DE1124173B - Process for the preparation of dyes of the anthraquinone series - Google Patents

Description

It is known that 1,4-diaminoanthraquinone-2,3-dicarboximides are suitable, the aliphatic, cycloaliphatic or aromatic substituents on the imide nitrogen atom wear, for dyeing textiles made of linear polyesters. The numerous in the literature, for example, dyes of these mentioned in U.S. Patents 2,628,963, 2,701,802 and 2,753,356 Art, however, have an unsatisfactory heat-setting fastness and sublimation fastness, as well as the color strength these dyes leave something to be desired.

It has now been found that very heat-setting and sublimation-fast dyes can be used for dyeing textiles from linear polyesters such as polyethylene glycol terephthalate or based on terephthalic acid and p-Dimethylolcyclohexane, obtained when 1,4-di- * 5 aminoanthraquinone-2,3-dicarboximide or its monohalogen derivatives with chloroacetic acid esters in Reacts the presence of acid-binding agents.

According to a further embodiment of the process, the new dyes are also obtained by that one 1,4-diaminoanthraquinone-2,3-dicarboximide or its monohalogen derivatives with aminoacetic acid esters implements.

As chloroacetic acid esters, esters may be mentioned, which differ from straight-chain or branched aliphatic, preferably low molecular weight aliphatic alcohols, which in turn also contain hydroxyl or alkoxyl groups and / or halogen atoms, such as chlorine or bromine atoms, can carry, of cycloaliphatic or aromatic Derive alcohols. Mixtures of such chloroacetic acid esters can also be used.

The implementation of the anthraquinone system if necessary a halogen system, such as a chlorine or bromine atom-bearing l ^ -diaminoanthraquinone ^ S-dicarboximide with the chloroacetic acid esters is expediently in the presence of the acid-binding agents, preferably of dry, finely ground potassium or sodium carbonate, in organic solvents, z. B. acetamide, dimethylformamide, N-methylpyrrolidone or nitrobenzene, or in mixtures of these organic solvents.

The reaction takes place at temperatures between 80 and 180 ⁰ C, preferably at 100 to 14O ⁰ C. In general, the reaction is completed within 2 to 15 hours.

In general, about 1.2 to 5 moles of chloroacetic acid ester are used for 1 mole of anthraquinonedicarboximide or aminoacetic acid and, if necessary, 0.55 to 1.5 mol of acid-binding agents.

If the corresponding aminoacetic acid esters are used instead of the chloroacetic acid esters, then the addition of acid-binding agents is not necessary - a process for the production of dyes
the anthraquinone series

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dr. Willy Braun, Heidelberg,

and Manfred Ruske, Ludwigshafen / Rhein,

have been named as inventors

borrowed. In this case, the reaction is from 60 to 12O ⁰ C at approximately and with elimination of ammonia.

The new dyes are generally very strong in color. They are also characterized by excellent Light and wet fastness properties.

The parts and percentages given in the examples are unless otherwise given to units of weight. The parts by volume relate to the parts by weight as below Normal conditions measured liters to the kilogram.

example 1

10 parts of ethyl chloroacetate (freshly distilled) are added in small portions to a mixture of 30 parts by volume of nitrobenzene, 1.8 parts of anhydrous, finely powdered sodium carbonate and 6.2 parts of 1 ^ -diaminoanthraquinone ^ jS-dicarboximide, heated with stirring to HO ^{0 C.} The reaction mixture is now heated to 120 ° C. and kept at this temperature for 3 hours. Thereafter, the temperature is raised to 14O ⁰ C and held for 12 hours. The reaction mixture is then cooled, diluted with approximately 100 parts by volume of methanol, the separated reaction mixture is filtered off with suction, washed with methanol and hot water and dried. The yield of 1,4-diaminoanthraquinone-2,3-dicarboximide-N-ethyl acetate

209 510/367

is 6.7 parts (= 85.1% of theory, based on and diluted with methanol. The deposited

the starting material l ^ -Diaminoanthraquinone ^^ - di- dye is suctioned off, with methanol, water and

carboximide). The dye contains approximately 3 to 4% aqueous sodium hydroxide solution and

11.2% nitrogen and melts at 253 to 254 ⁰ C. It was washed again with water and dried. Man

colors the fabric made of polyethylene terephthalate in 5 receives 14.3 parts (= 81% of theory) 1,4-diamino

pure turquoise blue tones of very good light, anthraquinone-2,3 - dicarboximide - N - acetic acid -

Fastness to washing and thermosetting. / 3-ethoxyethyl ester with a melting point of 235 to 236 ° C.

. . , - The new dye contains about 10.1% stick-

iseispiei ι _{fabric and dyes fibers made of} polyethylene terephthalate in

In a mixture of 120 parts by volume of nitrobenzene, io strong turquoise blue tones. 8 parts of potassium carbonate and 24.8 parts of 1,4-diamino

Anthraquinone-2,3-dicarboximide is left in Example 5

110 ^° C. 40 parts of methyl chloroacetate slowly

flow in. The reaction mixture is stirred then heated to 15O ⁰ C A mixture of 30Volum-

first 3 hours nitrobenzene, 2 parts of potassium carbonate and 10 hours share at 12O ⁰ C and then for 15 seconds at 140 ° C. Now bears one further 6.2 parts of l, 4-diaminoanthraquinone-2,3-dicarboxylic 8 parts of potassium carbonate and the mixture is kept acid imide is cooled to 120 ° C and maintained at this for 5 hours at 140 ⁰ C. After cooling, ver - Temperature with 10 parts of isopropyl chloroacetic acid, the reaction mixture is diluted with 120 volume esters. Now, heating the reaction of methanol, sucks the deposited colorant mixture 20 within 2 hours at 14O ⁰ C and holds, it is washed with methanol, water, and again it for 12 hours at this temperature. That with methanol and dry it. The yield of reaction material is worked up in the manner indicated in Example 1 on l ^ -diammoanthracHnon ^ -dicarboximide. 7.4 parts are obtained (= 90% of methyl N-acetic acid is 26.8 parts (= 87.5% of theory), 1,4-diaminoanthraquinone-2,3-dicarbone theory). The dye melts at 284 to 285 ° C 25 imide-N-acetic acid isopropyl ester from the melt and contains approximately 11.3% nitrogen. The new point 275 to 276 ⁰ C with a nitrogen content of dye provides about 10.5% on textile material made of polyethylene tere.

phthalate turquoise-blue colorations with those in Example 1.

specified authenticity properties. propyl ester 11 parts of 4-methylpentanol (2) chloroacetate,

30 so one obtains the l ^ -Diaminoanthraquinone ^ S-di-

Example 3 carboximide-N-acetic acid ester of 4-methylpene

A mixture of 25 parts by volume of N-methylpyrroletanol- (2) with a yield of 87% of theory, idone, 2 parts of potassium carbonate and 6.2 parts of 1,4-di- The dye has a melting point of 193 to aminoanthraquinone-2 , 3-dicarboximide is below 195 ° C and contains 63.5% carbon, 5.2% stirring to 150 ⁰ C heated. The hydrogen, 9.4% nitrogen and 21.7% oxygen are then cooled. Mixture to 12O ⁰ C from and carries 10 parts of glycol- If you go from the corresponding amount of chlorine

monomethyl ether chloroacetate. Now heating of butyl acetate, is obtained the 1,4-Didas reaction mixture for 2 hours at 140 ° C, aminoanthraquinone-2,3-dicarboximide-N-acetic bears 1 part of potassium carbonate and stirred for another säurebutylester of melting point 243-244 ⁰ C. . ^ 3 ¹ hours at 14O ⁰ C. The yield of 1,4-di- 40 This dyestuff dyes fabrics of Polyäthylentereaminoanthrachinon-2,3-dicarboxylic acid imide N-essigphthalat in pure turquoise shades of very good acid-jS-methoxyäthylester is 7.2 parts (= 85% fastness to light, washing and thermosetting. Of theory). The dye has a melting point of 233 to 234 ° C. The example 6 obtained by exhausting with a little 3 to 5% strength aqueous sodium hydroxide 45

solution-purified dye contains approximately 59.7% A mixture of 25 volumes heated to 150 ° C

Carbon, 4.3% hydrogen, 10.1% nitrogen and share N-methylpyrrolidone, 1.8 parts sodium carbon-25.7% Oxygen. nat and 6.2 parts 1,4-diaminoanthraquinone-2,3-di-

Assuming instead of the carboxylic acid imide Glykolmonomethyläther- is cooled to 120 ⁰ C and with chloroacetate of the appropriate amount of glycol 50 14 parts of 2,2-dimethylpropane (l) -3-monochlormonoisopropylätherchloracetat from, one obtains acetate stirred. Now the mixture is stirred for 6 hours the l ^ diaminoanthraquinone ^^ - dicarbonsäureimid- long at 120 to 125 ⁰ C and 2 hours at 140 ⁰ C. N-acetic acid ester of l-hydroxyethane-2-isopropyl The reaction is, as in Example 1 illustrates, ethers from melting point 227 to 228 ° C and one worked up. 7.6 parts are obtained (= 84.5% of the nitrogen content of approximately 9.8% · 55 theory) of l ^ diammoanthraquinone ^ -dicarboxylic acid-

The two dyes provide fiber based on imide-N-acetic acid monoester of 2,2-dimethylpropane Ethylene glycol and terephthalic acid luminescent diols-1,3 from melting point 224 to 226 ° C. The color and strong colors. material contains about 61% carbon, 4.7%

Hydrogen, 9.3% nitrogen and 24.8% oxygen. Example 4 _{6o Go to yon 12} T _e ji _en Chloressigsäurediglykol-

A mixture of 3.6 parts of sodium carbonate and ester gives 7.7 parts (= 85.6% of the

12.4 parts l ^ -Diaminoanthraquinone ^ S-dicarbon- theory) 1,4-Diaminoanthraquinone-2,3-dicarboxylic acid-

Acidimide is 50 parts by volume of N-methylpyrrolidone imide-N-acetic acid-co-hydroxy-ß-ethoxyethyl ester.

heated to 150 ° C. Thereafter, the mixture is allowed to If, 9 parts of chloroacetic acid (8-hydroxy-120 ⁰ C to cool and wears at this temperature for 65 ethyl and proceed in a similar manner, we obtain

Divide glycol monoethyl ether chloroacetate. You get 7.1 parts (= 86.9% of theory) 1,4-diamino

Now stir the reaction mixture for 4 hours anthraquinone - 2,3 - dicarboximide - N - acetic acid-

at 120 ⁰ C and 2 hours at 140 ° C, cooled ß-hydroxyäthylester.

Claims (1)

5 6 The aforementioned dyes stain fabric on hold. The reaction mixture is then stirred Based on terephthalic acid and p-dimethylolcyclohexane terephthalate for a further 2 hours at 14O ⁰ C. The Umsetzungsgut hexane in strong turquoise blue tones. is recorded in the manner given in Example 2. -I _{7 is} working. 9.2 parts of 1,4-diamino-x-mono- Example 7 ₅ b _roman thrachinone-2,3-dicarboximide-N-acetic acid A mixture of 25 parts by volume of N-methylpyrrolic acid - ^ - methoxyethyl ester. The dye contains ungeidon, 1.8 parts of sodium carbonate and 7.7 parts of 15.9% bromine and 8.3% nitrogen.
l ^ -Diamino-x-monobromanthraquinone- ^ jS-dicarbon-.
acid imide (obtainable by brominating 1,4-di- Example 11
aminoanthraquinone-2,3-dicarboxylic acid is heated in place of the Glykolmonomethylätherminiumchlorid sodium chloride melt at 80 ⁰ C) of 12 parts chloroacetate Chloressigsäurecyclohexylwird to 150 ° C in an aluminum io Go. It is then cooled from the micro ester and stirring the reaction mixture 3 hours research to 12O ⁰ C., stirred for 10 parts by volume of chlorine at 12O ⁰ C and 30 minutes at 140 ° C, then methyl acetate and holds it for 5 hours receives is long in a the details of example 3 entbei 12O ⁰ C and 3 hours speaking at 14O ⁰ C. the environmental 15, 7.5 parts (= 84% of theory) is setzungsgut as indicated in example 2, on overall 1,4-diaminoanthraquinone - 2, 3 - dicarboximide works. This gives 8.3 parts (= 90.6% of theory) of N-cyclohexyl acetate of melting point 267 l, 4-diamino-x-monobromoanthraquinone-2,3-dicarboxylic ⁰ to 269 C. The novel dye contains approximately acid imide N- methyl acetate. The new dye 63.5% carbon, 4.6% hydrogen, 9.3% nitrogen dyes textiles made of polyethylene terephthalate in 20 fabric and 22.7% oxygen and dyes textiles made of turquoise blue tones. Polyethylene terephthalate in greenish turquoise blue example 8 shades with good fastness properties. A mixture of 50 parts by volume of N-methylpyrrole- Example 12 idon, 4 parts sodium carbonate, 12.4 parts 1,4-di- 25 110 parts 1,4-diaminoanthraquinone-2,3-dicarbon- Aminoanthraquinone-2,3-dicarboximide and 20.4 acidimide are freshly distilled in 360 parts by volume. Parts Chloressigsäurephenylester is 3 hours liertem N-methyl short time to 14O ⁰ C. stirred at 120 ⁰ C and 4 hours at 14O ⁰ C. heated and then cooled to 80 ° C. At this The reaction mixture is worked at the temperature in Example 1, 90 parts of a-aminoacetic acid are now In this way, 13.7 parts (= 80.5% 3 ° ethyl ester added to the solution) are obtained. The mixture is heated the theory) l, 4-diaminoanthraquinone-2,3-dicarbon- the mixture to 100 ° C within one hour acid imide-N-acetic acid phenyl ester from the melting point and stir it until the ammonia 286 to 289 ° C. The dye contains approximately 64.8% development at 100 to 110 ° C. Then you cool it Carbon, 3.5% hydrogen, 9.7% nitrogen and reaction mixture to 8O ⁰ C, carries 360 volume 22.1% oxygen. He dyes fibers based on 35 parts of methanol and lets it cool down. The Ethylene glycol and terephthalic acid in clear turquoise-colored crystals are suctioned off with methanol blue tones. and water washed and dried. You get Example 9 ^to 106 parts (= 75.2% of theory) of a dye, that with the dye described in Example 1 If one proceeds in Example 3 of 10 parts of chloroacetic acid 40 is identical.
acid-jS-chloroethyl ester instead of glycol mono- methyl ether chloroacetate and stirs the implementation.
mixture for 6 hours at 120 ^° C. and 2 hours long at 140 ° C., 6.9 parts are obtained (= 80.7% 1. Process for the preparation of dyes of theory) M-diaminoanthrachmone ^ S-dicarbon- 45 of the anthraquinone series, characterized in acidimide-N-acetic acid-ß-chloroethyl ester from the melting that one 1 ^ -Diaminoanthraquinone ^^ - dicarbon- point 272 to 273 ⁰ C. The dye supplies acid imide or its monohalogen derivatives weave from polyethylene terephthalate turquoise blue dye chloroacetic acid esters in the presence of acid-binding exercises. who implements funds. BeisoiellO ⁵ ° 2. Modification of the method according to claim 1, characterized in that 1,4-diamino A heated to 15O ⁰ C mixture of 25 Volum- anthraquinone-2,3-dicarboximide or its share N-methylpyrrolidone, 1.8 parts sodium carbon monohalogen derivatives with aminoacetic acid esters nat and 7.7 parts of 1,4-diamino-x-monobromanthra implemented. quinone-2,3-dicarboximide is off at 12O ⁰ C 55 cools, with 10 parts glycol monomethyl ether chlorine- Publications considered: acetate and stirred for 5 hours at 120 ⁰ C USA. overall Patent Nos. 2 701 801, 2753356. When the application was announced, two staining tables were displayed. © 209 510/367 2.62