DE2504925A1 - PROCESS FOR THE MANUFACTURING OF XANTHENE DYES - Google Patents

Description

Process for the production of xanthene dyes

It is known to use 3,6-dichloro-9-phenyl-xanthene-9-ol compounds in organic solvents which are inert under the reaction conditions with aromatic amino compounds and acidic catalysts, such as " z. B. zinc chloride to implement (see. DT-PS 2 013 168, Ex. 8).

In this case, solvents are always used which is already used for the preparation of the 3> 6 ~ dichloro-9-plienylxanthene-9-ol compound Find use, such as. B. chlorobenzene, o-dichlorobenzene, nitrobenzene, toluene or xylene. Using this solvent becomes aqueous after the dye has melted worked up, the working up of the three-phase system Water / solvent / crystalline dye big trouble prepares. If the dye is isolated by suction, it contains considerable amounts of solvent, which in the subsequent Drying process must be recovered. If the solvent is blown over with steam, the precipitating dye usually clumps together in a greasy way. In addition, those that are saturated with solvents arise Wastewater that has to be processed "

It has now been found that xanthene dyes are particularly advantageous by reaction of 9-phenylxanthene compounds of

formula

CL ^ Y

6 09834 / 07Sδ

wherein R ₃ or R is a hydrogen or a halogen atom, an alkyl or alkoxy radical, where R 1 or R _{4 can be} identical or different or together also an iso- or heterocyclic radical

Can form ring, R is hydrogen or an alkyl radical, Y is

Halogen atom or an alkoxy group and Z a hydroxy or alkoxy group or the radical of an organic or inorganic acid, with primary or secondary aromatic or heterocyclic acids Can produce amines in the presence of a Lewis acid and an organic solvent ^ if one is an organic Solvent the aromatic or heterocyclic amine is used.

Preference is given to aromatic or heterocyclic amines of the formula

used, in which R ^ an aromatic or heterocyclic Ring, which is continued by one or more, optionally substituted alkyl, hydroxy, alkoxy, amino, alkylamino, dialkylamino, alkylthio, aryl, arylamino, aryloxy, arylthio, Halogen, alkyl sulfone, nitro or cyano radicals may be substituted can, and R "is hydrogen, an optionally further substituted Mean alkyl or aralkyl radical. This is how you get xanthene dyes of the formulas Ia, I b. or I c

(I a)

(I b)

6 Q 9 8 3 47 0 7 8 8

7504925

(I c)

in which IL and R "have the abovementioned meaning and R_ or R. a hydrogen or a halogen atom, an alkyl or alkoxy radical, where R" or R _{4 can be} identical or different or together also an iso- or heterocyclic one Ring can form, R _r hydrogen or an alkyl radical, X an organic or inorganic anion, such as a halide, sulfate, nitrate, phosphate, fluoroborate, rhodanide, acetate, trihloroacetate, lactate or Mean formation.

In the above definitions for R ₁ to R, Y and Z, preference is given to alkyl and alkoxy radicals which have 1 to 4 carbon atoms. Phenyl groups are preferred as aryl groups, benzyl or phenethyl groups are preferred as aralkyl groups,

Particularly preferred starting materials are amines of the Fox'mel HNR ₁ R ", in which R" denotes a hydrogen atom or a lower alkyl group which can be substituted by a hydroxyl or cyano group, and R ₁ denotes a naphthyl radical and in particular a phenyl radical, which is substituted by 1 to 3 identical or different of the following substituents:

1 to 3 alkyl groups with 1-4 carbon atoms, 1 or 2 alkoxy groups with 1-4 C atoms, 1 or 2 chlorine or bromine atoms, a phenyl, phenoxy, phenylamino, alkylthio group with 1-4 C atoms or an amino group substituted by 1 or 2 lower alkyl groups can be.

60 98 347-07

As a starting material for the dyes of the formulas Ia, Ib and I c are 9-phenyl-xanthene compounds of the formula II

(II)

wherein R, R ₁ and R ₁ - have the abovementioned meaning, Y is a halogenator or an alkoxy group and Z is a hydroxyl or alkoxy group or the remainder of an organic or inorganic acid.

R 1 and R ₄ preferably stand for hydrogen or chlorine atoms, methyl groups or together for a fused-on benzene ring. R- preferably represents a methyl group, but especially a hydrogen atom.

The reaction takes place in the presence of a Lewis acid, such as, for example

wise ZnCl ₂ , AlCl ₃ , AlBr ₃ ,

FeCl.

BF.

SbF ", SbF ^ or CuCl.

with an excess amount of the aromatic solvent or heterocyclic amine used.

60 983470788 ORIGINAL INSPECTED

7 504925

According to the method according to the invention, red "to Produce blue xanthene dyes in excellent yield and purity.

The preparation of the starting xanthene compound of the formula II takes place in a known manner, for example according to the method of German patent specification 5 ^ 34-8.

The following compounds, which also serve as solvents at the same time, come into consideration as amines R ^ Rg NH: aniline, 2-amino-toluene, 3-amino-toluene, 4-aminotoluene, 2-amino-ethylbenzene, 4-amino-ethylbenzene , 3-amino-1,2-dimethylbenzene, 4 ~ Απΰηο-Ί, 2-dimethylbenzene, 2-amino-1 -, 3-di - "- methylbenzene, 4-amino-1,3-dimethylbenzene, 5-A .MINO-1,3-dimethylbenzene, 2-amino-1,4 ~ dimethylbenzene, 2-Axüinö-i, 3,5-trimethylbenzene, 4 ~ ^r Isoprop3 l-aniline, 4 ~ tert. butyl-aniline, 2 -Amino-. Phenol, 3-Amino-phenol, 4-Amino-phenol, 4-Amino -2-oxy-toluene, 5-Amino-2-oxy-toluene, 6-Amino-3-oxy-toluene, 2-Amino-4- ~ oxytoluene, 3 - ^ tiiiio-4-oxy-toluene, 2-Amino-anisole, 3-Aniino-anisole, 4-Amino-anisole, 2-Amino-phenetol, 3 - A -minophenetol, 4-aminopphenetol, 6-amino-3-methoxy-toluene, 2-amino-1,4-dimethoxybenzene, 2-amino-1,4-diethoxy-benzene, 1-aminO'-2,4- dimethoxybenzene, 1,2-diamino-benzene, 1,3-diamino-benzene, 1,4-diaminobenzene, 2,4-diamino-toluene, 2,5-diamino-toluene, 3i4 ~ diaminotoluene, 2-amino-N- me ethyl-aniline, 4-amino-N-methyl-aniline, 4-amino-N-ethyl-aniline, 2-amino-IT, N-dimethyr-aniline, 3-ainino-F, M "-dimethyl-aniline, 4 -Amino-N ^ N-dimethyl-aniline, 4-amino-N, IT-diethyl-aniline, 4-methylmercapto-aniline, 4-amino-no-diphenylamine, 2-amino-diphenyl ether, 4-amino-diphenyl ether, 2 -Chloroaniline, 3-chloro-aniline, 4-chloro-aniline, 2-bromo-aniline, 3-chloro-2-aminotoluene _t 4-chloro-2-aminotoluene, 5-chloro-2-aminotoluene , G-chlorine - ^ - amiüo-toluene, 1-faphthylamine, N-methyl-aniline, 2-N-methyl-aminotoluene, 2-amino-pyridine,

60983 4/07 8 8

The amines R ^ 1 * 2 ^ * are according to the invention in one used in such an amount that they also serve as solvents. They are so good solvents that even very highly concentrated ones Dyestuff melts always remain easily stirrable. The required amount can be in a wide range vary and be about 6-30 moles, preferably about 10-20 moles per mole of the xanthene compound of the formula II.

The too low reactivity of the xanthene compound of the formula II is greatly increased according to the invention by the use of a Lewis acid, which accelerates the reactions with some amines that take place only slowly without this addition and enables the reactions that would otherwise not take place with inert amines in the first place. The Lewis acid used can be used in catalytic amounts up to, with respect to the xanthene compound (II), above stoichiometric amounts. For example, the above-mentioned Lewis acids come into consideration5 but the use of AlCl _x is particularly favorable.

According to the invention, there are several possibilities for carrying out the reaction. One can proceed in such a way that the xanthene compound of the formula (II) is initially charged in the amine R-R ₂ NH and then the Lewis acid is added. Thereby forms; A reactive addition xanthenium compound forms with a sometimes strongly exothermic reaction. In this case, a strongly exothermic reaction between the amine and Lewis acid, cooling and thorough stirring are required so that gel or crust formation in the reaction mass is avoided.

It is also particularly advantageous to proceed in such a way that by first adding the amine R — R “NH and the Lewis acid produces the corresponding complex with a weak exothermic reaction and from this by the subsequent addition the xanthene compound of the formula (II) under again weak

609 8 3 4/0788

exothermic reaction quantitatively or in equilibrium the produces activated xaiithenium compound. Through this way of working one avoids both a too stormy exothermic reaction and the formation of reaction masses that are difficult to stir. The addition of the individual reactants can also be used when using very reactive Lewis acids take place very quickly. The complex formation or remodeling also takes place very quickly, and it can continue immediately and quickly to the point of dye formation required reaction temperature are heated, -The Maintaining an always thin, easily stirrable reaction mass leads to an optimal course of the reaction and thus very pure dyes in high yield. This procedure is particularly favorable when AlCl ^ as Lewis acid is used.

The reaction temperature and the reaction time depend on the respective reactivity of the reactants. The temperature may preferably but move between about 80 ⁰ C and 220 ⁰ C, between about I50 C and 180 C.

After the reaction has ended, it can be worked up in various ways will. One possibility is that the dye is suctioned off directly as a crystalline salt. Furthermore, you can first by reaction with an aqueous alkali solution in the Transfer the dye base of the formulas (Ib) or (I c), then suction directly or drive off the excess amine by steam distillation and then the water- isolate soluble dye base by aspiration. Another The possibility is that the entire reaction mass is stirred directly into an aqueous acid, the corresponding Dye salt (I a) precipitates in crystalline form and is filtered off with suction and the excess amine remains as a soluble salt in the aqueous phase and can be recovered therefrom.

609834 / Q788

The xanthene dyes obtainable according to the invention possess high purity and very high color strength. They can be made water-soluble by sulfonation with sulfuric acid and then lead from acidic aqueous solution to brilliant, deeply colored dyeings on wool, silk or with acid dyes dyeable synthetic fibers. The dyes prepared according to the invention can also be used according to the German patent application P 23 59 466.3-4-3 are used for spin dyeing polyacrylonitrile fibers, with strong, brilliant dyeings with excellent wet, rub, heat-setting and light fastness properties can be obtained.

In the following examples, parts mean parts by weight, % =% by weight.

Example 1 :

82.3 parts of 3,6-dichloro-9-phenyl-xanthydrol are added to 470 parts of 2,6-dimethylaniline. It is at 50 - 6O ⁰ C is heated, whereupon within 10 minutes with good stirring (expediently using a stirrer with a large blade) 2 parts of anhydrous aluminum chloride, with external cooling to 50 - 60 C are added?. It is for 1 hour at 50 - 6O ⁰ C is stirred, then at 180 - 190 ° C heated and stirred for 3 hours at this temperature. The mixture is then allowed to cool to 130-140 ° C. and the reaction mass is then pressed onto 1150 parts of a 12.5% strength aqueous sodium hydroxide solution at room temperature, 2 liquid phases being formed from which the excess 2,6-dimethylaniline is driven off by steam distillation. After the end of the steam distillation, the remaining aqueous phase is ^{cooled to 50 °} C. and the dyestuff base of the following formula, which is present in granulated form, is isolated by suction, washed neutral and dried.

609834/0 7 88

This dye base dissolves, e.g. in glacial acetic acid, with formation. of the acetate with a brilliant bluish red color.

Example 2:.

200 parts of 2,3-dimethylaniline are added at room temperature within 5 minutes with 4-0 parts of anhydrous aluminum chloride, whereby the temperature rises to about 60 * C ^0. 4-0 parts of 3r6-Diehlor-9-phenylxanthydrol are then added over the course of 5 minutes, a further rise in temperature to about 80 ° C. being established. Stirred, _wherein: 180 ⁰ C ER- "hitzt and stirred for 3 hours at that temperature then cooled to ⁰ C and 14-0 with vigorous stirring to 800 parts of a 10% aqueous hydrochloric acid of room temperature - then 0 is set to 1?. the temperature of the dye suspension obtained: ca. 60 ⁰ C rises from 1 hour After a subsequent stirring is filtered off hot, washed neutral with water and dried at 60 ⁰ G ".. 60 parts of one in glacial acetic acid or dimethylformamide with very high color strength and a brilliant red violet are obtained. Color soluble dye of the following formula

CH.

609834/07 88

In a manner analogous to that given in Examples 1 and 2, the following dyes can be prepared, with corresponding the dye base in Example 1 or in accordance with the example 2 a dye chloride or, if another acid is used, a corresponding salt is formed:

R-

C- shade in glacial acetic acid

CH-

CH,
CH

CH.

H H

H H

H H

H blue-violet

red-violet

HH 4-CH _$ H bluish red

blue-violet

HH

H blue-violet

H ₂ CO
w

H H

H H

H H

red-violet

blue-violet

H 'blue-violet

60 9834/078

R ₂ RR ₁ - shade in glacial acetic acid

Cl

Cl

H H

H H

H purple

H blue-violet

Cl

H H

H purple

CH
Cl

H H

H bluish red

CH,

H H

H red-violet

_tl - OCH-,

Cl

H H

2-Cl

H purple

H. bluish purple

CH-

CH, H 2-Cl H H bluish purple

H purple

H red-violet

OH

H H

GEL bluish red

609834 / 0.788

R _n . Hue in glacial acetic acid

OH H H H

H bluish purple

H H

H reddish blue

NH,

H H

H reddish blue

H H

H purple

H H

H bluish purple

0-L /> H ■. H ■ HH bluish purple

H H

H H

H red-violet H bluish violet

H H purple

2,3-CH = CH-CH = CH-

609 834/0788

? 5Q4925

Example 3 ^:

160 parts of m-anisidine are added to 40 parts Jjö xanthydrol with 1 part FeCl then: heated with good stirring to 150 ⁰ C. The compartment is stirred for 3 hours to 800 parts of a 10% strength aqueous hydrochloric acid, stirred for 1 hour at 50.degree. C., filtered off with suction, washed with water and dried at 60.degree. A dye of the following formula which is soluble in glacial acetic acid or dimethylformamide with a blue-violet hue and high depth of color is obtained in very good yield

Example 4: "::

200 parts of 2 ~ methyl-6-chloro-aniline are heated at room temperature within 5 minutes with 40 parts of anhydrous aluminum chloride and then mixed with 40 parts 3V6 xanthydrol, whereupon the now approximately 80 C warm reaction mass to 190 ⁰ C. The mixture is stirred at this temperature for 5 hours, ^{cooled to 140 °} C., stirred into 500 parts of a 12.5% strength aqueous sodium hydroxide solution, the AlCl ^ complex of the dye decomposing after a short time at the boiling temperature. The aqueous phase is removed and discarded} the organic phase is washed with hot water and drained by applying a vacuum. After cooling to room temperature, filtration and washing with methanol give a dye base of the following formula in very. obtained high purity.

609834/078 8

- 14- -

This dye base dissolves in glacial acetic acid or 85% formic acid with a brilliant, bluish red color.

Example ^:

3.4 parts of 35 6 ~ chloro-9- (4-methyl-phenyl) -xanthydrol are placed in 15 parts of glycol and, after the addition of 10 parts of aniline and 0.1 part of ZnCl _2, to 170 ° -180 ° C heated. A red-violet melt forms which, after J hours, is stirred into 50 parts of an aqueous 10% strength sulfuric acid. After filtering off with suction, washing with water and drying at 60 ° C., a dye of the following formula which is soluble in dimethylformamide with a blue-violet color is obtained in high yield

SO ₁

If, instead of the 3 _i 6-dichloro-9- ( ^z tr-methyl-phenyl) -xanthydrol, equivalent amounts of 3,6-dibromo- or 3j6-dimethoxy-9- (4-methyl-phenyl) -xanthydrol are used, the result is the same dye also in high yield.

6098 3 4/0788

Claims (4)

HOE 75 / F 038 - 15 - Claims: 1) Process for the production of xanthene dyes by Implementation of 9-phenylxanthene compounds of the formula wherein EL · or R _; a hydrogen or a halogen atom, an alkyl or alkoxy radical, where "R _7. or R ^, can be identical or different or together can also form an iso- or heterocyclic ring, R ₁ - hydrogen or an alkyl radical, Y is a halogen atom or an alkoxy group and Z is a hydroxyl or alkoxy group or the residue of an organic or inorganic acid, with primary or secondary aromatic or heterocyclic amines in the presence of a Lewis acid and an organic solvent the aromatic or heterocyclic amine is used. " 2) Method according to claim 1, characterized in that one per mole of 9-phenylxanthene compound 8-JO moles, preferably 10-20 Moles of amine used. 3) Method according to claim 1 and 2, characterized in that the amines used are those of the aniline series which are in 2- or 2,6-position are substituted by alkyl or alkoxy groups or negative substituents in the benzene radical, in particular Halogen atoms. 609834/0 7 88 7504925 HOE 75 / F 038 - 16 - 4) Method according to claim 1 to 3 »characterized in that that the amine is first reacted with the Lewis acid and the resulting adduct is then reacted with the Xanthene compound implemented. 609834/07 8 8