DE2632401A1 - Acyl-acetyl-amino benzene photographic yellow couplers - have anellated (di) oxo heterocycle, giving high reactivity - Google Patents

Abstract

New acylacetylamino colour couplers (I) have formula:- (in which R is H or a simple substit., pref. halogen, esp. Cl or Br; Z is -O-CH2-O-, -O-CH2-CH2-O-, -CH-2-CH2-O-, -CH2-CH2-CH2-O- or -CH=CH-O-; X is a gp. with an aromatic carbocyclic ring linked with the HN gp.). Used as yellow coupler in colour photographic recording materials. Cpds. have high reactivity towards the oxidation prods. of the colour developer, favourable absorption spectra and formation of light-fast dyes. (I) can be prepd. by conventional methods, pref. by reacting the appropriate ester and amine. (I) is e.g. 1-(3',4'-dioxolobenzoyl-acetylamino)-2-chloro-5-(2",5"-di-tert.-a- mylphenoxy-acetylamino)-benzene.

Description

Acylacetylamino compounds and their photographic use Color coupler.

graphic color couplers.

It has long been known, as photographic yellow couplers, acylacetylaminoaryl compounds with acyl radicals or benzoylacetylaminoaryl compounds derived from aliphatic carboxylic acids, the other substituents on the benzoyl radical or the aryl radical attached to the amide group can wear, use.

In British Patent 819 827, acylaceL-ylaminoaryl compounds of the formula which can be used as color couplers described, wherein Z 'represents the atoms of a saturated carbon chain which are required to complete a five- to six-membered heterocyclic ring, X represents a hydrogen or chlorine atom and R' represents an aryl radical.

It has now been found that certain acylacetylaminoaryl compounds with condensed in the 3,4-position of the benzoyl radical instead of 2,3-position, five- up to six-membered oxygen-containing hetero rings also compared to the color couplers of formula (1 ') have advantages.

The invention accordingly relates to the acylacetylamino compounds which can be used as photographic color couplers where R is a hydrogen atom or a simple substituent, Z is the addition to a five- to six-membered ring, the skeleton of which is composed of carbon atoms and one to two oxygen atoms bonded to the benzene ring, X is a molecular part that is split off during the color coupling and A is a radical with a aromatic carbocyclic ring bonded to the -HN group.

The compounds of the following formulas are preferred here In the formulas (1) to (6) the same symbols always have the same meaning, namely they mean the following (the meaning of A, R, X and Z was already given above): A1 - a residue with an an -HN group bound benzene ring; B1 - a substituent which makes the color coupler diffusion-resistant, in particular the radical of a phenoxyalkanecarboxamide which is bonded with the amide nitrogen atom to the benzene ring further substituted by Q1 and can also carry further substituents on the phenoxyring, the phenoxyalkanecarboxylic acid radical containing, for example, 16 to 25 carbon atoms; Q1 - a hydrogen atom, a chlorine atom or a lower alkoxy group, ie one with at most 5 carbon atoms; R1 - a hydrogen or halogen atom; R2 - a hydrogen, chlorine or bromine atom; xl - a hydrogen or chlorine atom Z1 - one of the atomic groups -O-CH2-O-, -O-CH2-CH2-O-, -CH2-CH2-O-, -CH2-CH2-CH2-O- and -CH = CH-O-, corresponding to the radicals of the formulas Z2 - one of the atomic groupings -O-CH2-, -O-CH2-CH2- and -CH2-CH2-CH2, corresponding to the radicals of the formulas (7.1), (7.2) and (7.4); m - an integer equal to or less than 3; n - an integer with a value of 13 or less; p - an integer worth 6 or less; q - an integer with a value not exceeding 15; r - one of the numbers 1 and 2.

As the fact man can easily see from the above formulas, the yellow couplers according to the invention are in the acylamino part of the molecule (anilide residue) appropriately provided with a so-called ballast group, which plays an important role plays when the coupler is in a water-immiscible, high-boiling solvent dissolved and the solution emulsified in gelatine containing silver halide (so-called protected couplers). The ballast groups should give the coupler as much as possible give good solubility in the oily phase and the tendency to crystallize Reduce. Such ballast groups are also described in the following patents: DT-AS 1,547,868, DT-OS 1,597,640, DT-OS 2,039,489, US-PS 2,652,329, US-PS 2,710 802, US-PS 2,721,798, US-PS 2,772,161, GB-PS 843,497, GB-PS 843,940, US-PS 2,920 961, DT-OS 1 772 953, DT-OS 1 804 167, DT-PS 1 959 594.

Couplers with particularly favorable properties are characterized, for example, by ballast groups of the following formulas: In the formulas (8.1) to (8.4), R11 denotes an alkyl group with 5 to 18 carbon atoms, R12 and R14, independently of one another, each denote an alkyl group with a maximum of 8 carbon atoms, R13 denotes a hydrogen atom, a methyl or ethyl group or also another alkyl group 13 maximum carbon atoms and s is an integer from 2 to 5.

Examples of a number of acylacetylamino compounds according to the invention now follow: (9.1). 1- (3 ', 4'-Dioxolobenzoyl-acetylamino) -2-chloro-5- (2 ", 5" -di-tertiary-amylphenoxy-acetylamino) -benzene of the formula (9.2). 1- (3 ', 4'-dioxolobenzoyl-acetylamino) -2-chloro-5- [gamma- (2 ", 4" -di-tertiaryamylphenoxy) butyramino] benzene; (9.3). 1- (3 ', 4'-dioxolobenzoyl-acetylamino) -2-chloro-5 - [«- (2", 4 "-di-tertiaryamylphenoxy) butyramino] benzene; (9.4). 1- (3 ', 4'-Dioxolobenzoyl-acetylamino) -2-chloro-5- [γ- (3 "-n-pentadecylphenoxy) -butyramino] -benzene; (9.5). 1- (3', 4'- Dioxolobenzoyl-acetylamino) -2-chloro-5- [α (3 "-n -pentadecylphenoxy) butyramino] benzene (9.6). 1- (3 ', 4'-dioxolobenzoyl-acetylamino) -2-chloro-5- [β- (2 ", 4" -di-tertiaryamylphenoxy) propoxy] benzene; (9.7). 1- (3 ', 4'-dioxolobenzoyl-acetylamino) -2-chlorobenzene-5-carboxylic acid n-dodecyl ester; (9.8). 1- (3 ', 4'-dioxolobenzoyl-acetylamino) -2-methoxy-5- [γ- (2 ", 4" -di-tertiaryamylphenoxy) butyramino] benzene; (9.9). 1- (3 ', 4'-Dioxolobenzoyl-acetylamino) -3- [α- (2 ", 4" -di-tertiary-amylphenoxy) -butyramino 1-benzene (9.10). 1- (3 ', 4'-Dioxolobenzoyl-acetylamino) -2-chloro-4- [γ- (3 "-n-pentadecylphenoxy) butyramino] benzene (9.11). A- [4- (3', 4 '-Dioxolobenzoyl-acetylamino) -phenyl] -propanephosphonic acid-di- (γ-methylbutyl) -ester of the formula (9.12). γ [-4- (3 ', 4'-dioxolobenzoyl-acetylamino) -phenyl] -p # opanephosphonic acid dibutyl ester; (9.13). 1-63 ', 4'-dioxolobenzoyl-chloroacetylamino) -2-chloro-5 - [(2 ", 4" -di-tertiaryamylphenoxy) -acetylamino] -benzene; (9.14). 1- [α- (3 ', 4'-Dioxolobenzoyl) -α- (1 "-benzyl-2", 4 "-dioxoimidazolin-3" -yl) -acetylamino] -2-chloro-5- [α- ( 2 "', 4"' - di-tertiSramylphenoxy) butyramino] benzene; (9.15). 1 - [(3 ', 4'-Dioxolobenzoyl) - (4'-methylsulfonylphenoxy) acetylamino] -2-chloro-5- [α- (3 "' - n-pentadecylphenoxy) -butyramino] benzene; (9.16) 1- (3 ', 4'-Dioxanobenzoyl-acetylamino) -2-chloro-5- [α- (2 ", 4" -di-tertiaryamylphenoxy) -butyraminol-benzene of the formula (9.17). L- (3f, 4'-Dioxanobenzoyl-chloroacetylamino) -2-chloro-5- (y- (3 "-n-pentadecylphenoxy) butyramino] benzene (9.18). 1- (3 ', 4'-Dioxanobenzoyl- acetylamino) -2-chloro-5- [γ (2 ", 4" -di-tertiaryamylphenoxy) -butyramino] -benzene; (9.19). 1- (3 ', 4'-dioxanobenzoyl-acetylamino) -2-methoxy- 5 - [- (2 "'4" -di-tertiaryamylphenoxy) -butyramino] -benzene; (9.20). 1- (3', 4'-dihydropyranobenzoyl-acetylamino) -2-chloro-5- [α-phenoxy- myristylamino] benzene of the formula (9.21). 1- (3 ', 4'-Dihydropyranobenzoyl-acetylamino) -2-chloro-5- [# - (2 "~ 4'1-di-tertiaryamylphenoxy) -butyraminoi-benzene; (9.22). 1- (3', 4'-Dihydropyranobenzoyl-chloroacetylamino) -2-chloro-5- [γ- (2 "'4" -di-tertiaryamylphenoxy) butyramino] benzene; (9.23). 1- [α-3', 4'-dihydropyranobenzoyl ) -α-dimethylmaleimido) -acetylamino] -2-chloro-5- [γ- (2 ", 4" -di-tertiaryamylphenoxy) -butyramino] -benzene.

The acylacetylamino compounds according to the present invention can be produced by methods known per se.

An advantageous production process consists in the fact that one has an ester of the formula preferably the methyl or ethyl ester with an amine of the formula (10.2) H2N -A. A, R and Z have the same meanings as in formula (1). If necessary, the four-equivalent couplers obtainable in this way can be converted into two-equivalent couplers in a manner known per se by replacing one hydrogen atom of the -CH2 group with a substituent, for example a chlorine atom; cf. for example DT-OS 2 263 875, DT-OS 2 402 220 and DT-OS 2 329 587.

The esters of the formula (10.1) used as starting materials are obtained, for example, by condensation of an acid chloride of the formula with the sodium compound of an acetoacetic acid alkylaster and subsequent cleavage with a base; see, for example, Organic Synthesis, Coll. Vol II, p. 266 and DT-OS 2 114 577.

The acylacetylamino compounds of the formulas (1) to (6) can be used in incorporated into photographic materials as a yellow coupler in a manner known per se will. How already from can be seen from the above statements expediently in a high-boiling, water-immiscible organic Solvent is dissolved and the solution is made into a gelatin-silver halide emulsion emulsified. Suitable coupling solvents are for example in US-PS 2,332,027, DT-OS 1 945 210 and DT-OS 2 140 309 are listed. As particularly suitable coupler solvents Triaryl phosphates such as tricresyl phosphate, and dialkyl phthalates such as dibutyl phthalate, proven.

The yellow couplers are preferably used, if appropriate using an auxiliary solvent such as ethyl acetate or methylene chloride in the coupler solvent dissolved, and the solution is then, for example using ultrasound, in a aqueous solution of gelatin or other for making photographic Materials usable layer former emulsified in the presence of a surfactant. The layer former can already contain the silver halide, or the aqueous one can be used Mix the emulsion of the coupler solution with a so-called gelatin-silver halide emulsion.

The emulsion of the coupler solution obtained in the manner indicated can be used in gelatine to make a material that contains the silver halide in a Contains color coupler-free layer. In the solution of the coupler in the organic solvent, or the emulsion obtained therefrom, further additives such as hardeners and light stabilizers can be used be incorporated.

The couplers according to the invention can be mixed with one another or dissolved together with other known couplers in organic solvents and further processed in the specified manner.

The rest of the construction and processing can also be done of the color photographic material in the usual, known manner. It is known that a p-phenylenediamine derivative is advantageously used as the developer substance.

The photographic materials made with the new couplers prove to be very valuable in various ways; by simultaneously have several advantageous properties such as high reactivity towards the oxidation products the color developer, favorable absorption spectra and high light resistance of the resulting dyes.

Example 1 A solution of 1.4 g of ethyl 3,4-dioxolobenzoyl acetate and 2.1 g of l-amino-2-chloro-5- (2 ', 5'-di-tertiaryamylphenoxy-acetylamino) -benzene in 5 ml of p-xylene, which contains 2 drops of symmetrical collidine as a catalyst, is used during Heated to 140 ° C for 6 hours. It is then cooled to 0 ° C., the precipitated Crystals are suction filtered, washed with a little ether and recrystallized from ethyl acetate.

1.7 g of the compound of the formula (9.1) are obtained in the form of white crystals with a melting point of 159 to 162 ° C.

The compounds (9.2) and (9.3) are established in an analogous manner (Melting point 132 to 1340 C or 122 to 1250 C.) Example 2 To a suspension of 1.0 g of the coupler (9.1) obtained according to Example 1 in 30 ml Carbon tetrachloride is allowed to slowly form a solution at 10 ° C. with thorough stirring add dropwise 0.21 g of sulfuryl chloride in 10 ml of carbon tetrachloride. One still lets Stir for one hour and then extract the solution with water and sodium carbonate solution, until the aqueous phase remains neutral.

The one after the solvent has been distilled off from the carbon tetrachloride solution The residue obtained is first extracted twice with 30 ml of petroleum ether and then recrystallized from ether. 0.65 g of the coupler (9.13) is obtained in the form of white Crystals (melting point 65 to 68 ° C).

Example 3 64 mg of the coupler (9.2) are in a mixture of 200 mg of tricresyl phosphate and 1.8 ml of methylene chloride dissolved, which becomes methylene chloride evaporated and 6.6 ml of a 6% gelatin solution, 1.2 ml of distilled water and 2 ml of an 8% solution of diisobutylnaphthalene sulfonic acid sodium admitted. The mixture is homogenized by means of ultrasound.

5.0 ml freshly sonicated coupler emulsion, 3.3 ml silver bromide emulsion pH 6.5 with a content of 1.4% silver and 6.0% gelatin, 2.0 ml 1% aqueous solution of the hardener the formula and 1.7 ml of water are mixed together and placed on a subbed glass plate of 13 cm at 40 ° C. 18 cm potted.

After solidifying at 100 ° C., the plate is placed in a drying cabinet dried with circulating air at 320 ° C.

A strip cut to 4.0 cm ~ 6.5 cm is placed under a step wedge exposed for 2 seconds at 500 lux / cm2 and then at 240 ° C. as follows treated: minutes 1. Color development 5 2. Soaking 5 3. First fixation 2 4. Soaking 2 5. Silver bleaching 2 6. Soaking 2 7. Second fixation 2 8. Soaking 2 9. Drying 10 The processing solutions have the following composition: 1. Color developing solution (pH = 10.7) 4-amino-3-methyl-N-ethyl-N-B- (methyl-sulfonamido) sthylaniline; 1 1/2 H2S04 ~ H20 10 mmol anhydrous sodium sulfite 2.0 g potassium bromide 0.5 g potassium carbonate 40.0 g benzyl alcohol 10.0 g water 1000 g II. Fixing solution (pH = 4.5) Sodium Thiosulfate 6H20 80.0 g anhydrous sodium sulfite 5.0 g sodium borate (Borax) 6.0 g potassium alum 7.0 g acetic acid 4.0 g water 1000 g III. Silver bleach (pH = 7.2) Potassium hexacyanoferrate (III) 100.0 g boric acid 10.0 g sodium borate (borax) 5.0 g of water 1000 g A clear, sharp yellow wedge with an absorption maximum is obtained at 448 nm and a color density of 1.62.

Claims (8)

Claims ~~~~~~~~~~~~~~~~~~ Color couplers of the formula where R is a hydrogen atom or a simple substituent, Z is the addition to a five- to six-membered ring, the skeleton of which is composed of carbon atoms and one to two oxygen atoms bonded to the benzene ring, X is a molecular part that is split off during the color coupling and A is a radical with a aromatic carbocyclic ring bonded to the -HN group. 2. Compounds according to claim 1, those of the formula where R1 is a hydrogen or halogen atom, Z1 is one of the atomic groupings -O-CH2-0-, -0-CH2-CH2-0-, -CH2-CH2-0-, -CH2-CH2-CH2-o- and -CH = CH-O-, X denotes a part of the molecule which is split off during the color coupling and A1 denotes a radical with a benzene ring bonded to the -HN group 3. Compounds according to claim 2, those of the formula where R2 is a hydrogen, chlorine or bromine atom, Z2 is one of the atomic groupings -O-CH2-, -0-CH2-CH2- and - (CH2) 3-, X is a residue that is split off during color coupling, Q1 is a hydrogen atom , a chlorine atom or a lower alkoxy group, and B1 a color coupler denoting a diffusion-proof group. 4. Compounds according to claim 3, those of the formula where R2 is a hydrogen, chlorine or bromine atom, Z2 is one of the atomic groupings -O-CH2-, -0-CH2-CH2- and- (CH2) 3-, X1 is a hydrogen or chlorine atom, m and n are each one an integer with a value of 13 or less, p an integer with a value of 6 or less, and q an integer with a value of 15 or less. 5. Compounds according to claim 3, those of the formula where X is a part of the molecule that is split off during the color coupling, m and n each an integer with a value of at most 3, p an integer with a value of at most 6, q an integer with a value of at most 15 and r one of the numbers 1 and 2 mean. 6. Compounds according to claim 3, those of the formula where X is a part of the molecule that is split off during the color coupling, m and n each an integer with a value of at most 3, p an integer with a value of at most 6, q an integer with a value of at most 15 and r one of the numbers 1 and 2 mean. 7. Use of the compounds according to one of claims 1 to 6 as yellow couplers in color photographic recording materials. 8. Color photographic recording material used as a yellow coupler a compound of the composition specified in one of claims 1 to 6.