DE941381C - Process for the production of Kuepen dyes - Google Patents

Description

It has been found that valuable vat dyes are obtained if dialkoxybenzene-meta- or para-dicarboxylic acids, expediently in the form of their chlorides, with two identical or two different ones aromatic amines, at least one of which can be vetted, are converted to acid amides and, if appropriate, the acid amides obtained are converted into azoles in the same or a separate operation.

Dicarboxylic acids of the type mentioned are, for example, 2,5-dimethoxyterephthalic acid, 2,5-diethoxyterephthalic acid, 2,3-dimethoxyterephthalic acid, 2,3-diethoxyterephthalic acid, 4,6-dimethoxyisophthalic acid or 4,6-diethoxyisophthalic acid.

To implement these dialkoxybenzenedicarboxylic acids, a wide variety of viable, Compounds containing amino groups are used, preferably those based on anthraquinone are constructed. You can use simple aminoanthraquinones or more highly condensed systems, be like aminodibenzanthrone or aminopyranthrone, ao You can condense further rings on the A.nthraquinone ring contain, such as aminoanthrapyrimidines or aminoanthraquinone benzacridones. Under the Aminoanthraquinones also come into consideration, for example, which have further substituents, such as halogen atoms, oxy, methoxy, acylamino or

Contain sulfonamide groups. Such linkable connections can also be used with advantage be that z. B. contain at least one substituent in the o-position to the amino group, which for Formation of a heterocyclic ring can give rise to. Such substituents are e.g. B. the Hydroxyl, mercapto, nitro or amino group, as well as halogen atoms. Depending on the test conditions can be the formation of oxazole, thiazole or imidazole rings in the same or in a particular Operation carried out according to methods known per se.

It is not necessary to react each of the dicarboxylic acids with 2 moles of the amines mentioned.

It is also possible to proceed in stages and first implement and react with ι moles of the amines mentioned then react the second carboxyl group with the same or a different amine, which is not necessarily needs to be connectable and therefore from the

other aromatic amines can be selected, e.g. B. Aniline, the toluidines, the alkoxyanilines and the like. The only condition is that one of the amines used is viable.
The corresponding carboxylic acid halides are expediently used to convert the dialkoxybenzenedicarboxylic acids mentioned. The reaction is advantageously carried out in inert distributing solvents, such as chloro-, dichloro-, trichloro- or nitrobenzene, preferably at a higher temperature, e.g. B. at 130 to 170 ⁰ , through. Acid-binding agents such as sodium or potassium carbonate, sodium acetate or pyridine can also be used.

The vat dyes obtained by the present process are particularly suitable for dyeing and printing a wide variety of vegetable fibers, especially of cotton, linen, rayon and

O NH-CO

Spun rayon made from regenerated cellulose and from mixtures of the fibers mentioned, you can also be used as pigments or in a known manner in leuco ester salts, e.g. B. sulfuric acid, and in this form by the dyeing process customary for this class of dyes and printing. Some of the dyes are very extensive and allow production pure yellow to orange tones with good to excellent fastness properties, but are at Use of suitable amine components also possible in red and blue shades.

The vat dyes obtainable by the present process are those from the French patent 807 939 and dyes of comparable constitution known from German patent specification 469 019 superior due to greater productivity and better fastness to light, soda cooking, visiting and mercerising; in contrast to the comparable dye known from German patent specification 469 019, the colors according to Example 9 obtainable dye polyamide fibers in the same shade as cotton. 8g

The parts mentioned in the following examples are parts by weight:

example 1

A mixture of 26 parts of 2,5-dimethoxyterephthalic acid dichloride, 46 parts of i-aminoanthraquinone and 800 parts of dry nitrobenzene is under Stirring heated to 130 ° for several hours; the new dye separates in the form of yellow ones Small needles, which are sucked off after cooling, washed with nitrobenzene and alcohol and dried will. It dissolves in sulfuric acid with a red-yellow color and dyes cotton from a red vat in yellow Tones of excellent fastness properties. The new dye has the following structure:

CO-NH O

OCH,

The 2,5-dimethoxyterephthalic acid dichloride used in this example is made as follows:

2, 5-Dioxyterephthalic acid diethyl ester is through

Methylation with dimethyl sulfate in the 2,5-dimethoxyterephthalic acid diethyl ester convicted and this

saponified with alcoholic caustic solution to 2,5-dimethoxyterephthalic acid. The bright yellow dichloride is obtained from it by heating with thionyl chloride in nitrobenzene.
If the equivalent amount of i-amino-6-chloroanthraquinone or i-amino-5-methoxyanthraquinone is used instead of the i-aminoanthraquinone mentioned in paragraph 1, dyes are obtained which also dye cotton from a red vat in yellow tones.

Example 2

6.8 parts of i-amino-5-benzoylaminoanthraquinone are dissolved in 200 parts of nitrobenzene at 100 to 100 ° and the solution of 2.6 parts of the 2,5-dimethoxyterephthalic acid dichloride described in Example 1 in 30 parts of nitrobenzene is added. Then, the whole is heated for about 5 hours at 130 °, drawn after cooling to about 70 ⁰ the precipitated red-yellow dye off, washed with nitrobenzene and methanol and dried.

A light orange powder is obtained which dissolves in concentrated sulfuric acid with a red-yellow color and cotton from a red vat dyes strong, reddish-yellow tones. The dye has the structure:

OCH,

0 NH-CO

C0 - NH 0

OCH,

H ₅ C ₆ -CO-NH 0

Replaces the i-amino-5-benzoylaminoanthraquinone by the same amount of i-amino-4-bezoylaminoanthraquinone, This gives a red powder which, in concentrated sulfuric acid, turns red-yellow Dye dissolves and dyes cotton from a red vat in yellow-red tones.

Example 3

To a 150 to 160 ° hot solution of 5.2 parts 2, 5-Dimethoxyterephthalic acid dichloride in 350 parts dry trichlorobenzene is allowed to stir a hot solution of 10.2 parts of i-mercapto-2-aminoanthraquinone flow in 300 parts of trichlorobenzene and

NH-CO-

C ₆ H ₅

the mixture is stirred for about 5 hours at 150 to 160 ° further, whereby hydrogen chloride and water are split off. The precipitated dye is in the Sucked off heat, washed with trichlorobenzene and alcohol and dried. He is a tan Powder that dissolves in concentrated sulfuric acid with a yellow-brown color and cotton from brown The vat colors in brownish-yellow tones. After the usual cleaning of the dye paste with alkaline Hypochlorite solution dyes cotton from a brown-red vat in orange tones. The solution color in concentrated sulfuric acid is red-yellow. The dye has the following structure:

OCH,

Example 4

To a solution of 4.9 parts of 4-amino-i, 9-anthrapyrimidine a solution of 100 parts of nitrobenzene and 1.8 parts of pyridine is left at 100 ° to 110 ° 2.9 parts of 2, 5-dimethoxyterephthalic acid dichloride in 30 parts of nitrobenzene flow in and the mixture is then heated to 130 bis for about 5 hours while stirring

140 ⁰ . After cooling, the precipitated dye is filtered off with suction, washed with nitrobenzene, hot pyridine, alcohol and water and dried. It is a greenish yellow powder that dissolves in concentrated sulfuric acid with a yellow-red color and dyes cotton from a red vat in yellow tones. The dye has the structure

OCH,

O NH-CO

CO-NH O

OCH,

Example 5

In a 150 ° hot mixture of 6.8 parts of 4-aminoanthraquinone-2,1 (N), 1 ', 2' (N) -benzolacridone and 200 parts of nitrobenzene are left with stirring Solution of 2.9 parts of 2,5-dimethoxyterephthalic acid dichloride pour in 30 parts of nitrobenzene and 1.8 parts of pyridine and stir the whole thing a few more Hours at 150 °. Then it is allowed to cool, and what is excreted in the form of blue needles is sucked up Dye off. washes it with nitrobenzene and alcohol

out and dry it. The dark blue powder obtained dissolves in concentrated sulfuric acid yellow-red color and dyes cotton from a blue-red vat in muted blue tones. The dye has the following structure:

OCH ₃

O NH- CQ

Example 6

2.9 parts of 2, 5-diethoxyterephthalic acid dichloride, as described in Example 1, reacted with 4.5 parts of i-aminoanthraquinone. The dye obtained is a yellow powder that dissolves in concentrated sulfuric acid with a yellow-red color and cotton dyes from a red vat in yellow tones. The dye has the following structure:

OC ₂ H ₅

O NH-CO

CO-NH O

That used 2,5-diethoxyterephthalic acid dichloride is made as follows:

2, 5-Dioxyterephthalic acid diethyl ester is through Alkylation with diethyl sulfate in the 2,5-dietboxyterep'hthalsäurediethylester and this by saponification with alcoholic potassium hydroxide solution into 2,5-diethoxyterephthalic acid convicted. By heating with

Thionyl chloride in nitrobenzene is obtained therefrom

bright yellow colored dichloride.

Example 7

5.8 parts of the 2,5-diethoxyterephthalic acid dichloride described in Example 6 are, as described in Example 2, with 13.8 parts of i-amino-5-benzoylaminoanthraquinone implemented. The new dye is a red-yellow powder that is dissolved in concentrated sulfuric acid dissolves with yellow-red paint and dyes cotton from a red vat in yellow tones. The dye has the following structure:

OC ₈ H,

NH-CO-;

CO -NHO

H ₅ C ₂ O

H, C _fi -CO-NH O

NH-CO-C _n H,

Example 8

3.5 parts of 2,5-diethoxyterephthalic acid dichloride are, as described in Example 4, reacted with 4.9 parts of 4-Ammo-i, 9-anthrapyrimidine. The new Dye is deposited in the form of yellow needles, which are dissolved in concentrated sulfuric acid with light red Loosen the color and dye the cotton from a red vat in yellow tones. The dye has the following structure:

OC ₂ H ₅

0 NH-CO- ^ V-CO- NHO H ₆ C ₂ O

_ig example 9

In a solution of 13.4 parts of i-aminoanthraquinone a solution of 7.8 parts is left in 200 parts of dry nitrobenzene at 100 ° with stirring 4,6-Dimethoxyisophthalic acid dichloride in 75 parts

Pour in ao nitrobenzene and then stir the whole thing for a further 4 hours at 130 ^° . The one in the form of yellow

H ₅ CO
O NH-CO

Dye deposited needles is filtered off with suction while warm, washed with nitrobenzene and alcohol and dried. It dissolves in concentrated sulfuric acid with a red color and dyes cotton from a red vat in yellow tones. The dye has the following structure:

OCH ₃

CO - NHO

The 4,6-dimethoxyisophthalic acid dichloride used is made as follows:

4, 6-Dioxyisophthalic acid diethyl ester is made by methylation with dimethyl sulfate in the 4, 6-dimethoxyisophthalic acid diethyl ester and this by saponification with alcoholic caustic soda into 4,6-dimethoxyisophthalic acid transferred, from which the crystallized, colorless dichloride is obtained by heating with thionyl chloride in nitrobenzene. '

Example 10

2.6 parts of the 4,6-dimethoxyisophthalic acid dichloride described in Example 9 are, as indicated in Example 2, with 6.8 parts of i-amino-5-benzoylaminoanthraquinone implemented. The new dye is a yellow powder that dissolves in concentrated sulfuric acid with a red-yellow color and cotton dyes from a red vat in yellow tones. It has the following structure:

H ₃ CO
O NH-CO

H ₅ C ₆ -CO-NH O OCH ₃

CO - NH O

NH-CO-C ₆ H ₆

Replaces the i-amino-5-benzoylaminoanthraquinone by the same amount of i-amino-4-benzoyl-

· ' Aminoanthraquinone, a dye is obtained which dyes cotton from a red vat in orange-red tones.

Example 11

2.9 parts of 4,6-dimethoxyisophthalic acid dichloride are, as described in Example 4, reacted with 4.9 parts of 4-amino-i, 9-anthrapyrimidine. The in gel-

The dye obtained ben crystals dissolves in concentrated sulfuric acid with a red color and stains Cotton from a red vat in muted yellow tones. The dye has the following structure:

H ₃ CO-ZN-OCH ₃ O NH-CO-IJ-CO -NHO

Example 12

2.3 parts of 2,3-dimethoxyterephthalic acid, 25 parts of nitrobenzene and 3.6 parts of thionyl chloride are heated to 100 ° with stirring until solution has occurred. Then, the excess thionyl chloride is distilled off in vacuo and the remaining solution of the dichlorides in the 130 ⁰ hot solution of 4.5 parts of i-aminoanthraquinone in 75 parts of dry nitrobenzene etragen en%. The mixture is then stirred for a further few hours at 130 ^0th It is then allowed to cool, the precipitated dye is filtered off with suction, washed out and dried. The new dye is a yellow powder that dissolves in concentrated sulfuric acid with a red-yellow color and dyes cotton from a red vat in yellow tones. It has the following structure:

ΗΧΟ OCH,

O NH-CO

CO - NHO

• The 2,3-dimethoxyterephthalic acid used is produced as follows:

2,3-Dioxyterephthalic acid diethyl ester is through Methylation with dimethyl sulfate in the 2,3-dimethoxyterephthalic acid diethyl ester and this then with alcoholic potassium hydroxide solution to 2,3-dimethoxyterephthalic acid saponified.

Example 13

2.3 parts of 2,3-dimethoxyterephthalic acid are, as described in Example 12, in the dichloride over-

H ₃ CO

O NH-CO

led and entered into the 130 ⁰ warm solution of 6.8 parts of jr-Ammo-5-benzoylaminoanthraquinone _v in 150 parts of nitrobenzene. After 4 hours heating at 130 to 140 ⁰ "of the precipitated dye is filtered off, washed with nitrobenzene, and alcohol and dried. It is an orange powder, which dissolves in concentrated sulfuric acid with red-yellow color and dyes cotton in red vat in yellow shades. The dye has the following structure:

CO -NHO

H ₅ C ₆ -CO-NH

Example 14

7.6 parts of 2,3-dimethoxyterephthalic acid are used, as described in Example 12, converted into the dichloride and into the X4O ° warm solution of 14.7 parts

NH-CO-CJH,

6 "B.

4-Amino-i, 9-anthrapyrimidine in 300 parts of dry Nitrobenzene entered. After 4 to 5 hours Warming to this temperature is the dye-xaj education ended. The one in greenish yellow crystals

The dye which has separated out is filtered off with suction, washed with nitrobenzene, warm pyridine and alcohol and dried. It dissolves in concentrated sulfur

H ₃ CO

O NH-CO acid with a red-yellow color and dyes cotton brown-red vat in muted yellow tones. The dye has the following structure:

OCH,

Claims (2)

Patent claims: 1. Process for the preparation of vat dyes, characterized in that dialkoxybenzene-meta- or para-dicarboxylic acids, expediently in the form of their carboxylic acid chlorides, with two identical or two different aromatic amines, of which at least one can be vetted is converted to acid amides. 2. The method according to claim i, characterized in that that such amino compounds of CO-NH O Anthraquinone series used, which in o-position to the amino group has a mercapto, hydroxyl or Contain amino group or a halogen atom, and the acid amides initially obtained in the same or converted into the corresponding azoles in a separate operation. Cited publications: German Patent No. 469 019; French patent specification No. 807 939. © 509 689 4.56