DE2949167A1 - Imidazothiazole cpds. and their di: and tetra:hydro derivs. - for use as bleaching inhibitor in silver dye bleach process - Google Patents

Abstract

New (di- or tetra-hydro)imidazo(2,1-b)thiazole cpds. have the formula: (where R1-4 are H, (substd.) alkyl, alkenyl, cycloalkyl, ar(alk)yl, halogen, NO2, CN, OH, SH, alkoxy, alkylmercapto, COOH, carboxylic ester, carbonamido or acyl. R1 and R4 together can form a bond. R2 and R3 together with the C atoms to which they are attached can form a (substd.) carbo- or hetero-cyclic ring). (I) are specified for use in photographic material for the Ag dye bleach process. They prevent undesirable bleaching adjacent to the exposed areas, so that colour pictures with purer tones and better contrast can be produced.

Description

Photographic material for silver color bleaching

travel Photographic material for the silver dye bleaching process The present invention relates to photographic material for the silver dye bleaching process, which contains at least one compound in at least one layer which is an undesired Prevent fading of dye in the areas adjacent to exposed areas and with it the production of color images in purer hues and improved Color contrast enables.

In the silver dye bleaching process, the exposed material is known to be first with a black-and-white silver halide developer solution to a negative one Developed the silver image and then placed the silver image in a bleach bath in which the silver image is oxidized to a silver salt and the dye or dyes are simultaneously decolorized (bleached) imagewise. Then it will Any silver salt present was removed by fixing and the material was washed. The bleach bath usually contains one or more color bleaching catalysts, e.g. quinoxalines, Pyrazines or phenazines (cf. e.g.

DE-AS 1547720 and 1547759).

Recording materials particularly suitable for the silver dye bleaching process contain red, green and blue sensitized silver halide emulsion layers on a substrate, which are bleachable cyan (cyan) dyes, purple (magenta) dyes and yellow dyes, respectively contain.

If necessary, these dyes can also be accommodated in layers adjacent to the silver halide emulsion layers.

During the bleaching (oxidation) of the silver, the bleaching catalysts are used reduced in the silver picture districts. In reduced form, the bleach catalysts accelerate the dye bleaching in the exposed areas. To make a sharp and high-contrast image, it is desirable that the dye only in the silver image areas is bleached. However, it has been shown that the bleach catalysts in reduced Form, if they do not work immediately during the bleaching process, in adjacent layers (possibly also through this) diffuse and there an undesired Can also cause bleaching of dyes in areas not exposed imagewise.

To solve the problem of undesired bleaching of image dyes in the so-called non-image districts by diffusing, present in reduced form Bleach catalysts are already p-quinones with a ballast group in US Pat. No. 3,457,074 suggested. These diffusion-resistant oxidizing agents oxidize the reduced ones Bleach catalysts and thus render them ineffective as such (bleach-inhibiting Effect). The disadvantage of quinones, however, is that their effectiveness is low, they have a noticeable self-absorption in the visible spectral range and also under development conditions with developer substances, e.g. hydroquinone, react and thus negatively affect the effectiveness of the developer.

From US-PS 3782948 it is also known for the same purpose Use nitro compounds as oxidizing agents. The bleach-inhibiting effects of this links is unsatisfactory, however, and the nitro compounds can not be in in all cases incorporated into the photographic layers in the desired distribution.

The object of the present invention is now to eliminate the unwanted bleaching of image dyes in the silver dye bleaching process, as they are caused by diffusing, reduced bleach catalysts and at the same time the disadvantages of the solutions proposed so far as far as possible to overcome. The object according to the invention is achieved through the use binuclear fused heterocycles, one imidazole and one imidazoline) Thiazole (thiazoline, thiazolidine) ring contain and good anti-bleaching properties Distinguish effect.

The present invention therefore provides a photographic material for the silver dye bleaching process which contains at least one compound of the formula in at least one layer contains, in which A and B are each the radicals of the formulas are, where R1, R2, R3 and R4 are each hydrogen, optionally substituted alkyl, alkenyl, cycloalkyl, aryl or aralkyl, halogen, nitro, cyano, hydroxyl, mercapto, alkoxy, alkylmercapto, carboxyl, carboxylic acid ester, carbonamido or acyl or (R2 and R3) together with the carbon atoms to which they are attached form an optionally substituted carbo- or heterocyclic ring.

The method according to the present invention enables more advantageous Way of producing color photographic images by the silver dye bleaching process. By largely eliminating unwanted color bleaching due to diffusing Color bleach catalysts (in reduced form) can significantly improve color rendering be achieved.

Further objects of the present invention are the method to produce the specified material for the silver dye bleaching process, the Use of the heterocyclic compounds of formula (1) to prevent the unwanted dye bleaching in photographic materials for the silver dye bleaching process, the compounds of the formula (1), insofar as they are new, and processes for their preparation of the compounds of formula (1).

The substituents R1, R2, R3 and R4 in the radicals of the formulas which represent (A) and (B) in the compounds of formula (1) can be hydrogen, alkyl, in particular with 1 to 20 carbon atoms, where the alkyl radicals can be straight-chain or branched, such as methyl, ethyl, propyl, i- Propyl, butyl, isobutyl, tert-butyl, amyl, tert-amyl (l, l-dimethylpropyl), 1,1,3,3-tetramethylbutyl, l-methylethylpentyl, hexyl, l-methylpentyl, neopentyl, 1 -, 2- or 3-methylhexyl, heptyl, n-octyl, tert. Octyl, 2-ethylhexyl, n-nonyl, isononyl, tert. Nonyl, decyl, tert. Decyl, undecyl; furthermore dodecyl, tetradecyl, hexadecyl, octadecyl, nonodecyl and eicosyl, and the associated isomers, and furthermore alkenyl with in particular 2 to 20 carbon atoms, the radicals mentioned for alkyl can apply analogously to alkenyl.

The alkyl or alkenyl radicals can be substituted with, for example, halogen, such as fluorine, chlorine or bromine; Hydroxyl (-OH), amino (-NH2), cyano (-CN), nitro (-NO2), Alkoxy, e.g. with 1 to 20 carbon atoms, the radicals mentioned for alkyl May be part of the alkoxy radicals (e.g. methyl-methoxy), aryloxy, especially optionally substituted phenoxy, aralkyloxy, in particular optionally substituted benzyloxy (Substituents C1-C4 alkyl, halogen, hydroxyl), or cycloalkoxy with 5 or 6 carbon atoms, such as.

Cyclopentoxy or cyclohexoxy.

Further substituents on the alkyl or alkenyl can be carboxyl (-COOH), Carboxylic acid ester (-COOR), carbonamido (-CON <) acyl (RCO, RSO2-), acylamino (RCON < RSO2N <), sulfonic acid (-S03M), or sulfonamido (SO @ N <).

If the substituents are carboxylic acid ester radicals, they can be carbalkoxy radicals, in which the alkoxy radicals preferably contain 1 to 20 carbon atoms, are straight-chain or branched and have the meanings already given for alkoxy, to carbocycloalkoxy radicals, in particular those which are derived from cyclopentanol or cyclohexanol, around carboaryloxy radicals, in particular carbophenoxy radicals which are optionally substituted on the phenyl ring (substituents: C1-C4-alkyl, halogen) or also carboaryloxy radicals, in particular radicals which differ from benzyl alcohol or optionally substituted benzyl alcohols (substituents, for example as indicated above for phenyl) derive If the substituents are carbonamido or sulfonamido radicals, those are considered which are unsubstituted on the nitrogen atom (-CONH2 or -SO @ NH2), mono- or disubstituted by alkyl, in particular with 1 to 5 carbon atoms, mono- or disubstituted by phenyl (optionally substituted) or are disubstituted by alkyl and phenyl.

The acyl substituents can be derived from sulfonic acids or carboxylic acids , the latter being preferred. They are preferably acyl residues of Carboxylic acids with 1 to 20 carbon atoms, especially formic acid and the Alkylcarboxylic acids with 2 to 20 carbon atoms, and optionally with e.g.

Alkyl (C1-C4) or halogen substituted benzoic acids or benzyl carboxylic acids or of cyclopentyl or cyclohexyl carboxylic acids.

The acylamino substituents (RCON <or RSO2N <are on the nitrogen atom optionally substituted by lower alkyl (C1-C4) or phenyl, but contain preferably a hydrogen atom bonded to the nitrogen atom (RCONH- or RS02NH-). The acid component in these substituents is preferably derived from lower ones (C1-C5) carboxylic acids or sulfonic acids, e.g. formic acid, acetic acid, propionic acid, Butyric acid or pentanoic acid or of alkyl sulfonic acids with 1 to 5 carbon atoms as well as optionally substituted with, for example, alkyl (C1-C4) or halogen Benzoic acids or benzenesulfonic acids.

Also suitable as substituents are carboxyl (-COOH) and the Sulfonic acid residue (-S03H). All the substituents mentioned can be one or more Times be present in the alkyl or alkenyl radicals.

If the substituents R1 to R4 are optionally substituted cycloalkyl, so cycloalkyl preferably contains 5 or 6 carbon atoms and can with halogen, e.g. fluorine, chlorine or bromine, hydroxyl, amino (-NH2), alkyl or arylamino substituted wherein alkyl preferably contains 1 to 5 carbon atoms and aryl preferably optionally substituted phenyl (substituents: e.g.

C1-C4 alkyl) and it is mono- or disubstituted on the nitrogen atom Can act alkyl or arylamino radicals; furthermore, the cycloalkyl with alkyl or Alkoxy, each containing, for example, 1 to 5 carbon atoms and straight-chain can be branched or substituted.

In particular, these substituents are methyl, ethyl, Propyl, isopropyl, butyl, tert-butyl or amyl or methoxy, ethoxy, propoxy, Butoxy or pentoxy.

Other substituents on the cycloalkyl radicals can be carboxyl (-COOH) or carbalkoxy, the alkoxy radicals preferably being those having 1 to 5 carbon atoms (cf. the aforementioned alkoxy radicals) can be considered.

If the substituents R1 to R4 are optionally substituted aryl, so naphthyl and especially phenyl radicals come into question, optionally with the following substituents may be substituted: halogen, e.g.

Fluorine, chlorine or bromine, hydroxyl, mercapto (-SH) amino (-NH2), alkyl- or arylamino (as indicated for substituted cycloalkyl), cyano (-CN), nitro (-N02), Carboxyl (-COOH), the sulfonic acid residue (-S03H) or the Carboxylic acid ester radical, which can be the same radicals as they are already were mentioned as substituents for alkyl or alkenyl.

The carbonamido and sulfonamido substituents on the aryl radicals can also be the same as indicated above.

The acyl substituents (RCO- or Rso2-) are preferably those in which R is hydrogen, alkyl with 1 to 20 carbon atoms, e.g. methyl, ethyl, Propyl, butyl, amyl, hexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, Octadecyl, eicosyl or their isomers, also phenyl or benzyl and cycloalkyl with 5 or 6 carbon atoms, these optionally with lower alkyl (C1-C4) or halogen may be substituted; R has the meanings given for R, excluding hydrogen. For acylamino (RCONH- or RCON (R #) -) as a substituent radicals in which R has the meanings given for acyl and can additionally be a pyridyl, thienyl or furyl radical, while R ″ can be, for example, hydrogen or is alkyl of 1 to 5 carbon atoms.

Further substituents for the aryl radicals can be alkyl, alkoxy or Be alkyl mercapto, which preferably contain 1 to 20 carbon atoms and are straight-chain or can be branched. Finally, aryl can also be phenyl-substituted be, which substituent can then be in any position.

If the substituents R1 to R4 are optionally substituted aralkyl, so they are preferably benzyl radicals, optionally with those mentioned for aryl Substituents can be substituted. The aryl and aralkyl radicals can be one or more of the named Contain substituents.

If the substituents R1 to R4 are halogen, they generally have the meaning fluorine, chlorine or bromine. The substituents R1 to R4 are also hydroxyl, in utQmrerna also.) Mercapto, nitro, cyano or carboxyl and can mean Carboxylic acid esters, carbonamido or acyl those already indicated for these substituents Have meanings.

If the substituents R1 to R4 are finally alkoxy or alkyl mercapto, then these usually contain 1 to 20 carbon atoms, the alkyl radicals being straight-chain or branched and can have the meanings given above.

Furthermore, the substituents R2 and R3 together with the carbon atoms, to which they are bound, an optionally substituted carbo- or heterocyclic Form a ring. These rings can be saturated or unsaturated, which are preferably 5- or 6-membered rings, such as cyclopentyl, cyclopentenyl, cyclohexyl, Cyclohexenyl or optionally substituted phenyl, where those for R1 to R4 (meaning optionally substituted aryl) also mentioned substituents can come into question here.

The compounds of the formula (1) can optionally also be in the form their salts are present, the anions of these salts being inorganic or can derive organic acids. Inorganic anions are, for example Fluoride, chloride, bromide, iodide, perchlorate, sulfate, nitrate, phosphate, hydrogen phosphate, Carbonate or hydrogen carbonate anion.

Organic anions are, for example, more saturated or unsaturated radicals aliphatic, cycloaliphatic, more aromatic and heterocyclic Carboxylic and sulfonic acids, such as the formate, acetate or chloroacetate anion; the anions the cyclohexanecarboxylic acid or an optionally substituted benzoic acid, the Benzenesulfonic acid or toluenesulfonic acid. Colorless or at most are preferred weakly colored anions.

Preferred is such a photographic material for the silver dye bleaching process which contains compounds having a bleach-inhibiting effect represented by the formula correspond, in which A1 and B1 each radicals of the formulas are, where R5 to R8 are each hydrogen, optionally with halogen, hydroxyl, amino, cyano, nitro, alkoxy, aryloxy, aralkoxy or cycloalkoxy, carboxyl, carboxylic acid ester, carbonamido, acyl, acylamino, sulfonic acid or sulfonamido substituted alkyl with 1 to 20 carbon atoms or Alkenyl of 2 to 20 carbon atoms; optionally substituted with halogen, hydroxyl, amino, alkyl- or arylamino, alkyl, alkoxy, carboxyl or carbalkoxy.

Cycloalkyl; optionally with halogen, hydroxyl, mercapto, amino, Alkyl or arylamino, cyano, nitro, carboxyl, carboxylic acid ester, carbonamido, acyl, Acylamino, sulfonic acid, sulfonamido, sulfonic acid ester, alkyl, alkoxy, alkylmercapto or phenyl substituted phenyl; Naphthyl; Benzyl; Halogen, hydroxyl, mercapto, Alkoxy, alkylmercapto, carboxy, carboxylic acid ester, carbonamido or acyl are or (R6 and R7) together with the carbon atoms, to which they are bound are, a cyclopentyl, cyclohexyl or optionally substituted phenyl ring form, where substituted phenyl has the same meaning as for R5 bis R8 is given as meaning substituted phenyl.

Particularly suitable compounds of the formula (2) are the compounds of the formulas where R5 to R8 are each hydrogen, optionally with chlorine, bromine, -OR9 '-COOR9 or R9CO-, where R9 is hydrogen, alkyl with 1 to 20 carbon atoms or optionally substituted phenyl, benzyl or cycloalkyl with 5 or 6 carbon atoms, with -NHCOR10 or -NHS02Rlo, where R10 is alkyl having 1 to 5 carbon atoms or optionally substituted phenyl, with where R11 and R12 are hydrogen or alkyl with 1 to 5 carbon atoms or optionally substituted phenyl, or alkyl with 1 to 20 carbon atoms substituted with -SO3H or alkenyl with 2 to 20 carbon atoms, R5 to R8 further each optionally with chlorine, bromine, hydroxyl , in which R11 and R12 have the meanings given, -COOR9, in which R9 has the meaning given, alkyl or alkoxy with 1 to 5 carbon atoms substituted cycloalkyl with 5 or 6 carbon atoms, optionally with halogen, hydroxyl, mercapto, cyano, nitro, -COOR9 '-S03H, -CORg, -S02R13, -N (R11) COR'13, in which Rg, R11 and R12 have the meanings given, R13 is alkyl with 1 to 20 carbon atoms, phenyl, benzyl, cycloalkyl with 5 or 6 carbon atoms and R13 has the meaning of R13 and also pyridyl, thienyl or furyl or phenyl substituted with alkyl, alkoxy or alkyl mercapto each with 1 to 20 carbon atoms or phenyl, R5 to R8 furthermore each naphthyl, benzyl, chlorine, bromine, hydroxyl, mercapto, alkoxy or alkyl mercapto each with 1 to 20 carbon atoms, -COOR9 '-COR9 or are, in which Rg, R11 and R12 have the meanings given, or (R6 and R7) together with the carbon atoms to which they are bonded form a cyclopentyl, cyclohexyl or optionally substituted phenyl ring, substituted phenyl having the same meaning as they are for R5 to R8 the meaning is substituted phenyl and also the compounds of the formulas or in which R5 to R8 have the meanings given.

Also preferred are photographic materials for the silver dye bleaching process which contain the compounds of the formula in which R14 and R15 each contain hydrogen, optionally with chlorine, -OR16 '-COR16 or -COOR16' in which R16 is hydrogen, alkyl with 1 to 12 carbon atoms or phenyl, substituted alkyl with 1 to 20 carbon atoms; -CF3, cyclopentyl, cyclohexyl; optionally with chlorine, bromine, -OR16 '-SR16' -COOR16 '-SO2R16' where R16 has the meaning given, cyano, nitro, where R11 is hydrogen or alkyl with 1 to 5 carbon atoms and R12 is hydrogen, alkyl with 1 to 5 carbon atoms or optionally substituted phenyl, -N (R11) COR17 'where R17 is alkyl with 1 to 12 carbon atoms or phenyl, or with alkyl with 1 up to 12 carbon atoms are substituted phenyl, R14 and R15 are also chlorine, bromine, -OR16, -COOR16 -COR16 are, in which R11'1, R12 and R16 have the meanings given, or R14 and R15 together with the carbon atoms to which they are bonded form a cyclopentyl, cyclohexyl, or optionally substituted phenyl ring, substituted phenyl having the same meaning as they are substituted phenyl is given for R14 and R15, and R5 and R7 have the meanings given.

Phenyl has the meaning given for R14 and R15, and R5 and R7 have the meanings given.

Finally, the use of the compounds of the formulas is of particular interest as bleach inhibitors in photographic materials for the silver dye bleaching process wherein, R14 and R15 have the meanings given.

The compounds of the formulas are also particularly valuable for the stated purpose in which R14 and R15 have the meanings given and R18 and R19 are each hydrogen, alkyl having 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, optionally with chlorine, bromine, -OR16 '-SR16' -COR16 '-COOR16' -SO2R16 'in which R16 is hydrogen , Alkyl with 1 bis or phenyl, with cyano, nitro, where R11 is hydrogen or alkyl having 1 to 5 carbon atoms and R12 is hydrogen, alkyl having 1 to 5 carbon atoms or optionally substituted phenyl, with -N (R11) COR17 'where R17 is alkyl having 1 to 12 carbon atoms or phenyl, or with alkyl having 1 to 12 carbon atoms are substituted phenyl, R18 and R19 are also hydroxyl, -COOR16 '-COR16 or are, in which R11 'R12 and R16 have the meanings given, or (R18 and R19) together with the carbon atoms to which they are bonded form a cyclopentyl, cyclohexyl or optionally substituted phenyl ring, substituted phenyl having the same meaning as it is given for R18 and R19 in the meaning substituted phenyl, and R14 and R15 have the meanings given.

The compounds of the formulas (1) to (24) can be prepared according to the following reaction schemes: 1. Compounds of the type: The preparation of 2-amino-2-thiazolines (II) is for example

from Elderfield, Heterocyclic Compounds, Vol. 5, 685 known.

x = Br or Cl 2. Compounds of the type: Compound (III) is prepared, for example, from the corresponding nitro compounds (cf., for example, Chem. Ber. 39, 1233; JCS 57 (1948)). The reaction of the compound (III) with carbon disulfide is likewise carried out by known methods (cf.

JACS 63, 3124 (1941)) R1-R # = H or H x 3 Cl, Hr.

3. Connections of the type: (See Elderfield, Heterocyclic Compounds, Vol. 5, pages 574 ff.) Equimolar amounts of the specified starting components are used in a polar non-aqueous solvent, for example in alcohols (methanol, ethanol), ethylene glycol, or their C1-C4 monoethers, pyridine or dimethylformamide also reacted chlorinated hydrocarbons or low molecular weight ketones, preferably temperatures between about 40 and 2000C, in particular between about 60 and 150 ° C are necessary. The reaction can usually take about 1 to 24 hours and depends on the temperature chosen. Customary work-up gives the desired reaction product or its acid addition salt.

Regarding processes for the production of those used according to the invention heterocyclic compounds, reference is made to the following publications: German Patents 1,795,652 and 1,900,974, U.S. Patents 3,954,784; JACS 96, 1957 (1974); - and JOC 26, 828 (1961).

The a-haloketones and aldehydes (e.g. R2COCH2X) can be produced by halogenation obtained in a known manner from the following ketones or aldehydes: acetone, Methyl ethyl ketone, diethyl ketone, dipropyl ketone, ethyl propyl ketone, methyl butyl ketone, Dibutyl ketone, diisobutyl ketone, methyl pentyl ketone, methyl neopentyl ketone, methylhexyl, -heptyl-, -octyl-, -nonyl-, -decyl-, -dodecyl-, -hexadecyl-, -octadecylketont Methylcyclohexylketon, Methylcyclopentyl ketone, cyclohexanone, cyclooctanone, cyclododecanone, methylhydroxyethyl ketone, methyl mercapto ethyl ketone, Phenyl ethyl ketone, phenyl propyl ketone, phenyl butyl ketone, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl ketone; p-, m- or O-substituted Phenyl alkyl ketones where, for example, substituents on the phenyl nucleus are: Cl, Br, NO2, OH, CH3-, CH30-, CH3S-, CH3so2- and the corresponding homologues with up to to 20 carbon atoms; -COOH, -COOCH3, -COOCH2CH3 up to and including -COO (CH2) 17CH3 ' -SO2OH, -SO2OCH3 '-SO3CH2CH3' -COONH2 '-COONHCH3' -COON (CH3) 2 '-COONHCH2CH3' -COON (CH2CH3 ' -COON (CH2CH3) 2 '-COONHC6H5' -CN, Cl3C-F3C-.

Acetophenone and optionally mono-, di- or trisubstituted acetophenones, where the ring substituents mentioned for the phenyl alkyl ketones are also possible here come.

Benzyl methyl ketone, benzyl ethyl ketone, benzyl octyl ketone, benzyl dodecyl ketone, benzyl phenyl ketone, Acetaldehyde, propionaldehyde, butyraldehyde, 2-phenylacetaldehyde, 2-hydroxyacetaldehyde, 2-cyclohexylaldehyde, 2-cyclopentylaldehyde, pentylaldehyde, hexylaldehyde, octylaldehyde, decylaldehyde, dodecylaldehyde, octadecylaldehyde.

As compounds of the formula The following can be used: 4-methyl-N, N'-ethylene thiourea, 4-ethyl-N, N'-ethylene thiourea, 4-octadecyl-N, N-ethylene thiohrane, 4,5-dimethyl-N, N '-aethylene thiourea, 4 -Methyl-5-ethyl-N, N'-ethylene thiourea, 4-phenyl-N, N '-aethylene thiourea (and analogs substituted in the phenyl part); 4,5-diphenyl-N, N'-ethylene thiourea, 4-phenyl-5-methyl-N, N'-ethylene thiourea, 4-phenyl-5-ethyl-N, N'-ethylene thiourea, 4,4-dimethyl-N , N'-ethylene thiourea, 5,5-dimethyl-N, N'-ethylene thiourea, 4,4,5-trimethyl-N, N'-ethylene thiourea, 4,4,5,5-tetramethyl-N, N'-ethylene thiourea.

The reaction of halogenated ketones or aldehydes with 2-aminothiazole or its compounds substituted in the 4- or 5-position gives rise to products of the formula Suitable aminothiazoles which can be used to prepare these compounds are, for example: 4-methyl-2-aminothiazole, 5-methyl-2-aminothiazole, 4-ethyl-2-aminothiazole, 5-ethyl-2-aminothiazole, 4,5- Dimethyl-2-aminothiazole, 4,5-diaethyl-2-aminothiazole, 4-propyl-2-aminothiazole, 5-propyl-2-aminothiazole, 5-butyl-2-aminothiazole, 5-isobutyl-2-aminothiazole, 5- t-Butyl-2-aminothiazole, 5-phenyl-2-aminothiazole, 5-benzyl-2-aminothiazole, 5- [p-dodecyl-phenyl) -2-aminothiazole, 5-chloromethyl-2-aminothiazole, 5-bromomethyl- 2-aminothiazole, 5-hydroxymethyl-2-aminothiazole.

Reaction of mercaptoimidazoles or of mercaptobenzimidazoles with α-halocarboxylic acids lead to compounds of the type Suitable a-halocarboxylic acids are, for example, 2-bromoacetic acid, 2-chloro (bromo) propionic acid, 2-chloro (bromo) butyric acid, 2-chloro (bromo) valeric acid, 2-chloro (bromo) caproic acid, 2-chloro (bromo) oenanthic acid, 2-chloro (bromo) caprylic acid, 2-chloro (bromo) pelargonic acid, 2-chloro (bromo) capric acid, 2-chloro (bromo) undecanoic acid, 2-chloro (bromo) lauric acid, 2-chloro (bromo) tridecanoic acid, 2- Chloro- (bromo) myristic acid, 2-chloro (bromo) pentadecanoic acid, 2-chloro (bromo) palmitic acid, 2-chloro (bromo) heptadecanoic acid, 2-chloro (bromo) stearic acid, 2-chloro (bromo) nonadecanoic acid, 2-chloro (bromo) arachidic acid.

Reaction of, for example, 2-mercaptoimidazole, 2-mercaptobenzimidazole or 2-mercaptoimidazoline with 2-chloro-acetic acid ester gives compounds of the formula Suitable 2-chloroacetoacetic acid esters are, for example

the methyl ester, ethyl ester, propyl ester, butyl ester, isobutyl ester, 2-methoxyethyl ester, 2-ethoxyethyl ester, pentyl ester, isopentyl ester, neopentyl ester, Hexyl esters, heptyl esters and the homologous esters with up to 18 carbon atoms in the alkoxy part of the ester.

The heterocyclic compounds of the formulas (1) to (24), die.auch The present invention, if they are new, can in known Manner can be incorporated into photographic layers of the silver dye bleach material.

Most of the compounds of formula (1) are practically colorless and usually in organic solvents, e.g. in alcohols, ethers, ketones also soluble in dibutyl phthalate or tricresyl phosphate. The application amount is usually 0.25 - 5.0 g / m² layer in which they are incorporated.

In a multilayer material, the compounds of the formula (1) Depending on the desired effect, all layers or only in individual emulsion, Dye, emulsion dye, intermediate or auxiliary layers added. Preferably the compounds of formula (1) are in the interlayers of the photographic Silver dye bleach material which is neither an image dye nor a silver halide emulsion contain. In the case of mixed grain emulsions, the compounds of the formula (1) the dispersed phase and / or the binder layer which serves as a matrix, be incorporated. Intermediate layers are primarily to be understood as separating layers and as auxiliary layers there are sliding layers, protective layers, filter layers, Antihalation layers, but also coatings or subbing layers, are considered.

The use of the compounds of formula (1) in the intermediate layers (which are free of image dyes and silver halide emulsions) brings with the Image bleaching in the presence of bleach catalysts is a particular improvement in the Picture quality. The bleaching catalysts are known to be used in the bleaching process metallic silver is reduced to the corresponding dihydro compounds, which then cause the dye to bleach with reoxidation. The reduced form, if it does not work immediately during the bleaching process, it migrates through the neighboring ones (Intermediate) layers and then causes an image dye in the subsequent ones containing layers an undesirable and harmful bleaching of this dye. The compounds of formula (1) in the intermediate layers prevent this disadvantageous Effect. For example, they can also be used in (dye-containing) silver bromide, silver chloride or silver iodide emulsions or in those emulsions which contain a Contains a mixture of silver halides, such as silver bromide iodide or silver chlorobromide emulsions.

The emulsions can be chemically sensitized, they can also customary organic stabilizers and antifoggants, as well as customary ones Contain plasticizers such as glycerine. The emulsions can can also be hardened with the hardening agents customary for gelatine. Furthermore can the emulsions contain customary casting aids. The emulsions can be customary Layer base for photographic recording material are applied. Possibly A mixture of several colloids can be used to disperse the silver halides will. Bleachable dyes used in the preparation of dye-containing silver halide emulsions suitable for the silver dye bleach material are disclosed in, for example, U.S. patents 3 454 402, 3 443 953, 3 804 630, 3 716,368, 3 877 949, 3 623 874, 3 931 142 and 4,051,123.

A transparent, metallic reflective material can be used as the silver dye bleach material or, preferably, white-opaque material can be used, the carrier of which is not liquid able to soak up from the baths.

The carrier can for example consist of optionally pigmented cellulose triacetate or polyester. If it is made of paper felt, it must be on both sides painted or coated with polyethylene. On at least one side of this The light-sensitive layers are located on the support, preferably in the known layer Arrangement, i.e. at the bottom a red sensitized silver halide emulsion layer, which contains a blue-green azo dye over it a green sensitized silver halide emulsion layer, which contains a purple azo dye and on top a blue-sensitive silver halide emulsion layer, which contains a yellow azo dye. The material can also be sub-layers, intermediate layers, Contain filter layers and protective layers. In particular, can also like this in German Offenlegungsschriften 2 036 918, 2 132 835 and 2 132 836 became the silver halide emulsion and the associated bleachable Contain dye in two or three separate, mutually adjacent layers , however, as a rule, the entire thickness of layers should be in a dry state Do not exceed 20 µ.

The exposed silver color bleaching materials are processed in the usual way and includes (1) silver development, (2) color bleaching, (3) the silver bleaching and (4) the fixation (see e.g. DE-OS 2 448 443). The color bleaching (2) and the silver bleaching (3) can be combined in a single treatment stage will.

Baths of customary composition can be used for silver development become, e.g. such. the developing substance hydroquinone and, if desired also contain l-phenyl-3-pyrazolidinone. It can also be cheap if the silver development bath, as described in Swiss patent specification 405 929, also contains a dye bleach catalyst.

As color bleaching baths - provided that color bleaching is a separate treatment stage is carried out - those that are used in addition to a strong one are advantageously used Acid, a water-soluble iodide and an antioxidant for the iodide contain a dye bleach catalyst.

Combined dye and silver dye bleach baths contain in addition to the specified ones Components usually also contain a water-soluble oxidizing agent. Suitable color bleach catalysts are primarily diazine compounds, e.g. derivatives of pyrazine, quinoxaline or phenazines.

They are e.g. in DT-AS 2 010 280, 2 144 298 and 2 144 297, in French Patent 1,489,460, U.S. Patent 2,270,118, and described in DT-OS 2,448,443.

Strong acids are to be understood here as those which the dye bleach bath or give the combined dye and silver bleach bath a pH value of at most 2. For example, hydrochloric acid, phosphoric acid and, in particular, sulfuric acid or Sulfamic acid can be used.

As the water-soluble iodide, alkali iodides such as Potassium iodide or sodium iodide.

Suitable oxidizing agents are nitrous compounds such as P-nitrosodimethylaniline, nitro compounds such as aromatic nitro compounds and preferably aromatic mono- or dinitrobenzenesulfonic acids, e.g.

m-Nitrobenzenesulfonic acid The antioxidant is used advantageously reductones or water-soluble mercapto compounds. Suitable reductones are in particular aci-reductones with a 3-carbonyl-enediol (1,2) group such as Reductin, triose reductone or, preferably, ascorbic acid.

Suitable mercapto compounds are those of the formula HSA (B), wherein A is an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic bridge member, B a water-solubilizing radical and m a whole Number of at most 4 is. (DE-OS 2 258 076, DE-OS 2423819) The silver fixer can be composed in a known and customary manner. Suitable as a fixative is e.g. sodium thiosulphate or, advantageously, ammonium thiosulphate, if desired with additives such as sodium bisulfite, sodium metabisulfite and or ammonium bisulfite and optionally complexing agents, such as ethylenediaminetetraacetic acid.

All treatment baths can contain other common additives such as hardening agents, Contains wetting agents, optical brighteners or UV protection agents.

In the examples below, parts and percentages relate to based on weight unless otherwise stated.

Preparation 1 3-Phenyl-5,6-dihydroimidazolo [2,1-b] -thiazole A solution of 6 g of N, N'-ethylene thiourea and 11.7 g of phenacyl bromide in 100 ml of ethyl alcohol is refluxed for 2 hours. The precipitate formed after cooling is filtered and washed on the filter with a little cold ethanol. The product obtained is dissolved in water, precipitated with an excess of 2N aqueous sodium hydroxyl solution, filtered, washed with water and then recrystallized from a methanol + water mixture. 9.5 g of the compound of the formula are obtained Melting point: 97-99 ° The nuclear magnetic resonance spectrum confirms the specified chemical structure of the compound.

Preparation method 2 3-Me + hyl-benzimidazolo- [2,1-bl-thiazole Ein Mixture of 10 g (0.73 mol) 2-mercapto-benzimidazole and 7.43 g (0.08 mol) chloroacetone in 50 ml of ethanol is refluxed for 18 hours. The one after cooling down The resulting precipitate is filtered off, washed with cold ethanol, in water dissolved and precipitated by adding aqueous ammonia. The resulting precipitate is filtered and recrystallized from hexane.

6.9 g of the compound of the formula are obtained Melting point: 159-1600 C Analysis: calculated: N 14.89 found: N 14.87 The nuclear magnetic resonance spectrum confirms the stated chemical structure of the use.

Preparation method 3 3 (P-methylsulfonylphendyl) 5-, 6-dihydroimidazolo- [2,1-b] -thiazole 5.4 g (0.02 mol) p-methylsulfonylphenacyl bromide and 2 g (0.02 mol) N, N'-ethylene thiourea are refluxed in 100 ml of ethanol for 4 hours.

The precipitate is filtered off and washed with ethanol. The compound obtained corresponds to the formula The signals of the nuclear magnetic resonance spectrum confirm this structure. The compound, dried under vacuum, is dissolved in concentrated sulfuric acid and left to stand for one hour at room temperature. The solution is then poured onto an ice-water mixture. Aqueous sodium hydroxide solution is added to the clear solution obtained. The resulting precipitate is filtered off and recrystallized from methanol. 4.1 g of the compound of the formula are obtained Melting point: 195-1960C.

The nuclear magnetic resonance spectrum confirms the specified chemical structure the connection.

With the help of the appropriate starting materials, in the other compounds of Tables 1 and 2 can also be prepared in an analogous manner. The necessary starting materials are generally known or can be prepared according to known ones Process can be easily established.

Table 1 RR R ' 101 o # EI HE 97-99 \. / 102 a 'CH3-H 93-95 \ / 3 103 ~ S Ca3-> 240 (8ydrobromide) 104 o '0 - CH - 87-88 1 3 3 105 cH30 # \ 00 / \\ 0 H / 3 HS 1) cH oo 106 cH3-0 / cs H 46-47 cH 107 C! J3 // oo / H g 1) CB3 108 3 2 \ / 0 BH 1> 0 a H 09 CB3 (CE2) 11-ss.,. / - 1) Table 1 (continued) r. RR 'R2 melting point OC 110 CBiO- \ 8 8 H 81-82 111 Br-- \\ 111 8- / HH 141-143 112 C1 - / <- a 1/1 1 104-106 113 C1 - / \\ H c13 109-110 CN 114 C1- / - ~ 8 E 141-143 \ / 115 C1- - H a3-113-114 \ / / - 116. ~ HH 173-178 117 2 NO2O / e H 8 216-218 118 cH3-CONH- '- RH> 240 119 C83-S02 - '\ / - g H 195-196 1 a 20 c13O \ / 0 / H 71-72 (acetate> 1) Compounds are viscous oils at room temperature. Table 2 N Formula focus point OC 201 1o1-N1-r1 0 142-143 201 11 I 11 w 202 C \ 5 / 150-151 No 0 -O 1 Y 210-212 (hydrochloride) 203 204 Y -! 159-160 6 V \ // 0 205! Y II! 1> 6th 0, / 206 L '. I - 212-214 I. left 0 07 -N- 1 II 1 II 0 0 0.-CH C83 \ \ / NY B7-89 208 CB ca, oI! 71-72 Table 2 (continued) r | Formula | sd1zptrnkt ec cH / 3 o9 99-100 OCH CH 23 0 10 B XSZ H 155-157 ocH '\ S / CH0V (acetate) 23 Example 1 A. A color gelatin solution of the following composition is poured onto a triacetate carrier of 13 x 18 cm, glued to a substated glass plate: 5.0 ml gelatin (6%, aqueous) 1.0 ml of a 5-10 molar aqueous solution of the dye of formula 1.7 ml of water 2.0 ml of 1,3-dichlorotriazine-5-aminobenzene-4'-sulfonic acid (1% in water) 0.25 ml of a silver bromide dispersion with a silver content of 5.5% silver.

2.0 ml of a bleach inhibitor emulsion as described below will be produced.

Bleach inhibitor emulsion: 20.2 mg of the compound of formula (101) 0.2 ml tricresyl phosphate 8.0 ml gelatin (6% aqueous) 1.0 ml diisobutylnaphthalene sulfonic acid Na salt as an 8% solution in water: ethanol (95: 5) 0.8 ml of water This The mixture was emulsified for 5 minutes with the aid of an ultrasound device.

B. On another carrier of the type specified under A is a Solution of the same composition, but not containing the compound of the formula (101) contains, cast The carrier material coated in this way serves as a blank sample.

Exposure and processing Two strips each (3x18cm) from A (A-1, A-2) and B (B-1, B-2) are under a Kodak step wedge No. 2 (21 steps) during a Second exposed at 500 lux / cm² and then at A-1, 1st development 8 minutes Bath 1 B-l 2. Bleach 4 "Bath 2 3. Fix 3" Bath 3 4. Wash 3 A-2, 1. Develop 8 Minutes Bath 1 B-2 2. Fixation 3 1 Bath 2 3. Soaking 3 The baths have the following Composition bath 1: developer ethylenediamine tetraacetic acid sodium salt 2g potassium hydroxide (85%, aqueous) 22 g potassium metabisulphite 15 g boric acid 13.35 g potassium bromide 1.65 g benzotriazole 0.25 g phenidone 2.5 g Hydroquinone 8.35 g of ascorbic acid 8.35 g water to 1000 ml bath 2: bleach bath metanitrobenzenesulfonic acid 12g sulfamic acid 280 g ethyl cellosolve 120 ml 2,3-dimethylquinoxaline 4 g potassium iodide 12 g water 1000 ml bath 3 fixing bath ethylenediamine tetraacetic acid Na salt 3 g ammonium thiosulphate (60%, aqueous) 333 g of ammonium bisulfite (60%, aqueous) 75 g of ammonia 21 ml of water to 1000 ml A clear, sharp magenta wedge is obtained with A-1 and B-1 and with A-2 and B-2 are partially obscured by the dye present in the casting Silver wedge.

The magenta density of wedges A-1 and B-1 is measured using a remission densitometer Gretag P 1 measured in the green spectral range.

The silver density is measured with the same instrument in the red spectral range certainly: DR-DR (stage 21) (R (stage 21,) = secondary color densities of the dye in red; Level 21 does not contain Silver0.

The values obtained are given in Table 3 and are shown in Fig. 1 shown graphically.

It turns out, for example, that for a silver density of 0.5 without the compound of the formula (101) a magenta density of 0.5 is obtained. In the presence of the connection of the formula (101), however, the density is at the same silver density of 0.5 0.8. It can be seen from this that the compound of the formula (101) drastically bleaches the color inhibits.

If the compound of the formula (114) is used, one obtains in one Silver density of 0.5 a magenta density of 1.25.

Similar good results are also obtained with the other compounds given in Tables 1 and 2. Table 3 Measurement 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 Zero wedge A-2: 3 3 3 3 3 4 4 6 7 10 17 33 63 106 139 163 174 180 180 180 180 100 DG sample wedge B-2: 86 86 86 86 86 84 82 80 77 72 64 56 46 35 24 13 6 3 1 0 0 (Dr-OR (21) 100 Wedge A-1: 11 11 11 12 12 14 17 20 25 40 71 108 138 162 175 178 180 180 180 180 180 bin- 100DG dung wedge B-1, 101 100 99 97 95 91 87 81 74 65 54 41 27 17 9 4 1 1 1 0 0 the For- 100DR mel (101) wedge A-1: 49 54 60 69 86 96 114 128 142 155 166 172 178 180 180 180 180 180 180 180 180 100DG am- manure the wedge B-1: Por- (DR-DR (21) 100 81 81 78 73 69 63 56 48 39 32 24 16 9 5 3 3 1 0 0 0 0 mel (144) DG = Gr @ ndfchte DR = Rotßichte Example 2 3 layers are poured onto a transparent polyester support. First a silver halide emulsion layer 2 (0.5 g silver / 2 g gelatine per m), over it an intermediate layer of gelatine (or gelatine and a bleach-inhibiting compound) and finally a dye layer (2 g gelatine / 0.186 g of the dye of the formula ( 301).

All layers are hardened. The composition of the intermediate layer is shown in Table 4. The bleach-inhibiting compound of formula (101) is shown in Tricresyl phosphate dissolved and in the presence of a wetting agent in the gelatin emulsion incorporated. The emulsion obtained is homogenized with the aid of an ultrasound device.

Strips of the three-layer material are behind a step wedge exposed and then processed as indicated in Example 1: A. Developing B. Developing Bleaching Fixing Fixing Soaking Soaking The samples according to treatment (B) result in black and white silver wedges and are used to control the development of silver. Samples which contain (or do not contain) the compounds of the formula (101) result identical silver wedges. The compound of the formula (101) thus interferes with the development of silver not.

In the case of the samples which are treated according to (A), the densities are measured in the green spectral range, specifically at level 1 (maximum silver development) and level 21 (no silver development). Table 4 contains the measured values. Table 4 samples intermediate layer of Maqenta density Gelatin Thick compound of formula Level 1 Level 21 Comments g / m in P (101) (maxisale (minimal (Amount in @ m / m Ag) Silberent- Silberent- winding winding) 1. 4 4 - 0.76 0.8 Blank sample: minimal Layer coupling 2.1.5 1.5 - 0.57 0.8 blank sample: shift coupling considerably 3.1.5 1.5 100 0.77 0.8 4.1.5 1.5 50 0.70 0.8 The data for the magenta density show that a thin intermediate layer containing the compound of the formula (101) (samples 3 and 4) can weaken the layer coupling (bleaching effect) in the same way as a 4 @ thick gelatin layer (sample 1).

Similar good results are obtained with the rest of the tables 1 and 2 specified compounds. Blank page

Claims (12)

Claims 1. Photographic material for the silver dye bleaching process which comprises at least one compound of the formula contains, in which A and B are each the radicals of the formulas are, where R1 ', R2, R3 and R4 are each hydrogen, optionally substituted alkyl, alkenyl, cycloalkyl, aryl or aralkyl, halogen, nitro, cyano, hydroxyl, mercapto, alkoxy, alkylmercapto, carboxyl, carboxylic acid ester, carbonamido or acyl or (R2 and R3) together with the carbon atoms to which they are attached form an optionally substituted carbo- or heterocyclic ring. 2. Photographic material according to claim 1, characterized in that it contains compounds of the formula contains, in which A1 and B1 each radicals of the formulas are, where R5 to R8 are each hydrogen, optionally with halogen, hydroxyl, amino, cyano, nitro, alkoxy, aryloxy, aralkoxy or cycloalkoxy, carboxyl, carboxylic acid ester, carbonamido, acyl, acylamino, sulfonic acid or sulfonamido, substituted alkyl with 1 to 20 carbon atoms or alkenyl of 2 to 20 carbon atoms; cycloalkyl optionally substituted with halogen, hydroxyl, amino, alkyl- or arylamino, alkyl, alkoxy, carboxyl or carbalkoxy; phenyl optionally substituted with halogen, hydroxyl, mercapto, amino, alkyl- or arylamino, cyano, nitro, carboxyl, carboxylic acid esters, carbonamides, acyl, acylamino, sulfonic acid, sulfonamides, sulfonic acid esters, alkyl, alkoxy, alkylmercapto or phenyl; Naphthyl; Benzyl; Halogen, hydroxyl, mercapto, alkoxy, alkylmercapto, carboxy, carboxylic acid ester, carbonamido or acyl or (R6 and R7) together with the carbon atoms to which they are attached form a cyclopentyl, cyclohexyl or optionally substituted phenyl ring, with substituted phenyl has the same meaning as Rg is given in the meaning substituted phenyl. 3. Photographic material according to claim 2, characterized in that it contains compounds of the formulas contains, in which R5 to R8 each hydrogen, optionally with chlorine, bromine, -OR9 '-COOR9 or R9CO-, in which R9 is hydrogen, alkyl with 1 to 20 carbon atoms or optionally substituted phenyl, benzyl or cycloalkyl with 5 or 6 carbon atoms, with -NECOR10 or -NHSO2R10 'where Rlo is alkyl having 1 to 5 carbon atoms or optionally substituted phenyl, with where R11 and R12 are hydrogen or alkyl with 1 to 5 carbon atoms or optionally substituted phenyl, or alkyl with 1 to 20 carbon atoms substituted with -SO3H or alkenyl with 2 to 20 carbon atoms, R5 to R8 furthermore each optionally with chlorine, bromine, hydroxyl , -NR11, R12, in which R11 and R12 have the meanings given, -COOR9, in which R9 has the meanings given, alkyl or alkoxy having 1 to 5 carbon atoms, substituted cycloalkyl having 5 or 6 carbon atoms, optionally with halogen, hydroxyl, mercapto, cyano , Nitro, COOR9 '-SO3H, -COR9'-SO2R13' -N (R11) COR'13, in which Rg, R11 and R12 have the meanings given, R13 is alkyl with 1 to 20 carbon atoms, phenyl, benzyl, cycloalkyl with 5 or 6 carbon atoms and R'13 has the meaning of R13 and also pyridyl , Thienyl or furyl or phenyl substituted with alkyl, alkoxy or alkyl mercapto each with 1 to 20 carbon atoms or phenyl, R5 to R8 furthermore each naphthyl, benzyl, chlorine, bromine, hydroxyl, mercapto, alkoxy or alkyl mercapto each with 1 to 20 carbon atoms, -COOR9 '-COR9 or -CON R11 R12, in which R9' R11 and R12 have the meanings given, or (R6 and R7) together with the carbon atoms to which they are bonded form a cyclopentyl, cyclohexyl or optionally substituted phenyl ring form, where substituted phenyl has the same meaning as given for R5 to R8 in the meaning substituted phenyl. 4. Photographic material according to claim 3, characterized in that it contains compounds of the formulas or contains, in which R5 to R8 have the meanings given in claim 3. 5. Photographic material according to claim 3, characterized in that it contains compounds of the formula contains, in which R14 and R15 are each hydrogen, optionally with chlorine, -OR16 '-COR16 or -COOR16, in which R16 is hydrogen, alkyl having 1 to 12 carbon atoms or phenyl, substituted alkyl having 1 to 20 carbon atoms; -CF3, cyclopentyl, cyclohexyl; optionally with chlorine, bromine, -OR16 '-COOR16' -SO2R161 in which R16 has the meaning given, cyano, nitro, where R11 is hydrogen or alkyl with 1 to 5 carbon atoms and R12 is hydrogen, alkyl with 1 to 5 carbon atoms or optionally substituted phenyl, -N (R11) COR17 'where R17 is alkyl with 1 to 12 carbon atoms or phenyl, or with alkyl with 1 up to 12 carbon atoms are substituted phenyl, R14 and R15 are also chlorine, bromine, -OR16, -COOR16 -COR16 are, in which R11 'R12 and R16 have the meanings given, or R14 and R15 together with the carbon atoms to which they are bonded form a cyclopentyl, cyclohexyl, or optionally substituted phenyl ring, substituted phenyl having the same meaning as it is given for R14 and R15 in the meaning substituted phenyl, and R5 and R7 have the meanings given in claim 3. 6. Photographic material according to claim 5, characterized in that it contains compounds of the formula contains, in which R14 and R15 have the meanings given in claim 5. 7. Photographic material according to claim 6, characterized in that it contains compounds of the formula contains, in which R18 and R19 are each hydrogen, alkyl with 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, optionally with with chlorine, bromine, -OR16 '-SR16' -COR16 '-COOR16' -SO2R16 'in which R16 is hydrogen, alkyl with 1 to 12 carbon atoms or phenyl, cyano, nitro, where R11 is hydrogen or alkyl having 1 to 5 carbon atoms and R12 is hydrogen, alkyl having 1 to 5 carbon atoms or optionally substituted phenyl, N (R11) COR17 'where R17 is alkyl having 1 to 12 carbon atoms or phenyl, or with alkyl having 1 up to 12 carbon atoms are substituted phenyl, R18 and R19 are also hydroxyl, -COOR16, -COR16 or are, in which R11 'R12 and R16 have the meanings given, or (R18 and Rlg) together with the carbon atoms to which they are attached form a cyclopentyl, cyclohexyl or optionally substituted phenyl ring, substituted phenyl having the same meaning as it is given for R18 and R19 in the meaning substituted phenyl, and R14 and R15 have the meanings given in claim 6. 8. Photographic material according to claim 7, characterized in that it contains compounds of the formula contains, in which R18 and R19 have the meanings given in claim 7. 9. A method for producing a photographic material according to one of claims 1 to 8, characterized in that at least one Layer of this material at least one thiazole compound of the claims 1 to 8 specified composition incorporated. 10. Use of the thiazole compounds in claims 1 to 8 specified composition for preventing undesired dye bleaching in photographic materials for the silver dye bleaching process. 11. Compounds of the formula wherein A and B have the meanings given in claim 1. 12. Process for the preparation of the compounds according to claim 1, characterized characterized in that one has 2-amino-thiazolines (2-imino-thiazolidines) or 2-thiono-imidazolidines (2-mercapto-imidazolines) with aliphatic aromatic or aliphatic-aromatic converts α-haloketones or halohydrins in polar non-aqueous solvents.