DE1003586B - Process for the incorporation of components in gelatine-halosilver emulsions, in particular for color photographic purposes, such as color formers - Google Patents

Description

GERMAN

The invention relates to a method of incorporating components, particularly the couplers, into Layers of halogen silver emulsions, in particular for color photographic purposes.

In the preparation of dispersions of color couplers in halogen silver emulsions, it is common to use the To dissolve color formers or couplers in a suitable high-boiling solvent, this solution in aqueous gelatin to disperse and before the preparation of the coating the resulting dispersion with the sensitive Mix halogen silver emulsion. In general, coupler to solvent ratios will be such as about 1: 2 or 1: 3 is used (see that in the USA 2,322,027 by Jelly and Vittum), although some couplers have a ratio 1: 1 can be used with success. The real solubility of the couplers in solvents for however, the coupler is considerably lower than indicated by the above ratios, and in In many cases no more than 1 part of coupler dissolves in 10 parts of coupler solvent. Most of the in Emulsion layers embedded color former, the dispersed phase is therefore usually one strongly supersaturated solution.

In the case of the coupler to solvent ratios that are usually used, in the Emulsion introduced a large amount of inert solvent; this is unfavorable because the material is inert has no photographic function and because it tends to increase the physical hardness of the emulsion layer to decrease.

In order to minimize the amount of the inert ingredients in the emulsion layer and to improve the physical hardness of the coatings, it is desirable to use coupler solvents in amounts smaller than the above-mentioned proportions. To this end, efforts have been made to prepare coupler dispersions with smaller proportions of the coupler solvent by e.g. B. Coupler to solvent ratios such as 1: ¹ Z ₂ or 1: ¹ Z _{4 were} used. Such low ratio dispersions have in some cases been successfully prepared using auxiliary solvents which are removed in the course of the preparation of the dispersion. The same technique was used to prepare coupler dispersions that contained essentially no coupler solvent.

With these low ratio dispersions, some couplers will recrystallize. No Dispersions containing coupler solvents can be obtained crystal-free, but these dispersions give almost always less dye during color development, unless the developer solution is organic Solvents such as B. Benzyl alcohol, and therefore contains

Procedure for storage
of components in gelatine-halosilver emulsions,
especially for color photographic
Purposes, such as color formers

Applicant:

Eastman Kodak Company, Rochester,
NY (V. St. A.)

Representative: Dr.-Ing. W. Wolff, patent attorney,
Stuttgart-N, Lange Str. 51

Claimed priority:
V. St. v. America December 20, 1954

Scheuring Session Fierke and Jonas John Chechak,

Rochester, NY (V. St. A.),
have been named as inventors

is of limited use where normal paint processing is required.

It has been found that low ratio coupler dispersions can be prepared by

1. Dissolve the coupler in a solvent containing a low-boiling, essentially water-insoluble organic solvent or a markedly water-soluble one organic solvent for the coupler and less than about one part to one part coupler of essentially one contains water-insoluble organic crystalloidal solvent with a low molecular weight, the latter solvent having a boiling point above about 175 ° C, a high dissolving effect acts on the coupler and dyes formed therefrom and for oxidation products of the photographic developer is permeable,

2. dispersing the solution in gelatin,

3. cooling and allowing the gelatin dispersion to solidify,

4. Removing at least 90% of the water and essentially all of the low boiling point, essentially water-insoluble organic solvent or the markedly water-soluble organic solvent from the dispersion by drying or by washing with water and subsequent drying, and

609 837/406

3 4

5. Mix the dried dispersion to any dissolved. The petroleum ether solution was successively with

later with a halosilver gelatin emulsion. 500 cm ³ containing 25 cm ^{3 of} concentrated hydrochloric acid

Couplers used according to the invention water, 500 cm ^{3 of} 2% sodium bicarbonate solution and

those in US Pat. No. 2,322,027 are washed ^{by 500 cm 3 of water.}

Jelley and Vittum described couplers and the 5 a possibly crystal-

the following: lized product was made using more

1. 1-Oxy-2- [o- (2 ', 4'-di-tert-amylphenoxy) -n-butyl] petroleum ether dissolved.

naphthamide (US Pat. No. 2,474,293), the petroleum ether solution was

2. l-Oxy-4-phenylazo-4 '- (p-tert-butylphenoxy) -2- zium chloride dried and filtered with suction, naphthanilide (US Pat. No. 2,521908), io

3. 2- (2,4-Di-tert-amylphenoxyacetamino) -4,6-di- are dissolved by more solvent. The clear chloro-5-methyl-phenol (Graham, USA.-Patent pink-red filtrate was concentrated in a steam bath to a volume of 2,725,291), 600 cm ³ . From this volume of the solution

4. 2- (a-Di "tert-amylphenoxy-n-butyrylamino) -4,6-di- means, the product crystallized within 1 hour chlororo-5-methyl-phenol, 15 as fine white, feather-like needles. The mixture

5. 6- {α- (4- [α- (2,4-Di-tert-amylphenoxy) -butyrami- was cooled in an ice bath, stirred gently and do] -phenoxy) -acetamido} -2,4-dichloro-3-methyl-phenol, filtered with suction; the product was in one

6. Wash the 2- [3 '- (2 ", 4" -Diamylphenoxy) acetamido] benzami funnel with 3 x 100 cm ^{3 of} cold petroleum ether. do-4-chloro-5-methyl-phenol, the product was white, gave no trace of color in it

7. l- (2 ', 4', 6'-trichlorophenyl) -3- [3 "- (2" ', 4 "' - di-tert-20 solvents and had a melting point of amylphenoxy) -acetamido-benzamido] -5-pyrazolone (USA.-117 to 118 ° C. Yield: 62 g.

Patent specification 2,600,788), the product was dissolved in 2 liters of petroleum ether under gentle

8. Dissolved l- (2 ', 4', 6'-trichlorophenyl) -3- [3 "- (2" ', 4 "' - di-tert-heating amylphenoxy) -acetamido-benzamido] -4- (p-methoxyphe- 5 g activated charcoal added, and the mixture nylazo) -5-pyrazolone, 25 was under suction through a layer of 5 g

9. N - ^ - BenzoylacetaminobenzolsulfonylJ-N-iy-phe- active charcoal filtered through a Buchner funnel. nylpropyl) -p-toluidine (USA. Patent 2 298 443). The colorless filtrate was reduced to a volume of 200 cm ³

10. ao-methoxybenzoyl-a-chloro-4- [a- (2,4-di-tert.- concentrated and the product crystallized. The mixture of amyl-phenoxy) -n-butyramido] -acetanilide was stirred gently, externally cooled to O ⁰ C and

11. α- {3- [α- (2,4-Di-tert-amylphenoxy) acetamido] - 30 filtered. The product was washed on the funnel with benzoyl} -2-methoxyanilide, 100 cm ^{3 of} cold petroleum ether (0 ° C.); it was

12. 3-Benzoylacetamino-4-methoxy-2 ', 4'-di-tert-dried at 50 ° C. Yield: 53 g (37%), melting point amylphenoxyacetanilide, 123 to 124 ° C.

13. 4-Benzoylacetamido-3-methoxy-2 ', 4'-di-tert.-

amylphenoxyacetanilide. 35 Production of 2-amino-4,6-dichloro

Coupler Nos. 4, 5, 6, 8, 11, 12 and 13 became like 5-methylphenol hydrochloride

is made as follows:

Into a 1-1 beaker was 100 g (0.634 moles) of 2-Amino-4-chloro-5-methylphenol (J. für Prakt. Chemie,

Coupler No. 4 _{4Q gij s>} ^ _{and 450 cm3} E _ss i _{g acid} re given; the mixture

2- (a-Diamylphenoxy-n-butyrylamino) -4, 6-dichloro- was taken as gently as possible with a glass rod

Stirring 5-methylphenol, the temperature rose from 23 to 35 ° C. At this point

Slurry were added all at once 132 cm ³ (142 g, 1.4 mol) of vinegar in a 2-1 three-necked flask with an acid anhydride; At no time had a solution formed, if the meter was equipped, it became a solution of 600 cm ³ because the acetyl derivative crystallized almost immediately. Acetone (dried over sodium sulfate) and 80 g. The mixture was gently stirred with a stick and then allowed to stand (0.62 mol of repeatedly distilled quinoline (practical) for ¹ _1/2 hours. Then the broth was added. To this solution was 68.5 g (0.30 mol) cooled to 20 ° C., and 55 cm ³ (92 g, 0.68 mol) practically repeatedly crystallized 2-amino-4,6-dichloro-5-me-pure sulfuryl chloride were added all at once , ethyl phenol hydrochloride. The chloride dissolved. The temperature rose to 46 ° C, a red partly with a yellow color formed. Soon solution separated. As soon as everything was dissolved and before the new one a white precipitate was plentiful. the mixture remained chlorine compound allowed to crystallize, but the liquid became easily stirrable, Stirring was poured into a 3-1 three-necked flask for 10 minutes, continued and 101 g (0.3 mol) of α-diamylder was added with a stirrer and with a reflux condenser phenoxy-n-butyryl chloride added. The temperature sator was provided. After 10 minutes the temperature rose rapidly from 28 to 46 ° C. Some bodies did not dissolve a mixture containing crystals in a solution of 500 cm ³ . denatured ethyl alcohol and 500 cm ³ concentrated

The mixture was added 1 ^x / ₂ hours under constant hydrochloric acid.

Stir heated in the steam bath. At no time was it 60. The mixture was boiled with stirring. Complete after solution. The mixture was externally boiled for 5 minutes, chloride began to cool to -10 ° C, and 1 liter of ice water was added to it to precipitate crystals. The mixture was given after. The mixture was kept under concentrated hydrochloric acid for 45 minutes until the Congo reflux changed color by adding 15 cm ^{3 of the first appearance of these crystals.} The mixture showed a distinctly acidic paper. A few seeds of the product with a tendency to foam, especially when boiled vigorously, from an earlier preparation were added and the mixture was refrigerated overnight and stirring continued for 1 hour. The product filtered off with suction (brown filtrate). The filter residue separated out as a white, cheese-like ball. The acidic was ^{washed with 1} Z ₂ 1 acetone, a white aqueous liquid was obtained and was decanted through 1200 cm ^{3 of} chloride. After drying at 70 ° C., petroleum ether was replaced in which the product was easily 70 113 g (78%).

5 6

A sample of sodium bicarbonate made from this (0.0455 mol) dimethylaniline and 15 g (0.0445 mol) a-

The amine liberated from chloride melted at 133 (2,4-di-tert.-amylphenoxy) -n-butyryl chloride (see above)

mixed up to 134 ° C. with mechanical stirring. The piston was

_TT _. . ,,. provided with a water-cooled condenser, and

Preparation of a-Diamylphenoxy-n-butyric acid _{5 the} reaction mixture was under for 2 hours

In a 3-1 three-necked flask kept at reflux. The cooled reaction mixture stirrer, a thermometer and a reflux was poured into 1 1 of cold water with stirring, a condenser was provided, 40 cm ^{3 of} water and the ^{2 cm 2 of} concentrated hydrochloric acid were contained; the excellent

660 cm ^{3 of} denatured alcohol filled. This falling precipitate was filtered off with cold water

80 g (2 mol) of sodium hydroxide tablets were washed thoroughly with alcohol and dried. The product weighed

dissolved with stirring and heating until boiling. works 31.5 g and was made twice from methyl alcohol

Stirring crystallized out throughout the preparation, using Darco once,

not interrupted. 19.8 g of a white solution which melted at 120 to 122 ° C. were added to this hot solution

234 g (1 mole) of repetitively distilled di-tert-amyl material was obtained, that is about 50% of the

phenol was added, and a reverse 15 theoretically calculated amount of 37.8 g was added for 5 minutes.
nut uphold. The solution was externally based

6O ⁰ C cooled, and 167 g (1 mol) of a-bromo-n-butter- production of 6- [a- (4-N ₁ trophenoxy) -acetamido] -

acid was added. The temperature of the solution ² > 4-dichloro-3-methylphenol

rose by 15 ° C. The solution was heated to boiling. 107 g (0.48 mol) of 2-amino-

and refluxing continued for 3 hours. 4, o-dichloro-S-methylphenol hydrochloride with 900 cm ³

set. Some salt precipitated. Of acetone and 121 cm ³ (1 mole) of dimethylaniline mixed

The mixture was cooled externally to room temperature and vigorously within about 5 minutes and diluted 107.5 g (0.5 mol) of p-nitrophenoxyacetyl chloride hydrochloric acid ^{with 1 l of ice water and 200 cm 3 of concentrated stirring.} The resulting mixture showed on being added to the flask. The flask was made with a Congo paper had a strong acidic effect. The oily product was provided with a reflux condenser and the mixture was ^{extracted with 500 cm 3 of} technical grade ethyl ether and refluxed for 2 hours. At the end and the ether extract was washed with 500 cm ^{3 of} water at this time, the reaction mixture was washed to 2.5 l cold. The ethereal solution was separated off and poured into water, and the 8 cm ^{3 of} concentrated hydrochloric acid was transferred to a suitable Clais flask. The moist one contained. An oily substance was formed, which was concentrated by means of ether extract by distillation, the last 30 decanting times were washed with cold water. Traces of ether and water were removed by suction. Denatured alcohol was removed to the oil, added, and a crystalline precipitate soon formed.

The syrupy residue was distilled in vacuo. This was filtered out with fresh denatured

using an oil bath until the last traces of alcohol were washed and dried in a hot oven,

recovered from diamylphenol. At the 35 yield: 153 g, 86%, melting point: 240 to 242 ° C.

Distillation was a forerun of about 15 g up to 110 ° A sample was made from dimethylformamide with re-

collected at 1 mm pressure. The diamylphenol was obtained by crystallization of 62%, melting point

collected at 111 to 169 ° C at 1mm pressure, 130 g 241 to 242 ° C.

from him were regained. Almost all of _r κ ■

Diamylphenol boiled at 123 to 12571mm. The 40 Production of 6- [a- (4-Ammophenoxy) -acetamido] -

Oil bath was then removed, and the α-diamylphenoxy- ² '4-dichloro-3-methylphenol

n-butyric acid was distilled over the flame. The 37.1 g (0.1 mol) of the nitro compound were in a

Product was collected at 170-200 ° / l mm. This pressure bottle along with about 3 g of nickel catalyst

Product can be given by the sudden increase in and 200 cm ^{3 of} pyridine. The bottle opened

Viscosity of the distillate can be recognized. No noticeable Parr hydrogenation apparatus and kept at 40 to 50 ° C

Licher residue remained in the distillation flask. shaken under a hydrogen pressure of 17.2 at.

Yield: 125 g (39%). The required 0.3 moles of hydrogen became rapid

_TT "_. . ,. , ..... added, after 2 hours the catalyst was

Production of a-diamylphenoxy-n-butyrylchlond filtered _{out of the water -white pyridine solution} and that

160 g (0.5 mol) of solvent were placed in a 500 cm ^{3 claw flask under reduced pressure in a water bath}

a-diamyl-phenoxy-n-butyric acid and 160 g (1.35 mol) at 5O ⁰ C removed. The white, solid residue was

Thionyl chloride (distilled over quinoline) given. After broken out and ^{disintegrated with 200 cm 3 of} methyl alcohol

heating to 4O ⁰ C started in the clear, amber rubbed, then filtered and dried. The yield was

colored liquid a slight development of 30 g, that is 93% of the theoretically expected amount

Sulfur dioxide and hydrogen chloride. The temperature 55 of 32.7 g; Melting point: 256 to 258 ° C. One off

was kept at 40 to 45 ° C until the gas evolution. Dimethylformamide crystallized sample melted

stopped. This generally stopped after 3 hours. 261 to 263 ° C.

Excess thionyl chloride was removed by distillation

removed the last traces of it by distillation to produce p-nitrophenoxyacetic acid

Vacuum of the water jet pump. The a-diamylphenoxy- 60 In a 5-1 flask was 278 g (2 moles) of p-nitro-

n-butyric acid chloride was at 138 to 140 ° C with 1 mm phenol, 190 g (2 mol) chloroacetic acid, 168 g (4.2 mol)

Distilled over pressure. Yield: 150 g (90%) sodium hydroxide and water added. The mixture

was boiled in the open flask until paint coupler no. 5 muspaper showed a neutral reaction. The reaction

6- {a- (4- [a- (2,4-Di-tert.-amylphenoxy) -butyramido] - ⁶ S ^ F ^ ^er f. ^{Ate 115} ° ^C - ^some water evaporated.

pnenoxy) -acetamido} -2, 4-dichloro-3-methylphenol £ when the neutralization point had been reached (after

^vy '' ^yv 2V ₂ to 3 hours) a further 84 g (2.05 mol)

In a 500 cm ³ three-necked flask, sodium hydroxide and 95 g (1 mole) of chloroacetic acid were added in

Add 14.8 g (0.045 mol) of 6- [α - (4-aminophenoxy) -acetamido] - to the flask and continue heating until

2,4-dichloro-3-methylphenol, 250 cm ³ acetone, 5.5 cm ³ 70 the mixture reacted neutrally.

7 8

The cooled reaction mixture was placed in an ice-water bath for a total of 2 hours

Stirring 500 cm ^{3 of} concentrated hydrochloric acid added. touched. The product was removed with suction.

The precipitate formed was filtered off, ice-filtered with 3 l, washed ^{in the funnel with 3 × 300 cm 3 of acetone}

Slurried cold water, filtered again and washed with 11 and in the steam cabinet to constant weight dry cold water. The dry product melted 5 net. The yield was 93 ° / ₀ (285 g), the melting

at 182 to 184 ° C and weighed 300 g. The yield point was 273-274 ° C. 76% of the theoretically expected amount of 394 g.

If necessary, the product can be used to produce 2- (3-aminobenzamido) -4-chloro-

are crystallized out. 5-methylphenol

IO

Preparation of p-nitrophenoxyacetyl chloride ¹ ^ ^egg nem with a condenser and a stirrer

equipped 2-1 round bottom flasks and three

In a 500 cm ³ flask, 19.7 g (0.1 mol) of Hälsenn was benzamido 61 g (0.2 mol) of 4-chloro-5-methyl-2- (3-nitrop-nitrophenoxyacetic acid and 100 cm ^{3 of} thionyl chloride ) -phenol mixed in 600 cm ^{3 of} 90% acetic acid. The mixture was suspended on a steam bath 15. To this suspension, which was initially refluxed for 5 hours and the excess reflux was heated, 62 g of iron powder excess thionyl chloride were added under reduced pressure. The mixture was removed with stirring. The removal of the thionyl chloride was kept under reflux for a ^{total of 1} J _{2 hours.} During this time continued until the weight of the remainder was constant, the nitro compound dissolved and that remained. The acid chloride was used without purification. Foam was over the refluxing solution and gave good results. To a white, colorless at 86 to 87 ° C. The solution was filtered and the filtrate in melting crystalline material can be poured 2 liters of water. The amines, which precipitated out as a fine white precipitate, the product crystallized from dried ligroin, were filtered out. and in a funnel twice with 250 cm ^{3 of} 10% strength

Coupler No. 6 ² 5 acetic acid and washed eight times with 250 cm ^{3 of water}

"," _R , _. ,. ,,,.,. and dried at about 50 ° C to constant weight.

4-chloro-2- {3- [a- (2,4-di-tert-amyphenoxy) -acetamido] - The _{type of product was 50 (93%} ). Melting point: benzamxdoj-5-methylphenol _{205 to 2Q6} o _{c (} crystallized amines melted at

In a three-necked 1-1 flask that has a 216 to 218 ° C). had round bottom and with a thermometer and 30

A stirrer was equipped, there were 27.6 g (0.1 mol) of the preparation of 2,4-di-tert-amylphenoxyacetic acid

2- (3-Aminobenzamido) -4-chloro-5-methylphenol in one

Solution of 13.3 g (0.11 mol) of N, N-dimethylaniline in a three-necked, with a stirrer, a thermostat

(97 ° / ₀ ) suspended in 250 cm ^{3 of} dry acetone. To thermometers and a reflux condenser equipped this suspension was added at 25 ⁰ C under stirring 35 3-1 flask, 40 cm ³ of water, ³ added 660 cm denatured during a period of 4 minutes, a solution of alcohol and 80 g (2 mol) sodium hydroxide . 34.1 g (0.11 mol) of a- (2,4-di-tert-amylphenoxy) -acetyl- The solution was stirred, then 234 g (1 mol) of chloride in 100 cm ^{3 of} dry acetone were added. The repeatedly distilled 2,4-di-tert-amylphenol added temperature rose rapidly to 38 ° C., a solution was obtained and the solution was complete for 5 minutes under reflux. The clear solution was kept in a 40. Then it was cooled to 60 ° C., and 94.5 g of ice water bath was stirred for 1 hour (the resulting (1 mol) chloroacetic acids were added. The temperature was approximately 5 ° C.), and 150 cm ^{3 of} 10 ° / ₀ mixture hydrochloric acid was added with stirring for 3 hours. The temperature rose nut, then cooled to room temperature, with to 15 ° C, and the white broth was diluted 1 ^{l of ice water for 1 hour and finally stirred with 200 cm 3 of} cone, filtered, the filter residue acidified at approximately 45 centered hydrochloric acid. The diamylphenoxy-50 ° C dried to constant weight. The acetic acid, which precipitated as an orange-brown oil, yielded the coupler was 83% (46 g). The melting 200 cm ³ ether extracted and the wet ether layer point was 165 to 166 ° C. concentrated under reduced pressure on the steam bath.

The heavy oil was in vacuo at 172-176 ° C

Production of 2- (3-nitrobenzamido) -4-chloro-5o and distilled at 1 mm Hg. Yield: 127 g (43%). That 5-methylphenol viscous oil soon solidified into a waxy one

Dimensions. The diamylphenoxy-acetic acid can be purified by means of a 2-1 Erlenmeyer flask, 158 g (1 mol) of crystallization from hexane. Melt-2-amino-4-chloro-5-methyl-phenol (magazine for prakpunkt: 116 to 117 ° C, snow-white powder, tische Chemie, 91, p. 414 [1915]) and 1.2 l dry 55
Given acetone. 20 g of Darco were added to this solution

added, the resulting mixture was allowed to produce about a- {2, 4-di-tert-amylphenoxy) -

Stand for minutes at room temperature, then became acetyl chloride

filtered with suction.

This solution was placed in a 5-1 flask with three 60-80 g (0.27 mol) 2,4-diamylphenoxy-acetic acid necks that had a round bottom and were melted on the steam bath and cooled to 50 ° C fitted with a thermometer and a stirrer. To the semisolid product, 88 g (0.74 mol) of thiowar were added. 121 g (1 mol) of N, N-dimethylaniline nyl chloride (repeatedly distilled over quinoline) were added to it (97%). This solution was poured into ice and the mixture was stirred until all solid water baths were cooled to 10 ° C. and 65 parts were dissolved with stirring. The clear liquid was poured into a solution with a stirrer and a thermometer of 186 g (1 mol) of m-nitrobenzoyl chloride in 540 cm ^{3 of} 500 cm ³ flask and with stirring for 4 hours of dry acetone added. The temperature was kept at 40 to 45 ° C. Excess thionyl chloride rapidly rose to 38 ° C and the product separated out in the form of a fine white precipitate upon heating under one of a kind of water. This mixture 70 jet pump generated reduced pressure away. That

9 10

Product was instantaneous at 143-146 ° C and under pressure from the edge of the funnel

distilled from 2 mm. Yield: 65 g (76.5%). together as if it had become rubbery.

After vacuuming and thoroughly pressing the low

No such change took place in Coupler No. 8 Schlages. Of the

1- (2 ', 4', 6'-trichlorophenyl) -3- [3 "- (2"', 4 "' - diamyl- ⁵ precipitate, which can be easily detached, was

_P henoxyacetamido) benzamido] -4- (p-methoxyphenyl * ^{n air} dried to give 60 g were obtained. The

^r azo) -5-pvrazolone temperature range in which it melted was indefinite,

it started above 95 ° C.

1 - (2 ', 4', o'-Trichlorophenyl) -3- [3 "- (2 '", 4 "' - diamyl- On the steam bath 1200 cm ^{3 of} cyclohexane were converted into phenoxyacetamido) -benzamido] -5-pyrazolone (92 g) was heated to the boil and 60 g of the crude product were dissolved in 1.25 l of pyridine and the solution was cooled to 0 ° C. Dissolved therein, a pink solution formed, which became a diazonium solution by dissolving with it Treated 2 g of Darco and filtered the solution hot through 2 g of 19.4 g of p-anisidine in 250 cm ^{3 of} water and 40 cm ^{3 of} kon-Darco on a 10 cm Buchner funnel C and the addition of clear filtrate was only a little less colored than 11.2 g of sodium nitrite in 100 cm ^{3 of} water produced before the Darco treatment without led, which did not exceed 5 ° C. The diazonium solution filtered out difficulties and on the funnel three was 500 cm ³ diluted denatured alcohol, washed with times with 100 cm ³ fresh cyclohexane, treated decolorizing charcoal and filtered. 47 g of the white coupler were obtained (82% of the

This clarified solution now became the amount of pyridine to be theoretically expected at 126 to 127 ° C

coupler solution melted at such a rate.

given that the temperature did not exceed 10 ° C. Production of

The stirring was continued for another half an hour after the α- (m-nitrobenzoyl) -2-methoxyacetanilide
Addition of the last coupler solution continued

The temperature was allowed to rise to 25 ° C. The reaction mixture was diluted to a refluxed mixture of 22 g with twice its volume (0.093 mol) ethyl - α - (m - nitrobenzoyl) acetate (Bülow water, the dye being a rubber & Hailer, Ber., 35, p. 915 [1902]) ^{precipitated in 150 cm 3} histolo-like mass. The liquid was decanted from the gischem xylene, 11 g (0.09 mol) of o-anisidine on a rubbery mass, which was added well once with water. The mixture was washed out while being washed out. The gummy mass was dissolved in 2 liters of boiling denatured alcohol by heating at reflux for 2 hours. Maintained in the temperature (oil bath from 145 to 155 ° C), with a cooled solution, an orange powder was obtained, steam jacket flask attachment was used, which allowed the removal of the azeotropic alcohol xylene from about 80 parts of denatured alcohol. That was crystallized. The yield was 70 g (63%) of the dye which separated out from the cooled reaction mixture and which had the same properties with regard to the melting point since the product was filtered out and suctioned dry. Various samples melted into a Buchner funnel; 24 g (82%) of a zen were obtained at 133 to 135 ° C, at 149 to 152 ° C, with 147 to yellow product with a melting point of 166 to 167 ° C. 150 ° C and after sintering at 138 ° C, at 142 to 144 ° C.

Coupler No. 11 Preparation of a- (m-Aminobenzoyl) -2-

,. _r , "."., _±,, ',., -, ⁴ ° methoxyacetanilide hydrochloride

α- {3- [α- (2,4-Di-tert-amylphenoxy) -acetamidoJ-

benzoyl} -2-methoxyacetanilide I _n a single-necked flask 12-1 (using In a three-necked equipped with a stirrer and a rubber stopper with a three holes), which provided with a thermometer 500-cm ³ flask were added 300 cm ³ of a stirrer , a thermometer and a reflux 90% acetic acid and 30 g (0.36 mol) of anhydrous 45 condenser, 150 g of a- (m-nitro-sodium acetate. To this solution were added at benzoyl) -2-methoxyacetanilide in a solution of 2.5 liters of room temperature 32 g (0.1 mol) of a- (m-aminobenzoyl) - acetone and 500 cm ^{3 of} concentrated hydrochloric acid suspen-2-methoxy-acetanilide hydrochloride, dated when lowering. 150 g of the finest iron powder (plast mixture. After this mixture had been added to ^{iron for 1} Z ₂ hours) was added to this mixture while stirring within the temperature to 2 ° C. The reaction was very exothermic; the more it was stirred, ^{37 g continued to progress for about x} / ₂ minute, the more nitro compound was (0.19 mol) 2,4-di-tert.-amylphenoxyacetyl chloride (see in solution, and the solution became dark , yellow-brown above) were added. The reaction mixture turned color. The heat of reaction caused the temperature to rise much thinner, but did not become clear, as the temperature rose to the boiling point of acetone; after all iron rose from 25.5 to 35.5 ° C; it was pinkish-gray in color. 55 was added, the solution was stirred for a further 10 minutes with subsequent 1 to ^ constant stirring. At this point in time, 100 cm ^{3 of} water and the mixture were introduced dropwise ^{into the reaction mixture over a period of 1} Z ₂ hours and the solution was distributed, ^{diluted with 30 cm 3 of} water and the coupler was stirred for a further 10 minutes. As the temperature of the germs added. By further stirring the mixture over the mixture had fallen to 50 ° C., the mixture was filtered overnight and the product separated as a finely divided white oil. The mass was made with 500 cm ^{3 of} acetone and the mass. The reaction mixture was poured into 5 1 of dilute hydrochloric acid while stirring (4.5 1 of water and half of 15 minutes ^{poured into 600 cm 3 of} water, the 500 cm ^{3 of} concentrated hydrochloric acid). The solution allowed the product to precipitate as white granules. Stand for 24 hours. Then it was filtered and the stirring was continued for 45 minutes, the filter residue was washed twice with 500 cm ³ traces of salt mixture then by a water containing 12.7 cm Buchner's acid. The down funnel is filtered. The white precipitate was removed and the ^{funnel with 500 cm 3 of} acetone filled with water that was not warmer than 20 ° C. was filtered and dried. 104.5 g were obtained, washed. When the precipitate was no longer covered by white, crystalline chloride (68% of the theoretical water, it shrank in a characteristic amount).

11 12

Coupler No. 12, 500 cm ³ of water and washed as dry as possible S-Benzoylacetamino ^ -methoxy sucked The wet mass was from 5 to 10 parts (2 ', 4'-di-tert-amyl _P henoxy) -acetanffid ^ J ^ ^ J ₊₁ ausknstahsiert and gave 16.3g ^{v J r J} ' (58.4%) white material that melted at 163 to 165 C. In a 250 cm ³ Erlenmeyer flask were 5.68 g of 5., _ -, _n _, -,
(0,02MoI) "-benzo _y l ~ 5-amino-2-Methox _y acetanilide, 2 g Preparation of a-Benzoy ^ -methoxy (0.02 mol) of anhydrous sodium acetate and 100 cm ³ of ice-4-nitroacetanilide
filled with vinegar. ^{With thorough stirring, 6.2 g of a 250 cm 3} round top equipped with a partially condensed (0.02 mol) of the vapors (0.02 mol) 2,4-di-tert.-amylphenoxyacetyl chloride (see sizing distillation attachment) in 25 cm ^{3 of} glacial acetic acid added all at once. 33.6 g (0.2 mol) of 2-methoxy-4-nitroaniline reaction mixture were added to the flask for 1 hour at room temperature (Ber., 13, p. 390) and 75 cm ^{3 of} histological xylene and ¹ l for ₂ hours stirred at 60 ° C. Give after cooling. Before the addition of 40 cm ³ (0.22 mol) of room temperature ethyl, the reaction mixture was benzoylacetate, the mixture was refluxed for 5 minutes with vigorous stirring in 1 l of cold water. About 9 cm ³ distilled within pours. The moist precipitate was filtered out, 15 of 2 hours in the template. Washed from the brown solution with cold water, as dry as possible, mechanical impurities were filtered out, then filtered off with suction and left to stand overnight at room temperature ^{from 200 cm 3 of denatured alcohol and crystallized.} 7.5 g (67 ° / ₀ ) of a yellow-brown color were obtained. The precipitate was filtered off, first with 100 cm ^{3 of} powder which melted at 124 to 126 ° C. A um-xylene, then ^{washed with 100 cm 3 of} petroleum ether, with crystallization from 200 cm ^{3 of} alcohol gave 6.2 g (55%) 20 200 cm ^{3 of} denatured alcohol slurried and a product which melted at 132 to 134 ° C. then dried. 39 g (62%) of a yellow one were obtained

_TT ,, _, mass that melted at 179-180 ° C.

Production of α- benzoyl-2-methoxy-

5-nitroacetanilide Manufacture of a-Benzoyl-4-amino-

In one with one the vapors partially condensed 25 2-methoxyacetane-hydride hydrochloride

250 cm ³ round in a three-necked still with a reflux condenser

flasks were 100 cm ^{3 of} histological xylene and 16.8 g of equipped 11-flasks were 31.4 g (0.1 mol) of a-ben- (0.1 mol) 4-nitro-2-aminoanisole (Ber., 13, P. 389). zoyl ^ -methoxy ^ -nitroacetanilide, 200 cm ^{3 of} 50% aqueous The mixture was brought to the boil, and 19.2 g of denatured alcohol and 150 cm ^{3 of} glacial acetic acid were added. (0.1 mol) ethyl benzoylacetate were added all at once. The mixture was brought to the boil and the heating was turned on. After the mixture had been removed under reflux for 2 hours, and 31.4 g of iron powder was kept flowing as quickly as possible, about 3 to 5 cm ^{3 of} ethyl alcohol could be added. When the initial reaction distilled over into the template. The yellow solution was calmed, heat was reapplied and the filtered hot, then allowed to reflux at room temperature for 20 minutes. The yellow precipitate which separated out. After filtering, the filtrate was filtered out as quickly as it was and ^{washed first with 50 cm 3 of} xylene and possibly with ^{1 liter of water and 300 cm 3 of} concentrated then with 100 cm ^{3 of} petroleum ether. Diluted hydrochloric acid was obtained. The solution changed its color to 26 g (83%) of a crude product, which at 170 to 175 ° C -from deep brown to deep yellow. After cooling the solution melted. The chloride was filtered out by recrystallization from 18 parts of glacial acetic acid overnight at 5 ° C. and 22.4 g (71%) of fine, pale yellow needles with 40 with 500 cm ^{3 of} 5% hydrochloric acid and 500 cm ^{3 of} cold, a melting point of 177 to 179 ° C. Washed water well. After drying, one obtained

_TT "24.8 g (77%) of a white mass, which at about 150 ° C

Production of a-benzoyl-5-ammo became red in places, cleaved HCl at about 200 ° C

2-methoxyacetamhd _{and with decomposition} melted at 2 06 to 209 ° C.

In a Parr hydrogenation bottle were 16 g (0.051 mol) 45 high-melting, crystalloidal organic coupler-benzoyl-2-methoxy-5-nitroacetanilide, 250 cm ³ abso- solvent, which are used according to the invention, pure ethyl alcohol and 2 to 5 g Raney nickel given. can include

The reaction mixture was under 2 to 3 at hydrogen 1. Alkyl esters of phthalic acid, in which the alkyl

Shaken overnight at room temperature. The radical, preferably less than 6 carbon atoms, nickel has been removed by filtration and the filtrate contains 50, e.g. B. methyl phthalate, ethyl phthalate, propylene chilled in an ice bath. The light yellow precipitate phthalate, n-butyl phthalate, di-n-butyl phthalate, n-amyl was filtered out, mixed with 50 cm ^{3 of} cold methyl alcohol phthalate, isoamyl phthalate and dioctyl phthalate,
washed and then dried. 13 g (90%) of 2nd esters of phosphoric acid were obtained, e.g. B. triphenyl phosphate,

a mass melting at 108 to 110 ° C. Tricresyl phosphate and diphenylmono-p-tert.-butyl-

Coupler No. 13-55 phenylphthalate; and

",,,.," - 3. Alkylamides or Acetanihd; z. B. N, n-butyl-

, 0, 4f enzoylacetamido-S-methoxy-acetanilide and N-methyl-p-methylacetanilide.

(2, 4 -di-tert-amylphenoxyj-acetanilide Low-boiling, water-insoluble organic solution

In a stirrer equipped with a 500-cm ³ - medium, in which the coupler is dissolved first, and the Erlenmeyer flask was added 16 g (0.05 mole) of a-benzoyl 60 are then removed to expose the substantially dry 4- To form amino-2-methoxyacetanilide hydrochloride and 10 g dispersion of the coupler in gelatin, add (0.1 mol) anhydrous sodium acetate to 200 cm ^{3 of} glacial acetic acid volatile, air-drying solution. With vigorous stirring, 16 g of agents such as methyl, ethyl, propyl and butyl acetates, iso- (0.051 mol) 2,4-di-tert-amylphenoxyacetyl chloride (see propyl acetate, ethyl propionate, sec-butyl alcohol, tetraoben) were added . After stirring for 1 hour at 65% carbon chloride and chloroform. Water-soluble room temperature was the ^{reaction mixture for 1} ^ hour organic solvents include: methyl isobutyl kept at 60 ° C for a long time, cooled and then poured into 21 cold water under ketone, ß-ethoxy-ethyl acetate, / S-butoxy-ß-ethoxy-ethyl vigorous stirring. The acetate, tetrahydrofurfuryl adipate, carbitol acetate (di-mixture was stirred until the precipitate was filterable, ethylene glycol monoacetate), methoxy triglycol acetate, then the precipitate was filtered out with 70% methyl cellosolve acetate, acetonyl -acetone, diacetone-alcohol-

Claims (11)

13 14 hol, butyl-carbitol, butyl-cellosolve, methyl-carbitol, coating on a substrate becomes the emulsion Methyl cellosolve, ethylene glycol, diethylene glycol and exposed and in a developer of the following composition Dipropylene glycol. Some of these water-soluble solution compositions dealt with: Medium, e.g. carbitol acetate, butyl cellosolve have p-amino diethylaniline sulfate 2g high flash points and therefore reduce the 5 sodium sulfate, anhydrous 5 g Fire hazard during removal from the emulsion. Sodium carbonate, anhydrous 20 g The water-soluble solvents are made from the potassium bromide for 2 s Removed emulsion by washing with water. Benzyl alcohol 10 g The coupler is made up to 11 in a solvent or in water Solvent mixture in such a composition io solved that the ratio of the coupler to the high. It was found that the emulsion had a sufficient purple boiling point organic solvent gives a part of coupler-colored dye density. to less than a part is high boiling solvent. Instead of p-amino-diethylaniline can also The solvent is always a low-boiling organic component containing other primary aromatic amines contain niche solvents used during development 15 Position of the emulsion layer is removed. The solution. . medium can high-boiling organic solvent in ice pie ο contain a suitable ratio or be completely free of such 8 g of the coupler used in Example 1 and 2 g, in the latter case a "solvent-free" coupler reflux temperature of the ethyl acetate is dissolved ^{in the dioctyl hydroquinone in 25 cm 3 of ethyl acetate when the coating is finished} . Get this dispersion. However, it is generally expedient solution is a ³ cm / ₀ gelatin default if some high boiling solvent and 16 cm ³ of a 5 ° / ₀ sodium Althylnaphthalinorganisches solvent is present in a 136 ° 10 in the finished coating. Poured solution containing sodium sulfonate solution and An appropriate ratio of coupler to high boiling point then milled five times in a colloid mill. 50 cm ³ of organic solvent is as shown by the following 25 water of the mill were used for rinsing.
Examples will be shown, 8 g of coupler to 4 cm ^3, 8.4 g of this dispersion to 133 g of a gelatin high-boiling solvent, or a ratio of 1: ¹ Z ₂ . Added silver halide emulsion containing about 0.03 mol. The solvent mixture preferably contains ethyl silver halide. After the application of an acetate as a low-boiling solvent and di-n-butyl coating on a layer support, the exposure and phthalate as the high-boiling solvent, although the further treatment according to Example 2 shows that other mixtures and ratios within the emulsion Vary a sufficient purple colored dye range mentioned at the beginning, with advantage condensing results,
can be turned. Example 4 The invention is further illustrated by the following examples explained: 35 80 g of coupler No. 5 are in 40 cm ^{3 of} dibutyl phthalate Example 1 and 175 cm ³ ethylene glycol monobutyl ether (»Cellosolve«) solved. This mixture is in 545 cm ^{3 of} a 10% 8 g of the coupler l- (2 ', 4', 6'-trichlorophenyl) -3- [3 "- gelatin solution poured, the 35 g of dissolved sodium sulfate (2 '", 4'"- di - tert-amylphenoxyacetamido) - benzamido] and 70 cm ^{3 of} a 7.5% solution of althylnaphthalene-5-pyrazolone are contained in a solution of 25 cm ^{3 of} ethyl sodium sulfonate, which is supplemented by an acetate and 4 cm ^{3 of} di-n-butyl phthalate Driven reflux colloid mill, cooled immediately, dissolved by the narrow open temperature of the ethyl acetate. This mixture is pressed and washed with water. The coupler is then at 50 ° C in a solution of 65 cm ^{3 of} a solvent ethylene glycol monobutyl ether (»Cello-10% gelatin solution and 8 cm ³ of a 5 ° / _o aqueous sodium solve ") triggers the coupler easily at low temperatures, poured triisopropylnaphthalinsulfonatlösung, is stirred for about 45 whereby a decomposition of the coupler to a minimum 1 minute and measured five times reduced by Colloids, and can be milled after the dispersion ben, after which the mill was quickly washed out of the emulsion ^{with 25 cm 3 of water of the coupler.} Which is rinsed. The dispersion is applied to a cooled dispersed particle plate produced in this way at 4.4 ° C., through narrow openings having a diameter of about 0.1 to 0.2 μm.
pressed and in the air at 78 ° C and 50% relative 50 By the method described can be dried in place of moisture. The total dry weight coupler removing stains such as B. 2, 5-di-iso-octylder dispersion is 18.5 g, the dispersed mass is hydroquinone and 2, 5-di-n-octyl-hydroquinone, and ultraim gelatin in particles that are smaller than 0.5 ΐημ substances absorbing violet light such as B. 5-o-sulfo goods without showing any crystals. benzal-3-phenyl-2-phenylimino-4-thiazolidone in gelatin ". . , _o 55 are dispersed.
Example 2 • inn j · υ · 1 λ j χ rr ι τ Patent claims:
IOD g of the coupler used in Example 1 will be in 250 cm ^{3 of} ethyl acetate at the reflux temperature of the 1st process for the incorporation of components in Ethyl acetate dissolved. The solution is converted into a solution of gelatin-halosilver emulsions, especially for poured, the 800 cm ^{3 of} 10% gelatin solution and 100 cm ^{3 of} 60 color photographic purposes, such as color formers, Contains 5 ° / ₀ sodium ethyl naphthalinnatriumsulfonatlösung, characterized in that the component in a and then ground five times in a colloid mill. Solvent is dissolved, the at least one 50 cm ^{3 of} water are used to rinse the mill. water-soluble, organic, or a low-boiling one The dispersion is at 4.4 ° C on a cooled plate water-insoluble, organic solvent (A) for applied, pressed through narrow openings and at the 65 the component and less than about one part per one Air dried at 78 ° C and 50 ° / ₀ relative humidity. Part component of an essentially water-insoluble The total weight of the dispersion is 193 g. borrowed, organic, crystalloidal, low molecular weight 7.9 g of this dispersion are converted into a gelatin solvent (B) for the ingredient, wherein Silver halide emulsion is added, which approximates the boiling point of the crystalloidal solvent (B) Contains 0.046 moles of silver halide. After making a 70 over about 175 ° C and a high dissolving effect has the component and is permeable to the oxidation products of the photographic color developer, whereupon the solution is dispersed in aqueous gelatin, the gelatin dispersion is cooled and solidified, at least 90 ° / ₀ water and essentially all of the above-mentioned organic solvent used from the dispersion is removed, and then finally the dry dispersion of the ingredient is mixed with a gelatin-halosilver emulsion. 2. The method according to claim 1, characterized in that color couplers are used as a component The crystalloidal solvent (B) also affects the dyes formed by the color couplers has a high dissolving effect. 3. The method according to claim 1, characterized in that as a constituent stain prevention agent, for example 2, S-di-iso-octyl-hydroquinone or 2, 5-di-n-octyl-hydroquinone can be used. 4. The method according to claim 1, characterized in that ultraviolet light as a component absorbing substances, for example 5-o-sulfobenzal-3 - phenyl - 2 - phenyl - imino - 4 - thiazolidone can be used. 5. Process according to Claims 1 to 4, characterized in that the component is in ethyl acetate and in less than about one part per one part constituent of an alkyl ester of phthalic acid having less than 6 carbon atoms containing alkyl groups is dissolved. 6. Process according to Claims 1 to 4, characterized in that the component is in ethyl acetate and di-n-butyl phthalate is dissolved in less than one part per one part of the ingredient. 7. The method according to claims 1 to 4 and 6, characterized in that the ethyl acetate by Air drying is removed from the dispersion. 8. The method according to claims 1 to 4, characterized in that the component is in a solvent is dissolved, which is about 3 parts of ethyl acetate and 0.5 parts of di-n-butyl phthalate per one part of the ingredient contains. 9. The method according to claims 1 to 4, characterized in that the component is divided into 3 parts Ethyl acetate is dissolved per one part ingredient. 10. The method according to claims 1 to 4, characterized in that the water-soluble, organic Solvent is removed from the emulsion by washing with water. 11. The method according to claims 1 to 4, characterized in that the water-soluble, organic Solvent (A) ethylene glycol monobutyl ether and, as an organic, crystalline solvent (B) dibutyl phthalate is used. © 1609 837/406 2.57