DE1283994B - Process for making blue anthraquinone dyes - Google Patents

Description

The invention relates to the preparation of new anthraquinone compounds of the general formula

O NH

acid (l-amino ^ -bromo-anthraquinone-l-sulfonic acid) with arylamines

H ₂ N

SO ₂ N

SO ₃ HI

in which X is hydrogen, alkyl or halogen, X 'is hydrogen, alkyl or halogen, Y is oxygen or sulfur, A is hydrogen or hydroxyalkyl and B is hydrogen, alkyl or hydroxyalkyl.

The new compounds are obtained by inserting into one of the aryl radicals of the anthraquinone compound the general formula

9 NH ₂

X '

and the exchange of the sulfonic acid group in the 2-position of the anthraquinone against the rest

The new compounds of the formula I can be prepared according to the invention in a manner known per se, for example by treating the compounds of general formula II with Chlorosulfonic acid in the sulfonic acid chlorides of the general formula

O NH

II

in which X, X 'and Y have the meaning given above, according to methods known per se Sulfonic acid amide group of the above constitution and a sulfonic acid group in the other aryl radical introduces. In the formulas I and II, the alkyl is preferably methyl and ethyl, the Halogen, preferably chlorine or bromine, the hydroxyalkyl group can, for example

SO ₂ Cl

SOoCl

transferred and on this then in aqueous solution a compound of the general formula

HN

-CH ₂ -CH ₂ -OH,
CH ₂ - CH ₂ - CH ₂ - OH
r
CH ₂ - CH - CH ₃

OH

The compounds of the general formula II can be prepared in a manner known per se from l-amino-2,4-dihalo-anthraquinone (Halogen is chlorine or bromine) and arylamines of the general formula

H ₇ N

via the corresponding l-amino-l-halogen - ^ - arylaminoanthrachihone and by reacting them with phenols or thiophenols of the general formula

HY

can be obtained. Another manufacturing option is the implementation of the so-called bromamine

in which A and B have the meaning given above, can act.

The compounds of formula II are conveniently combined with the five- to ten-fold amount by weight, based on the weight of the anthraquinone, of chlorosulfonic acid, advantageously between O and 6O ⁰ C, is reacted. The end of the reaction with chlorosulfonic acid, referred to as sulfochlorination, can usually be recognized by the fact that a sample of the reaction mixture precipitated on ice is insoluble in cold water, but completely soluble in hot, dilute alkali.

The sulfonic acid chloride obtained can be obtained from the reaction mixture in a customary manner by precipitation on ice, ice-water or ice-sodium chloride solution isolate, whereby it is expedient to choose an agent in which the respective sulfonic acid chloride is obtained in easily filterable form. The sulfonic acid chloride is washed with cold water acid-free and continues to convert it advantageously while it is still moist.

However, the process can also be carried out in such a way that one accesses the compounds of the general Formula II allows concentrated sulfuric acid or oleum to act and the here obtainable Sulfonic acids with halogenating agents such as phosphorus halides, thionyl chloride or chlorosulfonic acid, optionally in the presence of reaction accelerators, such as dimethylformamide, in the sulfone

Acid chlorides of the general formula III transferred, which then in turn with amines of the general formula

HN

implemented.

The reaction of the sulfonic acid halides with ammonia or the other amines of the formula

HN

is advantageously carried out in an aqueous medium in which the sulfonic acid amide groups-containing anthraquinone compounds are finely distributed under normal or moderately elevated temperature, for example at 0 to 80 C, but advantageously at 20 to 50 ⁰ C. In general, a reaction time sufficient for a 5- to lOgewichtsprozentigen aqueous solution of ammonia or of amines 1-5 hours at about 20 to 40 ⁰ C, but the reaction is usually already terminated after 2 hours.

The base (i.e. ammonia or amine) is usually added in large excess, e.g. B. in the 100 times the equimolar amount, although theoretically only half the molar amount, based on the number the sulfonic acid chloride groups, would be necessary. In this case, however, the reaction speed would be too low, and it would have to be done by adding suitable acid-binding agents, such as alkali or alkaline earth carbonates or bicarbonates, the released hydrogen chloride can be captured.

The new dyes can expediently be removed from the reaction mixture with cooling and acidification precipitated with aqueous dilute mineral acid and then isolated by suction. at the reaction of the sulfonic acid chlorides with ammonia or the other amines mentioned takes place the reaction in such a way that only one of the two sulfonic acid groups is converted into the sulfonic acid amide, the other but is hydrolyzed to the sulfonic acid group; it is therefore advantageous to dilute it when rewashing aqueous salt solutions, such as 5 to 10% sodium chloride or potassium chloride solutions, to be used.

The dyes which can be prepared according to the invention are valuable blue anthraquinone dyes with excellent results coloring properties, such as light and wet fastness. They are used for coloring and Printing of fiber material, preferably textile material, such as fibers, threads, flakes, woven and knitted fabrics, and of structures, such as films, made of polyamides and polyurethanes and are therefore particularly suitable as disperse dyes.

The dyes which can be prepared according to the invention are better than those described in the French patent 1,264,242 known dyes due to their considerably greater drawability on polyamide and are in the Lightfastness of the polyamide dyeings of the dyes known from French patent specification 1290 522 think.

The parts given in the examples are parts by weight and the percentages given are percentages by weight.

example 1

20 parts of l-amino-2-thiophenyl-4-anilino-anthraquinone are in at room temperature with stirring 300 parts of chlorosulfonic acid added in portions. After stirring at room temperature for 2 hours the mixture on ice (200Θ parts) / water (500 parts) / sodium chloride (100 parts) and precipitated with ice water washed.

The pressed material obtained is made up to 800 parts with an ammonia solution of a concentration such that the solution then contains 10% ammonia, while cooling with ice and stirring. After stirring for 2 hours at room temperature and 1 hour at 50 to 55 ¹ C is cooled, suction filtered, washed with 5 ° / cent sodium chloride solution, washed until neutral and finally washed with ice water so long starts to run until the wash water blue. After drying, a blue dye of the formula is obtained in excellent yield

O NH

SO ₇ NH,

SOJi

the polyamides in brilliant blue shades with good fastness properties.

If you use the sulfonyl chloride pressed material instead of an ammonia solution with a monoethanolamine solution implements and processes analogously to the manner described in the previous paragraph a blue dye of the formula is also available in excellent yield

O NH

O NH

SO ₂ NH-CH ₇ -CH ₇ -OH

SO.H

the polyamides in brilliant blue shades with good fastness properties.

Example 2

15 parts of 1-amino-2-thiophenyl-4- (p-chloroanilino) anthraquinone are introduced in portions into 200 parts of chlorosulfonic acid at room temperature. After stirring for 1 hour at room temperature and 2 hours at 40 to 45 ^° C., the mixture is precipitated on ice (1500 parts) / water (500 parts) / sodium chloride (100 parts), filtered off with suction and washed vigorously with ice water. The moist material to be pressed is made up to 400 parts with so much percent ammonia solution that the solution is 10% ammoniacal. It is stirred for 30 minutes at room temperature, then for 2 hours at 40 to 45 ° C, filtered off and washed with 5 ⁰ / cent sodium chloride solution until neutral, then with ice water so long after until the filtrate blue

begins to expire. After drying, the blue dye lies

. P NH ₂

SO ₂ NH ₂

SO, H

10

in almost quantitative yield. He dyes polyamides in brilliant blue tones with good fastness properties.

Example 3

The procedure is as indicated in Example 2, but instead of the l-amino-2-thiophenyl-4- (p-chloroanilino) anthraquinone the 1-amino-2- (p-chlorothiophenyI) -4-anilino-anthraquinone used, a dye of the formula is obtained in good yield

SO ₂ NH ₂

20th

SO ₃ H

30th

the polyamides in blue tones with high brilliance and good fastness properties.

Claims (1)

Claim: Process for the preparation of blue anthraquinone dyes of the general formula O NH in which X is hydrogen, alkyl or halogen, X 'is hydrogen, alkyl or halogen, and Y is oxygen or sulfur, A is hydrogen or hydroxyalkyl and B is hydrogen, alkyl or hydroxyalkyl, characterized in that one of the aryl radicals of the anthraquinone compound the general formula O NH in which X, X 'and Y have the meaning given above, according to methods known per se a sulfonic acid group and in the other aryl radical a sulfonic acid amide group of the above Introduces constitution.