DD269697A1 - PROCESS FOR PREPARING 2-EQUIVALENT YELLOW COUPLERS - Google Patents

Abstract

A process is described for preparing 2-equivalent yellow couplers of the type a-substituted by a phenoxy group or a nitrogen-bonded group b-keto-carboxylic acid amides. These compounds are used to produce the yellow color image in silver halide photographic materials and are characterized by a sparing silver requirement. The aim and object is a generally applicable, simple method for the reaction of α-halo-b-keto-carbonsaeureamiden with phenols or NH-acidic compounds in the presence of a base, in which the synthesis and reaction of the α-halo-b-keto-carbonsaeureamide can be carried out in the same solvent and said 2-equivalent yellow couplers can be recovered after simple workup in high yield and purity. According to the invention, the reaction of α-halo-b-keto-carbonsaeureamiden with phenols or NH-acidic compounds in the presence of a base in a water-immiscible, aprotic solvent or in a two-phase system consisting of a water-immiscible, aprotic solvent and Water, in the presence of a phase transfer catalyst performed.

Description

VEB Filmfabrik Wolfen Wolfen, 5. 9. 84

PN 1 149 RM / B _r

Dr. Hanisch, G. Int. Cl .: G 03 C 7/36

Dr. Ebisch, R ₄ Or. Gröger, R

 Dr. GröSl, H

 Riohter, O.

Process for the preparation of 2-equivalent yellow couplers

Field of application of the invention

The invention relates to a process for the preparation of 2-equivalent yellow couplers for use in photographic silver halide materials. These couplers are mainly used in color materials for producing the yellow color image in the blue-sensitive layer.

Characteristic of the known technical solutions

In color photographic materials, it is common to use open-chain α 3 -dicarbonyl compounds, preferably α-keto-carboxylic acid anilides, for the formation of yellow image dyes. These color couplers react with oxidized developing agent, in particular derivatives of p-phenylenediamine, to form the yellow dye. In silver halide materials, une-substituted methylene group couplers require 4 moles of silver halide to form one mole of image dye. The silver halide requirement is reduced to 2 mol, if the coupling-capable methylene group is substituted by a group which can be split off during chromogenic development. Significant amounts of silver can be saved with these 2-equivalent yellow couplers, thinner ones

Layers are poured, thereby improving image sharpness and resolving power (see T.H. Dames, Theory of the Photographic Process, Macmillan Publishing Co., Inc., New York 1977, pp. 354-356).

DE-OS 2 406 087 mentions various leaving groups suitable for 2-equivalent yellow couplers. For practical use, yellow couplers which are substituted on the coupling-capable methylene group by a phenoxy-chain or by an NH-acidic group, preferably by an NH-acidic heterocycle, are particularly suitable. You have e.g. compared to chlorine-substituted couplers the advantage of a very low color fog. Such 2-equivalent yellow couplers have been described repeatedly, e.g. in US-PS 3,644,198 and 3,9y4,967, DE-OS 2,455,076, DD-PS 142 765, EP-PS 80 355; DE-OS 2 219 917, 2 528 638, 2 559 190, 2 600 166 and 2 713 022 and DD-PS 149 720.

In the preparation of the described 2-equivalent yellow couplers, the corresponding 4-equivalent couplers in the methylene group are generally hülogeni ert ι and then in a second synthesis stage, the halogen is substituted by the phenoxy group or the NH-acidic group. The following processes are known in detail for this synthesis route:

In a first method, which will be described Z ₀ example in US-PS 3,644,498 and DE-OS 2,219,917, it is ^ ^C-halo-1 B. keto-carboxamides with the Alkalisalzeii of phenols and

NH-acidic heterocycles or with phenols and NH-acidic heterocycles in the presence of triethylamine by Kochen in acetonitrile to. This process produces various by-products and in most cases the couplers are difficult to isolate in low yield.

In a second method, claimed in DE-OS 2,554,321, the formation of by-products is reduced by the fact that the reaction of c-chloro-yQ-ketocarboxamides with phenols or NH-acidic heterocycles in the presence of tetraalkylguanidines, in particular tetramethylguanidine.

In a third method, claimed in DE-OS 2,840,381, a further improvement is achieved by the use of tertiary, bicyclylen diamines, old »Helpebase. However, the bases used in the second and third methods are expensive, are also used in excess and are recoverable only with considerable effort.

In a fourth method, claimed in DE-OS 2,645,285, in the methylene group, halogen substituted GsI couplers in an inert solvent, e.g. Toluene, reacted with the 0- or N-trimethylsilyl derivative of a phenol or a, NH-acidic, helerocycliochen compound. However, additional raw materials and an additional stage of synthesis under anhydrous conditions are required for the recovery of trimethylsilyl derivatives.

In a fifth method, proposed in DD »WP C 07 C / 215 957, the reaction of δ-halo-ß-ketocarboxamides with phenols in the presence of bases is carried out with an excess of phenolic compound, it is preferably carried out in the melt , The process gives good yields but in some cases the separation of reaction product and excess phenol is difficult and expensive. In addition, the process is limited to the introduction of phenolic leaving groups.

In a sixth process, claimed in British Pat. No. 1,420,560 and German Offenlegungsschriften Nos. 2,663,875, 2 402 220 and 2 329 587, yellow couplers substituted by halogen are prepared in the methylene group with NH-acidic compounds, preferably NH-acidic Heterocycles, in the presence of a base in an organic amide or sulfoxide, especially hexamethylphosphoric triamide, as the solvent, but in this process it is difficult to remove these high boiling polar solvents from the coupler after reaction and they are contaminated with these solvents In addition, the method is limited to NH-acidic leaving groups.

In a seventh process claimed in DE-OS 2,545,756, the 4-equivalent coupler with unsubstituted methylene group and the relevant phenol or the NH-acidic heterocycle in a polar, aprotic solvent (preferably

white hexamethylphosphoric triamide) in a one-step reaction with a halogen or halogen releasing agent in the presence of a basic condenser to form the 2-equivalent coupler. However, this process is rationally limited to leaving groups which do not react with halogen except at the point of attachment to the coupler molecule. This process also has the disadvantages of the sixth process, which result from the use of a high-boiling, polar, aprotic solvent. With the exception of the last process, it is disadvantageous in all known methods that two separate synthesis steps have to be carried out starting from the 4-equivalent coupler .

Object of the invention

The aim of the invention is a generally applicable, simple and feasible with cheap tools method for the synthesis of 2-equivalent yellow couplers by reacting oC-halo-yÖ-keto-carboxylic acid amides with phenols or NH-acidic compounds, with the 2-Equivglent- Yellow couplers can be obtained after simple workup in high yield and purity,

Show the gist of the invention

The object of the invention is to provide a synthesis method for 2-equivalent yellow couplers of the Ir dero type (position by a phenoxy group or a nitrogen-bonded group-substituted β- ketocarboxylic acid amides, in which the reaction of cC-halogenated B-keto-carboxylic acid amides are reacted with phenols or NH-acidic compounds in the presence of a base in a solvent which is also useful for the preparation of the cC-halo -ketocarboxamides and which is easily removed after the overall synthesis There should be no or only small amounts of by-products and no polluting by-products.

The object of the invention is achieved by a process for the preparation of 2-equivalent yellow couplers by reacting. ^ .- Halogen- β -keto-carboneäureamiden with phenols or NH-acidic compounds in the presence of a base ^ u / * -Keto -carboxamides substituted in the L- position by a phenoxy group or by a group bonded via a nitrogen group, containing 1-C-halo-2-ketocarboxamides, containing by-products of Phnrnlp <, or of N-acidic compounds; reacted with phenols or NH-acidic compounds in the presence of a base in a water-immiscible, aprotic solvent or in a two-phase system consisting of a water-immiscible aprotic solvent and water, with the addition of a phase transfer catalyst.

As the water-immiscible aprotic solvents, especially aliphatic and cyclic hydrocarbons and other halogen derivatives such as e.g. Benzene, toluene, di-, tri-tetrachloromethane or chlorobenzene. For the process according to the invention, the phase transfer catalysts used are quaternary ammonium and phosphonium salts, polyethers, crown ethers and cryptands, as described, for example, in US Pat. M. Makosza, Inuryur of Progress in Chemistry, Vol. 9, Academic Press, New York 1979, pp. 1-53. The catalytically active group may also be attached to a polymeric support material. Such catalysts for three-phase catalysis are e.g. in detail by S.L, Regen, Angew. Chem. 91, 464 (1979).

For dae method according to the invention are as Phaoen ransfer Kotaiycotoren particularly quaternary ammonium and Phoephoniumealze, in particular tetraalkylammonium salts or Benzyltrialkyl-ammonium salts. And also such Phosphnniumaalze, eg tetrabutyl-ammonium-hydrogen sulfate, Triethy.T-benzyl-ammonium chloride, Benzyltiimethyl- dodecyl-ammonium chloride, methyl trioctyl-amrnoniumchlorid or tetra ^ butyl-phosphonium bromide, of which 0,005 are applied to 0.05 Moläquivaiertte gee ⁱ gnet. In carrying out the process according to the invention, it is of particular advantage to use the halogenation, the .beta.-ketocarboxamides to the .alpha.-halogen derivatives and their conversion.

2 <9 6 9

Settling to the 2-A'quivalentkupplern with phenoxy group or via nitrogen-bonded group in oC-position in the same solvent can perform and thereby the isolation deroC-halo ß-keto-carboxylic acid amides deleted. The preparation of the preferred oC-chloro-3-keto-carboxylic acid amides by chlorination of β-keto-carboxylic acid amides with sulfuryl chloride is e.g. in U.S. Patent 2,728,658. The solution desoC-halo-ß-keto-carboxylic acid amide obtained after dor halogenation desß-keto-carboxylic acid amide is neutralized with an alkali metal salt, preferably the sodium or Kali - .. / salt, the phenol or the NH-acidic compound, or with the Phenol or the NH-acidic compound and a base, Phasentranefer catalyst and optionally mixed with water and heated with stirring to the complete Um ~ Constitution. The addition of water / is not essential, but it significantly speeds up the reaction when working with inorganic base.

As the base, tertiary amines (e.g., triethylamine), alkali metal alcoholate (e.g., sodium methylate) and the hydroxides, carbonates and bicarbonates of the alkalis and alkaline earths, preferably those of sodium and potassium, can be used. The possibility of using cheap inorganic bases is another advantage of the process. It is convenient to use the base in an excess amount in the range of 1.01 to 2.5 mol equivalents.

The combining of the reactants can be done at the beginning of the reaction all at once or continuously during the reaction. For dia implementation, the temperature range of 40 to 140 ° C is suitable. Conveniently, you never select reaction temperature, the boiling point of the solvent or the boiling point of its azeotrope with water. After completion of the reaction, the aqueous solution is separated, the organic solvent distilled off and the 2-equivalent yellow coupler recrystallized from a suitable solvent.

I- ^;

The ancestors of the present invention can be particularly used to convert from g-halogeno / 9-keto-carbonic acid amides to 2-equivalent yellow couplers for photographic materials or to intermediates for the synthesis of such yellow couplers, e.g. in the patents cited on page 2 are listed.

According to the invention, in particular O-halo-yl-keto-carboxylic acid amides of the formula

R ²

R ³ -CO-CH-CO-N

I \ _R 3

implemented, in which

1 ? 3

R, R and R are common for the β- keto-carboxylic acid amide yellow coupler Radicals are, as listed for example in K.Ven-

kataraman, The Chemistry of Synthetic Dyes, Vol. 2 (1952),

S, 1201, Academic Press, New York; J. Bailey and L, A, Williams

in: ibid., Vol. 6 (1971), p. 359; in DE-OS 2,114,577 and in US-PS 2,875,057, 3,384,657 and 3,725,072, and

X represents a halogen atom, preferably a chlorine atom.

In particular, R, R, and R may represent one of the following groups:

R is alkyl, preferably tert-butyl, a heterocycle or a phenyl group which may contain one or more substituents, such as alkyl, alkoxy, aryloxy, halogen, nitro, cyano, acyl, carboxyl, alkoxycarbonyl, amino, acylamino, carbamoyl, sulfo, Sulfonamido or sulfamoyl, which in turn may be substituted by alkyl, aryl, aralkyl or heterocyclic radicals,

R is a hydrogen atom or an alkyl group having 1 to 5 C atoms, R is alkyl, a heterocycle or preferably a phenyl

group which may contain one or more substituents, such as nylgruppe.

•1

can, as they are called in the case that R a pha-

2 ^ 9697

The phenols which can be used in the reaction may contain one or more substituents, as in the case of genan.it, in which R is a phenyl group. A particularly high coupling activity of the resulting 2-equlvalent yellow couplers is achieved when phenols with electron-withdrawing substituents are introduced. Such 2-equivalent decouplers are e.g. in DE-OS 2 456 076 and in EP-PS 80 355 described. The employed NH-acidic compounds are preferably heterocyclic compounds of the formula 0 0

C .. C,

HN 'Z¹ , HN ^/ Z² and HN "Z³ .\ _c . '· '.. ·' · ·, ... '

Z is the nonmetal atoms necessary to complete a 5-membered or 6-membered ring,

Z ^{2 is} the non-metal atoms used to complete a

unsaturated 5-membered or 6-membered ring are required, and

Z is the non-metal atoms necessary to complete an imidazole, triazole or tetrazole ring. The heterocyclic compounds may contain fused rings.

In the process according to the invention, bifunctional leaving groups, e.g. Bisphenols, are used. In this way, bis couplers are obtained in which two coupler molecules are linked by a bifunctional leaving group, as described, for example, in US Pat. Nos. 3,644,498 and 4,157,919. The process according to the invention is illustrated by the following synthesis examples. The process is not limited to the examples mentioned. "

Execution Example 1

2-phenoxy-3-phenvx-3-oxo-propioneäure-anil.ld

27 _e 4 g (O ₁ l mol) of 2-chloro-3-phenyl-3-oxo-propionic acid -anilide, 14.5 g (0.11 mol) of celium phenolate and 1.28 g (5 mmol) of 1,4 , 7,10, 13,16-hexaoxa-cyclooctadecane (usually referred to as 18-crown-6) are boiled in 200 ml benzene for 1 h ur.ter reflux. It is filtered, concentrated to 100 ml and allowed to crystallize at room temperature. Yield 23 g (70%), mp 156 ⁰ C.

Example 2

2-phenoxy-3-oxo-3- (4-öteart)-ylamino pheny.l) propion8äure (2-chloroanilide)

59 g (0.1 mol) of 2-chloro-3-oxo-3- (4-steroylamino-phenyl) -propionic acid (2-chloro-anilide), 9.9 g (0.105 mol) of phenol, 250 ml of toluene, 105 ml N NaOH and 0.4 g (1 mmol) of methyl trioctyl-ammonium chloride are boiled under stirring and reflux for 6 hours. The mixture is filtered while still warm from a little undissolved material, the phases are separated, the toluene solution is concentrated in vacuo and recrystallized from ethanol , Yield 37 g (57%), mp 95-97 ⁰ C.

Example 3

4,4-Dimethyl-2- (4-methoxycarbonyl-phenoxy) -3-oxo-pentanoic acid, 2-chloro-5 - [4- (2,4-di-tert-pentyl-phinoxy) -butyricamido-5-yl-ylide 57.1 g (0 , 1 mol) of 4,4-dimethyl-3: xo-pentanoic acid 2-chloro-5- [4- (2,4-di-t6'-t-pentyl-phenoxy] -butyramido-yl-yl-yl * are dissolved in 200 μl of tetrachloromethane and by dropwise addition of 8.1 ml (0.1 mol) of sulfuryl chloride with stirring into the? .- Chlorine compound is neutralized by stirring with 160 ml of 2 N Na ₂ CO ₃₀ The separated solution of the 2-chloro compound in carbon tetrachloride 100 ml of water, 16 g (0.105 mol) of 4-hydroxybenzoic acid methyl ester and 0.68 g ( mmol) of tetrabutylammonium hydrogene sulfate are added, with stirring and refluxing, 80 ml of 2 are added over the course of 2 hours NK ₂

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run in and cook for another 9 hours. The organic phase is partitioned with 50 ml of water, the tetrachloromethane is distilled off, finally in vacuo and recrystallized from methanol. Yield 59 g (8Σ%!), Mp 110-120 ⁰ C.

Example 4

4,4-Dimethyl-2- [4- (4-benzyloxy-phenyl-sulfonyl-phenoxy-3-yl) OXopen-t-acid ^ 2-chloro-5- (4- (2,4-di-tert-penylene-phenoxy) -butyl ramidojanilidj

To a suspension of 37.4 g (0.11 mol) of 4-benzyloxy-4-hydroxy-diphenylsulfone in 160 ml of water containing 10.6 g (0.1 mol) of Na ₂ CO ₃ and 1 g (3 mmol). Benzyl-dodecyl-dimethy] -reinmoniumchloro.d, a solution of 60.6 g (0.1 mol) of 4,4-dimethyl-2-chloro-3-oxopentanoic acid, 2-chloro-2-chloro-3-one, is dissolved in the course of 3 hours. Add 5- [4- (2,4-di-tert-pentyl-phenoxy) butyramidojanilidin in 250 ml of trichloromethane while stirring and boiling, and continue to boil for 27 h. The phases are separated, washed with 50 ml of Wasoor, the trichloromethane is distilled off and crystallized from methanol and methanol. Yield 86 g (95%), mp 157-158 ⁰ C.

Example 5

4,4-Dimethyl-2- {4- (4-benzyloxy-phenylsulfony}} -phenoxy-3-oxn-pentanoic acid (2-chloro-5-hexadecanesulfonamido-ranilide)

55.7 g (0.1 mol) of 4,4-dimethyl-3-oxo-p _e ntansäure (2-chloro-5-hexadecanesulfonamido-anilide) in 500 ml Toluon added dropwise with stirring 8.1 ml (0, 1 mol) of sulfuryl chloride and stirred for 1 h. The resulting solution of the 2-chloro compound is neutralized by stirring with 160 ml of 2N Na ₂ CO ₃ . The toluene solution is allowed to stir within 1 h to a suspension of 37.4 g (0.11 mol) of 4-benzyloxy-4'-hydroxydiphenyl sulfone in a solution of 18.5 g (0.22 mol) of NaHCO ₃ and 0.68 g ( 2 mmol) tetrabutylphosphonium bromide in 200 ml of water with stirring and reflux under reflux and boil for a further 6 h. The phases are separated, washed twice with 100 ml of water, the toluene is distilled off in vacuo and recrystallized from absolute ethanol. Yield 61 g (68%), mp 93-95 ⁰ C.

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ί 26 9 69

Example 6

4 _# 4'-bis-2-chloro-5-4- (2,4-di-tert-pentyl-phenoxy) -butyramido-5-phenylcarbamoyl-3,3,3-dimethyl-2-oxo-butoxy-diphenylsulfone

17 g (0.05 mol) of ^{4,4-dihydroxy-1} dlphenylsulfon _l Waoser 75 ml, 0.53 g (2 mmol) Dodecyl-trimethyl-ammonlumchlorid and 8.5 g (0.08 CEE) Na ₂ CO ₃ Heated to 95 - 100 ⁰ C for 30 min. The mixture is cooled to 80 C, is added with stirring, a solution of 60.6 g (0.1 mol) of 4,4-dimethyl-3-oxo-pentanoic acidF2-chloro-5 · ^ 4- (2,4-di-tert penta-phenoxy) butyramido / anilide in 200 ml of toluene and boiled for 15 hours with stirring and reflux. After phase separation, the toluene solution is concentrated in vacuo and the residue is recrystallized from cyclohexane. Now 55 g (79 ft), mp 107-109 ° C.

Example 7

4,4 'dimethyl-2- (l _# 3-dimethyl-2,6-dioxo ~ tetrahydro-purin-7-yl) -

3-oxo-pentanoic acid, f2-chloro-5,4,4-di-tert-pentyl-phenoxy-butyramido-ynamide

60.6 g (0.1 mol) of 4,4-dimethyl-2-chloro-3-oxo-pantanoic acid 2-chloro-5- [4- (2,4-di-tert-o-pentyl-pheioxy) butyramidojanilide ^ , 19.8 g (0.11 mol) of theophylline, 14 g (0.14 mol) of KHCO ₃ , 300 ml of chlorobenzene, 100 ml of water and 1.56 g (3 mmol) of a 50% aqueous solution of tetrabutylammonium hydroxide are boiled under stirring and reflux for 20 h. The phases are separated, the chlorobenzene solution concentrated in vacuo and recrystallized from acetonitrile. Yield 53 g (71%), mp 206-207 ⁰ C.

Example 8

4,4-Dimethy1-2- (3-chloro-1, 2,4-t-riazol-1-yl) -3-oxo-pentanoic acid, 2-chloro-5- [4- (2,4-di-tert-pentyl -phenoxy) butyramidoJanilicQ ·

60.6 g (0.1 mol) of 4,4-dimethyl-2-chloro-3-oxo-pentanoic acid

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j [2-chloro-5- (4- (2,4-di-tert-pentyl-phenoxy) -butyramide-q / anilide], 13.8 g (0.11 mol) of the sodium salt of the 3-chloro-1, 2.4 triazole, 1 * 14 g (5 mmol) of triethylbenzylammonium chloride and 300 ml of benzene are refluxed for 15 hours. It is filtered off with suction and allowed to crystallize at room temperature. Yield 49 g (73 %), mp 166-169 ° C.

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Claims (3)

- II - E r f i η d υ η g 8 β η 8 ρ r u c h 1. A process for the preparation of 2-ubiquitous yellows by reaction ofoO-Halorjen - ^ - keto-carboxylic acid amides with phenols or NH-acidic compounds in the presence of a base to <Ö-keto-carboxamides, the inijG position are substituted by a phenoxy group or a group bonded via nitrogen. drew 'in that the "C-halogen-keto-keto carbonoäureamide with the alkali metal salts of phenols or NH-acidic compounds or with phenols or NH-acidic compounds in the presence of a base in a water-immiscible, aprotic solvent or in a two-phase system consisting of a water-immiscible, aprotic solvent and water, with the addition of a phase transfer catalyst is reacted · 2. Method for the preparation of 2-equivalent yellow couplers according to item 1, characterized in that aliphatic or cyclic hydrocarbons and their halogen derivatives are used as water-immiscible, aprctischo solvent. 3. A process for the preparation of 2-equivalent yellow couplers according to item 1 and 2, characterized in that a crown ether, a quaternary ammonium or phosphonium salt is used as Phesentransfer catalyst.