DE3525109A1 - Heterocyclic compounds - Google Patents

Abstract

Heterocyclic compounds which in one of their tautomeric forms correspond to the formula <IMAGE> in which R1 and R2 denote optionally substituted aryl or optionally substituted hetaryl and R3 and R4 denote hydrogen or a substituent, processes for their preparation and their use for dyeing organic macromolecular substances.

Description

The invention relates to heterocyclic compounds in one of their tautomeric forms of the formula correspond, processes for their preparation and their use for dyeing high molecular weight organic material.

Denote in Formula I:
R ₁ , R ₂ optionally substituted aryl, optionally substituted hetaryl and
R ₃ , R _{4 are} hydrogen or a substituent.

Aryl preferably represents such carbocyclic aromatic Radicals, the 1, 2, 3 or 4, especially 1 or 2 rings contain like phenyl, diphenylyl and naphthyl.  

Hetaryl preferably represents such heterocyclic aromatic radicals which are 1, 2, 3 or 4, in particular 1 or contain two five-, six- or seven-membered rings, at least one of which is 1, 2 or 3, preferred Contains 1 or 2 heteroatoms from the O, N, S series. As heterocyclic aromatic radicals named as an example:

Pyridyl, pyrimidyl, pyrazinyl, triazinyl, furanyl, Pyrrolyl, thienyl, quinolyl, coumarinyl, benzofuranyl, Benzoimidazolyl, benzoxazolyl, dibenzofuranyl, benzothienyl, Dibenzothienyl, indolyl, carbazolyl, pyrazolyl, Imidazolyl, oxazolyl, isooxazolyl, thiazolyl, indazolyl, Benzthiazolyl, pyridazinyl, cinnolyl, quinazolyl, Quinoxalyl, phthalazinyl, phthalazinedionyl, phthalimidyl, Chromonyl, naphtholactamyl, benzopyridonyl, ortho- Sulfobenzimidyl, maleimidyl, naphtharidinyl, benzimidazolonyl, Benzoxazolonyl, benzthiazolonyl, benzthiazolinyl, Quinazolonyl, pyrimidonyl, quinoxalonyl, Phthalazonyl, dioxapyrimidinyl, pyridonyl, isoquinolonyl, Isoquinolinyl, isothiazolyl, benzisoxazolyl, benzisothiazolyl, Indazolonyl, acridinyl, acridonyl, quinazolinedionyl, Quinoxalinedionyl, benzoxazinedionyl, benzoxazinonyl and naphthalimidyl.

The aryl and hetaryl radicals can, for example, by halogen such as chlorine, bromine, fluorine, -CN, -R ₅ , -OR ₆ , -SR ₆ , -N (R ₇ ) (R ₈ ), -COOR ₉ , -N (R ₁₀ ) COR ₉ , -N (R ₆ ) COOR ₉ , N (R ₆ ) CON (R ₇ ) (R ₈ ), -NHSO ₂ R ₉ , -SO ₂ R ₉ , -SOR ₉ , -SO ₂ OR ₉ , -CON (R ₇ ) (R ₈ ), -SO ₂ N (R ₇ ) (R ₈ ), -N = NR ₁₁ , -OCOR ₉ and -OCONHR ₉ .

R ₅ denotes optionally substituted alkyl, preferably C ₁ -C ₁₈ alkyl, in particular C ₁ -C ₄ alkyl and optionally substituted cycloalkyl, preferably C ₃ -C ₇ cycloalkyl, in particular cyclopentyl and cyclohexyl.

As substituents of the alkyl and cycloalkyl radicals R ₅ z. B. in question: halogen such as Cl, Br, F, -CN, -OCOR ₉ , -OR ₇ , -COOR ₉ , -SR ₇ , -CON (R ₇ ) (R ₈ ) and -OCONHR ₉ .

R ₇ and R ₈ denote hydrogen, optionally substituted alkyl, in particular C ₁ -C ₁₈ alkyl, preferably C ₁ -C ₄ alkyl, optionally substituted cycloalkyl, in particular cyclopentyl and cyclohexyl, optionally substituted aralkyl, in particular phenyl and naphthyl-C ₁ -C ₄ alkyl, optionally substituted aryl, in particular phenyl and naphthyl and an optionally substituted heterocyclic radical, in particular the radical of a 5- or 6-membered heterocyclic ring with 1, 2 or 3 heteroatoms from the series O, N, S to which a benzene ring can be fused.

The alkyl and cycloalkyl radicals (R ₇ , R ₈ ) z. B. by Cl, Br, F, -CN, -OH, mono-C ₁ -C ₄ -alkylamino, di-C ₁ -C ₄ -alkylamino, phenyl or naphthyl, which by Cl, Br, F, C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy may be substituted or heterocyclic aromatic radicals of a 5- or 6-membered heterocyclic ring system with 1 or 2 heteroatoms from the series O, N, S, to which a benzene ring is fused can be substituted.

R ₇ and R ₈ in the group -CON (R ₇ ) (R ₈ ) together including the N atom can be a 5- or 6-membered heterocyclic ring, e.g. B. form a morpholine, piperidine or phthalimide ring.

The aryl and aralkyl radicals (R ₇ , R ₈ ) can be, for example, Cl, Br, F, C ₁ -C ₁₈ alkyl, preferably C ₁ -C ₄ alkyl, C ₁ -C ₁₈ alkoxy, preferably C ₁ - C ₄ alkoxy may be substituted.

R ₉ denotes optionally substituted alkyl, in particular C ₁ -C ₁₈ alkyl, preferably C ₁ -C ₄ alkyl, optionally substituted cycloalkyl, in particular cyclopentyl and cyclohexyl, optionally substituted aralkyl, in particular phenyl- and naphthyl-C ₁ -C ₄ - alkyl, preferably benzyl, optionally substituted aryl, especially phenyl and naphthyl and an optionally substituted heterocyclic radical, in particular the radical of a 5- or 6-membered heterocyclic ring with 1, 2 or 3 heteroatoms from the series O, N, S, on the a benzene ring can be condensed.

The radicals mentioned for R ₉ can be substituted, for example, like the corresponding radicals R ₇ , R ₈ .

R ₆ denotes hydrogen or assumes the meanings of R ₇ .

R ₁₀ denotes hydrogen, -COR ₉ or assumes the meanings of R ₇ .

R ₁₁ denotes the remainder of a coupling component, preferably a coupling component from the benzene, naphthalene, acetoacetic acid arylide, pyrazole or pyridone series or an optionally by Cl, Br, F, C ₁ -C ₁₈ alkyl, preferably C ₁ -C ₄ -Alkyl and C ₁ -C ₁₈ alkoxy, preferably C ₁ -C ₄ alkoxy substituted phenyl radical.

R ₃ , R ₄ preferably represent hydrogen, optionally substituted alkenyl, preferably C ₂ -C ₁₈ alkenyl, in particular C ₂ -C ₆ alkenyl, optionally substituted alkynyl, preferably C ₂ -C ₁₈ alkynyl, in particular C ₂ -C ₆ -alkynyl, epoxyethyl, optionally substituted aryl, preferably phenyl and naphthyl,
R ₅ , -COR ₆ , -CON (R ₇ ) (R ₈ ), or a residue of the formula in which

R ₅ , R ₆ , R ₇ and R _{8 have} the above meanings,

R ₁₂ denotes hydrogen, optionally substituted alkyl, preferably C ₁ -C ₈ alkyl, optionally substituted aryl, in particular phenyl and naphthyl,

R _{13 represents} hydrogen or can have the meanings of R ₃ , R ₄ except the rest of the formula Ia,

R ₁₄ for a divalent saturated or unsaturated aliphatic bridge member with 1-8 C atoms, an optionally substituted arylene radical, preferably phenylene radical, e.g. B. xylylene, a rest of the formulas wherein R _{15 is} a C ₁ -C ₁₀ alkylene or an optionally substituted aryl radical, preferably phenylene or naphthylene, e.g. B. Toluylene, and

A for the divalent residue of a compound with two exchangeable hydrogen atoms on a C or N atom, especially for the divalent radical one methylene-active compound, an amine, hydrazine, Hydrazids or hydrazone stands.  

As substituents of the alkenyl and alkynyl radicals R ₃ , R ₄ come, for. B. those mentioned for the alkyl and cycloalkyl radicals R ₅ .

As substituents of the aryl radicals R ₃ , R ₄ , R ₁₂ come, for. B. F, C1, Br, -NO ₂ , -CN, -CF ₃ , C ₁ -C ₁₈ alkyl, especially C ₁ -C ₄ alkyl, C ₁ -C ₁₈ alkoxy, especially C ₁ -C ₄ -Alkoxy, phenyl, phenoxy, C ₁ -C ₆ -alkoxy-carbonyl and phenoxycarbonyl.

If A stands for the divalent radical of a methylene-active compound, it is preferably a radical of the formula wherein R _{16 represents} a radical activating the methylene group, for example cyan; C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkoxycarbonyl; carbamoyl optionally substituted by C ₁ -C ₆ alkyl, benzyl, naphthyl or phenyl, phenyl, benzyl, naphthyl, e.g. B. by chlorine, bromine, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, nitro, trifluoromethyl, C ₁ -C ₆ alkylcarbonyl in particular acetyl, cyano, C ₁ -C ₆ alkylamino, benzoylamino, phthalimidyl , Carbamoyl, may be substituted; C ₁ -C ₆ alkylcarbonyl, especially acetyl; Benzoyl, C ₁ -C ₆ alkoxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl, where benzoyl, benzyl and phenoxy, for example by halogen, such as chlorine and bromine, nitro, C ₁ -C ₆ alkyl, acylamino, in particular C ₁ -C ₆ alkylcarbonylamino, Phthalimidyl, may be substituted; phenyl optionally substituted by halogen, in particular chlorine and bromine, nitro, cyano, trifluoromethyl.

Preferred radicals A are also radicals of the formula in the
R ₁₇ , R _{18 are} hydrogen, C ₁ -C ₆ alkyl, optionally substituted by halogen such as chlorine and bromine, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or nitro, phenyl, α-naphthyl and β-naphthyl describe.

R ₁ , R ₂ are preferably in which

R ₁₉ , R ₂₀ , R _{21 are} hydrogen, halogen such as Cl, Br, F, -CN, -R ₅ , -OR ₆ , -SR ₆ , -N (R ₇ ) (R ₈ ), -COOR ₉ , -N (R ₁₀ ) COR ₉ , -N (R ₆ ) COOR ₉ , -N (R ₆ ) CON (R ₇ ) R ₈ ), -NHSO ₂ R ₉ , -SO ₂ R ₉ , -SOR ₉ , SO ₂ OR ₉ , -CON (R ₇ ) (R ₈ ), -SO ₂ N (R ₇ ) (R ₈ ), -N = NR ₁₁ , -OCOR ₉ and -OCONHR ₉ with the above meanings for R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ denote.

Compounds with R ₁₉ , R ₂₀ = H and R ₂₁ ≠ H and with R ₁₉ , R ₂₁ = H and R ₂₀ ≠ H are particularly preferred.

R ₁ , R ₂ are particularly preferably a radical of the formula in the

R ₂₂ , R _{23 are} hydrogen, halogen such as chlorine, bromine, fluorine, CF ₃ , C ₁ -C ₄ alkyl, in particular methyl and ethyl, -CN, C ₁ -C ₄ alkoxy, in particular methoxy and ethoxy, mono- or di -C ₁ -C ₄ alkylamino, especially dimethylamino, optionally chlorine-substituted benzoyl or benzoylamino, naphthyl or radicals of the formula. describe.

R ₃ , R ₄ are particularly preferably hydrogen.

Of particular interest is the dye of formula I in which R ₁ , R ₂ 4-chlorophenyl and R ₃ , R _{4 are} hydrogen.

To prepare the compounds of the formula I, compounds are used which are in one of their tautomeric forms of the formula correspond with compounds of the formula and releases the compounds of formula I from the resulting reaction product by hydrolysis.

In the formulas II and III, R ₁ , R ₂ , R ₃ and R _{4 have} the meanings given for formula I; X denotes halogen such as chlorine and bromine or alkoxy, cycloalkoxy, aryloxy, aralkoxy, in particular C ₁ -C ₄ alkoxy.

Practical implementation of connections of the formula II with the keto esters of the formula III is similar to that known from EP-A3-94 911 Implementation of nitriles with succinic diester to 1,4-diketo-pyrrolo- [3,4-c] pyrroles.

The keto ester of the formula III is reacted with the compound of formula II preferably in one Solvent through.

Suitable solvents are, for example, primary secondary or tertiary alcohols with 1 to 10 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, 2-methyl-2-butanol, 2-methyl-2-pentanol, 3-methyl 3-pentanol, 2-methyl-2-hexanol, 3-ethyl-3-pentanol, 2,4,4-trimethyl-2-pentanol or glycols, such as ethylene glycol or diethylene glycol, furthermore ethers, such as tetrahydrofuran  or dioxane, or glycol ethers, such as ethylene glycol methyl ether, ethylene glycol ethyl ether, Diethylene glycol monomethyl ether or diethylene glycol monoethyl ether, also dipolar aprotic solvents, such as acetonitrile, benzonitrile, dimethylformamide, N, N-dimethylacetamide, nitrobenzene, N-methylpyrrolidone, aliphatic or aromatic hydrocarbons, such as Benzene or substituted by alkyl, alkoxy or halogen Benzene, such as toluene, xylene, anisole or chlorobenzene or aromatic N-heterocycles, such as pyridine, Picolin or Quinoline.

It is expedient to use 5-20 parts by weight. solvent to 1 part by weight the reactant.

The process according to the invention is preferably used an alcohol as a solvent, especially one secondary or tertiary alcohol. Preferred tertiary alcohols are tert-butanol and tert-amyl alcohol. Mixtures of these are also preferred Aromatic hydrocarbon solvents such as Toluene or xylene, or with halogen-substituted Benzene, such as chlorobenzene, is of great interest.

The process according to the invention is carried out in the presence of a strong base performed. Suitable bases are in particular the alkali metals themselves, such as lithium, sodium or potassium, or alkali amides, such as lithium, sodium or potassium amide or alkali hydrides, such as lithium, Sodium or potassium hydride, or alkaline earth or alkali alcoholates, which are particularly different from primary, secondary or tertiary aliphatic alcohols with 1 to Derive 10 carbon atoms, such as. B. lithium, sodium or potassium ethylate, ethylate, n-propylate, isopropylate,  -n-butylate, -sec.-butylate, -tert.-butylate, -2-methyl-2- butylate, -2-methyl-2-pentylate, -3-methyl-3-pentylate, -3-ethyl-3-pentylate. But you can also use a mixture use the bases mentioned.

In the process according to the invention one uses as strong Base prefers alkali alcoholates, alkali in particular Means sodium or potassium, and that Alcoholate preferred from a secondary or derives tertiary alcohol. Particularly preferred strong Bases are therefore z. B. sodium or potassium isopropylate, -sec.-butylate, -tert.-butylate and -tert.-amylate. Here the alkali alcoholates can also be prepared in situ by using the appropriate alcohol with the Reacts alkali metal, alkali hydride or alkali amide.

The strong base can be used in the process according to the invention in an amount of in particular 0.1 to 10 mol, preferred 1.9 to 4.0 moles based on 1 mole of the compound use the formula II. Although basically stoichiometric amounts of base suffice in many cases an excess of base yield Cheap.

The method according to the invention is used in particular a temperature of 60 to 140 ° C, preferably 70 to 120 ° C.

One can for the hydrolysis of the condensation product Water, an alcohol with 1 to 4 carbon atoms, such as  Methanol or ethanol, but preferably an acid, use. As acids come e.g. B. aliphatic or aromatic carboxylic or sulfonic acids into consideration, such as for example formic acid, acetic acid, propionic acid, Oxalic acid, benzoic acid or benzenesulfonic acid. Farther mineral acids are also suitable as acids, such as hydrochloric acid, sulfuric acid or phosphoric acid, preferably an organic one is used for the hydrolysis Acid, especially an aliphatic carboxylic acid, such as Acetic acid.

The compound of the formula I precipitates out during the hydrolysis and can be isolated by filtration.

To implement the reactants, it is basically possible to submit all components at a lower temperature and then the mixture in the range of the reaction temperature to warm up, or in any order the individual components in the range of the reaction temperature admit to each other. A preferred embodiment which are usually particularly cheap affects the yield is that one Present compound of formula II together with the base and the α-ketoester in the range of the reaction temperature added. Another option is there in that a mixture of the reactants metered in simultaneously to the base provided. It is possible, not only the inventive method to be carried out batchwise, but also continuously.  If one uses an alcohol as solvent and as Base an alcoholate, it may be advantageous to use one Alcohol and an alcoholate with the same alkyl parts choose. It can also be just as advantageous if, in addition the α-keto ester also contains such alkyl groups.

Is used to prepare the compounds of formula I. Instead of the α-keto ester of the formula III, the acid halide of formula III (X = Br, preferably C1), so is preferred in aprotic solvents such as dioxane, tetrahydrofuran, pyridine, diglycol ether such as diethylene glycol monomethyl ether or Diethylene glycol monoethyl ether, dimethylformamide, Benzene, toluene, xylene or the like worked, at least another equivalent of the base must be used.

The compounds of formula III are known or in Analogy to processes known from the literature.

To prepare the compounds of the formula II, compounds of the formula are used the z. B. from JACS 72 , p. 1236 ff. And J. org. Chem. (London) 21 , pp. 1211 ff. (1956) are known with amines of the formula

H ₂ NR ₄

in a manner known per se (cf. the known implementations of βDicarbonyl compounds with amines Enamines).

The compounds of formula I in which R ₃ , R ₄ for stand, z. B. can be prepared by using compounds of the formula with compounds of the formula where R 'preferably denotes C ₁ -C ₄ alkyl, is implemented in a manner known per se.

The yellow to red compounds of the formula I are preferably found Use as pigments, depending on their structure and the type of polymers to be colored, however, also as polymer-soluble dyes for e.g. B. polystyrene, Polyamides, ABS, especially for linear polyesters, in particular Polyethylene terephthalates are used.  The compounds of formula I fall into one for the Pigment application suitable form or can by known aftertreatment methods into the appropriate ones Form are transferred, e.g. B. by dissolving or swelling in strong inorganic acids such as sulfuric acid and discharge on ice. The fine distribution can also be done by grinding with or without grinding aids such as inorganic salts or sand, optionally in the presence of solvents such as toluene, xylene, dichlorobenzene or N-methylpyrrolidone be achieved. Color strength and transparency of the pigment can be achieved by varying the after-treatment to be influenced.

The compounds of formula I are suitable because of their Fastness to light and migration for a wide variety Pigment applications. So they can be used to manufacture very real pigmented systems, like mixing with others Substances, preparations, paints, printing inks, colored paper and colored macromolecular Fabrics are used. Mixing with other substances can e.g. B. those with inorganic white pigments such as Titanium dioxide (rutile) or be understood with cement. Preparations are z. B. Flush pastes with organic liquids or dough and fine dough with water, dispersing agents and optionally preservatives. The label Paint is available e.g. B. for physically or oxidatively drying lacquers, stoving lacquers, reaction lacquers, Two-component paints, emulsion paints for weatherproof Coatings and glue colors. There are such inks  to understand for paper, textile and tin printing. The macromolecular substances can be of natural origin be like rubber, obtained by chemical modification are like acetyl cellulose, cellulose butyrate or Viscose or synthetically produced like polymers, Polyaddition products and polycondensates. Be mentioned plastic masses such as polyvinyl chloride, polyvinyl acetate, Polyvinyl propionate, polyolefins, e.g. B. polyethylene or Polyamides, super polyamides, polymers and copolymers from acrylic esters, methacrylic esters, acrylonitrile, Acrylamide, butadiene, styrene as well as polyurethanes and polycarbonates. The pigmented with the claimed products Substances can be in any form.

The pigments of formula I are still excellent watertight, oil-resistant, acid-fast, lime-fast, alkali-fast, solvent-resistant, over-lacquer, over-splash, sublimation, heat-resistant, vulcanization-resistant, very economical and easy to distribute in plastic masses.

The following examples illustrate the invention.  

example 1

237 g of (N-phenacetyl) aminoacetic acid ethyl ester are refluxed in 1500 ml of dry toluene with 160 g of 95% potassium tert-butoxide for 2 hours. After cooling, 500 ml of ice water are stirred in. The aqueous phase is separated off and acidified to pH 1 with dilute hydrochloric acid. The precipitated crystals are isolated, washed with water and dried. 170 g of substance are obtained, in one of its tautomeric forms of the formula NMR (DMSO): δ = 3.85 (s, 2H), 7.05 (m, 1H), 7.25 (m, 3H), 8.86 (m, 2H), 11.45 (s, 1H)
corresponds.

Comparable yields are obtained if in place of potassium tert-butoxide, sodium methylate or sodium ethylate be used.  

Example 2

18 g of the compound prepared in Example 1 are boiled in 200 ml of xylene with 20 g of ammonium acetate on a water separator under reflux. As soon as no more water is separated off, the mixture is allowed to cool, the precipitated product is isolated, washed with toluene and water and dried. 16 g of substance are obtained, in one of its tautomeric forms of the formula NMR (DMSO): δ = 3.74 (s, 2H), 6.40 (s, 2H), 6.76 (s, 1H), 7.0 (m, 1H), 7.20 (m, 2H), 7.45 (m, 2H)
corresponds.

Example 3

9 g of the compound prepared in Example 2 are refluxed in 200 ml of tert-butanol with 18 g of potassium tert-butoxide and 10 ml of methyl phenylglyoxylate for 5 hours. The mixture is allowed to cool to 50 ° C., 300 ml of methanol and 25 ml of glacial acetic acid are added to the suspension. The precipitated crystals were isolated, washed well with methanol and water and dried. 8 g of a yellow substance are obtained, which is in one of its tautomeric forms of the formula Mass spectroscopy: MS: M⁺: 288 as base peak UV (DMF): λ _max = 360 nm, corresponds to ε _max = 26 500, and which, when incorporated into PVC, gives a yellow color.

Example 4

11 g of 2-hydroxy-3- (4'-chlorophenyl) -4-amino-pyrrole are heated to reflux in 200 ml of tert-butanol with 18 g of potassium tert-butoxide. 15 ml of methyl phenylglyoxylate are added dropwise in the course of 2 hours. After refluxing for 3 hours, a mixture of 200 ml of methanol and 20 ml of glacial acetic acid is added dropwise. The precipitated crystals are isolated, washed with methanol and water and dried. 10.5 g of substance of the formula are obtained UV (DMF): λ _max = 363 nm, ε _max = 27 100
incorporated in PVC gives a yellow color.

Example 5

9 g of the compound prepared in Example 2 according to the information in Example 3 with 15 g of p-chlorine phenylglyoxylic acid ethyl ester implemented. You get 11 g of substance with that prepared according to Example 4 is identical.

Example 6

11 g of 2-hydroxy-3- (4'-chlorophenyl) -4-amino-pyrrole are heated in 200 ml of tert-amyl alcohol with 18 g of potassium tert-butoxide and 15 g of methyl p-chlorophenylglyoxylate at 100 ° C. for 4 hours , while distilling off the resulting methanol. After hydrolysis with glacial acetic acid, isolation and drying, 14 g of pigment of the formula are obtained which is incorporated in PVC gives a reddish yellow color.

Example 7

7 g of sodium are dissolved in 200 ml of anhydrous ethanol. 9 g of the compound prepared in Example 2 are added and drips at 78 ° C over 1 hour 15 ml of ethyl phenylglyoxylate. After finished The reaction mixture is metered in for a further 3 hours Boiled reflux and then worked up as in Example 3. 2 g of pigment are obtained, which is the same as that of Example 3 manufactured is identical.

Example 8-53

Analogously to Example 3, further pigments of the formula are obtained wherein R 'and R ″ have the meanings listed in the following table.

Example 54 (application example)

4 g of finely ground pigment according to Example 3 are dispersed in 92 g of a stoving lacquer of the following composition:
33% alkyd resin
15% melamine resin
5% glycol monomethyl ether
34% xylene
13% butanol

Products based on synthetic come as alkyd resins and vegetable solid acids such as coconut oil, Castor oil, castor oil, linseed oil u. a. in question. Instead of of melamine resins, urea resins can be used will.

After dispersing, the pigmented Lacquer on paper, glass, plastic or metal Foils applied and baked at 130 ° C for 30 minutes. The paintwork has very good light and weather resistance as well as good fastness to painting.

The stoving lacquer, produced according to Example 54, is spread on white paper and at 130 ° C branded.

Example 55

A mixture of 65 g polyvinyl chloride, 35 g diisooctyl phthalate, 2 g dibutyltin mercaptide, 0.5 g titanium dioxide and 0.5 g of the pigment from Example 6 is on a mixing mill colored at 165 ° C. You get one intensely yellow colored mass used for the production of foils or Shaped bodies can serve. The coloring is characterized excellent light and very good softening properties.

Example 56

0.2 g pigment according to Example 3 are mixed with 100 g polyethylene, Polypropylene or polystyrene granules mixed. The mixture can either be in directly at 220 to 280 ° C sprayed in an injection molding machine, or in an extrusion press  to colored bars or on the mixing mill colored skins are processed. The rods or skins are optionally granulated and in an injection molding machine splashed.

The yellow moldings have very good fastness to light and migration. Similarly, at 280-300 ° C, if necessary under a nitrogen atmosphere, synthetic polyamides Caprolactam or adipic acid and hexamethylenediamine or the Condensates from terephthalic acid and ethylene glycol can be colored.

Example 57

1 g pigment according to Example 6, 10 g titanium dioxide (rutile type) and 100 g of a copolymer in powder form based on acrylonitrile butadiene styrene mixed and colored on a rolling mill at 140-180 ° C. An orange-colored fur is obtained which is granulated and in an injection molding machine is sprayed at 200-250 ° C. Man receives yellow colored moldings very good light and Fastness to migration and excellent heat resistance. In a similar way, but at temperatures of 180-220 ° C and without the addition of titanium dioxide, plastics are based of cellulose acetate, cellulose butyrate and their mixtures with similar fastnesses.  

Example 58

0.2 g of pigment according to Example 6 are in finely divided form with 100 g of a plastic based on polycarbonate in one Extruder or mixed in a kneading screw at 250-280 ° C and processed into granules. You get a yellow one transparent granules with excellent lightfastness and Heat resistance.

Claims (8)

1. Heterocyclic compounds in one of their tautomeric forms of the formula correspond in the
R ₁ , R ₂ optionally substituted aryl, optionally substituted hetaryl and
R ₃ , R ₄ denote hydrogen or a substituent. 2. Compounds according to Claim 1, in which the aryl radicals contain 1, 2, 3 or 4, in particular 1 or 2, rings and the hetaryl radicals 1, 2, 3 or 4, in particular 1 or 2, contain five-, six- or seven-membered rings, of which at least 1, 2 or 3, preferably 1 or 2, has heteroatoms from the series O, N, S, and furthermore the aryl and hetaryl radicals are replaced by halogen such as chlorine, bromine, fluorine, -CN, -R ₅ , OR ₆ , SR ₆ -N (R ₇ ) (R ₈ ) -COOR ₉ , - N (R ₁₀ ) COR ₉ , -N (R ₆ ) COOR ₉ , N (R ₆ ) CON (R ₇ ) (R ₈ ) , -NHSO ₂ R ₉ , -SO ₂ R ₉ , -SOR ₉ , -SO ₂ OR ₉ , -CON (R ₇ ) (R ₈ ), -SO ₂ N (R ₇ ) (R ₈ ) -N = NO ₁₁ , -OCOR ₉ and -OCONHR ₉ may be substituted, wherein
R ₅ optionally substituted alkyl and optionally substituted cycloalkyl,
R ₇ , R ₈ denote hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aralkyl, optionally substituted aryl and an optionally substituted heterocyclic radical, or R ₇ , R ₈ in the group -CON (R ₇ ) (R ₈ ) together under Inclusion of the N atom form a 5- or 6-membered heterocyclic ring,
R ₉ optionally substituted alkyl,
optionally substituted cycloalkyl,
optionally substituted aralkyl,
optionally substituted aryl,
an optionally substituted heterocyclic radical,
R _{6 is} hydrogen, R ₇ ,
R _{10 is} hydrogen, R ₇ , -COR ₉ and
R ₁₁ denotes the rest of a coupling component. 3. Compounds according to claims 1 and 2 in which R ₃ , R ₄ for hydrogen, optionally substituted alkenyl, optionally substituted alkynyl, epoxyethyl, optionally substituted aryl, -R ₅ , -COR ₆ , -CON (R ₇ ) (R ₈ ), or a residue of the formula stand where
R ₅ , R ₆ , R ₇ and R _{8 have} the meanings given in Claim 2,
R ₁₂ denotes hydrogen, optionally substituted alkyl, optionally substituted aryl,
R _{13 represents} hydrogen or the meaning of R ₃ , R ₄ can assume the rest of the formula Ia,
R ₁₄ for a divalent saturated or unsaturated aliphatic bridge member with 1-8 C atoms, an optionally substituted arylene radical, a radical of the formulas wherein R ₁₅ denotes a C ₁ -C ₁₀ alkyl or an optionally substituted arylene radical, and
A stands for the divalent radical of a compound with two interchangeable hydrogen atoms on a C or N atom, in particular for the divalent radical of a methylene-active compound, an amine, hydrazine, hydrazide or hydrazone. 4. Compounds according to claims 1-3, in which R ₁ , R ₂ for stand where
R ₁₉ , R ₂₀ , R ₂₁ hydrogen, halogen such as C1, Br, F, -CN, -R ₅ , -OR ₆ , -SR ₆ -N (R ₇ ) (R ₈ ), -COOR ₉ , -N ( R ₁₀ COR ₉ , -N (R ₆ ) COOR ₉ , -N (R ₆ CON (R ₇ (R ₈ ), -NHSO ₂ R ₉ , -SO ₂ R ₉ , -SOR ₉ , SO ₂ OR ₉ , - CON (R ₇ ) (R ₈ ), -SO ₂ N (R ₇ ) (R ₈ ), -N = NR ₁₁ , -OCOR ₉ and - OCONHR ₉ with the meanings given in claim 2 for R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ denote. 5. Compounds according to claims 1-4, in which R ₁ , R ₂ for stand in the
R ₂₂ , R _{23 are} hydrogen, halogen such as chlorine, bromine, fluorine, -CH ₃ , C ₁ -C ₄ -alkyl, in particular methyl and ethyl, -CN, C ₁ -C ₄ -alkoxy, in particular methoxy and ethoxy, mono- or Di-C ₁ -C ₄ alkylamino, in particular dimethylamino, optionally chlorine-substituted benzoyl or benzoylamino, naphthyl and residues of the formulas describe. 6. Compounds according to claims 1-5, in which R ₃ = R ₄ = H. 7. A compound according to claim 1, wherein R ₃ = R ₄ = H and 8. Process for coloring organic macromolecular Fabrics d. g. that one heterocyclic Compounds according to claims 1-7 used.