DE1040154B - Process for the preparation of an anthrapyridonsulfonic acid - Google Patents

Description

GERMAN

The present invention relates to a process for the preparation of an anthrapyridone sulfonic acid. The procedure consists in that either 3'-benzoyl-2-halo-4-arnino-l, 9-anthrapyridone reacting with an alkali sulfate or that a 3'-benzoyl-4-alkylsulfonyl- or -arylsulfonylamino-l ^ -anthrapyridone-2-sulfonic acid treated with a hydrolyzing agent.

That according to the two embodiments of the method The product obtained is 3'-benzoyl-4-amino-l, 9-anthrapyridone-2-sulfonic acid. It is characterized in that it is wool, silk, and synthetic polyamide fibers in particular Dyes polyacrylonitrile fibers in valuable scarlet shades. The colorations are characterized by excellent wash and lightfastness.

The reaction according to the first embodiment of the process is preferably carried out in an aqueous medium and at higher temperatures. Temperatures of 100 to 160 ° are appropriate. A Treatment required for a period of around 10 to 24 hours. Of those to be applied by definition Alkali sulfites, sodium sulfite deserves a special mention. Potassium sulfite is also excellent for the Implementation.

The hydrolysis according to the second embodiment of the process takes place with advantage at temperatures of 20 to 40 °.

As hydrolyzing agent, preferably concentrated sulfuric acid, is used wherein 90 to 100 ° / ₀ sulfuric acid is particularly suitable.

Compared to the next comparable known from German patents 581 161 and 905 658 The new anthrapyridone sulfonic acid is characterized by its better absorption of dyes of the anthrapyridone series on polyacrylonitrile fibers.

The following examples illustrate the invention. Unless otherwise stated, denotes is, the parts are parts by weight, the percentages are percentages by weight. The temperatures are given in degrees Celsius.

example 1

100 parts of 3'-benzoyl-4- (4'-methyl) -phenylsulfonylamino 1,9-anthrapyridone-2-sulfonic acid are introduced into 300 parts of 95% strength sulfuric acid at 30 °. The mixture is stirred at 30 ° until complete dissolution has occurred. The starting body is now hydrolyzed, and there is 3'-benzoyl-4-amino-l, 9-anthrapyridone-2-sulfonic acid. Pouring the mass into 1500 parts of 10 ° / ₀ owned Glauber's salt solution, draws the resulting precipitate off and washed with 10 ° / ₀ sodium Glauber's salt solution. The filter cake is then taken up in 1000 parts of water. The suspension is made alkaline with the aid of sodium hydroxide solution, and it is added.

Method of manufacture
an anthrapyridone sulfonic acid

Applicant:
Sandoz AG, Basel (Switzerland)

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

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

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

Frankfurt / M., Große Eschenheimer Str. 39

Claimed priority:
Switzerland from October 8, 1954

Dr. Jacques Günthard, Basel,

and Dr. Alb in Peter, Binningen (Switzerland),

have been named as inventors

with 100 parts of Glauber's salt, sucks off the dye, which has now completely separated out, washes the filter cake with 5% Glauber's salt solution and dry it.

The new dye is a red powder that dissolves in water with a vivid scarlet color. the Solution color in sulfuric acid is yellow; it turns red when boric acid is added and formaldehyde is added to purple red. The dye dyes wool, silk, synthetic polyamide fibers and especially polyacrylonitrile fibers In washable and lightfast, scarlet tones.

100 parts of a washed strand of polyacrylonitrile (Staple fiber) are placed in a dye bath at 70 °, in which 20 parts of a network of copper wires 0.2 mm in diameter are attached and which is a solution of 1 part of 3'-benzoyl-4-amino-l, 9-anthrapyridone-2-sulfonic acid (in the form of the sodium salt), 1 part crystallized copper sulfate, 4 parts more concentrated Contains formic acid and 4000 parts of water. The liquor is brought to a boil; after 80 minutes Cooking time, the bath is completely exhausted, and the textile material is bright scarlet and real colored.

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

EOT 640/383

15 parts of 3'-benzoyl-4-amino-l, 9-anthrapyridone

2-sulfonic acid (in the form of the lithium salt)

50 Thiodiethylene glycol Parts 405 " hot water 400 ,, Crystal rubber 1: 2 60 "Tartaric acid 1: 1 50 crystallized copper sulfate 1:10 20th Copper bronze 1000

After drying, the pressure is attenuated at 104 ° for 30 minutes, then rinsed with cold water and then rinsed Soaped at 50 to 60 ° with a fatty alcohol sulfonate. With very good tissue penetration, one obtains a strong scarlet print with very good wet fastness properties.

The 3'-benzoyl-4 - (4 '- methyl) - phenylsulfonylamino -1,9 - anthrapyridone-2-sulfonic acid used as the starting material is obtained, for example, by reacting the sodium salt of l-amino-4- (4'-methyl) -phenylsulfonylaminoanthraquinone ^ -sulfonic acid with ethyl benzoyl acetate at 170 ° in the presence of phenol and working up the condensation product on the usual Way.

Example 2 ^a5

10 parts of 3'-benzoyl-2-bromo-4-amino-1,9-anthrapyridone are heated with 40 parts of a saturated aqueous solution of sodium sulfite for 18 hours im Autoclave to 140 °. At the end of this time, the mass is taken up in 5% Glauber's salt solution and the excreted is sucked off Dye off, washes it with 5% Glauber's salt solution and dries it.

The new dye is identical to the product obtained according to Example 1.

3'-Benzoyl-2-bromo-4-amino-l, 9-anthrapyridone is obtained, if, for example, 3'-benzoyl-2-bromo-4- (4'-methyl) -phenylsulfonylamino-l, 9-anthrapyridone with treated with concentrated sulfuric acid.

Example 3

10 parts of 3'-benzoyl-4-phenylsulfonylamino-1,9-anthrapyridone-2-sulfonic acid are stirred in 40 parts of sulfuric acid monohydrate at 20 ° until one in ! "/ (, ige soda solution sample of the reaction mixture shows that the starting product is completely hydrolyzed. The resulting dye is after Details of Example 1 worked up. It is identical to the product described there.

Example 4

Dissolve 10 parts of 3'-benzoj ^T l-4-äthylsulfonylamino-1,9-anthrapyridone-2-sulfonate in 60 parts of 95 ° / ₀ sulfuric acid and stirred mass at 35 to 40 ° until a chromatographed sample the same indicates the end of hydrolysis. The mass is then poured into 500 parts of a 10% Glauber's salt solution at 60 °. The precipitated dye is filtered off, the filter cake is washed with a little cold water and pasted with sodium carbonate until a weakly alkaline reaction occurs. After drying, a dye is obtained which is identical to that obtained according to the information in Example 1.

Example 5

In an autoclave, 8 parts of 3'-benzoyl-2-chloro-4-amino-l , 9-anthrapyridone and 50 parts of a saturated sodium sulfite solution heated to 160 ° for 20 hours. The sulfonation product is separated off by filtration. The filter cake is dissolved in 200 parts of water, filtered the solution of undissolved by-products and precipitates the dye from the Filtiat by adding Table salt. The precipitated dye is filtered off and dried. It is the same as that described in Example 1 Identical product.

To carry out the sulfonation, the 50 parts of the saturated sodium sulfite solution can be through Replace 50 parts of saturated potassium sulfite solution.

Claims (3)

PA TENT CLAIMS: 1. Process for the production of an anthrapyridone sulfonic acid, characterized in that 3'-benzoyl-2-halogen-4-amino-l, 9-anthrapyridone with an alkali metal sulfite or that one converts a 3'-benzoyl-4-alkylsulfonyl or -arylsulfonylamino-1,9-anthrapyridone-2-sulfonic acid treated with a hydrolyzing agent. 2. The method according to claim 1, characterized in that that the reaction with the alkali metal sulfite in an aqueous medium and at higher Temperature. 3. The method according to claim 1, characterized in that that you can do the hydrolysis with concentrated sulfuric acid and at room temperature or slightly increased temperature. Considered publications:
German patent specifications No. 581 161, 905 658. When the registration was announced, a staining table and 3 pages of explanations were displayed. © 80S 640/383 9. 5 «