DE1126400B - Process for the preparation of yellow dye formers - Google Patents

Description

GERMAN

PATENT OFFICE

G 29711 IVb / 12q

REGISTRATION DATE: MAY 19, 1960

NOTICE THE REGISTRATION AND ISSUE OF EDITORIAL: MARCH 29, 1962

The invention relates to the preparation of dye formers for the production of photographic Color images can be used by color development.

In general, color development is done by having a in a photographic material existing reducible silver salt image by means of an aromatic amino developer in the presence of a Dye-former is developed. The dye-former that is present either in the photographic material or in may be contained in the baths, and the oxidation products of the developer formed during development couple with each other, which means that at the point where the silver image is developed, they engage at the same time Dye image is created.

In order to prevent that in a multilayer material these dye formers from their layer in diffuse a neighboring layer, these dye formers are usually substituted in a suitable manner, z. B. with a long aliphatic chain of several carbon atoms. To facilitate incorporation such dye-former in the photographic layer also often becomes a solubilizing agent Group introduced into the molecule.

In practice, the acylacetarylides are used as dye formers for yellow. The one in their arylide part sulfonated aroylacetarylides are obtainable by condensation of an aroyl acetic ester with a compound the general formula

NH ₂ -aryl - SO ₂ F

and hydrolyzing the resulting sulfonyl fluoride the corresponding sulfonic acid or the alkali salt (German Patent 1,038,559).

The aryl group of the aroyl acetic ester or of the NH ₂ - aryl - SO ₂ F compound can contain a diffusion-proofing group. Another possibility should be that the aroyl acetic ester contains a nitro group which, after the condensation, is reduced to an amino group into which a group which makes it diffusible can be introduced.

In the above-mentioned patent there is only one example (Example 6) according to which an aminobenzenesulfonyl fluoride is used which contains a diffusion-proofing group.

Method of manufacture
of yellow dye formers

Applicant:

Gevaert Photo-Products NV,
Mortsel, Antwerp (Belgium)

Representative: Dr. W. Muller-Bore

and Dipl.-Ing. H. Gralfs, patent attorneys,

Braunschweig, Am Bürgerpark 8

Dr. Arthur Henri de Cat, Mortsel, Antwerp,

Raphael Karel von Poucke, Mechelen, Antwerp,

and Marcel Hendrik Verbrugghe,

Wilrijk, Antwerp (Belgium),
have been named as inventors

However, it was later found that in the catalytic reduction of p-myristoylammo-m-nitrobenzenesulfonyl fluoride to p-myristoylamino-m-aminobenzenesulfonyl fluoride also a ring closure of the the latter to the tridecylbenzimidazole derivative takes place. The same occurs with condensation with Benzoylacetic acid ester, so that pure dye formers cannot be produced by this process.

A new process has now been found, according to which any acylacetarylide dye formers with a diffusion-proofing and a solubilizing group can be produced in the arylide core. This process is used to produce diketene or acyl acetic acid esters with aromatic aminosulfonyl fluorides condensed, which contain a certain diffusion-proofing group.

The reaction can be illustrated generally by the following scheme:

R-CO-CH ₂ -CO-OR '+ H ₂ N-aryl;

R "R-CO-CH ₂ -CO-NH-aryl;

SO ₂ FR "

209 557/427

In the formulas: R denotes an aliphatic, aromatic or heterocyclic radical, R 'denotes a lower alkyl radical and R "denotes an _{aliphatic chain connected to the aryl radical via - O -, - S -, - SO 2} - or - N (alkyl) - at least 5, preferably of 16 or 18 carbon atoms.

Then then the sulfofluoride group saponified to the sulfonic acid alkali salt using alkali lye.

The aromatic aminosulfonyl fluorides used as starting compounds according to the invention show do not have the above-mentioned disadvantage of ring formation and work well with a large number of β-ketone esters condense; this results in pure dye formers with very high yields. The so available Dye formers are of course much more numerous because it is not much easier to get a large number more diffusion-resistant /? - ketone ester than the corresponding Can produce diffusion-resistant /? - ketone ester, while the production of diffusion-resistant aromatic aminosulfonyl fluorides poses no particular difficulties power.

The condensation products prepared according to the invention separate in high yield as white crystalline compounds. These fluorosulfonyl derivatives can be cleaned very easily by recrystallization and are very stable in storage.

According to the invention, the sulfonyl fluoride derivative can be hydrolyzed during or before the preparation of the emulsion and the dye-former thus obtained are incorporated into the emulsion.

In the first case, the condensation products obtained are obtained by dissolving 1 mole of sulfonyl fluoride derivative saponified very quickly in 3 mol of sodium hydroxide solution to the analogous sulfonate. The received water-clear Solution is then optionally after setting the acidity as a 5 or 10% solution added to the emulsion. In the second case, the sulfonyl fluoride derivatives can be used as described below Process in acetone as a medium saponified with aqueous sodium hydroxide or potassium hydroxide solution will; the dye former from the saponification medium can be converted into a white crystalline compound in a pure state and in a practically quantitative yield. It is enough to get the one so obtained To dissolve dye formers in water before use; in this form he can then, if necessary after setting the acidity, the emulsion can be added.

Examples

1. «-Furoyl acetic acid (2-cetylmercapto-5-sulfoanilide) sodium salt

a) «-Furoylacetic acid- (2-cetylmercapto-5-fluorosulfonyl-anilide)

2-1.5 g of 2-cetylmercapto-5-fluorosulfonylaniIin prepared by the process of Belgian patent specification 587 525) and 9.1 g of a-furoyl acetic acid ethyl ester (prepared according to J. Am. Chem. Soc, 73, p. 5857, 1951) are refluxed in 100 cm ^{3 of} anhydrous xylene. A mixture of xylene and ethanol is distilled off over the course of 2 hours. The remaining xylene is evaporated in vacuo.

The residue is taken up in acetonitrile and the mixture is cooled to ^{0 ° C.} The precipitate formed is recrystallized from η-hexane, 18 g of white crystals being obtained. Melting point: 83 ⁰ C.

b) «-Furoylacetic acid- (2-cetylmercapto-5-sulfo-
- anilide) sodium salt

11.7 g of the above compound a) are ^{refluxed with 100 cm 3 of} acetone while stirring. After adding 12 cm ^{3 of} 5 η sodium hydroxide solution, the mixture is heated for a further 30 minutes with stirring. The reaction mixture is acidified with acetic acid and then cooled to room temperature with stirring. The precipitate formed is filtered off and recrystallized from methanol. 7 g of Jobigen product b) are obtained in the form of a white. Powder.

2. «-Furoyl acetic acid (2-cetylsulfonyl-5-sulfoanilide) sodium salt

a) »-Furoylacetic acid- (2-cetylsulfonyl-5-fluoro-

sulfonyi-anilide)

9.26 g of 2-cetylsurfonyl-5-fluorosulfonyIanirin (prepared according to the process of German Auslegeschrift 1 109 522) and 3.64 g of "-Furoylessigsäureäthylester are ^{heated with 50 cm 3 of} anhydrous xylene on the reflux condenser. Within 2 hours it will be slow

a mixture of xylene and the ethanol formed was distilled off ^{in a total amount of 40 cm 3.} Η-hexane is added to the reaction mixture. After cooling to room temperature, the precipitate formed is filtered off and recrystallized from η-hexane.

Yield: 7 g. Melting point: 72 ° C.

b) «-Furoylessigsäure- (2-cetylsulfonyl-5-sulfo-

anilide) sodium salt

5.99 g of the above compound a) are ^{refluxed with 60 cm 3 of} acetone while stirring. After adding 6 cm ^{3 of} 5 η-sodium hydroxide solution, the mixture is heated with stirring for a further 1 hour. The reaction mixture is acidified with acetic acid and then cooled to room temperature with stirring. The precipitate formed is recrystallized from acetic acid and gives 5 g of white end product.

3. Isonicotinoyl acetic acid (3-sulfo-4-cetylmercaptoanilide) sodium salt

a) Isonicotinoyl acetic acid (3-fluorosulfonyl-4-cetyl-

mercapto-anilide)

12.9 g of 3-fluorosulfonyl-4-cetylmercapto-aniline (produced according to the method of German Auslegeschrift 1 109 522) and 5.4 g of isonicotinoyl acetic acid methyl ester (produced according to J. Am. Chem. Soc, 65, p. 2460, 1943) are refluxed with 120 cm ^{3 of} anhydrous xylene. A mixture of xylene and methanol formed is distilled off over the course of one hour, about 50 cm ^{3 of} distillate being obtained. The xylene solution is concentrated further in vacuo and η-hexane is then added. After the precipitate formed has been recrystallized from a mixture of n-hexane and acetone, 8 g of white crystalline product are obtained. Melting point: 108 ⁰ C.

b) Isonicotinoyl acetic acid (3-sulfo-4-cetylmercapto-

anilide) sodium salt

5.78 g of this sulfonyl ^{fluoride derivative are heated with 40 cm 3 of} acetone on a reflux condenser, 6 cm ^{3 of} 5 η sodium hydroxide solution are added and the mixture is heated for a further 30 minutes with stirring. The reaction mixture is acidified with acetic acid and then cooled to room temperature with stirring. The precipitate formed

5 6

is filtered and recrystallized from dimethylformamide umkristalli- stirring for 45 minutes at 60 to 7O ⁰ C allowed to the

sated. 4.5 g of white end product are obtained. Cool the reaction mixture to room temperature,

4. p-Methoxybenzoyl acetic acid-C-cetylmercapto- ^s * ^{m noc} _u ^h ^ ^{00 cm} *. ⁿ " ^Hex ?? ^{zu ma} } ^Üh ^ f ^uf °° ^{C from} "

5-sulfo-anilide) sodium ^{salt De} JS formed precipitate is filtered off with

,,,,. .. 5 η-hexane and washed from a mixture of

a) p-Methoxybenzoylessigsaure- 2-cetylmercapto- _{ethanol and recrystallized water} . _The yield

5-fluorosultonyl-anihd) _{is 35 g white} crystal flakes. Melting point:

34.5 g of 2-Cetylmercapto-5-fluorosulphonylaniline and 90 to 92 ⁰ C.

17.7 g of p-methoxybenzoyl acetic acid ethyl ester will be. ..

with 150 cm ^{3 of} anhydrous xylene on the reflux condenser ₁₀ ^b > Acetylessigsaure - ^ - cetylsu fonyl-5-sulfoerhitzt. Within 2 hours, a mixture of amlid) sodium salt
distilled off from 120 cm ^{3 of} xylene and ethanol. After 19.1 g of this sulfonyl fluoride derivative are cooled, the reaction ^{mixture is heated with 100 cm 3 of} 150 cm ^{3 of} acetone in a reflux condenser. The hexane is added. The precipitate formed is removed; solution is added to 20 cm ^{3 of} 5 η-sodium hydroxide solution and filtered, washed with η-hexane and boiled under reflux for a further 1 hour with stirring. Yield: 30 g of white crystalline Pro-cooler. After acidification with acetic acid, it is left to duct. Melting point: 105 ⁰ C., the reaction mixture with stirring at room tempera -, "cool ,, ...., temperature.. The white precipitate formed will

b) p-Methoxybenzoylessigsaure-C ^ cetylmercapto- filtered off, washed with a little water and from aceto-

5-sulfo-amlide) sodium _salt ^ nitrile recrystallized. 15 g of white final

21.5 g of this sulfonyl fluoride derivative are with product.

150 cm ^{3 of} acetone heated on the reflux condenser, with 21 cm ³ _? Benzoylacetic acid (2-cetylsulfonyl-5-sulfo-

5 η-sodium hydroxide solution and another 30 minutes under anilide) sodium salt

Stirring heated at the reflux cooler. After acidification. _ ..... ",,. , - _a

the reaction mixture is left with acetic acid under _a5 ^a ) Benzoylessigsaure-a-cetylsulfonyl-S-fluoro

Stir to cool to room temperature. The formed sulionyl anilide)

The precipitate is filtered off and treated with a little water. 46.3 g of 2-cetylsulfonyl-5-fluorosulfonylaniline and 19.2 g

to wash. After recrystallization from methanol, benzoylacetic acid ethyl ester is obtained with 150 cm ³

one 17 g of white end product. anhydrous xylene heated on the reflux condenser. Inner

, τ, _Λ ..., *. . ,. , _1C 30 half of 2 hours are 100 cm ^{3 of} a mixture

5. benzoylacetic-a-cetylmercapto-S-sulfonated _{yon XYm uM ethanol abdestüliert The öUgß back!}

aninaj-Kaiiumsaiz _{stand is mixed with 3Q () cm} 3 of _{methanol and on}

a) Benzoylacetic acid- (2-cetylmercapto-5-fluoro- _O o _{c cooled} . _The white precipitate formed is

sulfonyl anilide filtered off, washed with methanol and extracted from ethanol

43.1 g of 2-cetylmercapto-5-fluorosulfonylaniline and 35 recrystallized. 30 g of white crystalline material are obtained

19.2 g of ethyl benzoyl acetate are added to 150 cm ^{3 of} product. Melting point: 117 ⁰ C.

anhydrous xylene heated on the reflux condenser. Inner. ..

half of an hour, 120 cm ^{3 of} a mixture ^b ) Benzoylessigsaure ^ -cetylsulfonyl-S-sulfo-

distilled off from xylene and ethanol. After the Abandoned) Natum Salt

Cool the reaction mixture to 5O ⁰ C to 4 ° 6.09 g of this Sulfonylfluoridderivates sets are with

50 cm ^{3 of} η-hexane are added and the reaction ^{mixture is heated to 40 cm 3 of} acetone on the reflux condenser. Cool this further to room temperature. ^{6 cm 3 of} 5 η sodium hydroxide solution are added to the resulting solution and the precipitate is filtered off, washed with η hexane and kept at the boil for _{1 ½ hours with stirring.} That and recrystallized from isopropanol. 40 g of reaction mixture are obtained, crystalline product whitened with acetic acid is then acidified with a melting point of 45 and cooled to room temperature. The range from 95 to 96 ° C. The precipitate formed is filtered off and washed with something

,. _,,. .., ",,." Water washed. After drying, one obtains

b) Benzoylessigsaure-p-cetylmercapto-S-sulfo- _{6 g white product5 which crystallized from methanol}

anilidJ potassium salt _{is The yield} is 5.5 g of white granular

28.9 g of the above sulfonyl fluoride derivative a) are 50 end products.

5 ^{1 15 0} Λ K rf ^{Eton at Rückfl} u ^ßkü Mfr heated with ₈ _ _B enzoylessigsäure- (2-cetyloxy-5-sulfo-anilide) -30 cm ³ 5 n-Kahl eye added and a further 1 hour under N ^{B J} _atr i _to sai _z

Stirring heated on the reflux condenser. After the arrival. _, ... ', ", _Γ ", ",

acidifying the reaction mixture with acetic acid allows ^a ) benzoyl acetic acid- (2-cetyloxy-5-fluorosulfonyl-

cool it to room temperature while stirring. 55 anuid)

The precipitate formed is filtered off, a mixture of 6.33 g of 2-cetyloxy-5-fluorosulfo-

Washed with water and recrystalline aniline from isopropanol (according to the method of the Belgian patent

sated. 27 g of white end product are obtained. script 590 934) and 2.88 g of benzoyl acetic acid

6. Acetyl acetic acid- (2-cetylsulfonyl-5-sulfo- ^ f ¹ Af ^ίη Ü ° ^Cm _T ^{3 w} f ^se * ^eiem ₀ ^X y ^l01 J ^{ird an} )

anilide) sodium ^salt 6o reflux condenser heated. Over the course of 2 hours

. . · .. <■ "1, j, c η ^e i ^ne mixture of xylene and ethanol formed off

a) Acetylessigsaure-i ^ -cetylsulfonyl-S-fluorine distilled, then the remaining xylene is in vacuo

sultonyl-amUd evaporated. During the narrowing, the final

46.3 g of 2-cetylsulfonyl-5-fluorosulfonylaniline are product from. After the addition of hexane, it becomes white

placed in 200 cm ^{3 of} anhydrous toluene and the gel 65 precipitate filtered off, washed with hexane and removed

mixed at 3O ⁰ C stirred. A little triethylamine is allowed to recrystallize ethanol.

add dropwise and then set in the course of 10 ml. 5 g of white crystalline product are obtained. 8.4 g of diketene were added dropwise to the melt grooves. After another point: 103 to 104 ⁰ C.

b) Benzoylacetic acid (2-cetyloxy-5-sulfo-anilide) sodium salt

4.48 g of this sulfonyl fluoride derivative are refluxed ^{with 30 cm 3 of acetone while stirring.} After adding 4.8 cm ^{3 of} 5 η sodium hydroxide solution, the mixture is heated for a further 45 minutes with stirring on the reflux condenser. The reaction mixture is acidified with acetic acid and then cooled with stirring. A white precipitate is obtained, which is recrystallized from methanol. Yield: 4 g of white crystalline end product.

9. Benzoylacetic acid [2- (N-methylcetyl-amino) -5-sulfo-anilide] sodium salt

a) Benzoylacetic acid [2- (N-methylcetyl-amino) -

5-fluorosulfonyl anilide]

6.42 g of 2- (N-methylcetylamino) -5-fluorosulfonylaniline (prepared by the process of Belgian patent 590 934) and 2.88 g of ethyl benzoyl acetate are refluxed ^{with 30 cm 3 of anhydrous xylene.} A mixture of xylene and the ethanol formed is slowly distilled off over the course of 2 hours; the remaining xylene is then evaporated off in vacuo. After the addition of hexane and cooling to 0 ^° C., the precipitate formed is filtered off and. recrystallized from η-hexane.

6 g of white, finely crystalline product are obtained. Melting point: 73 ° C.

b) Benzoylacetic acid [2- (N-methylcetyl-amino) -

5-sulfo-anilide] sodium salt

5.74 g of the above sulfonyl ^{fluoride derivative a) are heated with 40 cm 3 of} acetone with stirring on a reflux condenser. 6 cm ^{3 of} 5 N sodium hydroxide solution are added to this solution and the mixture is heated for a further hour while stirring. The reaction mixture is acidified with acetic acid and then cooled with stirring. The precipitate formed is recrystallized from methanol. Yield: 4 g of white powder.

Claims (1)

PATENT CLAIM: Process for the preparation of yellow dye formers of the general formula R " R_CO — CH ₂ —CO — NH-aryl; "SO ₃ alkali characterized in that one diketene or a compound of the general formula R-CO-CH ₂ -COOR '
with a compound of the general formula H ₂ N aryl; R " ¹ SO ₂ F reacted and then saponified the sulfofluoride group with alkali to the sulfonic acid alkali salt, where R is an aliphatic, aromatic or heterocyclic radical, R 'is a lower alkyl radical and R "is via - O -, - S -, - SO ₂ - or - N (alkyl) - denotes an aliphatic chain linked to the aryl radical and having at least 5, preferably 16 or 18 carbon atoms. © 209 557/427 3.62