DE4340560A1 - Furanone dyestuff cpd. for bulk colouration of plastic - Google Patents

Abstract

New furan-2-one dyestuffs (IA) are of formula (I); where T = O; n = 1 or 2; R1 = (het)aryl or heterocyclylidene methyl if n = 1 or a direct bond or arylene if n = 2; R2 + R3 = a gp. forming an opt. substd. (hetero)aromatic or heteroaliphatic ring, with certain exceptions. Also claimed are: (1) the bulk colouration of plastics with furan-2-one or pyrrolin-2-one dyestuffs (IB) of formula (I) where T = O or N-R0; R0 = H, alkyl, aryl or acyl, or R0 + R3 or R0 + R2 = a 5-7 membered ring; R2, R3 = H, alkyl, aryl, aryl- or alkyl-sulphonyl, CN or -COR; and R = alkoxy, NH2, mono- or di-alkylamino, arylamino, alkyl or aryl; and (2) plastics coloured with (IA) or (IB). The exceptions to (IA) are (I; n = 1, R2 + R3 = an unsubstd. fused benzene ring, R1 = N-methyl-2-quinolinyl-methylene, 1, 3, 3, -trimethyl-2- indolinyl-methylene, 2-furyl, 2-, 3- or 4-pyridyl, 3,4-dichlorophenyl, 2,4-dihydrophenyl, 2- or 4-bromophenyl, 2-, 3- or 4-chlorophenyl, 2-fluorophenyl, 2-, 3- or 4-nitrophenyl, 4-methylphenyl, 3,4-methylenedioxyphenyl, 2-, 3- or 4-methoxyphenyl, 2-ethoxyphenyl, 3,4-dimethylphenyl, 4-dimethylaminophenyl, 1- or 2-naphthyl or 3,4-diethoxyphenyl) and cpds. of formulae (IC-G).

Description

The present invention relates to a method for mass coloring art fabrics. The mass coloring of plastics, for example thermoplastics known from z. B. GB-A-1 386 846, US-A-3 655 670.

A disadvantage of the known methods is that they are used Dyes only weak yellow (see GB-A-1 386 846, US-A-3 655 670) Deliver shades.

The present invention relates to a method for mass coloring art substances with dyes of the formula (I)

wherein
n denotes 1 or 2, preferably 1,
T represents O or N-R₀, wherein
R₀ denotes H, alkyl, aryl, acyl or together with R₃ or R₂ forms a 5- to 7-membered ring,
R₁ for n = 1, aryl, hetaryl or heterocyclylidene methyl and
for n = 2, means a direct bond or arylene,
R₂, R₃ independently of one another are H, alkyl, aryl, aryl or alkyl sulfonyl, cyano, a radical of the formula -COR, where R is alkoxy, amino, alkylamino, dialkylamino, arylamino, alkyl or aryl or together the rest of one optionally substituted aromatic, heteroaromatic or heteroaliphatic ring form.

"Alkyl" here and in the following, unless otherwise defined, means given if substituted open chain alkyl, open chain alkenyl or optionally substituted cycloalkyl.

In a preferred embodiment of the method, dyes come from Formula (II)

to use, in which
TO or N-R₀ means wherein
R₀ has the meaning given above,
R₄ and R₆ together the rest of an optionally substituted aromatic, in particular phenyl or naphthyl, or heteroaromatic, in particular an optionally mono- or di-benzanellated thiophene, furan, pyrrole, thiazole, oxazole, imidazole, pyridine - Form, pyran or pyrimidine residue and
R₅ represents H, alkyl, halogen, OH, alkoxy, acyloxy, aryloxy, alkylthio, arylthio, dialkylamino or acylamino, the possible substituents on the ring formed by R₄ and R₆ preferably having the meaning of R₅, or
R₅ and R₆ together form the residue of an optionally substituted heterocyclic ring and
R₄ represents H or alkyl and
R₂ and R₃ have the meaning given above.

In a particularly preferred embodiment of the method Dyes of the formula (III)

to use, in which
T, R₂ and R₃ have the meaning given above,
and the ring E is optionally substituted with alkyl, halogen, OH, alkoxy, aryloxy, acyloxy, dialkylamino, acylamino, alkylthio or arylthio.

Dyes of the formula (III) in which the ring E bears one to three mutually independent C₁-C₄ alkoxy radicals which are optionally substituted by Cl, CN, OH, alkoxycarbonyl, alkoxy or acyloxy or two of the alkoxy radicals are linked to one another via a methylene bridge are preferred are or
carries an aryloxy radical, in particular a phenyloxy or naphthyloxy radical which is optionally substituted by alkyl, Cl, Br, alkoxy or alkoxycarbonyl, or
carries a C₁-C₄ dialkylamino radical which is optionally substituted by Cl, phenyl, CN, OH, alkoxy, dialkylamino, alkoxycarbonyl or acyloxy or is optionally linked to one or both ortho positions of the E ring to form a heterocyclic ring, or carries a heterocyclic amino radical,
carries a C₁-C₄ alkylthio radical which is optionally substituted by phenyl, OH, acyloxy or alkoxycarbonyl or
a phenyl or naphthylthio radical which is optionally substituted by Cl, alkyl or alkoxycarbonyl and
is optionally further substituted with
up to two mutually independent C₁-C₄ alkyl groups, halogen atoms, in particular Cl or Br and / or
an acylamino, acyloxy or hydroxy group.

In a particularly preferred embodiment, the para position of the ring E by one of the above alkoxy, aryloxy, alkylthio, arylthio or Dialkylamino residues substituted.

Particularly suitable rings E are, for example:

In a further particularly preferred embodiment, dyes of the formula (II) are used in which
R₅ and R₆ together form the rest of an optionally mono- or disubstituted benzanellated and / or further substituted pyrrole, thiazole, oxazole, imidazole, pyridine, pyran or pyrimidine, and R₂, R₃ and R₄ have the above meaning.

Dyes of the formula (IV) are very particularly preferably used,  

wherein
T, R₂ and R₃ have the above meanings,
R₄ has the above meaning, preferably represents H,
R₇, R₈ independently of one another are C₁-C₄-alkyl, preferably CH₃, C₂H₅ or C₃H₇ or together form the rest of an optionally substituted carbocyclic 5- or 6-ring, preferably a tetra or penta-methylene group,
R₉ is a C₁-C₄-alkyl group optionally substituted by phenyl, Cl, OH, CN, alkoxycarbonyl, alkoxy, dialkylamino or acyloxy and
R₁₀, R₁₁ together form the residue of an optionally substituted benzene or naphthalene ring, the preferred substituents being Cl, C₁-C₄-alkyl, C₁-C₄-alkoxycarbonyl and C₁-C₄-alkoxy.

Suitable radicals of the formula

are for example:  

In another embodiment of the process, dyes of the formula (I) are used in which n = 2 and
R₁ is a direct bond or an arylene radical, preferably phenylene, in particular 1,4-phenylene, and
T, R₀, R₂ and R₃ have the above meaning.

In a further embodiment of the process, the dyes described above, in particular those of the formulas (III) and (IV), are preferably used, in which
R₂ for hydrogen and
R₃ is C₁-C₄-alkyl, in particular CH₃ or optionally by C₁-C₄-alkoxy, preferably OCH₃, Cl, Br or C₁-C₄-alkyl, especially methyl, substituted phenyl or naphthyl, for example C₆H₅ or

or
R₂ and R₃ together represent a radical of the formula

form,
the bond marked with * identifies the R₂ linkage and where
X represents O or N-R₁₆, where R₁₆ is H, C₁-C₆-alkyl or phenyl,
R₁₂ represents H, phenyl or C₁-C₄ alkyl,
R₁₃ represents H, phenyl, C₁-C₄-alkyl, C₁-C₄-alkoxycarbonyl, amino carbonyl, mono- or di-alkylaminocarbonyl, arylaminocar bonyl, C₁-C₄-alkylcarbonyl, benzyl or Cl,
R₁₄ and R₁₅ independently of one another are H, Cl, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkoxycarbonyl or together form the residue of an optionally substituted benzo ring with these substituents or
R₂ and R₃ form the remainder of an optionally substituted benzo or naphtho ring, the naphtho ring preferably being unsubstituted and 1,2-, 2,1- or 2,3-linked and the benzo ring preferably by
0 to 2 independent C₁-C₆ alkyl groups or chlorine atoms or
0 to 1 C₁-C₄-alkoxy or C₁-C₄-alkoxycarbonyl radicals is substituted.

Suitable radicals which are formed together by R₂ and R₃ are for example:

the bond marked with * denotes the R₂ linkage.

In a further particular embodiment, R₀ is H, C₁-C₆-alkyl or Phenyl, in particular for H or C₁-C₄-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-, sec- or tert-butyl.

The invention further relates to new dyes of the formula (I), in which
n = 1 or 2,
T = O
R₁ for n = 1 aryl, hetaryl or heterocyclylidene methyl and for n = 2 is a direct bond or arylene and
R₂ and R₃ together form the residue of an optionally substituted aromatic, heteroaromatic or heteroaliphatic ring,
excluding dyes of the formula

and dyes of the formula

wherein
R 2-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3,4-dichlorophenyl, 2,4-di nitrophenyl, 2-bromophenyl, 4-bromophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 4-methylphenyl, 3,4-methylenedioxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3,4-dimethoxyphenyl, 4- Dimethylaminophenyl, 1-naphthyl, 2-naphthyl and 3,4-diethoxyphenyl from J. Heterocycl. Chem. 1, (1964) pp. 205-206.

New dyes of the formula (I) which have the preferred embodiment are preferred form of the above procedure for T = 0 correspond.  

Another object of the invention is a method for producing the new Dyes of the formula (I) according to the invention, characterized in that

• a) Compounds of the formula wherein R₂ and R₃ together have the meaning given for the new dyes of the formula (I) with T = O,
  with compounds of the formula R₁-CH = Y (E5) in which
  R₁ for n = 1 or 2 has the meanings above and
  Y for O, (C₆-C₁₀-aryl) N, in particular phenyl-N, (C₁-C₄-alkyl) ₂N⊕, in particular (CH₃) ₂N⊕, (C₆-C₁₀-aryl) (C₁-C₅-acyl) N ⊕, in particular (phenyl) (CH₃CO) N⊕ or (C₆-C₁₀-aryl) (C₁-C₅-alkyl) N⊕, in particular (phenyl) (CH₃) N⊕,
  with the elimination of YH₂ (and optionally H₂O, alkyl-OH or NH₃) in a solvent or in the melt, optionally in the presence of a catalyst at a temperature of 0 to 250 ° C, preferably the YH₂ by the addition of binding agents (z Can be removed by means of physical methods (e.g. by distillation), or
• b) compounds of the formula in which
  R₂ and R₃ together have the meaning given for the new dyes of the formula (I) with T = 0,
  Z for OH, O (C₁-C₄-alkyl), in particular -OCH₃, O (C₁-C₅-acyl), in particular O-CO-CH₃, Cl, Br, (C₁-C₄-alkyl) ₂N, in particular (CH₃) ₂N, (C₆-C₁₀-aryl) NH, especially phenyl-NH, (C₆-C₁₀-aryl) (C₁-C₄-alkyl) N, especially (phenyl) (CH₃) N, (C₆-C₁₀-aryl) (C₁ -C₅-acyl) N, in particular (phenyl) (COCH₃) N, NH₂ or (C₁-C₄-alkyl) NH, in particular CH₃NH, and R₂ and R₃ have the meaning given under a),
  with compounds of the formula R₁-H (E7), with the elimination of ZH, optionally in a solvent or a melt at a temperature of 0 to 250 ° C. It is also advantageous here to add a catalyst and to bind ZH.

Preference is given to manufacturing variant a) using the Move connection (E1) or (E2).

Generally suitable as solvents for the two processes mentioned Alcohols such as As ethanol, methanol, propanols, butanols etc., carboxylic acids such as B. formic acid, acetic acid, propionic acid etc., esters, e.g. B. ethyl acetate, polar aprotic solvents, e.g. B. dimethylformamide, N-methylpyrrolidone, Dimethylacetamide, dimethyl sulfoxide, etc., aromatics, e.g. B. benzene, toluene, xylenes, Chlorine, dichloro, trichlorobenzene etc., ethers, e.g. B. tetrahydrofuran, dioxane, Methyl t-butyl ether, etc., glycols and their ethers, e.g. B. mono-, di-, tri-, tetra ethylene glycol, propylene glycol, their methyl, ethyl, butyl ether etc., Halogen aliphatics, e.g. B. dichloromethane, dichloroethane, chloroform etc.

Acidic and basic catalysts are suitable as catalysts.

The following may be mentioned as acidic catalysts: carboxylic acids, e.g. B. acetic acid, Propionic acid, chloroacetic acid, benzoic acid etc., sulfonic acids, e.g. B. toluene sulfonic acid, methanesulfonic acid, etc., inorganic acids such. B. sulfur, Hydrochloric, phosphoric, hydrobromic, etc., zinc chloride, aluminum chloride, Boron trifluoride etc.

Basic suitable catalysts are for example: organic bases, e.g. B. Amines such as triethylamine, dialkylamine, piperidine, pyrrolidine, morpholine, N, N-Di methylaniline, etc., alcoholates, e.g. B. sodium methylate, potassium t-butoxide, etc., Carboxylic acid salts, e.g. As sodium or potassium acetate, etc., alkali or alkaline earth oxides, hydroxides or carbonates e.g. B. sodium, potassium hydroxide, calcium oxide, Magnesium oxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate etc., ammonia, tetrabutylammonium hydroxide etc.

As the reaction temperature for the manufacturing described under a) or b) the range from 0 to 250 ° C, preferably between 15 and 220 ° C.  

The dyes of the formula (I) which are already known can be prepared analogously to the inventions Process according to the invention are prepared, wherein T = O or N-R₀ and R₀ has the above meaning.

For dyes of the formula (I) with T = N-R₀ is preferred according to the Production variant (a) using the compound (E1) with T = N-R₀ method. Compounds of formula (I) with T = N-R₀ are known in part from J. Chem. Soc. Perkin Trans. II 4: 615-619 (1984); Khim. Geterosikl. Soedin. 1972, 1237.

The listed starting products in which T = 0 are commercially available or easily accessible e.g. B. according to WO 9208703; J. Org. Chem. 16 (1951), pp. 1588, 1590, u. a.

The starting products, in which T = N-R₀ and R₀ has the meaning given above, are commercially available or easily accessible e.g. B. according to J. Med. Chem. 32 (1989), Pp. 437-444; EP-A-252 713 or US-A-4 690 943.

Mass coloring is understood to mean, in particular, processes in which the dye is incorporated into the molten plastic mass, e.g. More colorful Using an extruder or where the dye is already the starting compo Nenten for the production of the plastic, for. B. monomers before polymerization, is added.

Particularly preferred plastics are thermoplastics, for example vinyl polymers, polyesters and polyamides.

Suitable vinyl polymers are polystyrene, styrene-acrylonitrile copolymers, styrene Butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, polymethacrylate u. a.

Other suitable polyesters are: polyethylene terephthalates, polycarbonates and Cellulose esters.  

Polystyrene, styrene copolymers, polycarbonates and polymeth are preferred acrylate. Polystyrene is particularly preferred.

The high-molecular compounds mentioned can be used individually or in mixtures, exist as plastic masses or melts.

The dyes of the invention are used in finely divided form brought, wherein dispersants can be used but do not have to.

If the dyes (I) are used after the polymerization, they are also used the plastic granulate mixed dry or ground and this mixture e.g. B. plasticized and homogenized on mixing rollers or in screws. Man can also add the dyes to the molten mass and this distribute homogeneously by stirring. The material so pre-colored is then like usual z. B. by spinning to bristles, threads etc. or by extrusion or further processed into molded parts by injection molding.

Since the dyes of the formula (I) compared to polymerization catalysts, in particular special peroxides are resistant, it is also possible to use the dyes add monomeric starting materials for the plastics and then in To polymerize the presence of polymerization catalysts. To do this, the Dyes preferably dissolved in the monomeric components or with them intimately mixed.

The dyes of the formula (I) are preferably used for dyeing the above Polymers in amounts of 0.0001 to 1 wt .-%, in particular 0.01 to 0.5 wt .-%, based on the amount of polymer used.

By adding pigments insoluble in the polymers, such as. B. titanium dioxide, corresponding valuable muted stains can be obtained.

Titanium dioxide can be present in an amount of 0.01 to 10% by weight, preferably 0.1 to 5 wt .-%, based on the amount of polymer, are used.  

The process according to the invention gives transparent or covered ones brilliant, greenish yellow to violet colors with good heat resistance as well as good light and weather fastness.

Mixtures of different colors can also be used in the process according to the invention substances of formula (I) and / or mixtures of dyes of formula (I) with other dyes and / or inorganic or organic pigments be set.

The following examples serve to illustrate the present invention without however, restrict them.

"Parts" are to be understood as parts by weight unless otherwise stated.

The abbreviations used in the examples mean:
Me = methyl
Et = ethyl
Ph = phenyl
Ac = acetyl

example 1 A) Presentation

A mixture of 2.0 g of benzofuranone of the formula

2.3 g of 4-dimethylaminobenzaldehyde, 0.2 ml of piperidine and 40 ml of toluene are heated under reflux for 1 hour on a water separator. After cooling, the precipitate formed is suction filtered, washed with a little toluene and methanol and then dried.
Yield: 2.9 g

B) Coloring examples Example a)

100 parts of polystyrene granules and 0.02 parts of a dye of the above formula are intensively mixed in the drum mixer for 15 minutes. That dry colored granulate is at 240 ° C on a screw injection molding machine processed. Transparent, yellow plates of very good light fastness are obtained.

Instead of polystyrene polymer, copolymers with butadiene can also be used and acrylonitrile can be used. If you add 0.5 parts of titanium dioxide, so you get strong colored muted stains.  

Example b)

0.015 parts of the dye from Example A) and 100 parts of polymethyl methacrylate are mixed dry and on a single-screw extruder at 230 ° C homogenized. The material emerging from the extruder as a strand is granulated. It can then be pressed into shapes. You get one transparent yellow colored plastic with good light and weather fastness.

Example c)

100 parts of a commercially available polycarbonate are in the form of granules 0.03 parts of the dye from Example A) mixed dry. That pollinated Granules are homogenized on a twin-screw extruder at 290 ° C. You get a transparent yellow color with good lightfastness. The colored one Polycarbonate is discharged as a strand from the extruder and becomes granules processed. The granules can be made using the customary methods of packaging thermoplastic masses are processed.

If you work as described above, but with the addition of 1% titanium dioxide, so you get a yellow muted color.

Example d)

With 100 parts of styrene-acrylonitrile copolymer, 0.04 part of the dye from Example A) dry mixed and in a 2-shaft extruder at 190 ° C. homogenized, granulated and then pressed into shapes in the usual way. Man receives a transparent yellow plastic with good lightfastness.

Example e)

0.025 part of the dye from Example A) are mixed with 100 parts Polyethylene terephthalate of a transparent type mixed and in a 2- Homogenized shaft extruder at 280 ° C. A transparent, yellow one is obtained Coloring with good lightfastness. After subsequent granulation, the colored plastic according to the usual methods of thermoplastic  Deformation can be processed. If you work with the addition of 1% titanium dioxide, so you get a muted color.

Example f

0.05 part of tert-dodecyl mercaptan and 0.05 part are added to 98.9 parts of styrene of the dye from Example A) dissolved. This solution is dispersed in a Solution from 200 parts of demineralized water, 0.3 parts of partially saponified Polyvinyl acetate (e.g. Mowiol® 50/88 from Hoechst) and 0.05 parts Dodecylbenzenesulfonate. After adding 0.1 part of dibenzoyl peroxide in 1 part Styrene is heated to 80 ° C with vigorous stirring and the Polymerization started. When using the following polymerization conditions: 4 h at 80 ° C, 2 h at 90 ° C, 3 h at 110 ° C, 2 h at 130 ° C, this is obtained Polymer in a yield of 98% of theory. The polymer falls into Form of pearls, which, depending on the stirring conditions, a diameter of 0.1 to 1.5 mm (D₅₀ value). The polymer is obtained by filtration of serum separated, dried at 110 ° C to a residual moisture of 0.5%. After this Melt in a mixing unit (hot roller) and 0.5% zinc stearate 0.2% ionol added and the polymer granulated.

The polymer can be prepared by the usual methods of thermoplastic Deformation, e.g. B. in the injection molding process, to yellow, transparent moldings are processed.

Example g)

In 74.8 parts of styrene and 25 parts of acrylonitrile, 0.2 part of tert-dodecyl mercaptan and 0.01 parts of the dye from Example A) dissolved, which then in a solution of 200 parts of fully demineralized water and 0.2 parts a copolymer of styrene and. neutralized with sodium hydroxide Maleic anhydride is dispersed. After adding 0.1 parts Dibenzoyl peroxide, dissolved in a part of styrene, the dispersion with vigorous Stirring heated to 80 ° C and the polymerization started. After the polymerization as in example f), in the same way as indicated in the example, worked up. 0.5% zinc stearate is used as the lubricant and  Anti-aging agent 0.5% ionol incorporated on the hot roller. The granular Polymer can be sprayed into transparent yellow molded parts.

Examples

In a continuously operating, flooded prereactor, a Solution of 99.95 parts of styrene, 0.04 parts of the dye from Example A) and 0.01 parts of di-tert-butyl peroxide retracted and at a temperature of 75 ° C. polymerized. The polymerized solution emerging from the pre-reactor (Polystyrene content 20%) is introduced in a 2-shaft screw unit. The two shafts run in opposite directions at 20 rpm. The four heatable or coolable Segments of the screw machine are ordered in the order of products occurs - product outlet kept at 110 ° C, 130 ° C, 160 ° C, 180 ° C. The polymer leaves the screw reactor with a solids concentration of 80%. In one downstream extruders are 3 parts by weight of ionol and 5 parts by weight Octyl alcohol per 1000 parts by weight of polymer solution metered in, the polymer degassed and then granulated. The yellow colored granules can Molded parts are processed.

Example i)

0.02 part of the dye from Example A) are in 74.97 parts of styrene and 25 Parts of acrylonitrile or methacrylonitrile dissolved. After adding 0.01 parts of di tert-butyl peroxide, the solution thus obtained is in a continuous working, flooded pre-reactor retracted. The polymerization and Working up takes place as indicated in example h). The transparent, yellow Granules can be processed by the usual methods of processing thermoplastic Masses to be processed into profiles and plates.

Example k)

in 99.97 parts of methyl methacrylate, 0.03 part of the dye is removed Example A) solved. After adding 0.1 part of dibenzoyl peroxide Solution heated to 120 ° C and the polymerization started. After 30 minutes the polymerized methyl methacrylate between two glass plates at 80 ° C  polymerized for 10 hours. Yellow, transparent ones are obtained Polymethyl methacrylate sheets.

Example 1

100 parts of polyamide 6 chips, obtained by polymerizing ε-caprolactam, with 0.05 parts of the dye from Example A) in a shaker intimately mixed. The powdered schnitzel thus obtained are in at 260 ° C. melted in an extruder, the melt obtained through a single-hole nozzle of diameter 0.5 mm and the emerging thread with a Speed of approx. 25 m / min. deducted. The thread can be hot Extend water 4 times. A transparent yellow color is obtained Thread of excellent lightfastness. If you want a muted coloring obtained, 0.5 parts of titanium dioxide are additionally added.

The dwell time in the extruder can be up to 30 without impairing the color Minutes.

Example 2

A mixture of 1.34 g of benzofuranone, 3.2 g of an aldehyde of the formula

0.2 ml of piperidine and 40 ml of toluene are heated under reflux on a water separator for 2.5 hours. After cooling, the precipitated product is suctioned off and redissolved from boiling toluene.
Yield: 2.2 g.

Analogous to the coloring examples from Example 1, strong yellow shades are obtained good fastness properties.

Example 3

A mixture of 1.34 g of benzofuranone, 2.01 g of the compound of the formula

0.2 ml of piperidine and 40 ml of toluene is heated for 1.5 hours under reflux on a water separator. The toluene is then removed in vacuo and the resinous product is overlaid with cyclohexane. After a few hours, the solidified product is triturated with cyclohexane and the precipitate is then suctioned off.
Yield: 2.6 g.

Dyed analogously to the dyeing examples from Example 1, intensive yellow are obtained Coloring.  

Example 4

A mixture of 1.84 g of the naphthofuran of the formula

1.5 g of 4-dimethylaminobenzaldehyde, 0.2 ml of piperidine and 25 ml of toluene are heated under reflux for 2 hours on a water separator. After cooling, the precipitate formed is suction filtered and washed with methanol.
Yield: 2.6 g.

If the above dye is dyed analogously to the dyeing examples from Example 1, then you get real, strong yellow tones.  

Example 5

A mixture of 2.76 g of the naphthofuranone from Example 4, 2.04 g of 4-methoxybenzaldehyde, 0.2 ml of piperidine and 30 ml of toluene is heated under reflux for 2 hours on a water separator. After a few hours, the precipitate is filtered off and washed with methanol.
Yield: 3.3 g.

Dyed analogously to the dyeing examples from Example 1, the above dye gives strong greenish yellow colorations.

Example 6

1.84 g of the naphthofuran from Example 4, 3.2 g of the aldehyde from Example 2, 0.2 ml of piperidine and 40 ml of toluene are heated to boiling on a water separator. After 4 hours, the reaction mixture is filtered and the product is precipitated from the filtrate in the cold with a lot of methanol.
Yield: 1.1 g.

If the above dye is dyed analogously to the dyeing examples from Example 1, then you get strong orange tones.  

Example 7

A mixture of 2.0 g of the furanone of the formula

2.6 g of the aldehyde from Example 2, 0.2 ml of piperidine and 30 ml of xylene are heated for 2 hours on a water separator. After cooling, the precipitate formed is filtered off and recrystallized from pyridine / methanol.
Yield: 1.0 g.

In plastics, the dye provides analogy to the coloring examples from example 1 intense red coloring.

Example 8

A mixture of 2.0 g of the furanone from Example 7, 1.5 g of 4-dimethylaminobenzaldehyde, 0.2 ml of piperidine and 30 ml of toluene are heated in a water separator for 2 hours. The precipitate is then filtered off and recrystallized from methanol.
Yield: 0.9 g.

The above dye dyes plastics in accordance with the dyeing examples from Example 1 in strong orange tones.

Example 9

A mixture of 1.6 g of a quinolone of the formula

1.15 g of 4-dimethylaminobenzaldehyde, 10 ml of glacial acetic acid and 12.5 ml of acetic anhydride are heated under reflux for 1 hour. After cooling, the precipitate formed is suctioned off and washed with a little glacial acetic acid and methanol.
Yield: 1.8 g.

The dye provides strong orange colorations if it is analogous to the Coloring examples from Example 1 is colored.  

Example 10

1.3 g of the quinolone from Example 9, 2.0 g of the aldehyde from Example 2, 10 ml of glacial acetic acid and 12.5 ml of acetic anhydride are heated under reflux for 30 minutes. The precipitate is then suctioned off cold and washed with methanol.
Yield: 2.4 g.

The dye, colored according to the dyeing examples from Example 1, shows intense orange-red shades with good fastness properties.

Example 11

A mixture of 9.8 g of the quinolone of the formula

6.7 g of 4-dimethylaminobenzaldehyde, 20 ml of glacial acetic acid and 25 ml of acetic anhydride are heated to boiling for 30 minutes and then suction filtered while hot. The precipitate is washed with a little glacial acetic acid and methanol.
Yield: 13.3 g.

Dyed analogously to the above dyeing examples, yellow dyeings with good results are obtained Fastness.

Example 12

3.7 g of the quinolone from Example 11, 3.16 g of the aldehyde from Example 3, 20 ml of glacial acetic acid and 25 ml of acetic anhydride are heated under reflux for 30 minutes. The product which precipitates on cooling is filtered off with suction, washed with glacial acetic acid and acetone and dried at 70 ° C. in vacuo.
Yield: 5.5 g.

Colored in accordance with the coloring examples from Example 1, the above color provides strong orange tones.

Example 13

A mixture of 3.7 g of the quinolone from Example 11, 5.04 g of the aldehyde from Example 2, 20 ml of glacial acetic acid and 25 ml of acetic anhydride is heated to boiling for 30 minutes and then allowed to cool. The resulting precipitate is filtered off, washed with acetic acid, methanol and acetone and dried.
Yield: 6.3 g.

Dyed analogously to the above dyeing examples from Example 1, the above is obtained Dye with strong orange colorations.

Example 14

A mixture of 3.3 g of the quinolone of the formula

1.6 g of 4-methoxybenzaldehyde, 20 ml of glacial acetic acid and 25 ml of acetic anhydride are heated under reflux for 5 hours. The resulting precipitate is filtered off at about 80 ° C and washed with methanol.
Yield: 1.6 g.

Greenish yellow colorations are obtained if the dye is analogous to colors above dyeing examples from Example 1.  

Example 15

3.3 g of the quinolone from Example 14, 1.8 g of 4-dimethylaminobenzaldehyde, 40 ml Glacial acetic acid and 50 ml of acetic anhydride are heated under reflux for 45 minutes.

The precipitate is then filtered off at about 80 ° C and washed with methanol.
Yield: 4.3 g.

Colored analogously to dyeing examples 1B), the dye gives an orange-red color Shades.

Example 16

4.42 g of the quinolone from Example 14, 5.04 g of the aldehyde from Example 2, 20 ml of glacial acetic acid and 25 ml of acetic anhydride are heated to boiling for 30 minutes. The mixture is then cooled to room temperature, the precipitate is filtered off and washed with methanol and acetone.
Yield: 7.1 g.

Dyed according to dyeing examples 1B), the above dye gives intense, bluish red coloring.  

Example 17

A mixture of 2.77 g of the compound of the formula

1.5 g of 4-dimethylaminobenzaldehyde, 12 ml of acetic anhydride and 10 ml of glacial acetic acid are boiled for 15 minutes. The resulting precipitate is filtered off hot and washed with glacial acetic acid and methanol.
Yield: 3.7 g.

Analogous to the dyeing examples 1B), strong, reddish yellow is obtained Coloring.

Example 18

A solution of 2.77 g of the compound of the formula  

and 3.15 g of the aldehyde from Example 2 in 12.5 ml of acetic anhydride and 10 ml of acetic acid are heated under reflux for 1 hour. Then allowed to cool and the resulting precipitate is suctioned off. The product is washed with glacial acetic acid and methanol and dried.
Yield: 4.8 g

Dyed according to dyeing examples 1B), the above dye gives strong Shades of red in plastics.

Example 19

A mixture of 1.65 g of the coumarin of the formula

1.1 g of 4-dimethylaminobenzaldehyde, 8 ml of acetic anhydride and 7 ml of acetic acid are heated to boiling for 1.5 hours. The resulting precipitate is filtered off at 70 ° C, washed with glacial acetic acid and methanol and dried.
Yield: 2.5 g.

The above dye intensively dyes plastics according to dyeing examples 1B) orange tones.

Example 20

1.65 g of the coumarin of the formula

and 2.4 g of the aldehyde from Example 2 are heated to boiling in 12 ml of acetic anhydride and 10 ml of acetic acid for 45 minutes. After cooling, the product is filtered off and washed with glacial acetic acid and methanol.
Yield: 3.3 g.

Dyed in plastics analogous to coloring examples 1B), strong ones are obtained Shades of red with good lightfastness.

Example 21

A mixture of 3.56 g of 3-benzoylpropionic acid, 2.98 g of 4-dimethylaminobenz aldehyde, 12.5 ml of acetic anhydride and 10 ml of glacial acetic acid is heated under reflux for 1 hour. After cooling, the precipitate formed is filtered off and recrystallized from 20 ml of glacial acetic acid.
Yield: 2.4 g.

The dye delivers colored strong in accordance with dyeing examples 1B) Yellows

Example 22

A mixture of 3.56 g of 3-benzoylpropionic acid, 6.4 g of the aldehyde from Example 2, 12.5 ml of acetic anhydride and 10.0 ml of glacial acetic acid is heated under reflux for 1 hour. After cooling, the product is suctioned off and purified by reprecipitation from DMF / water.
Yield: 2.8 g.

According to dyeing examples 1B), the above dye dyes plastic parts in intensive orange tones.

Example 23

A mixture of 2.2 g of α-angelicalactone (5-methyl-2-furanone), 3.0 g of 4-di methylaminobenzaldehyde and 0.1 ml piperidine is added over 3 hours Heated from 180 to 185 ° C and then held at this temperature for 3 hours.

During this time, the water of reaction is distilled off. Spread over 2 Portions are placed at intervals of a total of 4.4 g of α-angelicalactone and 0.5 ml Piperidine after. The reaction mixture is then dissolved in glacial acetic acid and that Precipitated product with ice / water, making a total of 1.35 g of pure product be preserved.

The dye supplies colored strong in accordance with dyeing examples 1B) Yellows.  

Example 24

A mixture of 2.2 g of α-angelicalactone, 6.3 g of the aldehyde from Example 2, 30 ml of toluene and 0.3 ml of piperidine is heated on a water separator for 18 hours. The solvent is then removed in vacuo and the residue is then recrystallized from 15 ml of glacial acetic acid.
Yield: 1.2 g.

According to dyeing examples 1B), the above dye dyes plastics in intensive Yellows.

Example 25

A mixture of 3.3 g of the benzofuranone from Example 1, 6.3 g of an aldehyde of the formula

12.5 ml of acetic anhydride and 10 ml of glacial acetic acid are heated under reflux for 3 hours and then concentrated to dryness in vacuo. The residue is rubbed through several times with ligroin and the ligroin is decanted repeatedly. Then the residue is stirred with a few portions of diethyl ether, and the ether phase is then concentrated. The precipitate is filtered off and dried.
Yield 1.7 g.

Dyed in accordance with dyeing examples 1B), the dye obtained is the above strong yellows.

Example 26

A solution of 2.7 g of the benzofuran from Example 1, 4.1 g of the aldehyde formula

and 0.3 ml of piperidine in 30 ml of toluene is heated to boiling under reflux for 1 hour. The volatile constituents are then removed in vacuo and the residue is triturated several times with fresh portions of Ligroin. The tough residue is then taken up in diethyl ether and cooled to 0.degree. The resulting precipitate is suctioned off cold and dried.
Yield 1.6 g.

Dyed in plastics analogous to dyeing examples 1B) gives the above dye intense yellow tones.  

Example 27

A mixture of 1.84 g of the naphthofuran from Example 4, 3.7 g of the aldehyde from Example 25, 0.3 ml of piperidine and 30 ml of toluene is 2 hours on Water separator heated to boiling. 10 ml of toluene are then distilled off and let it cool down. The resulting precipitate is filtered off and with Washed diethyl ether. Yield 0.9 g. Another 2.0 g fall from the combined Toluene and ether filtrates from standing overnight.

Dyed analogously to dyeing examples 1B), the dye obtained is obtained with the above dye strong reddish yellow tones.  

Example 28

A solution of 1.84 g of the naphthol furan from Example 4 and 2.3 g of the Aldehyde from Example 26 in 12.5 ml acetic anhydride and 10.0 ml glacial acetic acid turns 30 Heated under reflux for minutes and then to dryness in vacuo constricted. The residue is dissolved in 100 ml of glacial acetic acid. About this solution 50 ml of water are now added dropwise with vigorous stirring; then you stir overnight after. The precipitate is filtered off, washed with water and dried. After recrystallization from 10 ml of toluene, 1.9 g of above product.

Colored in plastics in accordance with coloring examples 1B), this results Dye strong orange tones.

Example 29

A mixture of 2.3 g of the quinoline from Example 14, 1.06 4-methylthiobenzaldehyde, 0.04 g of sodium acetate, 12.5 ml of acetic anhydride and 10 ml of acetic acid is heated under reflux for 1 hour. The product is then filtered off hot, washed with acetic acid and methanol and dried.
Yield: 2.3 g.

Dyed analogously to dyeing examples 1B), the above dye gives brilliant strong yellow tones in plastics.

Example 30

A solution of 3.6 g of the naphthofuran from Example 4, 3.0 g of 4-methylthiobenzaldehyde and 0.08 g of sodium acetate in 12.5 ml of acetic anhydride and 10.0 ml of acetic acid is heated under reflux for 1 hour. After cooling, the precipitate is filtered off and washed with methanol.
Yield: 2.5 g.

Colored in accordance with dyeing examples 1B), the above dye gives intense, yellow plastic coloring.

Example 31 1st stage

A mixture of 3.5 g of the quinoxaline of the formula

4.6 g of the aldehyde from Example 2, 12.5 ml of acetic anhydride and 10 ml of acetic acid are stirred at 110 ° C. for 2 hours. After cooling, the mixture is filtered and the filtrate is freed from solvent in vacuo. The residue is dissolved in methanol while hot. The product which precipitates on cooling is filtered off, washed with methanol and dried.
Yield: 3.9 g.

2nd stage

3.0 g of the first stage product are combined in 30 ml of 1-chloronaphthalene briefly heated to 240 ° C. with 0.1 g of p-toluenesulfonic acid hydrate. After cooling 50 ml of methanol are added and the precipitated end product is filtered off with suction. After this Washing with methanol and drying give 1.4 g of the above end product.

Analogous to dyeing examples 1B) colored with this dye intense shades of red.  

Example 32

3.5 g of the quinoxaline from Example 31, 2.3 g of 4-dimethylaminobenzaldehyde, 12.5 ml of acetic anhydride and 10.0 ml of acetic acid are heated to boiling for 30 minutes. The volatile constituents are then removed completely in vacuo and 30 ml of 1-chloronaphthalene and 0.1 g of p-toluenesulfonic acid hydrate are added to the residue. The solution is heated to 240 ° C. for 45 minutes and then, after cooling to 50 ° C., methanol is added. The precipitate is filtered off and washed with methanol.
Yield: 0.5 g.

Colored in plastics in accordance with coloring examples 1B) gives the above Strong orange coloring.

Example 33

A solution of 4.5 g of benzoylpropionic acid, 1.4 g of terephthalaldehyde and 0.04 g of sodium acetate in 12.5 ml of acetic anhydride and 10 ml of acetic acid is heated to boiling for 20 minutes with stirring. A further 10 ml of acetic acid are then added and the precipitate is suctioned off while hot, which is washed thoroughly with acetic acid and methanol.
Yield: 3.5 g.

Plastics are by the above dye according to the coloring examples 1B) intense orange color.  

Example 34

A mixture of 6.7 g of the benzofuranone from Example 1, 2.7 g of terephthalaldehyde, 0.08 g of sodium acetate, 12.5 ml of acetic anhydride and 10 ml of acetic acid is heated under reflux for 1 hour. After cooling, the precipitate is filtered off, washed with methanol and dried.
Yield: 5.8 g.

Intense yellow tones are obtained when the above dye is analogous to the dye examples 1B) colors in plastics.

Example 35

A suspension of 2.5 g of naphthofuran from Example 4, 0.73 g of terephthalaldehyde, 0.025 g of sodium acetate, 10 ml of acetic anhydride and 8 ml of acetic acid is heated under reflux for 1.5 hours. The precipitate is filtered off and washed with acetic acid and methanol.
Yield: 2.0 g.

Dyed according to dyeing examples 1B), the above dye leads to brilliant oranges Shades.  

Example 36

A mixture of 4.95 g of the quinolone from Example 11, 1.34 g of terephthalaldehyde, 12.5 ml of acetic anhydride and 10 ml of acetic acid is heated under reflux for 2 hours. The resulting precipitate is filtered off at 80 ° C, washed with glacial acetic acid and methanol and dried.
Yield: 2.8 g.

Dyed in accordance with dyeing examples 1B), the dye obtained is the above Yellows.

Example 37

A mixture of 2.2 g of 2-indolone of the formula

2.3 g of 4-dimethylaminobenzaldehyde, 0.3 ml of piperidine and 30 ml of toluene are heated for 2 hours on a water separator. The mixture is then cooled to room temperature and the precipitate is filtered off with suction. It is washed with toluene and diethyl ether and dried.
Yield: 3.8 g.

Dyed according to dyeing examples 1B), one obtains with the above dye Yellows.  

Example 38

A mixture of 2.2 g of 2-indolone, 3.1 g of 4-diethylamino-2-methylbenzaldehyde, 0.3 ml of piperidine and 30 ml of toluene is heated in a water separator under reflux for 3 hours. After 18 hours at room temperature, the precipitate is filtered off, washed with toluene and diethyl ether and dried.
Yield: 1.5 g.

Dyed analogously to dyeing examples 1B), the above dye gives brilliant strong yellow tones in plastics.

Example 39

2.2 g of 2-indolone are analogous to Example 1 with 3.5 g of an aldehyde of the formula

implemented. The mixture is then concentrated in vacuo and the product is precipitated with diethyl ether.
Yield: 4.1 g.

Colored in accordance with dyeing examples 1B), the above dye gives intense, yellow plastic coloring.

Example 40

2.2 g of 2-indolone, 5.5 g of the aldehyde of the formula

0.3 ml of piperidine and 30 ml of toluene are stirred for 1 hour with the reac tion water heated. The product is then suctioned off and washed with toluene and ether and dries. After recrystallization from toluene, 3.7 g are obtained.

Dyed in plastics analogous to dyeing examples 1B) gives the above dye intense yellow tones.  

Example 41

A mixture of 2.2 g 2-indolone, 4.8 g 4-dimethylaminonaphthalene-1-carbalde hyd, 0.3 ml piperidine and 30 ml toluene is 1 hour on a water separator heated. The mixture is then diluted with toluene and the precipitate is filtered off with suction. To washing with toluene and diethyl ether gives 4.1 g of the dye above Formula.

Dyed analogously to dyeing examples 1B), the dye obtained is obtained with the above dye strong yellows.

Example 42

3.0 g aldehyde of the formula

and 2.2 g of 2-indolone are placed in 30 ml of toluene in the presence of 0.3 ml Piperidine in the usual way. After filtering and toluene and Diethyl ether washing produces 4.6 g of the above product.

Analogous to the dyeing examples from Example 1, strong reddish tones are obtained Yellows with good fastness properties.

Example 43

A mixture of 2.2 g indolone, 4.6 g of the aldehyde of the formula

0.3 ml of piperidine and 30 ml of toluene is heated on a water separator for 30 minutes.

The resulting precipitate is filtered off at 100 ° C and washed in the usual way.
Yield: 4.4 g.

If the above dye is dyed analogously to the dyeing examples from Example 1, then you get real, strong yellow tones.  

Example 44

A mixture of 2.2 g of 1-methyl-2-indolone of the formula

2.3 g of 4-dimethylaminobenzaldehyde, 0.3 ml of piperidine and 30 ml of toluene are heated for 4 hours on a water separator. The solvent is then removed in vacuo and the residue is dissolved in hot methanol; on cooling, the product precipitates, is suctioned off and washed with methanol.
Yield: 2.3 g

Dyed analogously to the dyeing examples from Example 1, the above dye gives strong yellow colors.  

Example 45

A solution of 2.4 g of 1-methyl-2-indolone, 3.8 g of the aldehyde from Example 39 and 0.3 ml of piperidine in 30 ml of toluene is heated on a water separator for 6 hours. The solvent is then removed in vacuo and the residue is boiled with methanol. The product precipitates as oil when it cools down. After decanting, it is dried and then extracted with ligroin. When it cools, the dye precipitates in crystalline form and is suctioned off.
Yield: 0.7 g.

The dye supplies colored strong in accordance with dyeing examples 1B) Yellows.

Example 46

Analogously to Example 45, 2.4 g of 1-methyl-2-indolone are reacted with 5.5 g of the aldehyde from Example 40 and worked up.
Yield 1.6 g.

According to dyeing examples 1B), the above dye dyes plastics in intensive Yellows.  

Example 47

A mixture of 2.4 g of 1-methyl-2-indolone, 4.8 g of 4-dimethylamino-naphthalene-1-carbaldehyde, 0.3 ml of piperidine and 30 ml of toluene is heated to boiling on a water separator for 2.5 hours. After cooling, the precipitate is filtered off and washed with toluene and methanol.
Yield: 2.9 g.

Dyed in accordance with dyeing examples 1B), the dye obtained is the above strong yellows.

Example 48

A suspension of 2.4 g of 1-methyl-2-indolone, 4.2 g of the aldehyde from Example 43, 0.3 ml piperidine and 30 ml toluene is 2 hours on a water separator heated. It is then filtered hot and with 10 ml of boiling toluene washed. When cooling, the dye falls out of the filtrate. After this Aspiration and washing with diethyl ether precipitate 3.9 g of the above product.

Colored in plastics in accordance with coloring examples 1B), this results Dye strong reddish yellow tones.  

Example 49

A solution of 2.0 g of 2-indolone, 2.3 g of 4-dimethylaminobenzaldehyde, 12.5 ml of acetic anhydride and 10.0 ml of acetic acid is heated under reflux for 4 hours and then freed from the solvent under reduced pressure. The residue is refluxed in 50 ml of methanol for 15 minutes. The resulting precipitate is filtered off at 60 ° C and washed with methanol.
Yield: 3.2 g.

Dyed analogously to the dyeing examples from Example 1, intensive yellow are obtained Coloring.

Example 50

Analogously to Example 13, 2.2 g of 2-indolone are reacted with the aldehyde from Example 43. After 20 minutes, the mixture is cooled, the product is filtered off with suction and washed with acetic anhydride and methanol.
Yield: 2.9 g.

In plastics, the dye provides analogy to the coloring examples from example 1 intense yellow coloring.

Claims (12)

1. Process for mass coloring plastics with dyes of the formula (I) wherein
T represents O or N-R₀, wherein
R₀ denotes H, alkyl, aryl, acyl or together with R₃ or R₂ forms a 5- to 7-membered ring,
n 1 or 2,
R₁ for n = 1, aryl, hetaryl or heterocyclylidene methyl and for n = 2 means a direct bond or arylene,
R₂, R₃ independently of one another are H, alkyl, aryl, aryl- or alkylsulfonyl, cyano, a radical of the formula -COR, in which R represents alkoxy, amino, alkylamino, dialkylamino, arylamino, alkyl or aryl or together the rest of an optionally form substituted aromatic, heteroaromatic or heteroaliphatic ring. 2. The method according to claim 1, characterized in that dyes of the formula (II) uses what
R₄ and R₆ together form the residue of an optionally substituted aromatic or heteroaromatic residue and
R₅ represents H, alkyl, halogen, OH, alkoxy, aryloxy, alkylthio, arylthio, acyloxy, dialkylamino or acylamino, or
R₅ and R₆ together form the residue of an optionally substituted heterocyclic ring and
R₄ represents H or alkyl. 3. The method according to claim 1, characterized in that dyes of the formula (III) uses what
the ring E is optionally substituted with alkyl, halogen, OH, alkoxy, aryloxy, acyloxy, alkylthio, arylthio, dialkylamino or acylamino. 4. The method of claim 2, wherein
R₅ and R₆ together form the rest of an optionally mono- or disubstituted and / or further substituted pyrrole, thiazole, oxazole, imidazole, pyridine, pyran or pyrimidine. 5. The method according to claim 2, characterized in that dyes of the formula (IV) are used, wherein
R₇, R₈ independently of one another are C₁-C₄-alkyl or together form the residue of an optionally substituted carbocyclic 5- or 6-ring,
R₉ is a C₁-C₄ alkyl group optionally substituted by phenyl, Cl, OH, CN, alkoxy carbonyl, alkoxy, dialkylamino or acyloxy and
R₁₀, R₁₁ together form the rest of an optionally substituted Ben zol- or naphthalene ring. 6. The method according to claim 1, characterized in that dyes of the formula (I) are used, in which
R₂ for hydrogen and
R₃ is C₁-C₄-alkyl or phenyl or naphthyl which is optionally substituted by C₁-C₄-alkoxy, Cl, Br or C₁-C₄-alkyl, or
R₂ and R₃ together represent a radical of the formula form,
the bond marked with * identifies the R₂ linkage and where
X represents O or N-R₁₆, where R₁₆ = H, C₁-C₆-alkyl or phenyl,
R₁₂ represents H, phenyl or C₁-C₄ alkyl,
R₁₃ represents H, phenyl, C₁-C₄-alkyl, C₁-C₄-alkoxycarbonyl, amino carbonyl, mono- or di-alkylaminocarbonyl, arylaminocarbonyl, C₁-C₄-alkylcarbonyl, benzyl or Cl,
R₁₄ and R₁₅ independently of one another are H, Cl, C₁-C₄-alkyl C₁-C₄-alkoxy or C₁-C₄-alkoxycarbonyl or together form the remainder of a benzo ring optionally substituted with these substituents or
R₂ and R₃ form the residue of an optionally substituted benzo or naphtho ring. 7. The method according to claim 1, characterized in that T = O means. 8. Dyes of the formula (I) wherein
T = O
n = 1 or 2,
R₁ for n = 1 aryl, hetaryl or heterocyclylidene methyl and for n = 2 is a direct bond or arylene and
R₂ and R₃ together form the residue of an optionally substituted aromatic, heteroaromatic or heteroaliphatic ring,
excluding dyes of the formula wherein
R 2-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3,4-dichlorophenyl, 2,4-di nitrophenyl, 2-bromophenyl, 4-bromophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 4-methylphenyl, 3,4-methylenedioxy phenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3,4-dimethoxyphenyl, 4 -Dimethylaminophenyl, 1-naphthyl, 2-naphthyl and 3,4-diethoxyphenyl. 9. A process for the preparation of dyes according to claim 8, characterized in that

• a) Compounds of the formula with compounds of the formula R₁-CH = Y (E5) in which
  Y for O, (C₆-C₁₀-aryl) -N, (C₁-C₄-alkyl) ₂N⊕, (C₆-C₁₀-aryl) (C₁-C₅-acyl) N⊕ or (C₆-C₁₀-aryl) (C₁ -C₄-alkyl) N⊕,
  in a solvent or in the melt, optionally in the presence of a catalyst at a temperature of 0 to 250 ° C, or
• b) compound of the formula in which
  Z for OH, O (C₁-C₄-alkyl), O (C₁-C₅-acyl), Cl, Br, (C₁-C₄-alkyl) ₂N, (C₆-C₁₀-aryl) NH, (C₆-C₁₀-aryl ) (C₁-C₄-alkyl) N, (C₆-C₁₀-aryl) - (C₁-C₅-acyl) N, NH₂ or (C₁-C₄-alkyl) NH,
  with compounds of the formula R₁-H (E7) with the elimination of ZH, if appropriate in a solvent or a melt at a temperature of 0 to 250 ° C.

10. The method according to claim 1, characterized in that the plastic is a thermoplastic, in particular a vinyl polymer, polyester or Polyamide. 11. Plastics colored by at least one of processes 1 to 7. 12. Plastics colored with at least one of the dyes according to claim 8th.