DE904336C - Process for the production of Kuepen dyes - Google Patents

Description

Process for the production of vat dyes It has been found that you get valuable vat dyes of the anthraquinone series if you q: -Oxy-7, 8-phthaloylcinnoline in the presence of agents that are commonly used for conversion of carboxyl groups in carboxylic acid halide groups, with ring-shaped primary Converts amines.

The implementation runs z. B. after; following scheme Presumably, the 4-oxy-7, 8-phth @ aloylcinnolines initially form the 4-halogen-7, 8-phthaloylcinnolines, the mobile halogen atom of which then reacts with the amines. One can therefore proceed in such a way that the q-oxy-7,8-phthaloylcinnols are first treated with one of the agents mentioned and the q-halogen-7,8-phthaloylcinnols formed in situ are reacted with the amines. On the other hand, in many cases, the aromatic amine can first be reacted with the agents mentioned; intermediate products being formed; z. B. with phosphorus trichlori, d the corresponding phosphazoamides, which can be isolated. and this then with the 4-Oxy-7; Implement 8-phth-aloylcinnolines. However, it is most advantageous to let the three implementation participants interact with one another at the same time.

The mentioned 4-Oxv-7, 8-phthalaylcinndline, any other S may contain substituents, for example, by treating i-amino-2-acetylanthraquinones obtained with nitrous acid. Suitable amines for the present process s.inrd z. B. Aniline, Tolui.dine, anisidines, aminodiphenyls, aminonaphthalenes, aminonapftole, i- or 2-aminoanthraquinones, halogen-aminoanthraquinones, nitro-amino- @anthraquinones, Aminoanthraquinonal, d! Ehyde, Amino-benzoylaminoanthraquinone, Ami.noanthanthrone, Am @ inopyranthrone, Aminodibenzanthmone, Aminopyrndine, Bz-Amino rhinoline, Aminoanthriachiinon-benzacri-done, Phenylenediamines, benzidines or D.iaminoanthraquinones.

Suitable agents for converting the carboxylic acids into carboxylic acid halides assets are, for example, sulfur chloride, thionyl chloride, chlorosulfonic acid, Phosphorus trichloride, phosphorus pentachloride, phosphorusc> xychlc> ri-d, phosphorus tribromide, Benzotrichloride or Phthaloylchlori'd.

The implementation winds in the presence or in the absence of an inert Solvent or diluent made at elevated temperature. the Reaction products separate from the reaction mixture mostly as hydrogen halide Salts from as such or after prior hydrolysis by water as Dyes are used. The dyes, whose hues are mostly purple, brown or are black, are characterized by very: good fastness properties, in particular you are Equalizing ability excellent.

The parts mentioned in the examples are parts by weight. example i To a slurry of 2 parts of 4-oxy-7,8-phthaloylcinnoline in 40 parts Nitrobenzene is yellowed with stirring, 5 parts of thionylchloride and the whole is stirred long at 80 °, until everything has gone into solution, which requires 1 to 2 hours are. After the excess thioenyl chloride has been distilled off, 2 parts of aniline are carried one, increases the temperature to 150 ° and stirs about i hour at this temperature Further. Then it is allowed to cool, and the reddish-brown crystalline fluid that has separated out is sucked off Precipitate interspersed with colorless crystals of aniline, chlorohydrate, and washes it off with benzene. To clean it, dissolve it in hot glacial acetic acid; filtered and the dye precipitates out of the filtrate with water. You get so 1.8 parts of 4-anili-do-7, 8-phth.aloylcinnoline in the form of a purple powder, that melts at 273 °. Recrystallization from nitrobenzene gives brown ones Crystals that can be ground to a v'ialette powder. The connection dissolves in hot, moderately concentrated sulfuric acid or hydrochloric acid with yellow Color and turns out to be violet, crystalline, when it cools down. The new Dye dyes cotton from a red vat in purple tones.

With m-toluidine a dye is obtained in a corresponding manner, ! which after recrystallization from nitrobenzene in the form of black-red, well-developed Crystals of melting point 242 ° is obtained. He dyes cotton from a red vat in purple tones. Example: A mixture of 27.6 parts of 4-oxy-7, 8-phth, aloylcinnoline, 600 parts of nitrobenzene and 50 parts of Thionylchlori.d is with exclusion of moisture and stirring heated to 80 ° for 2 hours and to 1200 for 1 hour. Dam is distilled the excess thionyl chloride in a stream of nitrogen is added to the remaining thionyl chloride Solution., Of 4-chloro-7,8-phthaloylcinnoline 9.2 parts (0.5 moles) benzi-dine, increases the temperature to 180 ° and stirring is continued for an hour at this temperature. To When it cools, the dyestuff which has separated out is suctioned off and washed with methanol out and dry it. 26 parts of a violet powder are obtained, which by dissolving in concentrated sulfuric acid, diluting the solution with water up to a content of 25% sulfuric acid, suction of the separated violet precipitate, Wash with water, dilute soda @ n: lye and again be cleaned with water can. The new dye dyes cotton from a red, thinned vat in corinth-colored Tones. Example 3 A mixture of i, 0.04 parts of 4-oxy-7, 8-phthalic> ylcinnolin, 8.92 Parts of i-aminoanthraquinone, 400 parts of nitrobenzene and 9.6 parts of thionyl chloride is initially set to 60 ° for 1 hour, then to 100 ° for 1 hour and finally heated to 180 ° for another hour. Then it is suctioned off hot and the residue with Washed out benzene. After drying, 17 parts of yellow, brown crystals are obtained, which in concentrated sulfuric acid with the evolution of hydrochloric acid solve red paint; on addition of water, the dye is precipitated in the form of red-brown flakes. With alkohoii: shem potassium hydroxide you get a grass-green salt, which with water hydrodyslerts to the original red-brown compound. The new dye stains Cotton from a dark blue vat in red-brown tones. If you use in place of i-Aminoanthrachnon ä- @ Amnoanthrach @ ino @ n, one obtains an orange-brown leaflet crystallizing chlorohydrate of the new dye. It dissolves in more focused Sulfuric acid with a red color and falls from it dark red-brown when diluted with water out again. The dye dyes cotton from a purple vat with a green-blue flower in red-brown tones.

With i-chloro-5-aminoanthraquinone you get a dye in the form of brown crystals, the cotton from black-violet vat in violet-brown tones. colors. Similar coloring vat forms are obtained with i-chloro-2-aminoanthrachinone or 2-chloro-5-aminoanthraquinone. A red vat dye is obtained with i-amino-2-bromoanthraquinone. Example 4 A mixture of 27.6 parts (1 mol) of 4-oxy-7,8-pht'h! Aloylcinnoline, 11.9 parts (0.5 mol) of 1,4-diaminoanthraquinone, 100 parts of nitrobenzene and 24 parts of thionyl chloride is heated to 180 ° within 2 hours with stirring. The mixture is then stirred for a further hour at this temperature and left. Cool to 80 °, suck off the precipitate that has separated out and wash it. with benzene and dry it. This gives 37.5 parts of a black-brown powder which dissolves as a hydrate of chlorine in concentrated sulfuric acid with evolution of hydrogen chloride and a red-orange color. When water is added, the new dye precipitates in the form of burdo-colored flakes, which dye cotton from a black-blue vat in real, bordeaux-colored shades.

Similar colorants are obtained with i, 5-D, i.aminoanthraquinone or 2,6-di @ aminoanthraquinone. With i A, minoanthraquinone-2- @ alidehyde, an olive-brown one is obtained Powder that dyes cotton from the vat in brown tones. For example a mixture from 27.6 parts (i mol) of 4-oxy-7, 8-phthadoylcinnoline, 34.2 parts (i mol) of i-amino-44benzoylaminoanthraquinone, 1,000 parts of nitro, benzene and 24 parts of thionyl chloride are slowly added with stirring heated to 180 ° and stirred at this temperature for 1 hour. The retired Dye is filtered off with suction at 80 °, washed thoroughly with methanol and dried. One receives 50.3 parts of a violet-brown crystal powder, which is concentrated in Sulfuric acid olive dissolves and cotton from a tail-blue vat in a strong bordo-colored one Tones colors.

In a corresponding manner, i-amino-5ybenzoylaminoanthraquinone is obtained a dye, the cotton from dark olive brown vat in lively brown Tones colors. The dye gives a bright orange-colored sulfate, which from the red-brown solution in concentrated sulfuric acid by adding a little water can be precipitated.

Example 6 A mixture of 27.6 parts (1 mol: 1) of 4-oxy-7,8-phthaloylcinnoline, 47.1 parts (1 mol) of monoamino-dibenzanthrone, 100 parts of nitrobenzene and 30 parts of thionylchloride is slowly reduced to 180 ° heated and stirred at this temperature for 1 hour. It is then allowed to cool to 80 °, the precipitated dye is filtered off with suction, washed out with benzene and dried. 69.1 parts of a black powder are obtained which: dissolves violet in concentrated sulfuric acid and dyes cotton from a blue vat in strong olive tones. Example? A @ Gem @ isch of 27.6 parts (1 mol) of 4-oxy-7,8-phthaloylcinnoline, 24.7 parts (1 mol) of 2-amino, 9-anthrapyrimidine, 100 parts of o-dichlorobenzene and 24 parts of Th. ionyl chloride is slowly heated to 180 ° with stirring and then stirred at this temperature for 1 hour. The usual work-up gives 49.7 parts of a black crystal powder which dyes cotton from a black-violet vat in strong blue-gray tones.

In a corresponding manner, a red-brown vat dye is obtained with 4-amino, 9-anthrapyrimidine and a dark brown vat dye with 5-amino-i, 9 = anthrapyrimidine. Example 8 A mixture of 27.6 parts (i mol) of 4-oxy-7, 8-phthaloylcinnoline, 40.9 parts (i Mal) of 4-aminoanthraquinone-3 ', 5'-dichloro-i, 2, 2', i'4ben2olacridone, i2oo Te, i, len nitrobenzene and 24 parts of thionylchloride are slowly heated to 180 ° with stirring and then stirred for a further hour at this temperature. After the usual work-up, 26.5 parts of a dark blue, crystalline powder are obtained which dissolves in concentrated sulfuric acid in a dark orange color and dyes cotton from a black-blue vat in strong purple tones. Example 9 A mixture of 39.5 parts (1 mol) of 4-oxy-7,8- (3'-benzoylaminoph.thal, oyl) -cinnoline of the formula 22.3 parts (1 mole) of i-aminoanthraquinone, 100 parts of nitrobenzene and 24 parts of thionyl chloride are slowly heated to 180 ° with stirring. Stirring is then continued at this temperature for about an hour, the dye formed is filtered off with suction at 80 °, washed out with benzene and dried. 50 parts of a brown crystal powder are obtained which dissolves in concentrated sulfuric acid to a dark red-brown color and dyes cotton from a violet vat in red-brown shades.

Claims (3)

PATENT CLAIMS: i. Process for the production of vat dyes or anthracine series, characterized in that 4-oxy-7, 8-phthaloylcinnoline in Presence of agents commonly used for converting carboxyl groups in carboxylic acid halide groups, reacts with ring-shaped primary amines. 2, embodiment of the method according to claim i, characterized in that one the q.-Oxy-7, 8-phthaloylcinnoline initially with the means that are used for conversion of carboxyl groups in carboxylic acid halide groups, treated and then with = converts the ring-shaped amines. 3. embodiment of the method according to claim r, characterized in that the ring-shaped primary amines are initially with the means that are suitable for converting carboxyl groups into carboxylic acid halide groups, treated and @diann with the q.-Oxy-7, 8-phthaloylcinnolinen implemented.