DE1025080B - Process for the production of dyes - Google Patents

Description

It is known that phthalocyanines can be obtained from o-dinitriles or can produce their metal complex compounds if one z. B. the dinitriles in the presence of Hydroxyl compounds heated. The hydroxyl compounds do not react with the dinitrile. the Common phthalocyanines are almost insoluble in organic solvents. Their color is predominant blue to green.

In the German patent .677 666 the production of dyes by heating aromatic o-dinitriles with ring-shaped ketones in the presence condensing agents and optionally sulfonation of the products obtained. At this Implementation, the ketones also do not react with the dinitriles, but instead form its phthalocyanines, while the ketones remain unchanged.

It has now been found that a different class of dyes is obtained when o-dinitriles with carbocyclic or heterocyclic ketomethylene compounds or those formed during the reaction Connections implemented. The dyes are generally soluble in organic solvents. Of the The hue of most dyes is on the long wave side of the visible spectrum.

Examples of possible o-dinitriles are: phthalonitrile, 4-methyl-phthalonitrile, 4-phenylphthalodinitrile, 4,5-diphenyl-phthalonitrile, 3- or 4-methoxy- or ethoxy- or -phenoxy-phthalonitrile, 3- or 4-nitro-phthalonitrile, 3- or 4-chlorophthalonitrile, S.o-dichlorophthalonitrile, tetrachlorophthalonitrile, Naphthalene-1,2- or -2,3-dinitrile, anthracene-2,3-dinitrile, Diphenyl maleindinitrile, pyridine-2,3- or -3,4-dinitrile, quinoline-2,3-dinitrile, thiophene-2,3-dinitrile and similar connections.

As ketomethylene compounds, for. B. can be used: 3-methyl-pyrazolon, l-phenyl-3-methylpyrazolon- (5), 1- (4'-nitro) -phenyl-3-methyl-pyrazolone- (5), l- (3'-sulfo) -phenyl-3-methyl-pyrazolone- (5), l- (2'-sulfo) -phenyl-3-phenyl-pyrazolone- (5), l- (2'-methyl-4'-sulfo) -phenyl-3-methyl-pyrazolone- (5), 2-phenyl-imidazolone- (5), rhodanine, N-ethylrhodanine, 3-ethyl-2-thione- thiazolidin-5-one, Barbituric acid, indoxyl, N-methylindoxyl, N-acetylindoxyl, Oxindole, N-methyl- or N-ethyl-oxindole, o-Nitro-oxindol.S-Oxo ^^ - dihydro-thionaphthen.o-Chlor-S-oxo ^ .S-dihydro-thionaphthen, 6-ethoxy-3-oxo-2,3-dihydro-thionaphthene, 6-chloro-4-methyl-3-oxo-2,3-dihydrothionaphthene, 5-chloro-7-methyl-3-oxo-2,3-dihydro-thionaphthene, 3-oxo-4,5-benzo-2,3-dihydro-thionaphthene, N-methyl ^^ - diketo-l ^^^ - tetrahydroquinoline, diketohydrind. In addition, products substituted on the reactive methylene group are also suitable for the reaction, which pass under the reaction conditions in the abovementioned compounds, e.g. B. Diketo procedure, for the production of dyes

Applicant:

Aniline & Soda Factory in Baden
Aktiengesellschaft, Ludwigshafen / Rhein

Dr. Arnold Tartter, Lambsheim (Palatinate),
has been named as the inventor

hydrindene carboxylic acid ester, indoxylic acid or 3-oxo-2,3-dihydro-thionaphthene-2-carboxylic acid.

The reaction is generally carried out at a higher temperature, expediently from 100 to 200 °. Sometimes is It is also cheaper to fuse the reaction components to one another at an even higher temperature let it take effect. The reaction is advantageously carried out in the presence of a diluent or Solvent by, such as higher hydrocarbons, halogenated hydrocarbons, higher boiling alcohols, Glycols, polyoxy compounds, ethers, esters, acid amides or tertiary amines.

In general, 2 moles of said reactive compounds sit with 1 mole of an o-dinitrile around with elimination of 1 mol of ammonia and formation of a dye, presumably the following structure:

R '- C = C C = C-R'

NH

R = residue of a ring-shaped organic compound, R '= residue of a ketomethylene compound.

However, molar amounts of the reaction components can also react with one another, with the reaction only takes place on one side.

The dyes easily obtainable by the process can be used as such. If they are insoluble or sparingly soluble in water, they can be sulfonated or converted be made water-soluble in quaternary ammonium or tertiary sulfonium compounds.

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

example 1

A mixture of 2 parts of barbituric acid and 1 part of phthalonitrile in 7 parts of glycol is a few hours

70S 907/355

heated to 180 °. After diluting the cooled reaction mixture with water, it is nitrated and with Methanol washed. A dye is obtained which dissolves in dimethylformamide with a red-brown color. He dyes polyamide threads, acetate artificial silk or wool in red shades from the dispersion. By treating with oleum you get a red-brown, water-soluble dye for cotton or viscose.

If molar amounts of barbituric acid and phthalonitrile are converted into dichlorobenzene at 180 ° for a few hours, so an orange-yellow dye is obtained.

Example 2

174 parts of l-phenyl-3-methyl-pyrazolone (5) and 65 parts of phthalodinitrile are heated in 400 parts of glycol 8 hours> ■ with stirring to 180 ^D. After diluting with water, the dye is filtered off with suction, dried and boiled with benzene or chloroform. A bronzing violet-blue dye is obtained which dissolves in concentrated sulfuric acid with a red color. If the dye dissolved in 23% oleum is heated to about 100 ° for some time, a water-soluble dye is obtained which dyes cotton or viscose rayon in blue shades. Sulphonation creates a water-soluble dye that dyes wool from an acetic acid solution in brownish-yellow shades.

If, instead of the above pyrazolone, l- (3'-sulfo) -phenyl-3-methyl-pyrazolone- (5) or 1- (2'-SuI-fo) -phenyl-3-phenyl-pyrazolone- (5) , in this way, water-soluble dyes are formed without further sulfonation.

Example 3

15 parts of perinaphthindanedione and 5 parts of phthalonitrile are stirred into 80 parts of glycol and up to End of the ammonia development heated to 180 °. The dye formed is separated off in the usual way and cleaned with acetone. A black-brown dye powder is obtained.

Example 4

75 parts of the sodium salt of the ethyl diketohydrindecarboxylate are added with 30 parts of glacial acetic acid stirred into 300 parts of pyrrolidone and heated to 50 °. At this temperature, 20 parts of phthalonitrile are introduced into the reaction mixture, whereupon the temperature is gradually increased. The result is a red solution, which turns deep black on further heating to 180 to 200 °. After an hour's reaction time, the resulting dye separated in the usual way. A brown-black dye powder is obtained which consists of concentrated sulfuric acid can dissolve and turns into a dye by treatment with oleum, which Dyes fabric made of linear polyamides from an acetic acid bath in brownish-gray tones.

Example 5

A mixture of 36 parts of N-methyl-2,4-dioxo-1,2,3,4-tetrahydroquinoline and 13 parts of phthalonitrile is heated in 200 parts of pyrrolidone or 200 parts of glycol for 7 hours at 185 °. The one separated in the usual way Dye is purified by boiling it with acetone and xylene. A violet dye is obtained which consists of concentrated sulfuric acid can be redissolved. Its sulfonation product dyes cotton from ammoniacal Solution in red-brown tones.

Similar dyes are obtained with 4-methoxy- or -chlorophthalodinitrile.

Example 6

A mixture of 13 parts of phthalonitrile and 36 parts of 6-chloro-3-oxo-2,3-dihydro-thionaphthene in 150 parts of glycol with stirring for 3 to 4 hours to 180 heated to 190 °. The cooled reaction mixture is diluted with hot water and the reaction product sucked off. It is cleaned by boiling it with acetone and xylene. 37 parts of a red violet are obtained Pigment.

Similar dyes are obtained if, instead of 6-chloro-3-oxo-dihydro-thionaphthene, 5,7-dichloro-3-oxo-4-methyl-dihydro-thionaphthene, 5,6,7-trichloro-3-oxo-dihydro-thionaphthene or 3-oxo-4,5-benzo-2,3-dihydro-thionaphthene used.

Example 7

5 parts of diphenylmaleindinitrile and 9 parts of 1- (3'-chlorophenyl) -3-methyl-5-pyrazolone are heated to 180 ° in 50 parts of ethylene glycol for 4 hours. After the reaction mixture has cooled down, the resulting mixture is sucked off Dye off and dry it. A dark brown dye powder and its sulfonation product are obtained Dyes wool from an acetic acid solution in reddish brown tones.

Example 8

14 parts of ethyl l-phenyl-S-pyrazolone-S-carboxylate and 4 parts of pyridine-2,3-dinitrile are stirred into 50 parts of ethylene glycol and heated to 175 for several hours heated to 185 °. After filtering off with suction and washing with methanol, a dye is obtained which reacts with oleum can be sulfonated. The sulfonation product dyes cotton from an alkaline solution in blue tones.

Claims (1)

PA TE N TA N S P R U C H Process for the preparation of dyes, characterized in that o-dinitriles with carbocyclic or heterocyclic ketomethylene compounds or those compounds which convert into ketomethylene compounds during the reaction and, if appropriate, the end products sulfonated. Publications considered: ■ German patent specification No. 677 666. A coloring table was displayed when the application was announced. © 709 907/356 2.