acid. The mixture is then poured onto approximately six times the amount of ice, and the NM blow that has formed is sucked off and removed

AG 204 - 20 -

109816/1976

a mixture of ethanol and ammonium hydroxide recrystallized. The resulting base is recrystallized

one
from a mixture of ethanol and 5 η hydrochloric acid into the hydrochloride

convicted.

Yield: 10.5 g of 2,6-dibromo-4- (IT-n-hexadecyl-N-3-sulfopropyl) aminoaniline hydrochloride.

Melting point: 110 ⁰ G (continuous decomposition).

On color development, p-phenylenediamine derivatives give by oxidative coupling with a magenta color coupler, a blue-green masking dye that removes the undesired Side absorption of the purple dye in the red area of the Compensated for the spectrum.

Those used in photographic color materials p-phenylenediamine derivatives described herein are thus preferably a light-sensitive silver halide emulsion incorporated containing a magenta color coupler of the pyrazolone type.

Similarly Veise can of course be p-phenylene diamine derivatives, etc., which form a green mask, together with compounds using a mask yellow form and then compensate for the undesirable ITebenabsorbtion in the blue region of the primary Purpurfarbsoffes formed in the color development.

The use of such compounds for yellow masking in connection with color couplers of the pyrazolone type is exemplified in British Patent 975,932. In this way, a well-balanced compensation of the

AG 204 - 21 -

109816/1976

Secondary absorption in both the red and blue areas of the purple image can be achieved.

Color couplers of the pyrazolone type which are particularly suitable for the masking process according to the invention are 3-acylaminopyrazolone compounds, such as, for example, the compounds described in Belgian patent 654.110 and in British patent 1.007.847 .

According to a preferred embodiment of the present method, the mask-forming compound is incorporated in the light-sensitive silver halide emulsion layer containing the magenta coupler in a diffusion-proof form.

The diffusion resistance is achieved by in the compounds mentioned have an aliphatic radical Incorporates 5 to 20 carbon atoms.

For the preparation of the silver halide emulsion, the usual photographic colloids are used, such as, for example Gelatin, polyvinyl alcohol, gasein, zein, gollodium or other natural or synthetic colloids. as Layer supports for the silver halide emulsion can be paper, glass, nitrocellulose, cellulose esters such as cellulotriacetate, Polyester, polystyrene and other natural or synthetic Resins can be used.

It will be understood that the process described herein can also be used in connection with multilayer color photographic materials can be used.

Diffusion-resistant color couplers do not have to be used in the light-sensitive

AG 204 - 22 -

109816/19? 6

16U046

Union silver halide emulsion layer itself can be used, but can also be an adjacent non-light-sensitive Colloid layer are incorporated, or a non-photosensitive layer that of the photosensitive Emulsion layer is separated by a water-permeable colloid layer.

Finally, it should be mentioned that one after the A masked color negative can be produced according to the method of the invention in the following manner. A photographic one Material contained in the green-sensitive silver halide emulsion layer a pyrazolone type magenta color coupler and a mask-forming compound according to the present invention Invention. This material is exposed to a color image.

Then the silver halide is processed in a color development

the
bath contains a primary aromatic amino compound, reduced to silver in the exposed areas. The oxidized developer then reacts with the color coupler to form a dye, the mask-forming compound according to the invention not being influenced. Following the Färbentwicklung is now the photographic material with an oxidizing _ä

alkaline liquid, for example with a photographic bleach bath. In this bath, the oxidative coupling of the mask-forming compound with the remaining pyrazolone takes place. Dns coloring material is subsequently fixed with ^v 'ater and dried.

The following aromatic amino compounds can be used as color developers for the material described: N, N-dialkyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine

and N, N -diethyl-2-methyl-p-phenyldiamine, so.vie its AG 204 - 23 -

10981R / 197fi

Derivatives such as N.N-dialkyl-N-sulfomethyl- or N, N, -dialkyl-N'-carbpxymethyl-p-phenylenediamine.

Example 1;

225 g of a photographer see! Silver bromoiodide, made of 50 grams of silver nitrate and 80 g of gelatin per emulsion are melted with 150 cnr> ^T ater at 40 ⁰ C.

Add to the emulsion one after the other

8 cnr 1 η acetic acid

a solution of 3.6 g of 1- (4'-n-hexadecylsulfonyl-phenyl) 3- (4 ^l -sulfobenaylamino) -pyrazolon-5 in 3.6 cm 2 of sodium hydroxide and 32.5 cnr of water

2.5 g of compound 7, dissolved in 5 cnr 2 η sodium hydroxide, 5 cnr ethanol and 15 cnr water.

After adding a hardening agent, a stabilizer and a dispersing agent, the emulsion is diluted with water to such an extent that a 10 cm film base can be coated with it. The so hergeetellte material is exposed to light through a gray filter (factor 0.15) and developed for 9 minutes at 20 ⁰ C in a color developer of the following composition:

2 g sodium hexametaphosphate

3 g of N, N-diethyl-p-phenylenediamine hydrochloride

4 g sodium sulfite
57 g sodium carbonate

1.5 g hydroxylamine hydrochloride

1 g of potassium bromide and up to
1000 cm ⁵ water (pH = 10.6)

The material is washed for 5 minutes and then ^{fixed for 5 minutes at 20 °} C. in a fixing bath of the following composition:

AG 204 - 24 -

10981R / 1976

1644048

200 g sodium thiosulfate
25 g sodium bisulfite
20 g of potassium alum

20 g of an equimolecular mixture of sodium acetate and acetic acid

7f5 g boric acid and water up to 1000 cm (pH = 4)

The material is then bleached and ge./asehen 5 minutes at 20 ⁰ C in a bleaching bath of the following composition:

100 g potassium hexacyanoferrate (III) 15 g potassium bromide
20 g borax
50 g of magnesium sulfate

and "water up to 1000 cm ⁵ (pH = 8.6)

The material is washed for 5 minutes and then ^{fixed for 5 minutes at 20 °} C. in a fixing bath of the following composition:

130 g sodium thiosulfate
20 g borax
50 g magnesium sulfate and

^T 'ater up to 1000 cm ⁵ (pH = 8.9).

The material is soaked for 10 minutes and then finally cleaned dries.

In this way an image is obtained that consists of a purple and a cyan wedge (absorption maximum: 650 mn). The gradations of the two wedges are opposite to each other »so that the unwanted absorption of the purple dye in the red spectral range compensated «vird.

AS 204 - 25 -

109816/1976

IG

Example 2;

225 g of a photograph see! Silver bromoiodide emulsion prepared from 50 g of silver nitrate and 80 g per kg of emulsion gelatin is melted with 150 cnr ^T -'asser at 40 ⁰ C. Add to this emulsion one after the other

12 cnr 1 η acetic acid

3.6 g 1 - (- 4'-n-Hexadecylsulfonylphenyl) -3- (4 »-

sulfobenaylamino) -pyrazolon-5, dissolved in

3.6 cnr 2 η sodium hydroxide and 32.5 cm water 2.5 g of 1-methyl-4-n-pentadecylquinolone-2- (4'-carb-

oxymethoxymethoxyphenylj-sulfonylhydrazone, dissolved in 5 cm 2 η sodium hydroxide
12.5 cnr diacetone alcohol and 32.5 cnr water

2.5 g of compound 7, dissolved in 5 cnr 2 η sodium hydroxide,
5 cm ⁵ ethanol and

I Ti

15 cnr ^TiT ater.

After adding a hardener, a stabilizer and a dispersing agent, is diluted with water to the extent that

2
that 10 m film bases can be coated with the emulsion. The material produced in this way is then exposed behind a gray filter (factor 0.15) and then processed further as described in Example 1. In this way, an image is obtained that consists of a purple and a green wedge, the gradations of which are opposite. The unwanted secondary absorption of the purple dye in the blue and red areas of the spectrum is compensated for.

- 26 A-G 204

Claims (8)

Claims 1.) Process for the formation of a dye which absorbs essentially in the red region of the visible spectrum, by oxidative coupling, characterized in that a color coupler of the pyrazolone type is coupled with a colorless compound of the general formula ^ NA-NH-R,
^R 2 corresponds to where R ^ is hydrogen, a monovalent organic radical, or _Λ denotes a divalent organic radical which is bonded to an atom in the ortho position of the aromatic group represented by A, R ₂ represents a monovalent or a divalent organic group attached to an ortho atom of the aromatic represented by A. Group is bound, R, denotes hydrogen, or a substituent which is represented by the oxidative coupling is split off, and A means an aromatic group which is in the p-position to the R ₁ grouping by an -NH-R- group \ ¹ ^ N - ^ ^R 2
is substituted and which bears a substituent in the o-position to the -NH-R, group, as a result of which the -NH-R, group experiences a steric hindrance, it also being possible for this aromatic group to be further substituted. AG 204 - 27 - 109816/1976 χ _% 16UCK6 2.) Method of producing a color corrected image in a photographic element comprising at least one silver halide emulsion layer, characterized in that that the silver halide emulsion layer contains a color coupler of the pyrazolone type, which upon development by Reaction with the oxidation product of a developer containing aromatic amino compounds Forms color image that absorbs light from the green part of the visible spectrum for the most part, and that too absorbs smaller parts of the blue and the red part of the visible spectrum and that the photographic Material after imagewise exposure and color development in the presence of a mask-forming compound corresponding to the formula given in claim 1 with an oxidizing one Bleach solution is treated. 3.) Method of producing a color-corrected image, in a photographic material consisting of at least a silver halide emulsion layer, characterized in that a color coupler of the pyrazolone type is used during development a primary by reaction with the oxidation product of a developer containing aromatic amino compounds Forms a color image that mainly absorbs light from the green part of the visible spectrum, and that too smaller parts from the blue and IfSten area of the AG 204 - 28 - absorbs the visible spectrum and that the photographic Material after imagewise exposure and color development in the presence of a mask-forming connection with · a oxidizing bleaching solution treated "'ird, being the inase-forming compound of the general formula corresponds to, in the Ru denotes hydrogen, an optionally substituted alkyl radical, ™ an optionally substituted aralkyl radical or an optionally substituted aryl group, R _{2 represents} an optionally substituted alkyl, an optionally substituted aralkyl or an optionally substituted aryl or R ₁ and R _{2 form} a nitrogen-containing nucleus which may optionally be substituted R and R ^ represent substituents that have a Bterisch hindrance of the -NHp Group, | R _c and R ₁ . a> ^T asserstoffatom or for another ο .ο Substituents are, and or R- together with R, and / or Rg together with R, a »Represent a aromatic, a partially hydrogenated aromatic or a heterocyclic condensed ring, where these rings can be substituted, R ₅ together with R forms a condensed, nitrogen-containing, heterocyclic, optionally substituted ring system and AQ 204 - 29 - 109816/1976 together with R _{2 represents} a condensed, nitrogen-containing, heterocyclic optionally substituted ring system. 4.) The method according to claim 3, characterized in that the steric hindrance of the -MH ₂ group of the mask-forming compound by a halogen atom, an alkyl, alkoxy or acyl radical, an amino group substituted by acyl, a sulfonyl, Sulfonylalkyl, sulfonylaryl, sulfo or carboxy group is effected in acidic or salt form. 5.) Process according to claims 3 and 4, characterized in that that as a substituent which can be split off by oxidative coupling, an optionally substituted one Sulfonylalkyl group, an optionally substituted one Sulfonylaryl group, a suIfo group, a carbamyl group, a halogen atom, a sulfomethyl group, a carboxymethyl en group or a methyl group bearing a phosphoric acid residue is used. 6.) Process according to claims 1 to 5, characterized in that the oxidative coupling is carried out using a photographic bleaching bath that contains potassium hexacyanoferrate (III). 7.) Photographic material with several on top of each other arranged silver halide emulsion layers that are sensitive in different regions of the visible spectrum are characterized in that at least one of these layers is a magenta coupler of the pyrazolone type AG 204 -. - 30 - 109816/1976 and ßine. diffusioiißf eote lu ^ slconbilueixile connection following end or general formula contains IT- // VWiH ₀ in the '' ■ ' R .. hydrogen, or an optionally substituted one Denotes an alkyl or aryl group, Rp for an optionally substituted alkyl or aryl group stands, or R. | together R _{2 form} an optionally substituted nitrogen-containing ring, R, and R. Halogen, alkyl or alkoxy are therefore a substituent which causes steric hindrance; and Rc and Rg represent hydrogen, alkyl, alkoxy or halogen. 8.) Photographer! This material with several on top of each other arranged silver halide emulsion layers, cUe in f different regions of the visible spectrum are sensitive, characterized in that at least one these layers contain a color coupler of the pyrazolone type and a mixture of mask-forming compounds, of which at least one of a general formula auo Äea. Corresponds to claims 1, 3 or 8. · AS 204 '- 51 - 109816/1976