DE2844606A1 - Heterocyclic dyestuffs for natural and synthetic fibre materials - give clear yellow to violet shades with good fastness - Google Patents

Abstract

Heterocyclic cpds. of formula (I) are new: where R1 and R2 are independently H, alkyl, aralkyl 1 or 2-3C alkylene linked to the adjacent o-position of ring A, and R1 may also be cycloalkyl or aryl, or R1 and R2 together are 4-6C alkylene opt. interrupted by NH, O or S; R3 and R4 are independently H, Hal, alkyl, aryl, alkoxy, -CN, carboxyl, alkoxycarbonyl, alkylsulphonyl or arylsulphonyl, and R3 may also be aralkyl, and R4 may also be -OH, -NO2, -CHO, -CONH2, ureido, amidino, amidinium, sulpho or a heterocyclic ring linked to a ring N atom; Z is O, S or -N(R)- where R is H, alkyl, alkenyl, aralkyl, aryl or acyl; p and q are each 0 or 1 but not both 1; and G completes a carbocyclic or heterocyclic ring; the radicals opt. with nonionic, carboxyl or sulpho substits. and opt. quaternised; and if G completes a thiazole ring, R3 is H, Hal, aryl, alkoxy, -CN, carboxyl, alkoxycarbonyl, alkylsulphonyl or arylsulphonyl. The cpds. may also be used as laser dyestuffs. Some may be used in transfer printing.

Description

Heterocyclic dyes

The invention relates to dyes of the general formula wherein R1 is hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl, aryl or a 2- or 3-membered alkylene radical linked to the adjacent ortho position of the ring A, R2 is hydrogen, alkyl, alkenyl, aralkyl or one with the adjacent ortho position Position of the ring A linked 2- or 3-membered alkylene radical, R1 and R2 also together for an alkylene radical optionally interrupted by NH, O or S with a total of 4 to 6 members, R3 for hydrogen, alkyl, aralkyl, aryl, alkoxy, halogen, Cyano, carboxy, alkoxycarbonyl, alkylsulfonyl or arylsulfonyl, R4 for hydrogen, alkyl, aryl, halogen, hydroxy, alkoxy, nitro, cyano, carboxy, alkoxycarbonyl, formyl, carbamoyl, ureido, amidino, amidinium, alkylsulfonyl, arylsulfonyl, sulfo or with a heterocyclic ring system linking a ring N atom, Z for oxygen, sulfur or -N (R) -, R for hydrogen, alkyl, alkenyl, aralkyl, aryl or acyl, p and q for the numbers 0 or 1, but not simultaneously for 0 and G for r are the remaining members of a carbo- or heterocyclic ring system, and in which the cyclic and acyclic radicals can carry nonionic substituents and carboxyl and sulfo groups customary in dye chemistry and can optionally be quaternized, with the proviso that R3 is hydrogen, aryl, alkoxy , Halogen, cyano, carboxy, alkoxycarbonyl, alkylsulfonyl or arylsulfonyl, when G stands for the remaining members of a ring of the thiazole series.

Suitable dye substituents are e.g. C1-C4-alkyl, OH, C1-C4-alkoxy, Halogen, CN or NO2.

Alkyl radicals R1, R2 and R are preferably C1-C4-alkyl radicals to understand that by chlorine, bromine, acetyl, Cyano, carboxy, C1-C4-alkoxycarbonyl, Carbamoyl optionally substituted by 1-2 C1-C4-alkyl radicals, Cl C4 -alkoxy, Acetoxy, phenoxy, sulfophenoxy, 1-2 hydroxy or sulfo can be substituted. In contrast, alkyl radicals R3 and R4 and those in carbamoyl radicals R4 are preferably unsubstituted C1-C4-alkyl radicals.

R3 can also mean CF @.

Preferred aralkyl radicals R1, R2 and R are phenyl-C1-C3-alkyl groups, which can be ring-substituted, for example, by 1-2 sulfo groups.

Suitable aryl radicals R1, R3, R4 and R are preferably phenyl radicals, which can carry 1 to 3 further substituents such as C1-C4-alkyl, C1-C2-alkoxy, halogen such as chlorine and bromine, nitro, cyano, carboxy, C1 -C4-alkoxycarbonyl or sulfo groups.

Alkenyl groups R1, R2 and R preferably have 2-4 carbon atoms; particularly the allyl radical is preferred.

Cycloalkyl stands for cyclopentyl or cyclohexyl, denoted by 1-3 Methyl groups can be substituted.

When R¹ and R² together form an alkylene radical, e.g.

- (CH2) 4-, - (CH2) 5, - (CH2) 6-, -CH2) 2O (CH2) 2-, - (CH2) 2-NH- (CH2) 2- or - (CH2) 2-S- (CH2) 2- into consideration.

A 2- or 3-membered alkylene radical R¹ or R2 is preferably an optionally through 1-3 methyl groups and / or a phenyl ring substituted ethylene or n-propylene radical.

Acyl radicals R are, for example, C1-C3-alkylcarbonyl or C1-C3-alkylsulfonyl radicals and C1 -C4 alkoxycarbonyl groups.

Alkoxy groups R3 and R4 and those in alkoxycarbonyl groups R3 and R4 preferably have 1 to 4 carbon atoms. Suitable halogen radicals R3 and R4 are chlorine, Bromine, fluorine and iodine, especially chlorine and bromine.

Alkyl radicals in alkylsufonyl radicals R3 and R4 preferably have 1 - 4 carbon atoms and can be substituted, for example, by chlorine or phenyl.

Suitable aryl radicals in arylsulfonyl groups R3 and R4 are preferred Phenyl radicals which are substituted, for example, 1-3 times by chlorine or C1-C4-alkyl could be.

4 carbamoyl, ureido and amidine (ium) radicals R4 can be used once or twice be substituted, preferably by C1-C4-alkyl, phenyl-C1-C3-alkyl or phenyl, where two alkyl radicals together with the common N atom form a pyrrolidine, Piperidine, morpholine or piperazine ring can form.

As heterocyclic ring systems R4, which are linked to a ring N atom, 5-rings are to be mentioned in particular, such as pyrazolyl- (1), 4-chloropyrazole- (1), 1 , 2,3-triazolyl- (1) 1, 2,3-triazolyl- (2), l, 2,4-triazolyl- (1), tetrazolyl- (1) and Benzo-s-triazolyl- (2), the triazoles also being quaternized by C1-C4-alkyl or benzyl May contain N atoms.

Carbo- and heterocyclic ring systems, the remaining members with G are known to be mono- or polycyclic. They preferably exist from one of the specified 5- or 6-membered CO group (s) containing carbo- or heterocyclic ring, the 1-2 further carbo- or heterocyclic 5- or 6 rings can be fused. Examples of such ring systems are those of cyclohexane-1,3-dione, cyclohexene-1,3-dione, pyrazolone (5) - (including of the quaternary salts with an antipyrin-like structure} barbituric acid, thiobarbituric acid, 2,6-dioxo-2H.6H-pyridine, 2.4.6-Trioxo-2H.4H.6H-pyridine-, 2.4.6-Trioxo-2H.4H.6H-thiazine- (1,3) -, 2.4.6-Trioxo-2H.4H.6H-oxazine- (1,3) -, 2-Aryl-4,6-dioxo-4H.6H-thiazine- (1,3) -, 2-Aryl-4.6-dioxo-4H.6H-oxazine- (1.3), 2-Aryl-4.6-dioxo-4H.6H-pyrimidine-, 2.4-dioxo-2H.4H-pyrido [1.2-a] pyrimidine- ( ium) -, 2.4-Dioxo-2H.4H-pyrimido [1.2-a] pyrimidine-, 4-hydroxy-coumarin-, 4-hydroxy-quinolone- (2) -, 1,3-Diaryl-4,6-dioxo-4H.6H-pyridazine-, 2.4-Dioxo-2H.4H-pyran-, BenzoZb7-furanone- (2), benzo / b7furanone- (3) -, benzofbithienone- (2) -, benzo [b] thienone- (3) -, 3-aryl-isoxazolone- (5) -, Indolone (2), indolone (3) and thiazolone (5) series called. Further suitable carbonyl-containing Ring systems are listed in the list of exemplary starting components.

Preferred substituents in ring A are C1-C3-alkyl, chlorine and C1-C3-alkoxy radicals.

Preferred compounds of formula I are those in which R³ is for Hydrogen, alkyl or aryl (especially for hydrogen), R4 for hydrogen, Z for oxygen and G for the remaining members of a radical of the indanedione (1,3) -, Pyrazolone (5), barbituric acid, Thiobarbituric acid, 2,6-dioxo-2H-6H-pyridine, 4-hydroxycoumarin or dehydracetic acid series.

In the context of the invention, a preferred group of compounds corresponds to the formula in which R1 -R4, A and Z have the meaning given above, R5 represents hydrogen, alkyl, aralkyl, aryl, chlorine, bromine, carboxy, alkoxycarbonyl, carbamoyl, cyano, hydroxy, alkoxy, acyloxy or a radical of the formula -N (R8R9 ), R6 for alkyl, alkenyl or aralkyl, n for 0 or 1, R7 for alkyl, aralkyl, aryl or a heterocyclic radical, R8 for hydrogen, alkyl, aralkyl, cycloalkyl, aryl or a heterocyclic radical, R9 for an acyl radical, R8 and R9 also together with the common N atom for a residue L stands for 1.2-phenylene, 1.2- or 1.8-naphthylene, 1 .2-cyclohexen- (1) -ylene, 1.2-ethenylene or 1.2-ethylene, An stands for an anion, and in which the cyclic and acyclic radicals are customary in dye chemistry Can carry substituents.

Alkyl radicals R5 preferably have 1-6 carbon atoms and can, for example be substituted by halogen such as fluorine, chlorine and bromine. Are particularly preferred Methyl and trifluoromethyl.

Suitable aralkyl radicals R5, R7 and R8 are benzyl and sulfobenzyl. As aryl radicals R5, in particular phenyl groups are to be mentioned, for example by 1-3 C1-C4-alkyl, C1-C4-alkoxy, 1-2 chlorine, bromine, nitro, sulfo or acylamino substituted could be.

Alkoxycarbonyl radicals R5 preferably contain 1-4 carbon atoms in the alkyl radical. Alkoxy radicals R5 are preferably C1-C4 alkoxy groups.

Suitable acyloxy radicals R5 are C1-C4-alkylcarbonyloxy, C1-C2-alkoxycarbonyloxy, Phenoxycarbonyloxy, benzoyloxy, methylbenzoyloxy, chlorobenzoyloxy, methoxybenzoyloxy, Phenylsulfonyloxy and toluenesulfonyloxy.

Alkyl radicals R6 preferably have 1-4 carbon atoms and can, for example be substituted by 1-2 hydroxyl groups or C1-C4-alkoxy groups.

A preferred alkenyl radical R6 is the allyl group, a preferred one Aralkyl radical R6 is the benzyl group.

Alkyl radicals R7 are C1-C4-alkyl groups, which are, for example, replaced by acetoxy, Cyan, carbamoyl, carboxy, C1-C2-alkoxycarbonyl or sulfo can be substituted.

Suitable aryl radicals R7 are, in addition to naphthyl groups, in particular phenyl groups, for example by 1-3 chlorine, bromine, 1-2 methyl, C2-C4-alkyl, C1-C2-alkoxy, Acylamino, nitro, cyano, carboxy, C1-C2-alkoxycarbonyl, carbamoyl, C1-C4-alkylsulfonyl, ß-sulfatoethylsulfonyl, ß-acetoxyethylsulfonyl, optionally by 1-2 C1 -C4-alkyl substituted sulfamoyl, pyrrolidinosulfonyl, piperidinosulfonyl, morpholinosulfonyl, Phenoxysulfonyl, sulfo and / or 6-methylbenzthiazolyl- (2) can be substituted.

Examples of heterocyclic radicals R7 are sulfolanyl- (3) and pyrimidin-2-yl. Alkyl radicals R8 preferably have 1-6 carbon atoms and can, for example, through C1-C4-alkoxy, chlorine, cyano, acetoxy, di- (C1-C2-alkyl) amino, tri- (C1-C2-alkyl) -ammonium, Carboxy, C1-C2-alkoxycarbonyl, carbamoyl, sulfo, acylamino or N- (C1-C2-alkyl) -acylamino be substituted.

As cycloalkyl radicals R, cyclohexyl radicals are mentioned, which are separated by 1-3 Methyl groups can be substituted.

Suitable aryl radicals R8 are, in addition to naphthyl groups, in particular phenyl groups, for example by 1-3 methyl, C2-C4-alkyl, cyclohexyl, benzyl, 1-3 chlorine, Bromine, 1-2 CF3, nitro, cyano, carboxy, C1-C2-alkoxycarbonyl, C1-C4-alkylsulfonyl, sulfamoyl, pyrrolidinosulfonyl optionally substituted by 1-2 C1-C4-alkyl, Piperidinosulfonyl, morpholinosulfonyl, phenoxysulfonyl, acylamino, N-C1-C2-alkyl-acylamino, N-phenyl-acylamino, 1-2 C1 -C4-alkoxy, phenoxy, methylenedioxy, -O-CH2-O-CH2- (= fused 1,3-dioxin ring) and / or sulfo can be substituted.

Examples of heterocyclic radicals R8 are pyridyl, thienyl and sulfolanyl- (3).

The acyl radicals R9 and those in acylamino groups may optionally be used C1-C4-alkylcarbonyl, C1-C2-alkoxycarbonyl substituted by 1-3 chlorine, optionally substituted by C1-C4-alkyl, cyclohexyl, phenyl, toluyl, chlorophenyl or sulfophenyl Aminocarbonyl, di-C1-C2-alkylaminosulfonyl, phenylacetyl, optionally by methyl, Methoxy or chlorine substituted benzoyl or phenylsulfonyl radicals, if appropriate C1-C4-alkylsulfonyl substituted by chlorine, formyl or - especially when present of more than one sulfo group in the molecule - also reactive radicals with acyl group character such as dichlorotriazinyl, difluorotriazinyl, 5-chloro-2,4-difluoropyrimidin-6-yl and 2,3-dichloroquinoxalin-6-yl-carbonyl into consideration.

Suitable substituents on the divalent radicals L are halogen atoms like chlorine and bromine. For example, 1,2-phenylene radicals can have 1-4 chlorine or bromine atoms carry or 1,2-athenylene groups can be substituted by 1-2 chlorine or bromine atoms.

The ane used in dye chemistry are inorganic or organic Anions such as chloride, nitrate, sulfate, hydrogen sulfate, phosphate, perchlorate, tetrafluoroborate, Chlorozincate or acetate, C1-C2-alkyl sulfate, C1-C4-alkyl phosphonate, toluenesulfonate, Lactate or amidosulfonate into consideration.

In the context of the invention, a particularly preferred group of compounds corresponds to the formula where z1 for methyl, methyl, chloroethyl, n-propyl, n-butyl, phenyl-C1-C3-alkyl, sulfophenyl-C1-C3-alkyl, cyclohexyl, phenyl, toluyl, sulfophenyl or sulfotoluyl, z2 for hydrogen, methyl, xthyl , Chloroethyl, n-propyl, n-butyl, phenyl-C1-C3-alkyl, sulfophenyl-C1-C3-alkyl, z1 and z2 also together for one of the radicals - (CH2) 4-, - (CH2) 5- or - (CH2) 2-O- (CH2) 2-Z3 for hydrogen or methyl, Z4 for hydrogen or methyl, h1 and Z3 also together for a C2-C3-alkylene radical optionally substituted by 1-3 methyl groups, z2 and Z4 also together for an n-propylene radical, Z5 for hydrogen, methyl, o-carboxyphenyl, o-C1-C4-alkoxycarbonylphenyl, phenyl or sulfophenyl, z6 for hydrogen, methyl or chlorine, Z for hydrogen, methyl, trifluoromethyl, phenyl or sulfophenyl, z8 for Methyl, xthyl, n-propyl, n-butyl, ß-hydroxyethyl, ß-hydroxy-n-propyl, allyl or benzyl, Z9 for methyl, ethyl, isopropyl, ß-acetoxyethyl, ß-cyanoethyl, benzyl, phenyl, chlorophenyl, bromophenyl , Dichlorpheny l, trichlorophenyl, Chlortoluyl, sulfophenyl, Sulfochlorphenyl, nitrophenyl, methylsulfonylphenyl, Xthylsulfonylphenyl, p-Acetoxyäthylsulfonylphenyl, B-Sulfatoäthylsulfonylphenyl, Propylsulfonylphenyl, Butylsulfonylphenyl, carboxyphenyl, methoxycarbonylphenyl, Xthoxycarbonylphenyl, sulfamoylphenyl, N, N-dimethylsulfamoylphenyl, N, N-Diäthylsulfamoylphenyl, Phenyloxysulfonylphenyl or 3-Sulfolanyl, n for the number 0 or 1 and An for an anion.

Compounds of the formula are of particular technical value where Q1 for methyl, methyl, n-propyl, n-butyl, benzyl, sulfobenzyl, B-phenylethyl or sulfo-ß-phenylethyl, 2 for a meaning of Q, Q³ for methyl, Q4 for methyl, ethyl, n-propyl, n -Butyl, ß-hydroxyethyl, ß-hydroxy-n-propyl, allyl or benzyl, 5 Q for methyl, ethyl, phenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, sulfophenyl, sulfochlorophenyl or nitrophenyl, n for the number 0 or 1 and Stand at # for an anion.

In the case of n = 1, Q¹ and Q² are preferably methyl, ethyl, benzyl or sulfobenzyl, for methyl Q4 for methyl, ethyl, B-hydroxyethyl or ß-hydroxyn-propyl and Q5 represents methyl, ethyl, phenyl or sulfophenyl.

The dyes of the formula I can be prepared by various processes. One of the processes by which dyes of the type of zero methine dyes described in Research Disclosure 1717, Referat 16 325 can also be advantageously prepared, is characterized in that compounds of the formula wherein R¹, R², A and Z have the meaning given above, R³ represents hydrogen, alkyl, aralkyl, aryl, alkoxy, halogen, cyano, carboxy, alkoxycarbonyl, alkylsulfonyl or arylsulfonyl, # X for = 0, = N-C6H5 or = N (CH3) 2 An # and An stand for an anion, with compounds of the formula wherein R4, p and q have the meaning given above, for the remaining members of a carbo- or heterocyclic ring system, D for -O-W1, -S-W¹, -N (W2W3) or halogen W1 for hydrogen or C1-C3- Alkyl and W2 and W3 stand for C1-C4-alkyl or together stand for - (CH2) 4-, - (CH2) 5- or = (CH2) 2-O- (CH2) 2, condensed with elimination of water and DH.

Compared to those known from Research Disclosure 1977, Referat 16 325 Process for the preparation of Benzopyranylidenrhodanin dyes stands out this process through better accessibility, stability and manageability the starting components and a higher yield of the process products.

Halogen radicals D are understood to mean, in particular, chlorine, bromine and iodine. D preferably stands for —OH.

The condensation is expediently in an inert solvent Temperature range of 60-180 ° C, preferably 80-15O0C.

In addition to inorganic solvents such as sulfur, Phosphoric or polyphosphoric acid, especially organic solvents, are considered, which the starting components V and Vi are able to solve sufficiently. Using of non-polar, water-immiscible solvents such as toluene, chlorotoluene, Dichlorotoluene, xylene, chlorobenzene or dichlorobenzene is recommended to use the condensation water during the reaction continuously by azeotropic distillation, for example by Boil on the water separator to remove.

However, polar organic solvents such as glacial acetic acid are also suitable, Isopropanol, n-butanol, ethylene glycol monomethyl ether or ethyl ether or dimethylformamide.

In the preferred case D = OH, the condensation is expediently carried out in Presence of a basic condensing agent, usually catalytic Amounts are sufficient. Suitable basic condensing agents are in addition to alkali metal alcoholates and alkali acetates, in particular cyclic secondary amines such as piperidine, pyrrolidine or morpholine. Piperidine is particularly suitable.

Most of the compounds of the formula V are known or can be obtained by known methods, in particular by reacting a compound of the formula in which R¹, R² and Z have the meaning given above, with known reagents which introduce the R³ (C = X) group, such as, for example, with the Vilsmeier reagent for introducing an aldehyde group (R³ = H), which can be obtained from dimethylformamide and POC13 or phosgene, as described, for example, in DT-OS 2,363,459, or with phthalic anhydride to introduce the o-carboxybenzoyl radical.

Suitable compounds of the formula V are, for example, 4-dimethylamino-salicylaldehyde, 4-diethylamino-salicylaldehyde, 4-di-n-butylamino-salicylaldehyde, 4-dibenzylamino-salicylaldehyde, 4-di-ß-phenylethylamino-salicylaldehyde, 4-piperidino-salicylaldehyde, 4-di-ß-cyanoethylamino-salicylaldehyde, 4-N-Benzyl-N-methylamino-salicylaldehyde, di-ß-chloroethylamino-salicylaldehyde, N-methyl-N-sulfobenzyl -amino-salicylaldehyde, di-ß-hydroxyethylamino-salicylaldehyde, 7-hydroxy-1.2.2.4-tetramethyl-1.2.3.4-tetrahydroquinoline-6-carbaldehyde, 5-hydroxy-1 .8 -tr imethylene 1.2.3.4. -tetrahydrochinoHn -carbaldehyde, 3-methyl-4-ethylamino-salicylaldehyde, 3,5-dimethyl-4-aminosalicylaldehyde, 4-acetamino-salicyladehydanil, 4-benzenesulfonylamino-salicylaldehyde, 2-amino-4-dimethylamino-benzaldehyde, 4-diethylamino-2-mercapto-benzaldehyde (precursor VII according to J. Org. Chem. 31 (1966) 3980) 4-Diethylamino-2-hydroxy-2'-carboxy-benzophenone, 4-dimethylamino-2-hydroxy-2 -carboxy-benzophenone, 4-diethylamino-2-hydroxy-acetophenone, 4-diethylamino-2-hydroxy-benzophenone.

Compounds of the formula VIt, in particular those with D = OH, are also largely known or can be obtained by known methods, for example by reaction of a methylene-active compound of the formula in which p, q and G have the abovementioned meaning with an acylating agent of the formula R4-CH2-COCl or R4-CH2-CO-O-CO-CH2-R4 (in which R4 has the abovementioned meaning).

The C-Acylation of Pyrazolone (5) Compounds with Acid Chlorides or anhydrides in the presence of calcium hydroxide is in Acta Chemica Scandinavia 13 (1959) 1668-70, of barbituric acid derivatives in Chemischeberichte 54 (1921) 1048 ff. and of 4-hydroxycoumarin with carboxylic acids and POC13 in archive der Pharmazie 268 (1955) 356-361.

2-Acetyl-indandione- (1.3) is according to Ind. Eng. Chem. 34 (1942) 494-7 by condensation of dimethyl phthalate with acetone in the presence of sodium ethylate shown. In J. Chem. Soc. (London) 1948.51 sodium amide is used for the same reaction Recommended as a condensing agent. Using the same method, 2-acetylperinaphthindanedione (1.3) and 2-acetyl-periacenaphthindanedione- (1.3) can be obtained. Instead of acetone you can according to Ind. Eng. Chem. 34 (1942) 494 also used other methyl alkyl ketones with equal success to 2-acyl-indanedione- (1.3) are condensed.

The C-acyl compounds of the formula VI with D = OH can exist in several different tautomeric structures: For 1-phenyl-3-methyl-4-acetyl-pyrazolones (5), Acta Chemica Scandinavia 13 (1959) 1668-70 describes the colorless keto form IX b obtainable from polar solvents in addition to the yellowish enol form a or c which can be isolated from non-polar solvents . All tautomeric forms are equally suitable for the condensation according to the invention with V.

Functional derivatives of IXa-c as contained in Formula VI (D = OH), such as enol ethers, entiols, enol thio ethers, enamines and enhalides are after known methods from IX a-c. Preferred functional derivatives are Enamines in which D is N-morpholino, N-piperidino or N-pyrrolidino. Man receives this conveniently from IX a-c and morpholine, piperidine and pyrrolidine in with water immiscible solvents such as toluene, xylene, chlorobenzene or chloroform Cooking on the water separator.

Suitable compounds of the formula VI are, for example: 1-phenyl-3-methyl-4-acet4yl-pyrazolone- (5), 1,3-dimethyl-4-acetyl-pyrazolone- (5), 1-methyl-3-phenyl-4-acetyl-pyrazolone- (5), 1-p-chlorophenyl-3-methyl-4-propionyl-pyrazolone- (5), 1-p-toluyl-3-methyl-4-chloroacetyl-pyrazolone- (5), 1-m-chlorophenyl-3-methyl-4-nitroacetyl-pyrazolone- (5), 1- (2 ', 5'-dichlorophenyl) -3-p-methoxyphenyl-4-acetyl-pyrazolone- (5), 1- (2'.4'.6'-Trichlorophenyl) -3-N-acetyl-N-anilino-4-acetylpyrazolone- (5), 1-p-carboxyphenyl-3-methyl-4-acetyl-pyrazolone- ( 5), 1-p-methoxycarbonylphenyl-3-methyl-4-acetyl-pyrazolone- (5), 1 -p-ethoxycarbonylphenyl-3-methyl-4-acetyl-pyrazolone- (5), 1-p-methylsulfonylphenyl-3-methyl-4-acetyl-pyrazolone- (5), 1-p-n-butylsulfonylphenyl-3-methyl-4-acetyl-pyrazolone- (5), 1-p-nitrophenyl-3-methyl-4-acetyl-pyrazolone- (5), 1-p-sulfamoylphenyl-3-methyl-4-acetyl-pyrazolone- (5), 1- (2'.6'-dichloro-4'-dimethylaminosulfonylphenyl) -3-methyl-4-acetyl-pyrazolone- (5), 1-p-Cyanophenyl-3-methyl-4-acetyl-pyrazolone- (5), 1-p-Carbamoylphenyl-3-N-acetyl-N-p-toluidino-4-acetyl-pyrazolone- (5), 1-p-piperidinosulEonylphenyl-3-1rethyl4-acetylwyrazolone- (5), 1-p-morpholinosulfonylphenyl-3-methyl-4-acetyl-pyrazolone- (5), 1-phenyl-3-carboxy-4-acetyl-pyrazolone- (5), 1-isopropyl-3-methoxycarbonyl-4-acetyl-pyrazolone- (5), 1-benzyl-3-ethoxycarbonyl-4-acetyl-pyrazolone- (5), 1-phenyl-3-cyano-4-acetyl-pyrazolone- (5), 1-phenyl-3-carbamoyl-4-acetyl-pyrazolone- (5), 1-p-Chlorophenyl-3-methoxy-4-acetyl-pyrazolone- (5), I-p-Bromophenyl-3-chloro-4-acetyl-pyrazolo 1-ß-acetoxyethyl-3-p-chlorophenyl-4-acetyl-pyrazolone- (5), 1- (2'.4'-dichloro-6'-methoxyphenyl) -3-methyl-4-acetylpyrazolone- (5) , 1-phenyl-3-trifluoromethyl-4-acetyl-pyrazolone- (5), 1-phenyl-3-N-acetyl-N-poanisidino-4-acetyl-pyrazolone- (5), 1-phenyl-3-N-acetyl-N-p-chloroanilino-4-acetyl-pyrazolone- (5), 1-phenyl-3-N-acetyl-N-p-trlfluoromethylanilino-4-acetylpyrazolone- (5), 1-phenyl-3-N-acetyl-N (3'.4'-dichloro-anilino) -4-acetyl-pyrazolone- (5), 1-phenyl-3-N-acetyl-N (3'.4 ' -methylenedioxyanilino) -4-acetylpyrazolone- (5), 1-phenyl-3-N-acetyl-N (1'.3'-benzodioxin-6-ylamino) -4-acetylpyrazolone- (5), 1- (3'-sulfolanyl) -3-N-acetyl-N- (3'-chloro-4'-methyl-anilino) -4-acetyl-pyrazolone- (5), 1-phenyl-3-N-acetyl-Np-acetanilino-4-acetyl-pyrazolone- (5), 1-methyl-3-N-acetyl-Np-phenetidino-4-acetyl-pyrazolone- (5 ), 1-phenyl-3-N-acetyl-N-p-nitranilino-4-acetyl-pyrazolone- (5), 1-phenyl-3-N-acetyl-N-p-methylsulfonyl-4-acetyl-pyrazolone- (5), 1-phenyl-3-acetylamino-4-acetyl-pyrazolone- (5), 1-phenyl-3-N-ethoxyzarbonyl-N-anilino-4-acetyl-pyrazolone- (5), 1-phenyl-3-p-toluyl-4-acetyl-pyrazolone- (5), 1-phenyl-3- (2'.4'-xylyl) -4-acetyl-pyrazolone- (5), 1- (3'-sulfolanyl) -3-methyl-4-acetyl-pyrazolone- ( 5), 1-p-Z6'-methylbenzthiazolyl- (2'L7-phenyl-3-methyl-4-acetyl-pyrazolone- (5), 1.2.3-trimethyl-4-acetyl-5-oxo-pyrazolium methosulfate, 1-phenyl-2,3-dimethyl-4-acetyl-5-oxo-pyrazolium methosulfate, also: 1,3-dimethyl-5-acetyl-barbituric acid, 1.3-dibutyl-5-acetyl-barbituric acid, 1.3-dibenzyl-5-acetyl-barbituric acid, 1.3-diphenyl-5-acetyl-barbituric acid, 1.3-diallyl-5-acetyl-barbituric acid, 1.3-dibutyl-5-acetyl-thiobarbituric acid, 1-butyl-3-methyl-5-acetyl-barbituric acid, 1-phenyl-3-butyl-5-acetyl-barbituric acid, 1-phenyl-5-acetyl-barbituric acid, 1-cyclohexyl-5-acetyl-barbituric acid, 1-benzyl-5-propionyl-barbituric acid, 1-benzyl-5-chloroacetyl-barbituric acid, 5-acetylbarbituric acid, 1-methyl-2.6-dioxo-3-methylaminocarbonyl-4-hydroxy-5-acetyl-2H.6H-pyridine, 1-ethyl-2.6-dioxo-3-cyano-4-hydroxy-5-acetyl-2H.6H- pyridine, 1-ß-methoxyethyl-2,6-dioxo-3-ethoxycarbonyl-4-hydroxy-5-acetyl-2H.6H-pyridine, 1-methyl-2-phenyl-4,6-dioxo-5-acetyl-4H.6H-pyrimidine, Dehydracetic acid, 3-acetyl-4-hydroxy-coumarin, 3-phenylacetyl-4-hydroxy-coumarin, 1-methyl-3-acetyl-4-hydroxy-quinolone (2), 1,3-diphenyl-4,6-dioxo-5-acetyl-tetrahydropyridazine, 2-acetylindandione- (1 .3), 2-acetyl-4-nitro-indandione- (1.3), 2-acetyl-4.5.6.7-tetrachloro-indandione- (1.3), 2-propionyl-4-acetamino-indandione- (1.3), 2-acetyl-perinaphthindanedione- (1.3), 2-acetyl-periacenaphthindanedione- (1.3), 2-acetyl-3-hydroxy-benzo [b] furan, 2-acetyl-2-hydroxy-benzo [b] furan, 2-acetyl-3-hydroxy-benzotb7thiophene, 3-acetyl-2-hydroxy-benzo [b] thiophene, 1-ethyl-2-acetyl-3-hydroxy-indole, 3-phenyl-4-acetyl-isoxazolone- (5), 2-phenyl-4-acetyl-oxazolone- (5), 3-ethyl-4-oxo-5-acetyl-thiazolin-thion- (2-phenyl-5-acetyl-thiazolin-4-one, 2-benzylmercapto-4-acetyl-thiazolin-5-one, 2-p-Toluyl-4,6-dioxo-5-acetyl-4H.6H-thiazine- (1.3), 2,4-dioxo-3-acetyl-2H.4H-pyrido.2-a7pyrimidine, 1-methyl-2.4-dioxo-3-acetyl-2H.4H-pyrido [1.2-a] pyrimidinium methosulfate, 6-acetyl-5.7-dioxo-5H.7H-thiazolo r3.2-a7pyrimidine, 3-acetyl-2.4-dioxo-2H.4H-pyrimido [1.2-a] pyrimidine, 2-acetyl-5.5-dimethyl-dihydroresorcinol, 5-cyano-6-hydroxy-7-acetyl-8-oxo-2.3-benzo-8H-imidazo [1.2-a] pyridine.

A second process for the preparation of compounds of the formula I is characterized in that compounds of the formula where R1-R4, A and Z have the meaning given above, M for = S or = NW and W for hydrogen, C1-C4-alkyl, benzyl, cyclohexyl, phenyl, toluyl, chlorophenyl, methoxyphenyl, C1-C3-alkylcarbonyl, C1 -C2 -alkoxycarbonyl or benzoyl, with compounds of the formula where p, q and G have the abovementioned meaning, and the splitting off of H2M condenses.

The condensation is expediently carried out in an inert organic solvent carried out in the temperature range of 80-2000C, preferably 100-1600C. As inert Organic solvents are higher-boiling solvents, their boiling point is above 900C, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol diacetate, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Dimethylformamide, di- methylacetamide, acetic anhydride, chlorobenzene, o-dichlorobenzene, xylene, chlorotoluenes.

Most of the compounds of the formula X are known or known Methods accessible, for example according to DT-OS 1 619 567, 2 010 492 and 2 129 565 as well as JA-PS 2 042 880.

Suitable examples of compounds of the formula X are: 2-imino-3-cyano-7-diethylamino-2H-benzo [b] pyran, 2-phenylimino-3-carboxy-7-dimethylamino-2H-benzo / b7pyran, 2-benzylimino-3-methoxycarbonyl-7-di-n-butylamino-2H-benzoZb7pyran, 2-p-Toluylimine-3-phenyl-7-N-benzyl-N-methyl-2H-benzodb7-pyran, 2-p-chlorophenyl imino-3-methylcarbamoyl-7-diethylamino-2H-benzo [b] pyran, 2-p methoxyphenylimino-3-methylsulfonyl-7-dimethylamino-2H-benzoZb7pyran, 2-Athylamino-3 nitro-7-di-n-propylamino-2H-benzozb7pyran, 2-Cyclohexyiimino-3-p-toluyl-7-dibenzylamino-2H-benzo / b7-pyran, 2-n-Butylimino-3-nitro-7-diethylamino-2H-benzodb7pyran, 3-p-chlorophenyl-7-piperidino (2), 2-imino-3-p-nitrophenyl-7-diethylamino-2H-benzo [b] pyran, 1-methyl-7-dimethylamino-1H.2H-quinoline-2-thione, 2-imino-3-cyano-7-acetamino-2H-benzo [b] pyran, 2-phenylimino-3-cyano-7-diethylamino-2H-benzo [b] thiopyran, 2-imino-3-Z4'-chloropyrazolyl- (1'27-7-dimethylamino-2H-benzo-Zb7pyran, 2-methylimino-3-Ll '.2'.4'-triazolyl- (1-7-7-diSthylamino-2H-benzo [b] pyran, 2-ethoxycarbonylimino-3-phenyl-7-diethylamino-2H-benzo [b] pyran.

Suitable examples of compounds of the formula VII are such as they have been listed for IXa-c (or VI), but in each case without the acyl group R4-CH2CO-.

A variant of the second process for the preparation of compounds of the formula I is characterized in that compounds of the formula in which R1-R4, A, Z and An have the meaning given above in formula I and E stands for -S-C1-C2-alkyl or -O-C1-C2-alkyl, with compounds of the formula VIII and cleavage of EH and possibly HAn condensed.

The condensation is expediently carried out in an inert organic solvent carried out in the temperature range of 80-200 ° C., preferably 100-160 ° C., preferably in the presence of an acid-binding agent such as triethylamine, pyridine, tributylamine, Morpholine, diethylamine, quinoline or sodium acetate, potassium carbonate, sodium hydrogen carbonate or magnesium oxide. Suitable solvents are of the liquids mentioned above especially the polar, water-miscible and acetic anhydride.

Another method is suitable for making special representatives of compounds of the formula I in which p and q are both 1 and G = G1 for a remainder of the indanedione (1.3), perinaphthindanedione (1.3) or periacenaphthindanedione (1.3) series stands (Formula XII).

A process for the preparation of compounds of the formula wherein R1-R4, A and Z are as defined above and G1 is a radical of the indanedione (1.3), perinaphthindanedione (1.3) or acenaphthindanedione (1.3) series, is characterized in that compounds of the formula in which R1-R4, A and Z are as defined above, or a tautomer of this compound or an acid salt thereof with anhydrides of the formula in which G1 has the meaning given above, condensed.

The condensation is in the temperature range of 140-240 ° C, preferably 160-220 ° C either in the melt or in a high-boiling organic solvent carried out. The water formed during the condensation is expediently running optionally distilled off together with a little solvent. As a solvent high-boiling liquids such as dichlorotoluenes, trichlorobenzenes, o-dichlorobenzene are suitable, Nitrobenzene, a mixture of diphenyl and diphenyl ether, N-methylpyrrolidone, diethylene glycol diethyl ether or quinoline.

Suitable compounds of the formula XIII are, for example, 7-diethylamino-2-methylene-benzene-pyran or the HCl salt of this compound, 7-dimethylamino-4-methyl-2-methylene-benzoZb7pyran or the HClO4 salt of this compound, 7-dimethylamino-2-methylquinoline, 7-diethylamino-2,4-dimethylquinoline, 7-diethylamino-2,6-dimethylquinoline, 7-dimethylamino-1-methyl-2-methylene-quinoline.

The acid salts of compounds of the formula XIII are obtained, for example by condensation of compounds of the formula VII with 1,3-dicarbonyl compounds of the formula R³-CO-CH (R4) - = CO-CH3 (XV) or with derivatives of these compounds such as Acetals, anils or enamines in an acidic medium, for example in boiling glacial acetic acid.

Suitable examples of compounds of the formula VII are those for V listed substances, but without the acyl group Pe3-CO-. Suitable 3.3-dicarbonyl compounds are for example 1.1.3.3-tetramethoxypropane 1 .1-diethoxy-butanone- (3) and acetylacetone.

The free methylene bases of the formula XIII be released in the usual way with the help of acid-binding agents such as sodium hydroxide solution.

Nitro, sulfo, chlorosulfonyl groups and halogen atoms can be advantageous also retrospectively with the help of known electrophilic reagents such as nitrating acid, Introduced oleum, chlorosulfonic acid or with halogenating agents such as SO2Cl2 or bromine be, the electrophilic substitution preferably in optionally present suitable aryl or anilino substituents such as phenyl, toluyla xylyl, methoxyphenyl, Ethoxyphenyl, acetaminophenyl, chlorophenyl, the corresponding anilino derivatives and / or takes place in a free position R4.

The dyes of the formula I are suitable for dyeing and printing natural, semi-synthetic and synthetic fiber and fabric materials and can also be used as laser dyes.

While the sulfo group-containing dyes are in particular to Dyeing and printing of polyamide, polyurethane and wool fibers and the cationic, Compounds free of acidic groups are preferred for those containing acidic groups Fibers such as polyacrylonitrile, acid modified polyesters and acid modified polyamides suitable, represent the dyes free of water-solubilizing ionic groups Formula I disperse dyes for dyeing and printing polyester, polyamide, Polyurethane, cellulose 21/2 acetate, cellulose triacetate, polypropylene and polyacrylonitrile fibers represent.

With the dyes of the formula I according to the invention are on the named fibers and fabrics clear, sometimes very brilliant yellow colorations to purple tones, which are characterized by good usage fastness.

Among the preferred dyes of the formula II, the cationic ones show Representatives with n = 1 usually have an orange-red fluorescence and are suitable as Luminous and as laser dyes. The neutrals show a similar fluorescence behavior and acidic dyes of the formula II in which R5 is an N-acyl radical. Even these can advantageously be used as luminous and laser dyes.

Neutral compounds of the formula I that are free from sublimation fastness-increasing Residues such as sulfamoyl and carbamoyl groups can also be advantageous in the transfer printing process can be used.

Example 1 174 g of 1-phenyl-3-methyl-pyrazolon- (5) are in 700 ml Acetic anhydride with the addition of 6 g of p-toluenesulfonic acid for 6 hours under reflux heated to boiling. The solvent is then distilled off in a water jet vacuum, the residue in 2 1 5%. Sodium hydroxide solution dissolved hot, the solution with 8 g of activated charcoal clarified, the filtrate acidified with hydrochloric acid at room temperature, the crystalline The precipitate is filtered off with suction, washed with water and dried at 40 ° C. in vacuo. 183 g of 1-phenyl-3-methyl-4-acetyl-pyrazolone- (5) are obtained in the form of colorless crystal needles.

32.4 g of this compound and 30 g of 4-diethylaminosalicylaldehyde are heated to boiling for 3 hours on a water separator in 75 ml of xylene with the addition of 1.5 ml of piperidine. After cooling, the crystalline precipitate is filtered off with suction, washed with ethanol and dried in vacuo at 70.degree. 34 g of compound of the formula are obtained in the form of dark red crystal needles. The dye dyes polyester in the HT process (1300C) in a clear, yellowish red shade with good fastness properties.

Those in the following table are given in an analogous manner Dyes made from the appropriate starting compounds. You own similar coloring properties.

Compound of formula Dyeing process: HT = 1300C (autoclave) Th = thermosol process (fixing temperature: 220 ° C) No. Z¹ Z² Z³ Z4 Z6 Z7 Z9 shade (polyester) (2) C2H5 C2H5 HHH C6H5 C6H5 red HT (3) C2H5 C2H5 HHH CH3 CH3 yellow. Red "(4) C2H5 C2H5 H HH C6H5 CH3 yellow. Red" (5) C2H5 C2H5 HHH CH3 C6H4Cl- (2) bluish. Scarlet "(6) C2H5 C2H5 HHH CH3 C6H3Cl2- (2.5) bluish. Scarlet" (7) C2H5 C2H5 HHH CH3 C6H4CH3- (4) yellow. Red "(8) C2H5 C2H5 HHH C6H4OCH3 (4) C6H5 Red" (9) CH3 CH3 HHH CH3 CH3 yellow. Red "(10) n-C3H7 n-C3H7 HHH CH3 C6H4Cl- (2) bluish. Scarlet" (11) n-C4H7 n-C4H7 HHH CH3 C6H3Cl2- (2.5) bluish. Scarlet "(12) C6H5-CH2 C6H5CH2 HHH CH3 C6H4Cl- (4) yellow. Red" (13) C6H5CH2-CH2 C6H5CH2-CH2 HHH CH3 C6H5 yellow. Red "(14) C6H5CH2 C2H5 HHH CH3 C6H4-Br (4) yellow. Red" (15) C2H5 C2H5 HH CH3 CH3 C6H5 orange "(16) C2H5 C2H5 HH Cl CH3 C6H5 orange" (17) C2H5 C2H5 HHH CF3 C6H5 yellow . Red "(18) C1-CH2-CH2 C1-CH2-CH2 HHH CH3 CH (CH3) 2 yellow. Red" (19) - (CH2) 5- HHHH C6H5 yellow. Red "(20) - (CH2) 2O (CH2) 2- HHHH C6H4CH3- (2) yellow. Red" (21) - (CH2) 4- HHH CH3 C6H4Cl- (4) yellow. Red "(22) C2H5 H CH3 HH CH3 C2H5 Red-orange" continuation No. Z¹ Z² Z³ Z4 Z6 Z7 Z9 color (polyester (23) n-C4H9 n-C4H9 HHH CH3 C6H3CH3- (3) -Cl (4) yellow. Red Th (24) C2H5 C2H5 HHH CH3 C6H4NO2- (4) bluish. Scarlet fever " (25) # - C2H5 HHH CH3 C6H4SO2CH3- (4) clear orange " (26) C6H5 (CH2) 3 C6H5 (CH2) 3 HHH CH3 C6H4SO2 (CH2) 3CH3 (4) clear orange " (27) C2H5 HH CH3 H CH3 C6H4COOCH3- (4) clear orange " (28) C2H5 C2H5 HHH CH3 C6H4COOC2H5 (4) clear orange " (29) C2H5 C2H5 HHH CH3 C6H2Cl3- (2.4.6) brill. Scarlet fever " (30) C2H5 C2H5 HHH CH3 C6H4SO2N (C2H5) 2- (4) clear orange " (31) C2H5 C2H5 HHH CH3 C6H4SO2N (CH3) 2- (4) clear orange " (32) C2H5 C2H5 HHH CH3 C6H4COOH- (4) Orange " (33) C2H5 C2H5 HHH CH3 C6H4SO2NH2- (4) clear orange " (34) C2H5 C2H5 HHH CH3 C6H5SO2OC6H5- (4) clear orange " (35) C2H5 C2H5 HHH CH3 C2H4OCOCH3 (4) dissolved. Red HT (36) C2H5 C2H5 HHH CH3 C2H5CH2 yellow. Red " (37) C2H5 C2H5 HHH CH3 O2S # yellow. Red " (38) C2H5 C2H5 HHH CH3 C6H4SO2 (CH2) OCOCH3- (4) clear orange Th (39) # CH3 HHH CH3 C6H5 Red HT (40) CH3- # C2H5 HHH CH3 C6H4Cl- (2) yellow. Red " COCH3 (41) C2H5 C2H5 HHH -N-C6H5 C6H4Cl- (4) clear strong as well as the connections clear blue. Scarlet (polyester, KT) clear blue. Scarlet (polyester, Hr) Example 44 18 g of the compound of the formula (3) are dissolved in 250 ml of chlorobenzene with heating, 10 ml of dimethyl sulfate are added at 60-70 ° C., the mixture is heated to 70 ° C. for 10 hours and then cooled. The crystalline precipitate is filtered off with suction, washed with toluene and recrystallized from 800 ml of isopropanol.

15 g of quaternary salt of the formula are obtained in the form of blue-violet crystals. A dilute chloroform solution shows strong orange-red fluorescence. On polyacrylonitrile, (44) gives an intensely fluorescent blue-tinged red dyeing with good fastness properties. It is suitable as a laser dye.

The following quaternary salts, which are also strongly fluorescent, are prepared in an analogous manner: Compounds of the formula No. Z¹ Z² Z7 Z8 Z9 An # Reaction color (PAN) conditions (45) C2H5 C2H5 CH3 CH3 C6H5 CH3SO4 # 120 hours 80 ° C fluoro bluish red (46) C2H5 C2H5 CH3 C2H5 CH3 C2H5SO4 # 15 hours 80 ° C """ (47) C2H5 C2H5 CH3 n-C3H7 CH3 Br # 10 hrs. 120 ° C """ (Autoclave) (48) C2H5 C2H5 CH3 n-C4H9 CH3 Br # 10 hours 135 ° C """ (49) C2H5 C2H5 CH3 C6H5CH2 CH3 Br # 5 hours 140 ° C """ (50) C2H5 C2H5 CH3 CH2 = CH-CH2CH3 CH3 Br # 7 hours 135 ° C """ (Autoclave) (51) C2H5 C2H5 CH3 (CH2) 2OH CH3 OCOCH3 # Ethylene Oxide """ Glacial acetic acid 3 hours 90 ° C (52) C2H5 C2H5 CH3 CH2-CH-CH3 CH3 OCOCH3 # propylene oxide " CH glacial acetic acid 3 hours 90 ° C (53) n-C4H9 n-C4H9 CH3 CH3 CH3 CH3SO4 # 8 hours 80 ° C """ (54) n-C3H7 n-C3H7 CH3 C2H5 CH3 C2H5SO4 15 hours 85 ° C """ (55) CH3 CH3 CH3 CH3 C2H5 CH3SO4 # 8 hours 80 ° C """ (56) C6H5CH2 C6H5CH2 CH3 CH3 CH3 CH3SO4 # 8 hours 80 ° C """ (58) C2H5 C2H5 CH3 C2H4COOCH3 CH3 Cl # CH2-CH-COOCH3 """ Glacial acetic acid, HCl 10 hours 95 ° C (59) # CF3 CH3 CH3 p-Tos # 20 hours 135 ° C """ (60) C2H5 C2H5 H CH3 CH3 CH3SO4 # 10 hours 75 ° C """ (61) C2H5 C2H5 CH3 CH3 CH (CH3) 2 CH3SO4 10 hours 70 ° C """ continuation No. Z¹ Z² Z7 Z8 Z9 An # Reaction color (PAN) conditions (62) C2H5 C2H5 CH3 CH3 CH-CH2-CN CH3SO4 # 10 hours 75 ° C fluoro blue. Red (63) C2H5 C2H5 CH3 CH2 = CH-CH2 CH2-CH2OH Br # 7 hours 135 ° C """ (Autoclave) (64) C2H5 C2H5 CH3 CH3 C6H5CH2 D CH3SO4 # 10 hours 75 ° C """ (65) C2H5 C2H5 CH3 CH3 CH2-CH2-OCH3 CH3SO4 # 10 hours 75 ° C """ (66) Cl-CH2-CH2 Cl-CH2-CH2 C6H4Cl (4) CH3 CH3 CH3SO4 # 10 hours 75 ° C """ (67) C2H5 C2H5 C6H5 CH3 C6H5 CH2SO4 # 120 hrs. 80 ° C """ (68) C2H5 C2H5 CH2Cl CH3 CH3 CH3SO4 # 10 hours 80 ° C """ (69) C2H5 C2H5 CH3 CH3 O2S # CH3SO4 # 15 hours 80 ° C """ Example 72 10 g of the compound of the formula (1) are introduced into 50 ml of oleum (20% free SO3) at 20-25 ° C. and the mixture is stirred for 15 hours at room temperature. The homogeneous solution is then poured onto 200 g of ice and stirred for 1 hour. The crystalline precipitate is filtered off with suction, stirred with 200 ml of acetone for 1 hour, filtered off with suction, washed with acetone and dried at 70 ° C. in vacuo. 11.3 g of compound of the formula are obtained in the form of deep red crystals. Dyes on polyamide fabric show a lightfast, strongly bluish scarlet shade, on wool a lightfast bluish red shade.

The following acidic dyes are produced in an analogous manner. - Compounds of the formula No. Z¹ Z² Z3 Z4 Z6 Z7 Z9 color (polyamide) (73) C2H5 C2H5 HHH CH3 # clear blue. Scarlet fever (74) HO3S - # - CH2 CH3 HHH CH3 # brill. bluest. Scarlet fever (75) C2H5 HO3S - # - CH2 HHH CH3 # brill. bluest. Scarlet fever (76) HO3S- # CH3 HHH CH3 # bluest. Scarlet fever (77) n-C3H7 n-C3H7 HHH CH3 # "" (78) n-C4H9 n-C4H9 HHH CH3 # " (79) C2H5 C2H5 HH CH3 H # orange (80) C2H5 C2H5 HHH HO3S - # - # clear blue. Scarlet fever (Continuation) No. Z¹ Z² Z3 Z4 Z6 Z7 Z9 color (polyamide) (81) HO3S - # - CH2 CH3 HHH CH3 CH3 bluish. Scarlet fever (82) HO3S - # - CH2 HO3S - # - CH2 HHH CH3 HO3SO- (CH2) 2SO2 - # - clear orange (83) C2H5 C2H5 HHH H3S - # - O2N - # - bluish. Scarlet fever (84) CH3 CH3 HHH CH3 HO3S - # - bluish. Scarlet fever (85) C2H5 H CH3 HH CH3 HO3S - # - bluish. Scarlet fever (86) CH3 HH CH3 H CH3 HO3S - # - bluish. Scarlet fever (87) C2H5 C2H5 HH Cl CH3 HO3S - # - Orange (88) C2H5 C2H5 HHH CH2Cl HO3S- # clear blue. Crowd laugh (89) C2H5 C2H5 HHH HO3S- Br- # bluust. Scarlet fever (90) C2H5 C2H5 HHH CH3 HO3S - # - bluish. Scarlet fever (91) - (CH2) 4- HHH CH3 HO3S - # - bluish. Scarlet fever (92) - (CH2) 2O- (CH2) 2- HHH COCH3 (93) C2H5 C2H5 HHH N-C6H5 HO3S - # - bluish. Red bluest. Scarlet (polyamide) bluish. Scarlet (polyamide) fluorwblaust. Red (polyamide) fluor blue. Red (polyamide) Example 98 31.3 g of 4-diethylamino-2-hydroxy-2'-carboxy-benzphenone and 21.6 g of 1-phenyl-3-methyl-4-acetyl-pyrazolone- (5) are in 300 ml Acetic anhydride heated to boiling under reflux for 2 hours and filtered hot. The filtrate is evaporated in vacuo and the residue is recrystallized from ethylene glycol monomethyl ether (140 ml). 23 g of compound of the formula are obtained in the form of black-violet crystals. On polyester (130 ° C., closed dyeing apparatus), the dye shows a slightly red shade with good fastness properties.

If 4-diethylamino-2-hydroxy-2'-carboxy-benzophenone is replaced by an equivalent amount of 4-diethylamino-2-hydroxy-acetophenone, 15 g of dye of the formula are obtained the polyester turns yellowish red. 4-Diethylamino-2-hydroxybenzophenone is also used in an analogous manner.

Example 100 10 g of compound (98) are suspended in 100 ml of methanol, saturated with dry HCl gas at 20-250 ° C. and heated to the boil for 20 hours. It is then poured onto a mixture of saturated sodium acetate solution (150 ml) and ice (300 g), the crystalline precipitate is filtered off with suction, washed with water and dried at 50 ° C. in a vacuum. 10.5 g of dye of the formula are obtained in the form of purple crystals. Coloring on polyester shows a slightly red shade with good fastness properties.

The ethyl ester is obtained in an analogous manner when using ethanol and when using n-butanol, the n-butyl ester. These show similar good dyeing properties Properties like (100).

Example 101 120 g of 4-hydroxycoumarin are dissolved in 600 ml of glacial acetic acid Boil heated and within 4 hours at the boiling point dropwise with 380 ml of phosphorus chloride are added. The reaction mixture is taking another 30 minutes Heated reflux to the boil, cooled and poured onto 4 l of ice water. The crystalline The residue is filtered off with suction, washed with water and dried at 50 ° C. in vacuo. 127 g of 3-acetyl-4-hydroxycoumarin are obtained.

51 g of this, together with 50 g of 4-diethylaminosalicylaldehyde and 5 ml of piperidine in 500 ml of toluene, are heated to boiling for 4 hours on a water separator and then cooled. The crystalline precipitate is filtered off with suction, washed with toluene, recrystallized from 300 ml of methanol, washed with methanol and dried at 50 ° C. in vacuo. 62 g of compound of the formula are obtained in the form of dark red crystals. A coloration on polyester (130 ° C.) shows a bright yellowish scarlet shade.

Example 102 358 g of N.N'-dibutylthiourea and 225 g of malonic acid are dissolved in 850 ml of glacial acetic acid while warming, dropwise at 60 ° C. while stirring 190 ml of acetic anhydride are added, the mixture is warmed to 70.degree. C. for 2 hours, and added dropwise 100 ml of acetic anhydride are added, the mixture is warmed to 70 ° C. for 1 hour, again drop by drop 100 ml of acetic anhydride are added, the mixture is heated to 90 ° C. for 3 hours and at 60-90 ° C. 70 ml of water are added dropwise. Then the solvent is in vacuo distilled off at 50-900C and the residue was stirred with 1 l of methanol. The crystalline Precipitate is filtered off with suction, washed with methanol and dried at 40 ° C. in vacuo. 212 g of N.N'-dibutyl-5-acetyl-thiobarbituric acid are obtained.

60 g of this and 40 g of 4-diethylaminosalicylaldehyde are in 300 ml Toluene in the presence of 3 ml of piperidine for 3 hours.

heated to boiling on the water separator. The solution is filtered hot, the filtrate is evaporated in vacuo and the residue is recrystallized from approx. 200 ml of ethylene glycol monomethyl ether, washed with ethanol and dried at 50 ° C. in vacuo. The dye of the formula is obtained in the form of dark red crystals that dye polyester fabric in a bright yellowish scarlet shade.

If N.N'-dibutylthiourea is replaced by an equivalent amount of N-methylthiourea, N-methyl-5-acetylthiobarbituric acid is obtained, which analogously gives the dye of the formula supplies, a dark red crystal powder that colors polyamide in a bright reddish orange.

It has very similar coloring properties in an analogous manner N-allyl dye made from N-allyl-5-acetylthiourea.

Example 104 84 g of dehydroacetic acid and 100 g of 4-diethylaminosalicylaldehyde are heated to boiling for 6 hours on a water separator in 500 ml of toluene, after 10 ml of piperidine have been added. The dye solution is clarified hot with 5 g of fuller's earth (Tonsil) and the filtrate is concentrated to about half. After standing for several days, the crystalline precipitate is filtered off with suction, washed with ice-cold methanol and recrystallized from 120 ml of methanol. 30 g of compound of the formula are obtained in the form of dark red crystals. On polyester, the dye produces a bright reddish shade of orange.

Examples 105 and 106 29.5 g of 2-amino-4-dimethylamino-benzaldehyde (prepared according to DT-OS 2,363,459) and 50 g of 1,3-diphenyl-4-acetylpyrazolone (5) and 3 ml of piperidine are dissolved in 300 ml of xylene Heated to the boil for 2 hours on a water separator and then cooled. The crystalline precipitate is filtered off with suction, washed with ethanol, recrystallized from 350 ml of dimethylformamide, washed with ethanol and dried at 60 ° C. in vacuo. 52 g of compound of the formula are obtained This shows a yellowish hue on polyester.

8 g of this substance are dissolved in 60 ml of oleum (20% SO3) at room temperature and the solution is poured onto ice after 16 hours. The crystalline precipitate is filtered off with suction, stirred with acetone, again filtered off with suction, washed with acetone and dried at 50 ° C. in vacuo. 8 g of compound of the formula are obtained On polyamide, this shows a brilliant greenish yellow color.

Claims (10)

Claims 1. Dyes of the formula in which R1 is hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl, aryl or a 2- or 3-membered alkylene radical linked to the adjacent ortho position of the ring A, 2 is hydrogen, alkyl, alkenyl, aralkyl or one is linked to the adjacent ortho position Position of the ring A linked 2- or 3-membered alkylene radical, R1 and R2 also together for an alkylene radical optionally interrupted by NH, O or S with a total of 4 - 6 members, R3 for hydrogen, alkyl, aralkyl, aryl, alkoxy, halogen, Cyano, carboxy, alkoxycarbonyl, alkylsulfonyl or arylsulfonyl, R4 for hydrogen, alkyl, aryl, halogen, hydroxy, alkoxy, nitro, cyano, carboxy, alkoxycarbonyl, formyl, carbamoyl, ureido, amidino, amidinium, alkylsulfonyl, arylsulfonyl, sulfo or with heterocyclic ring system linking a ring N atom, Z for oxygen, sulfur or -N (R) -, R for hydrogen, alkyl, alkenyl, aralkyl, aryl or acyl, p and q for themselves for the numbers 0 or 1, however not at the same time for 0 un d G stand for the remaining members of a carbo- or heterocyclic ring system, and in which the cyclic and acylic radicals in dye chemistry can carry nonionic substituents as well as carboxyl and sulfo groups and can optionally be quaternized, with the proviso that R 3 is hydrogen, Aryl, alkoxy, halogen, cyano, carboxy, alkoxycarbonyl, alkylsulfonyl or arylsulfonyl is when G stands for the remaining members of a ring of the thiazole series. 2) dyes according to claim 1, characterized in that R³ is for Hydrogen, alkyl or aryl, R4 for hydrogen, Z for oxygen and G for the remaining members of a radical of the indanedione (1,3) -, pyrazolone (5) -, barbituric acid, Thiobarbituric acid, 2,6-dioxo-2H-6H-pyridine, 4-hydroxycoumarin or dehydracetic acid series stand. 3. Dyestuffs according to Claim 1 of the formula in which R¹ - R4, A and Z have the meaning given in claim 1, R5 represents hydrogen, alkyl, aralkyl, aryl, chlorine, bromine, carboxy, alkoxycarbonyl, carbamoyl, cyano, hydroxy, alkoxy, acyloxy or a radical of the formula -N ( R8R9), R6 for alkyl, alkenyl or aralkyl, n for 0 or 1, R7 for alkyl, aralkyl, aryl or a heterocyclic radical, R8 for hydrogen, alkyl, aralkyl, cycloalkyl, aryl or a heterocyclic radical, R9 for an acyl radical R8 and R9 also together with the common N atom for a residue L stands for 1.2-phenylene, 1.2- or 1.8-naphthylene, 1.2-cyclohexene (1) -ylene, 1.2-ethenylene or 1.2-ethylene, An stand for an anion, and in which the cyclic and acyclic radicals carry substituents customary in dye chemistry can. 4. Dyestuffs according to Claim 1 of the formula where z1 for methyl, xethyl, chloroethyl, n-propyl, n-butyl, phenyl-C1-C3-alkyl, sulfophenyl-C1-C3-alkyl, cyclohexyl, phenyl, toluyl, sulfophenyl or sulfotoluyl, Z2 for hydrogen, methyl, ethyl , Chloroethyl, n-propyl, n-butyl, phenyl.C1-C3-alkyl, sulfophenyl-C1 -C3-alkyl, Z¹ and Z2 also together for one of the radicals - (CH2) 4-, - (CH2) 5- or - (CH2) 2-O- (CH2) 2-Z3 for hydrogen or methyl, Z4 for hydrogen or methyl, z1 and Z3 also together for a C2-C3-alkylene radical optionally substituted by 1-3 methyl groups, Z2 and Z4 also together for an n-propylene radical, Z5 for hydrogen, methyl, o-carboxyphenyl or o-C1-C4-alkoxycarbonylphenyl, phenyl or sulfophenyl, for hydrogen, methyl or chlorine, Z7 for hydrogen, methyl, trifluoromethyl, phenyl or sulfophenyl Z8 for methyl, Ethyl, n-propyl, n-butyl, ß-hydroxyethyl, ß-hydroxy-n-propyl, allyl or benzyl, Z9 for methyl, ethyl, isopropyl, ß-acetoxyethyl, benzyl, phenyl, chlorophenyl, bromophenyl, dichlorophenyl, trichlorop henyl, Chlortoluyl, sulfophenyl, Sulfonchlorphenyl, nitrophenyl, methylsulfonylphenyl, Äthylsulfonylphenyl p-Acetoxyäthylsulfonylphenyl, ß-Sulfatoäthylsulfonylphenyl, Propylsulfonylphenyl, Butylsulfonylphenyl, carboxyphenyl, methoxycarbonylphenyl, Äthoxycarbonylphenyl, sulfamoylphenyl, N, N-dimethylsulfamoylphenyl, N, N-Diäthylsulfamoylphenyl, 3- or Phenyloxysulfonylphenyl Sulfolanyl, n for the number 0 or 1 and An for an anion. Dyestuffs according to Claim 1 of the formula where Q1 for methyl, methyl, n-propyl, n-butyl, benzyl, sulfobenzyl, ß-phenylethyl or sulfo-B-phenylethyl, for a meaning of Q1, Q3 for methyl Q4 for methyl, ethyl, phenyl, chlorophenyl, dichlorophenyl, Trichlorophenyl, bromophenyl, sulfophenyl, sulfochlorophenyl or nitrophenyl, n represents the number 0 or 1 and represents an anion. 6. Dyes according to claim 4, characterized in that n is for the number 1, Q¹ and q2 for methyl, ethyl, benzyl or sulfobenzyl, for methyl, Q4 for methyl, ethyl, ß-hydroxyethyl or B-hydroxyn-propyl and for methyl, xthyl, Are phenyl or sulfophenyl. 7. Process for the preparation of dyes of the formula wherein R1, R, R4, Z, A, p and q have the meaning given in claim 1, for hydrogen, alkyl, aralkyl, aryl, alkoxy, halogen, cyano, carboxy, alkoxycarbonyl, alkylsulfonyl or arysulfonyl, G for the remaining members a carbo- or heterocyclic ring system, and in which the cyclic and acylic radicals can carry nonionic substituents and carboxyl and sulfo groups customary in dye chemistry and can optionally be quaternized, characterized in that compounds of the formula in which R1, R2, R3, Z and A have the meaning given above, X stands for = 0, = N-C6H5 or = N (CH3) 2 An # and An # stand for an anion, with compounds of the formula where R4, G, p and q have the meaning given above, D for -O-W1, -S-W1, -N (W2W3) or halogen, W1 for hydrogen or C1-C3-alkyl and W2 and W3 for C1- C4-alkyl or together for - (CH2) 4-, - (CH2) 5- or - (CH2) 2-O (CH2) 2-, condensed with elimination of water and DH. 8. The method according to claim 7, characterized in that dyes of claim 1 are produced. 9. A method for dyeing and printing fiber materials, thereby characterized in that dyes according to Claim 1 are used. 10. Use of the dyes according to Claim 1 as laser dyes.