DE1040153B - Process for the preparation of acid dyes of the isothiazole anthrone series - Google Patents

Description

It has been found that valuable acid dyes of the isothiazole anthrone series are obtained if S-acylamino-ljQ-isothiazolanthrone, wherein acyl is a The remainder from the series of halogen fatty acids means that it is reacted with alkali metal sulfites.

To implement the acylaminoisothiazole anthrones according to the invention with aqueous solutions of alkali metal sulfites so long to temperatures: from about 100 to 150 ° C heated until no water-insoluble Starting material is more available. Implementation can be made easier if you can adding hydrophilic solvents, e.g. alcohols or phenols, to the reaction mixture. The reaction is there in exchange of the halogen atom for the sulfonic acid group. Small remnants of unresponsive Water-insoluble accompanying substances can be separated off by filtering the aqueous solution of the reaction product. Added organic Solvents are advantageously removed by distillation with steam before filtration. From the In clarified solutions, the dyes are separated off by salting out, then filtered off and dried. According to the invention, the acyl radicals belong to the halogen fatty acid series. Above all, those are suitable low molecular weight radicals containing up to 6 carbon atoms. Preferred halogen atoms are Chlorine or bromine atoms; the place of substitution is essential for the success of the procedure not essential. The fatty acid residues present in the starting materials can therefore, for. B. Remnants of the Chloroacetic acid, 1-chloropropionic acid, 1-bromopropionic acid, 2-chloropropionic acid, 1-bromobutyric acid, 1 -Bromo valeric acid, 1-bromocaproic acid and 5-bromocaproic acid.

The new acid dyes of the isothiazole anthrone series dissolve in water with a yellow color and color from these solutions nitrogenous fibers such as wool, silk and synthetic polyamides in yellow Tones. Fibers made of polyacrylonitrile and its copolymers are produced using the cupro-ion method Dyed in yellow shades of excellent wash and lightfastness.

The new method differs from the method claimed in German patent specification 646 786 Process in that, firstly, the starting substance contains an isothiazole ring which compares to the molecule an altered reactivity to the anthraquinane molecule and, secondly, the group bearing the exchangeable halogen atom gives an acylamino group which is known to be much easier to cleave than an alkylamino group. It was therefore not foreseeing that the halogen atom of the haloacylaminoisothiazole anthrones will be treated with aqueous or aqueous-organic alkali processes

for the production of acid dyes
the isothiazole anthrone series

Applicant:
Sandoz AG, Basel (Switzerland)

Representative: Dr. W. Schalk, Dipl.-Ing. P. Wirth,

Dipl.-Ing. G. E. M. Dannenberg

and Dr. V. Schmied-Kowarzik, patent attorneys,

Frankfurt / M., Große Eschenheimer Str. 39

Claimed priority:
Switzerland from September 17, 1954

Dr. Paul Bücheier and Dr. Albin Peter,

Binningen (Switzerland),
have been named as inventors

Metal sulfite solution in the heat would replace smoothly with the sulfonic acid group. The new procedure enables new, water-soluble and therefore technically valuable dyes in a simple manner the isothiazole anthrone series for wool, silk and synthetic polyamide fibers as well as for polyacrylonitrile fibers to win.

The following examples illustrate the invention. The parts mean parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius.

example 1

10 parts of S-chloroacetylammo-l.Q-isothiazolanthron, 30 parts of phenol, 65 parts of 40% aqueous sodium bisulfite solution and 34 parts of sodium hydroxide solution 30% are stirred at 100 °. Once a sample is largely soluble in hot water, pour the reaction mass in 1000 parts of water. The solution is heated to 95 °, filtered hot and with 100 parts of sodium sulfate are added. The acid dye which precipitates out on cooling is filtered off with suction with sodium sulfate solution Washed 10% until the filtrate is free of phenol and has a neutral reaction shows and dried. Fibers and fabrics made from polyacrylonitriles can be mixed with the acid dye obtained according to the cupro-ion method in yellow shades of excellent lightfastness and washfastness to dye.

100 parts of a washed strand of polyacrylonitrile (staple fiber) are dyeing at 70 ° 640/382

bath, in which 20 parts of a copper mesh of >, wires 0.2 mm in diameter are attached and which contains a solution of 1 part of the dye obtainable according to the above example, 1 part of crystallized copper sulphate, 4 parts of concentrated formic acid and 4000 parts of water. The liquor is brought to a boil. After 80 minutes of cooking, the bath is completely exhausted and the textile material is yellow and real colored.

Example 2

10

5 parts of 5- (2'-chloro) propionylamino-l, 9-isothiazolanthrone, 65 parts of aqueous sodium bisulfite solution 40% and 34 parts of sodium hydroxide solution 30% are stirred in an autoclave for 7 hours at 130 °. The reaction mass is poured into 1000 parts of water and heated to 95 °. The hot solution will nitrated and mixed with 100 parts of sodium sulfate. The precipitate that occurs when it cools is sucked off, washed with sodium sulfate solution 10% and dried. The acid dye obtained is colored Fibers and fabrics made of wool, silk or synthetic polyamides from acidic solution in light yellow Tones. Fibers and fabrics made of polyacrylonitrile «: are made in bright tones using the cupro-ion method dyed of excellent lightfastness and washfastness.

Example 3

11 parts of 5- (r-bromo) -propionylamino-l, 9-isothiazolanthrone, 30 parts of n-propyl alcohol and 50 parts of neutral potassium sulfite solution 50% are used for so long Stirred 100 ° until a sample is largely soluble in hot water. The reaction mass then becomes heated in 800 parts of water to 98 °, the solution filtered and the resulting acid dye precipitated by Zugalx * of potassium sulfate. He is sucked off washed with potassium sulfate solution 8% and dried. The acid dye has similar properties like that which is described in Example 2.

A fabric made of polyacrylonitrile (staple fiber) is printed with a printing paste. the following composition having:

30 parts of the ₄ g

permanent dye
50 parts of butyl carbitol (2 '- (2-butoxyethoxy) -

ethanol)

310 parts of water
500 parts crystal rubber 1: 2
50 parts copper oxide 1: 1
60 parts of ammonium sulfate 1: 2

_: The print is dried, steamed at 104 ° for 10 minutes without and for 20 minutes with an overpressure of 0.5 atmospheres (temperature about 110 °), then rinsed well with cold water, soaped at 50 to 60 ° with a fatty acid condensation product and rinsed again. A strong, bright print of very good fastness to light, washing and rubbing is obtained.

Using the method of the preceding examples, the following compounds with alkali metal sulfites are converted to acid dyes.

example
No.

S-haloacylamino-l ^ -isothiazolanthrone

5- (1'-bromo) -isovalerylamino-1,9-isothiazolanthrone

5- (l'-bromo) -capronylamino-1,9-i so th i azole anth ron

5- (5'-bromo) -capronylamino-1,9-isothiazolane throne

Hue of

Coloring on

Orion 42

yellow

yellow

yellow

Claims (6)

Claims 1. A process for the preparation of acid dyes of the isothiazole anthrone series, characterized in that that one 5-acylamino-l, 9-isothiazolanthrone, wherein acyl is a radical from the series Halogen fatty acids means that it is reacted with alkali metal sulfites. 2. The method according to claim 1, characterized in that the reaction is carried out in aqueous Medium executes. 3. Process according to Claims 1 and 2, characterized in that the reaction is carried out at increased Temperature. 4. Process according to Claims 1 to 3, characterized in that the reaction is l> ei increased Printing. 5. Process according to Claims 1 to 4, characterized in that the reaction is carried out in the presence a hydrophilic solvent. 6. The method according to claim 5, characterized in that one is used as the hydrophilic solvent chooses an alcohol or a phenol. 1000 parts Considered publications:
German patent specification No. 646 786. 809 640/382 9.