DE4327855A1 - Phthaloperinone dyes - Google Patents

Abstract

Phthaloperinone dyes of the formula (I) <IMAGE> where Z is SO2 or CO, A is optionally substituted alkyl or aryl, and the other substituents are each as defined in the description, are prepared by condensation of appropriate phthalic acids or their functional derivatives and optionally substituted 1,8-naphthalenediamines. The dyes of the invention have very good fastness properties and are used in processes for the mass coloration of plastics.

Description

The invention relates to perinone dyes, a process for their preparation and their Use for mass coloring plastics.

DE-A-22 36 555 describes acyloxyphthaloperinones, but they still do have certain disadvantages. Now phthaloperinone dyes became the general NEN formula (I) found

wherein
Z is SO₂ or CO,
A represents optionally substituted alkyl or aryl,
X represents C₁-C₆-alkyl, halogen, C₁-C₆-alkoxy, C₁-C₇-acyloxy or a fused-on cycloaliphatic ring,
Y represents C₁-C₆-alkyl, C₆-C₁₀-aryl, halogen, C₁-C₆-alkoxy, C₁-C₇-acyloxy or an amino group which is optionally substituted by C₁-C₇-acyl or C₁-C₆-alkyl,
m is a number from 0 to 6,
n is a number from 0 to 3,
and
p means 1 or 2,
n + p stands for a number from 1 to 4 and
for m <1 X each can have different or identical meanings of the abovementioned,
and
for n <1 Y may have different or the same meanings of the abovementioned.

Particularly preferred phthaloperinones are those in which A is C₁-C₁₈ alkyl, which is optionally unsaturated and / or further substituents such as halogen such as Cl, F, Br, C₁-C₄ alkoxy, phenoxy or optionally by halogen, C₁-C₄ -Alkyl or C₁-C₄-alkoxy substituted phenyl, or
represents phenyl or naphthyl, which may optionally be substituted by halogen, C₁-C₄-alkyl, cyano, C₁-C₄-alkylmercapto, C₁-C₄-alkylcarbonylamino, phenyl, phenoxy or C₁-C₄-alkoxy, and
X for chlorine, bromine, fluorine, OCH₃, OC₂H₅, OCH₂ (C₆H₅), OC₃H₅, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or one preferably in peri Position, ie each cycloaliphatic 5- or 6-membered ring fused in the para position to the N atoms, where —C₆H₆ here and also below stands for phenyl,
Y represents fluorine, chlorine, bromine, OCH₃, NHCOCH₃, N (C₂H₅) ₂, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or an optionally substituted phenyl,
m is a number from 0 to 4,
n is a number from 0 to 2,
p represents 1 or 2, and
n + p represents a number from 1 to 3.

In a very special embodiment means
X is chlorine, bromine, methyl, ethyl or a cycloaliphatic 5- or 6-ring fused in the peri (4,5) position,
m is a number from 0 to 2,
n the number 0 and
p 1 or 2,
and
A and Z have the meaning given above.

In a very particularly preferred embodiment, m stands for 0.  

In another very particularly preferred embodiment, p stands for 1.

The alkylcarbonyls formed together from A and Z are, for example:

Acetyl, propionyl, butyryl, 1-methyl-butyryl, 2-butyl-butyryl, 1-ethyl-butyryl, Dimethyl-propionyl, pentanoyl, hexanoyl, 1-ethyl-hexanoyl, heptanoyl, octanoyl, Nonanoyl, decanoyl, dodecanoyl, tetradecanonyl, hexadecanoyl, octadecanoyl, Ethoxyacetyl, cyclohexylcarbonyl, 4-methyl-cyclohexylcarbonyl, 3,5-dimethyl cyclohexylcarbonyl, phenylacetyl, β-phenylpropionyl, 4-methylphenylacetyl, Phenoxyacetyl, 4-chlorophenoxyacetyl and cinnamoyl.

The arylcarbonyl radicals formed together from A and Z are, for example:

Benzoyl, 2-, 3- and 4-chlorobenzoyl, 2-, 3- and 4-methylbenzoyl, 4-methoxybenzoyl, 4-ethoxybenzoyl, 2,3-dichlorobenzoyl, 3,5-dimethylbenzoyl, 4-phenylbenzoyl, naphthoyl-1, naphthoyl-2,2-methoxy-naphthoyl-1.

The alkylsulfonyl radicals formed together from A and Z are, for example:

Methanesulfonyl, ethanesulfonyl, n-propanesulfonyl, n-butanesulfonyl, n-octane sulfonyl, n-dodecanesulfonyl, n-hexadecanesulfonyl, β-methoxyethanesulfonyl, β-ethoxy-ethanesulfonyl, cyclohexanesulfonyl, 4-methyl-cyclohexanesulfonyl.

The arylsulfonyl radicals formed together from A and Z are, for example:

Benzenesulfonyl, 4-methylbenzenesulfonyl, 4-methoxybenzenesulfonyl, 4-iso propylbenzenesulfonyl, 2- or 4-chlorobenzenesulfonyl, 2,4-dichlorobenzenesulfonyl, 4-methyl mercaptobenzenesulfonyl, 4-acetaminobenzenesulfonyl, 1-naphthalenesul fonyl, 2-naphthalenesulfonyl.

Those dyes in which A and Z together for are particularly preferred Benzoyl or benzenesulfonyl are available.  

The very special embodiment of the invention Dyes correspond to formulas (IIa), (IIb), (IIIa) and (IIIb)

or mixtures of any composition thereof, preferably any Compound mixtures of the isomers (IIa) and (IIb) or (IIIa) and (IIIb) are called.

The invention also relates to a method for producing the invention Dyes of the formula (I) by condensation of phthalic acids of the formula (IV) or their functional derivatives, preferably the anhydrides.  

in which
A, Z, Y, n and p have the meaning given,
with naphthalene-1,8-diamines of the formula (V)

in which
X and m have the meaning given,
in a molar ratio of 1: 0.8 to 1: 1.2, preferably in equimolar amounts, at a temperature of 50-220 ° C., if appropriate in the presence of a catalyst, if appropriate under pressure and if appropriate in the presence of a solvent.

The condensation can accordingly in the melt or, more advantageously, in one Solvents are carried out.

The melt process is preferably carried out at a temperature of 120-180 ° C, and the process in a solvent is preferably carried out at 80-150 ° C.

The water of reaction is preferably distilled from the reaction mixture  away.

The product is preferably isolated by filtration, the Reaction mixture previously acting solvent can be added can.

So arise. B. from 1,8-diaminonaphthalene and in the 4-position by A-Z substituted phthalic acid isomer mixtures from dyes of the formulas (IIa) and (IIb) or from the amine mentioned and substituted in the 3-position by A-Z Phthalic acid isomer mixtures of compounds of the formulas (IIIa) and (IIIb). However, the phthalic acid substituted by A is itself a mixture of the 3- and 4-isomers before, mixtures of the isomeric dyes are obtained Formulas (IIa), (IIb), (IIIa) and (IIIb).

Suitable solvents for the reaction are, for example: chlorobenzene, o-di chlorobenzene, trichlorobenzene, xylene, dimethylformamide, N-methylpyrrolidone, ice sig, propionic acid, phenol, cresols, phenoxyethanol, glycols and their mono- and Dialkyl ethers, alcohols, e.g. B. methanol, ethanol, i-propanol, water and aqueous Solvents such as B. dilute sulfuric acid u. a.

If necessary, the reaction can be carried out with the addition of an acidic catalyst.

Suitable catalysts are, for example: zinc chloride, p-toluenesulfonic acid, Hydrochloric acid, sulfuric acid, organic acids such as B. glacial acetic acid or benzoic acid u. a.

When using catalysts, preferably up to 0.1 mol Equivalents, based on the component of formula (IV), are used.

Similar procedures are already available from D.R.P. 202 354, Chem. Ber. 75 (1942), 719, and Liebigs Ann. Chem. 365 (1909), 128.

The corresponding phthalic acids (or their functional derivatives) can, for. B.  as in US-A-5 061 810; US 1155 588; EP 245 729; Zh. Prikl. Khim. 49, 1353-8 (1976); Zh. Org. Khim. 14: 1046-51 (1978); ibid. 9, 121-8 (1973); DE 22 43 283 or by analogy.

Of particular interest due to the industrially feasible Reaction conditions is therefore the process variant that is characterized is that acid chlorides of the formula (VI)

A-Z-Cl (VI)

with o-dialkylbenzenes of the formula (VII)

in the presence of acidic catalysts in the sense of Friedel-Crafts acylation Compounds of formula (VII)

converts and this in a second step to phthalic acids of formula (IV) oxi dated. Instead of acid chlorides of formula (VI), in which Z is CO, read sen also use the corresponding benzotrichloride A-CCl₃.

This is not described above and is therefore also an object of the invention The above method in which

Z = SO₂,

A = phenyl, which is optionally substituted by up to two chlorine or one bromine atom, or 1- or 2-naphthyl,
p = 1 or 2, preferably 1,
n = 0 and
R₁ and R₂ independently of one another are C₁-C₄-alkyl, preferably methyl, or together represent a tri- or tetramethylene radical.

The acidic catalysts used are preferably iron (III) chloride or aluminum minium chloride. Other suitable catalysts are tin (IV) chloride, Ti tan (IV) chloride, aluminum bromide, zinc chloride, iron and the like. a.

The catalyst is used in amounts of 0.0001 to 1.1 moles per mole of sulfochloride Formula (VI) used, preferably 0.0005 to 0.01 mol.

The molar ratio of the compounds of formula (VI) and (VII) can be for verbin of formula (VIII) with p = 1 from 1.5: 1 to 1: 100, preferably 0.9: 1 to 1: 0.9, for p = 2 from 1.5: 1 to 3: 1, preferably from 2: 1 to 2.5: 1. The in Excess component can itself act as a solvent, as well but you can also an inert solvent such as nitrobenzene, o-dichlorobene zole, 1,2-dichloroethane and the like. a. clog. It is preferable to work without a solvent in the melt.

The reaction temperature is 0 to 180 ° C for p = 1.80 to 200 ° C for p = 2.

Excess o-dialkylbenzene (VII) or solvent are distilled removed, if necessary in vacuo or with the aid of steam. The product obtained is preferably used directly without further purification.  

The oxidation is carried out according to methods known per se for dialkyl aromatics by. The preferred oxidizing agent is nitric acid. Are also suitable Oxygen, air, (di) chromates, chromic acid, permanganates, manganese dioxide, hypo chlorite u. a.

When using nitric acid, the concentration of which is 5 to 50% can, one works preferably under pressure at temperatures of 120 to 180 ° C. The nitric acid can be regenerated with air or oxygen, which at low nitric acid concentrations can be advantageous, as can the Implementation as a cycle process should be cheap.

Suitable starting materials of the formula (IV) are, for example:

4- (benzenesulfonyl) phthalic acid, 3- (benzenesulfonyl) phthalic acid, 4- (4'-methyl-benzene sulfonyl) phthalic acid, 3- (3'-methyl-benzenesulfonyl) phthalic acid, 4- (2'-methylbenzene sulfonyl) phthalic acid, 4- (4'-tert-butyl-benzenesulfonyl) phthalic acid, 4- (2 ', 4'-di methyl-benzenesulfonyl) phthalic acid, 4- (4′-chloro-benzenesulfonyl) phthalic acid, 4- (3′- Chlorobenzenesulfonyl) phthalic acid, 3- (2′-chlorobenzenesulfonyl) phthalic acid, 4- (4′- Fluorobenzenesulfonyl) phthalic acid, 4- (4′-bromo-benzenesuffonyl) phthalic acid, 4- (3 ′, 4′- Dichlorobenzenesulfonyl) phthalic acid, 4- (4′-methoxy-benzenesulfonyl) phthalic acid, 3- (4'-methoxy-benzenesulfonyl) phthalic acid, 4- (3'-methoxy-benzenesulfonyl) phthalic acid, 4- (4'-ethoxy-benzenesulfonyl) phthalic acid, 4- (3'-butoxy-benzenesulfonyl) - phthalic acid, 4- (methanesulfonyl) phthalic acid, 3- (methanesulfonyl) phthalic acid, 4- (Ethanesulfonyl) phthalic acid, 4- (n-butanesulfonyl) phthalic acid, or 4- (cyclohexane sulfonyl) phthalic acid, 4- (acetyl) phthalic acid, 4- (propionyl) phthalic acid, 4- (butyryl) - phthalic acid, 4- (cyclohexane carbonyl) phthalic acid, 4- (benzoyl) phthalic acid, 3- (benzo yl) phthalic acid, 4- (methyl-benzoyl) phthalic acid, 4- (ethyl-benzoyl) phthalic acid, 3- (Chlorobenzoyl) phthalic acid, 4- (chlorobenzoyl) phthalic acid, 4- (dichlorobenzoyl) - phthalic acid, 4- (dimethyl-benzoyl) phthalic acid, 4- (tert-butyl-benzoyl) phthalic acid, 4- (fluoro-benzoyl) phthalic acid, 4- (acetylamino-benzoyl) phthalic acid, 4- (methylmer capto-benzoyl) phthalic acid, 4- (methanesulfonyl-benzoyl) phthalic acid, 4- (methoxy benzoyl) phthalic acid, 4- (ethoxy-benzoyl) phthalic acid, and 4- (butoxy-benzoyl) - phthalic acid or its anhydrides.  

The substituted naphthalene-1,8-diamines used can be, for. B. after D.R.P 122 475; D.R.P 108 166; J. Chem. Soc. (1932) 2310; ibid. (1936), 556, 1338; ibid. (1945), 454, 543; ibid. (1951) 221; J. Prakt. Chem. 94 (1916), 45; Compt. red. 224 (1947), 1569; At. Soc. espan. 31 (1933), 861, 876; J. Org. Chem. 24 (1959), 214 u. a. or in analogy.

Suitable naphthalene-1,8-diamines of the formula (V) are:

1,8-naphthalenediamine, chloro-1,8-naphthalenediamine, dichloro-1,8-naphthalene diamine, bromo-1,8-naphthalenediamine, methyl-1,8-naphthalenediamine, dimethyl 1,8-naphthalenediamines, methyl-chloro-1,8-naphthalenediamines, methoxy-1,8- naphthalenediamines, ethoxy-1,8-naphthalenediamines, acetamino-1,8-naphthalenes diamines and 4,5-dimethylene-naphthalene-1,8-diamine, the substituents are preferably bonded in the 2-, 4-, 5- or 7-position of the naphthalene.

The dyes according to the invention are outstandingly suitable for dyeing art fabrics in bulk.

Mass coloring is understood to mean in particular methods in which the Dye is incorporated into the molten plastic mass, e.g. B. under Zu 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 poly mers, polyesters and polyamides.

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

Other suitable polyesters are: polyethylene terephthalate, polybutylene tere phthalates, 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 mixed with the Plastic granules mixed dry or ground and this mixture z. B. on Mixing rollers or plasticized in screws and homogenized. You can change the color but also add substances to the molten mass and stir them distribute homogeneously. The so pre-colored material is then z. B. by Spinning to bristles, threads etc. or by extrusion or by injection molding processed into molded parts.

Since the dyes of the formula (I) compared to polymerization catalysts, ins special peroxides that 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% by weight, in particular 0.01 to 0.5% by weight, 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, orange to violet colors with good heat resistance and 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 used become.

The invention is illustrated, but not limited to the following examples, in where the parts are given by weight and percentages by weight percentages (% by weight) mean.  

example 1 A) Presentation

A mixture of 3.1 parts of naphthalene-1,8-diamine, 5.7 parts of 4-benzenesulfonylphthalic anhydride and 30 parts of glacial acetic acid is heated to 80 ° C. for 10 minutes. After cooling, the precipitate obtained is suction filtered and washed with methanol and water.
Yield: 7.7 parts (95%) of an isomer mixture of the two dyes of the formulas above.

The representation of the 4-benzenesulfonylphthalic anhydride can follow like this:

4-benzenesulfonyl-1,2-dimethylbenzene

110 g o-xylene, 176 g benzenesulfochloride and 0.16 g iron (in) chloride are combined at room temperature and within 2 hours heated to 110 ° C. After the HCl development is finished Heated 140 ° C and the product discharged onto a sheet. When cooling the melt solidifies to a colorless mass. Yield: 243 g.

4-benzenesulfonyl phthalic acid

20 g of the above product are in 600 ml of water and 200 ml of 65% Nitric acid suspended. Then heated in an autoclave for 6 hours to 160 ° C, which creates a pressure of 10 to 13 atm. After this  Relaxation is cooled to approx. 0-5 ° C and the precipitate is sucked up a few hours. It is washed with a little ice water and dried. Yield: 18-22 g.

4-benzenesulfonylphthalic anhydride

19 g of the free acid are boiled in 100 ml of acetic anhydride for 10 minutes heated. The mixture is then cooled to 5 ° C. and the precipitate is suctioned off a few hours. Yield: 16 g.

B) Coloring examples Example a)

100 parts of polystyrene granules and 0.02 parts of the dye from Example A) are intensively mixed in the drum mixer for 15 minutes. The Dry-colored granules are sprayed at 240 ° C on a screw casting machine processed. You get transparent, red plates of very good lightfastness. Instead of polystyrene polymer can also Copolymers with butadiene and acrylonitrile can be used. Puts if you add 0.5 parts of titanium dioxide, you get strong colored muted Coloring.

Example b)

0.015 parts of the dye from Example A) and 100 parts of polymethyl meth Acrylates 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 a transparent red colored plastic with good light and weather authenticity.  

Example c)

100 parts of a commercially available polycarbonate are in the form of granules dry mixed with 0.03 parts of the dye from Example A). That so Dusted granules are homogenized on a twin-screw extruder at 290 ° C siert. A transparent red color with good light fastness is obtained. The colored polycarbonate is discharged as a strand from the extruder and closed Granules processed. The granules can be processed according to the usual methods Packaging thermoplastic masses are processed.

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

Example d)

With 100 parts of styrene-acrylonitrile copolymer, 0.04 part of the color substance from Example A) mixed dry and in a 2-shaft extruder Homogenized at 190 ° C, granulated and then molded in the usual way pressed. A transparent red plastic of good light is obtained authenticity.

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 one 2-shaft extruder homogenized at 280 ° C. You get a transparent, red color with good lightfastness. After subsequent granulation can the colored plastic by the usual methods of thermo plastic 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 98.9 parts of styrene 0.05 parts of the dye from Example A) dissolved. This solution dispersed one in a solution of 200 parts of deionized water, 0.3 part saponified polyvinyl acetate (e.g. Mowiol® 50/88 from Hoechst) and 0.05 part of dodecylbenzenesulfonate. After adding 0.1 part of dibenzoyl Peroxide in 1 part of styrene, the dispersion is stirred at 80 ° C with vigorous stirring heated and the polymerization started. When using the following poly Merization conditions: 4 h at 80 ° C, 2 h at 90 ° C, 3 h at 110 ° C, 2 h at 130 ° C, the polymer is obtained in a yield of 98% of theory. The polymer is obtained in the form of beads, depending on the stirring conditions have a diameter of 0.1 to 1.5 mm (D₅₀ value). The polymer sat is separated from the serum by filtration, at 110 ° C for a residue dried moisture of 0.5%. After melting in a mixer aggregate (hot roller) are 0.5% zinc stearate and 0.2% Ionol® from Shell (2,6-di-tert-butyl-p-cresol) mixed in 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 red, transparent form parts are processed.

Example g)

In 74.8 parts of styrene and 25 parts of acrylonitrile, 0.2 part of tert.- Dissolved dodecyl mercaptan and 0.01 part of the dye from Example A), this solution is then completely in a solution of 200 parts salted water and 0.2 parts of one neutralized with sodium hydroxide Dispersed copolymer of styrene and maleic anhydride. After To Set of 0.1 parts of dibenzoyl peroxide, dissolved in one part of styrene, the Dispersion heated to 80 ° C with vigorous stirring and the polymerization started. After the polymerization as in Example f) is also the same  Worked up as indicated in the example. As a lubricant 0.5% zinc stearate and as an anti-aging agent 0.5% Ionol® from Shell (2,6-di-tert-butyl-p-cresol) incorporated on the hot roller. That gra nulated polymer can be sprayed into transparent red moldings.

Example h)

In a continuously working, flooded pre-reactor 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 polymerized at 75 ° C. The anpoly emerging from the pre-reactor merized solution (polystyrene content 20%) is in a 2-wave screw unit introduced. The two waves run against each other at 20 rpm common. The four heatable and coolable segments of the screw machine are in the order of product entry - product exit to 110 ° C, Maintained 130 ° C, 160 ° C, 180 ° C. The polymer leaves the snails reactor with a solids concentration of 80%. In a downstream 3 parts by weight of Ionol® from Shell (2,6-di-tert-butyl-p-cresol) and 5 parts by weight of octyl alcohol per 1000 parts by weight of polymer solution are metered in, the polymer is degassed and then granulated. The red colored granulate can form into molded parts be working.

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 part of di-tert-butyl peroxide is the solution thus obtained in one continuously operating, flooded prereactor retracted. The polymerization and working up are carried out as indicated in Example h). The transparent, red granulate can be made according to the usual methods of ver processing of thermoplastic materials into profiles and sheets become.  

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 min. the polymerized methyl methacrylate between two glass plates Polymerized 80 ° C for ten hours. You get red, transparent Polymethyl methacrylate sheets.

Example l)

100 parts of polyamide 6 chips, obtained by polymerization of ε-caprolactam, with 0.05 part of the dye from Example A) in a shaker mixed intimately. The powdered so obtained Chips are melted in an extruder at 260 ° C, which he holding melt through a single-hole nozzle with a diameter of 0.5 mm presses and the emerging thread at a speed of approx. 25 m / min. deducted. The thread can be put on the four in hot water stretch times. A transparent red colored thread is obtained from excellent light fastness. If you want to get a muted coloring, so 0.5 parts of titanium dioxide are added.

The residence time in the extruder can be up to without impairing the color 30 minutes.

Example 2

The procedure is as given in the manufacturing instructions in Example 1, but under Use of 3-benzenesulfonylphthalic anhydride instead of there if 4-isomers are used, the above isomer mixture is obtained in 90% yield, which correspond to the coloring examples in Example 1B) plastics in orange tones colors and provides a high level of authenticity.

Example 3

Is used instead of the isomerically pure benzenesulfonylphthalic anhydrides according to Examples 1 and 2, mixtures of 3- and 4-benzenesulfunylphthalic acid anhydride, so you get mixtures of the four isomeric dyes as in Bei Game 1 and 2 described in plastics according to the coloring examples in Example 1B) give colored red shades with good fastness properties.

Example 4

5.9 parts of 1,8-diaminonaphthalene are dissolved in 50 parts of dimethylformamide. After adding 9.1 parts of 4-benzoylphthalic anhydride, the reaction mixture heated to 140 ° C for 1 hour. It is then cooled to approx. 80 ° C and diluted with 60 parts of methanol, suction filtered at room temperature and the residue washed with methanol and water. After drying, 15.2 parts of above mixture of isomers. Dyed analogously to the dyeing examples in Example 1 the above dye gives a yellowish red, highly fast coloration.  

Example 5

In Example 4, 4-benzoylphthalic anhydride is replaced by 3-benzoylphthal acid anhydride and continues as indicated there, a mixture is obtained of two isomeric dyes that have the specified structure. (Yield: 87%)

The above mixture of isomers leads according to the dyeing examples in Example 1, to very real orange colors.

Example 6

Is used in the manufacturing instructions of Examples 4 and 5 instead of isomerically pure benzoylphthalic anhydride mixtures of 3- and 4-benzoyl phthalic anhydride, mixtures of the four in Examples 4 and 5 are obtained described isomeric benzoylphthaloperinones, which are used in plastics according to Dyeing examples in example 1B) colored high-fast yellowish red shades deliver.

Examples 7 to 66

In an analogous manner as described in Example 1A, the compounds of the formulas IV and V obtained the dyes described in Table 1, which in Plastics are colored according to 1B) a) -1) and that in Table 1 achieve the specified colors.  

Claims (10)

1. Phthaloperinone dyes of the general formula (I) wherein
Z is SO₂ or CO,
A represents optionally substituted alkyl or aryl,
X represents C₁-C₆-alkyl, halogen, C₁-C₆-alkoxy, C₁-C₇-acyloxy or a fused-on cycloaliphatic ring,
Y represents C₁-C₆-alkyl, C₆-C₁₀-aryl, halogen, C₁-C₆-alkoxy, C₁-C₇-acyloxy or an amino group which is optionally substituted by C₁-C₇-acyl or C₁-C₆-alkyl,
m is a number from 0 to 6,
n is a number from 0 to 3,
and
p means 1 or 2,
n + p stands for a number from 1 to 4 and
for m <1 X each can have different or identical meanings of the abovementioned,
and
for n <1 Y can each have different or identical meanings given above. 2. Phthaloperinone dyes according to claim 1, characterized in that
A represents C₁-C₁₈-alkyl, which is optionally unsaturated and / or optionally further substituted with halogen, C₁-C₄-alkoxy, phenoxy or optionally substituted by halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy or
represents phenyl or naphthyl, which is optionally substituted by halogen, C₁-C₄-alkyl, cyano, C₁-C₄-alkylmercapto, C₁-C₄-alkylearbonylamino, phenyl, phenoxy or C₁-C₄-alkoxy, and
X for chlorine, bromine, fluorine, OCH₃, OC₂H₅, OCH₂ (C₆H₅), OC₃H₅, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or one preferably in peri- Position of fused cycloaliphatic 5- or 6-membered ring,
Y represents fluorine, chlorine, bromine, OCH₃, NHCOCH₃, N (C₂H₅) ₂, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or an optionally substituted phenyl ,
m is a number from 0 to 4,
n is a number from 0 to 2,
p represents 1 or 2, and
n + p represents a number from 1 to 3. 3. phthaloperinone dyes according to claim 1, characterized in that
X chlorine, bromine, methyl, ethyl or a cycloaliphatic 5- or 6-membered ring fused in the peri-position,
m is a number from 0 to 2,
n the number 0 and
p means 1 or 2. 4. Phthaloperinone dyes according to claim 1, wherein m is 0 and p is 1 stands. 5. Phthaloperinone dyes according to claim 1 of the formulas or mixtures of any composition thereof, preference being given to mixtures of the isomers (IIa) and (IIb) or (IIIa) and (IIIb) of any composition. 6. A process for the preparation of phthaloperinone dyes according to claim 1, characterized in that phthalic acids of the formula (IV) or their functional derivatives, preferably their anhydrides in which
A, Z, Y, n and p have the meaning according to claim 1,
with naphthalene-1,8-diamines of the formula (V) in which
X and m have the meaning according to claim 1,
in a molar ratio of 1: 0.8 to 1: 1.2, preferably in equimolar amounts, at a temperature of 50-220 ° C., if appropriate in the presence of a catalyst, if appropriate under pressure and if appropriate in the presence of a solvent. 7. A process for mass coloring plastics, characterized in that a phthaloperinone dye of claim 1 is used. 8. A method for bulk dyeing plastics according to claim 7, characterized characterized in that the plastic is a thermoplastic, in particular a Vinyl polymer or a polyester. 9. Process for the preparation of compounds of formula (IV) wherein
Z = SO₂,
A = phenyl, which is optionally substituted by up to two chlorine or one bromine atom, or 1- or 2-naphthyl,
p = 1 or 2, preferably 1,
n = 0 means
characterized in that acid chlorides of the formula (VI) AZ-Cl (VI) with o-dialkylbenzenes of the formula (VII) wherein
n = 0 and
R₁ and R₂ independently of one another are C₁-C₄-alkyl, preferably methyl or together represent a tri- or tetramethylene radical,
in the presence of acidic catalysts for the compounds of the formula (VIII) wherein
p = 1,
reacted and oxidized to phthalic acids of formula (IV). 10. Plastics colored with at least one phthaloperinone dye Claim 1.