DE1154587B - Process for the preparation of dyes of the anthraquinone series - Google Patents

Description

It has been found that valuable dyes of the anthraquinone series are obtained if anthraquinone-2-carboxylic acid hydrazides, which can carry one or more substituents and / or an attached carbocyclic or heterocyclic May contain ring, with cyclic imino ethers that have 3 to 7 carbon atoms as ring members, to amidrazones of the general formula

Λ /

NH-NH

CO C

N (CH,) »

converts this with intramolecular elimination of water in 4,5-polymethylene-1,2,4-triazoles of the general formula

* N Ni

- ■ \ I!
.! N 3C 4th / I! ^A. X Ä '

II

transferred, if necessary in the anthraquinone nucleus in the 1-position reduced or in 4-position bromine atoms in amino, hydroxyl or mercapto groups and, if necessary, the compounds of general formula II with alkylating agents to form compounds of the general formula

2N Ni

Il
3C CS

: n
• 1 \

(CH ₈ ) *

X @

Ί O

III

reacted, where X is an optionally substituted low molecular weight alkyl radical, [Y] ' ^{3 is} an anionic radical and η is an integer from 3 to 7 and A is a process for the preparation of dyes
the anthraquinone series

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dr. Ernst Anton, Ludwigshafen / Rhine,
has been named as the inventor

represents an anthraquinonyl radical which has one or more substituents and / or attached may contain carbocyclic or heterocyclic rings.

As anthraquinone-2-carboxylic acid hydrazides, which can carry one or more substituents and or or an attached carbocyclic or heterocyclic ring are for example Anthraquinone-2-carboxylic acid hydrazide, 1 -chloroanthraquinone-2-carboxylic acid hydrazide, 1-nitroanthraquinone-2-carboxylic acid hydrazide, 1-aminoanthraquinone-2-carboxylic acid hydrazide, 3-aminoanthraquinone-2-carboxylic acid hydrazide, S-nitroanthraquinone ^ -carboxylic acid hydrazide, 1-amino ^ -bromoanthraquinone ^ - carboxylic acid hydrazide, 5,8-dichloroanthraquinone-2-carboxylic acid hydrazide, thiazole-anthrone-2-carboxylic acid hydrazide, pyrazole-anthrone-2-carboxylic acid hydrazide or called C-phenylpyrazole anthraquinone-4'-carboxylic acid hydrazide.

Cyclic imino ethers, especially O-alkyl ethers, which have 3 to 7 carbon atoms as ring members are, for example, those that differ from low molecular weight Derive alcohols and contain three to seven methylene groups as ring members, such as butyrolactim-O-methyl ether, valerolactim-O-methyl ether, Caprolactim-O-methyl ether, caprolactim-O-ethyl ether or capryllactime O-methyl ether.

Suitable alkylating agents are, for example, those agents which are capable, if appropriate to introduce substituted low molecular weight alkyl radicals, such as methyl, ethyl, iso-propyl or n-butyl chloride, bromide or iodide, ethyl chloroacetate, chloroacetamide, Dimethyl sulfate, diethyl sulfate, methyl p-toluenesulfonate or benzyl chloride.

309 688/22 +

The invention thus relates to manufacture of 4,5-alkylene-l, 2,4-triazoles of the anthraquinone series, preferably to the production of Colorants of the formulas

-—Ni

(CH ₂ ) _m

O Z

»Ν - Ni

Ha

(CHJ ₁ ,

X ©

ο ζ

as well as dyes of the formulas
O

III a

(CH ₂ ) "

NH.

Man

N (CH ₈ ),

] Y] ^e

and where η stands for an integer from 3 to 7, preferably for the number 5, and where Y stands for an anionic radical, expediently for the anionic radical of a hydrohalic acid, such as Cl ^e , Br ^e 5 or J ^e , or for the anionic radical Remainder of an expediently low molecular weight alkylsulfuric acid or an optionally substituted arylsulfonic acid, such as H ₃ C · O · SO? or

-SOi

stands.

III b

where Z is an appropriately primary amino group, a hydroxyl group or a thioether group, e.g. B. an expediently low molecular weight alkyl mercapto group or an optionally substituted aryl mercapto group, such as an H ₃ C - S group or a

H ₁₁ C-

) - S group,

and X is an optionally substituted low molecular weight alkyl radical, e.g. B. an H ₃ C-, H ₃ C · H ₂ C-,

H ₃ C

; CH-, H ₃ C · H ₂ C · H ₂ C · H ₈ C-,
H ₃ C

/ - CH ₂ -,

H ₅ C ₂ O · CO · CH ₂ - or H ₂ N · CO · CH ₂ group, the reaction of the anthraquinone-2-carboxylic acid hydra-

* 5 zide with the cyclic imino ethers of the type specified above in organic solvents, as are common in the production of anthraquinone derivatives, e.g. B. in chlorobenzene, o-dichlorobenzene or nitrobenzene, at temperatures between 70 and 10O ⁰ C by. The alcohol in question is split off. As a rule, per mole of anthraquinone-2-carboxylic acid hydrazide from 1.1 to 1.6, preferably 1.4 to 1.5, mol of a cyclic imino ether is used. It is also possible to use mixtures of two or more anthraquinone-2-carboxylic acid hydrazides and / or of two or more cyclic imino ethers. The amidrazones obtainable according to the invention separate from the reaction mixtures generally in crystallized form and with good yields.

The amidrazones may be converted by heating above the melting point in the corresponding triazoles, advantageously, however, cyclizing the amidrazones by heating in the presence of organic solvents of the type mentioned above to temperatures between 150 and 200 ⁰ C and removed the formed in this reaction water with the aid of inert gases, e.g. B. of nitrogen. In some cases it is advantageous to carry out the cyclization in the presence of small amounts of glacial acetic acid. It is according to the invention also possible to manufacture the amidrazones with their cyclization in a single step, advantageously to connect, by preparing the amidrazones first at temperatures between 70 and 100 ⁰ C and this then, without separating them by heating the reaction mixtures cyclized at temperatures between 190 and 200 ⁰ C to triazoles.

The triazoles, too, generally separate themselves from the reaction mixtures in good yields and in crystallized form. Those of the new S-anthraquinonesM ^ -alkylene-l ^^ -triazole, which on Anthraquinonyl radical carry reactive substituents, such as nitro groups and / or halogen atoms, can in the usual way in the corresponding amino, alkylamino, dialkylamino, arylamino, hydroxyl, Derivatives bearing alkoxyl, alkyl mercapto and / or aryl mercapto groups are converted.

In this way, new yellow, orange, red, violet to blue colored compounds are obtained, which as Dyes or pigments for coloring films, foils, moldings or textiles such as fibers, Threads, flakes, woven and knitted fabrics, from acetyl cellulose, for example from two and a half acetate or made from triacetate, from linear synthetic polyamides such as polycaprolactam or based on adipic acid and hexamethylenediamine, or from linear polyesters such as polyethylene glycol terephthalate or on the

Based on terephthalic acid and p-dimethylolcyclohexane, or from polyacrylonitrile and / or copolymers of acrylonitrile with other vinyl compounds can serve. Many of these new dyes or pigments are characterized by a excellent lightfastness.

The dyeings available with these dyes on polyethylene glycol terephthalate and polyacrylonitrile fibers are stronger in color than those colorations obtained with the US Patents 2,884,424 and 2,898,343 known triazole dyes can be obtained on the same material.

The 3-anthraquinonyl-4,5-alkylene-1,2,4-triazoles obtainable according to the invention can also, if they have acylatable amino groups on the anthraquinonyl radical, in the usual manner into the corresponding Acylaminoanthraquinones are converted.

The implementation of the new 3-anthraquinonyl-4,5-alkylene-l, 2,4-triazoles with alkylating agents of the above type is advantageously carried out in organic solvents such as xylene or nitrobenzene at temperatures between 120 and 150 ⁰ C. In general, approximately 1.2 to 1.5, preferably 1.4 to 1.5, moles of alkylating agent are chosen per mole of 2-anthraquinonyl-4,5-alkylene-1,2,4-triazole. The new 2-anthraquinonyl-4,5-alkylene-4-alkyl-1,2,4-triazolium salts are very easily soluble in water. Many of these compounds, as dyes for dyeing textiles made of polyacrylonitrile and / or copolymers of acrylonitrile with other vinyl compounds, or in some cases also for dyeing textiles made of wool, natural silk or linear synthetic polyamides, have excellent drawability. This gives yellow to blue dyeings with excellent fastness properties.

The parts and percentages given in the examples are weight units. The parts of the room relate to parts by weight like the liter to the kilogram measured under normal conditions.

example 1

14 parts of l-aminoanthraquinone-2-carboxylic acid and 9.8 parts caprolactim-O-methyl ether are heated for 30 minutes at 100 ⁰ C in 100 parts of nitrobenzene together. The reaction mixture soon becomes thick with deepening of color. After cooling, the reaction material is filtered off with suction, washed with nitrobenzene and then with methanol and dried. 16.5 parts are obtained of red crystals which melt at 218 to 219 ° C. with decomposition and dissolve in concentrated sulfuric acid with a yellow color. The connection has the following constitution:

Implementation mixture displaced. After the mixture has cooled down, the new dye is removed by suction and washing with nitrobenzene and then recovered with methanol. 9.2 parts of the are obtained Triazoles of the formula

N-NH ₂ 1

- N

N (CH ₂

This 3 - (1 - amino - 2 - anthraquinonyl) - 4,5 - pentamethylene-1,2,4-triazole is obtained in the form of coarse red crystals which ^{melt at 309 to 311 °} C. and dissolve almost colorlessly in concentrated sulfuric acid . When paraformaldehyde is added, the solution of the new dye in sulfuric acid turns blue. The dye dyes fabrics made of polycaprolactam in red tones.

7.2 parts of the dye of the formula V are dissolved in 40 parts of nitrobenzene at 15O ⁰ C. 4 parts of dimethyl sulfate are introduced into this solution in small portions. When the reaction liquid cools, red crystal needles separate out, which are suctioned off and then washed one after the other with nitrobenzene, dioxane and ether. After drying, 8.2 parts of a red compound are obtained which dissolves in water with an orange color and has the following structure:

N τ-— Ν

O NH ₂

N (CH ₂ ) ₆

CHf

[CH ₃ OSO ₃ ] ^e.g.

NH - NH

O NH.,

CO

N (CH ₂ ) ₅

IV

10 parts of 2 - β - (1 - aminoanthraquinone - 2 - carbonyl) hydrazino-1-aza-J! -Cyclohepten of the formula IV are heated in 60 parts of nitrobenzene IV to 200 ^° C. for _{2 hours.} The water split off during the reaction is removed by passing nitrogen over the The new dyestuff produces dyeings on textile material made of polyacrylonitrile with excellent fastness properties in clear orange shades.

3- (1-Amino-4-nitroanthraquinonyl) -4,5-pentamethylene-1,2,4-triazole can be obtained by nitrating the dye of the formula V in a sulfuric acid solution with nitric acid. ^{A blue dye with a melting point of 280 to 290 °} C. which is identical to the dye of the formula IX described in the fourth paragraph of Example 3 can be obtained from this compound by reducing the nitro group with sodium sulfide.

Example 2

6.2 parts of l-nitroanthraquinone-2-carboxylic acid are heated together with 3.9 parts of caprolactim-O-methyl ether in 50 parts of nitrobenzene for 1 hour at 100 ⁰ C. The solution becomes red in color. After cooling, the reaction mixture is filtered off with suction, washed first with nitrobenzene and then with methanol and dried. 7.4 parts of the amidrazone obtained in the form of orange crystals with a melting point of 268 to 270 ° C. are obtained.

6 parts of this compound is heated with the mixture of 24 parts of nitrobenzene, and 1 part glacial acetic acid 1 ¹ I _{for 2} hours at 160 ° C. The starting material goes into solution with a lightening of the color. When it cools down, the nitrotriazole of the formula separates

N N

O NO

VII

in the form of yellow crystal needles with a melting point of 283 to 285 ° C.

5 parts nitro compound of formula VII are recrystallized from concentrated sulfuric acid, filtered off with suction, washed free of acid, slurried in 75 parts of water listed zo and 12 parts of crystallized after the addition of sodium sulfide is heated for 1 hour at 90 ⁰ C. The red reaction material is then filtered off with suction, washed with water and dried. 4.5 parts of a compound with a melting point of 309 to 310 ° C. which is identical to the dye of the formula V described in Example 1, paragraph 3, are obtained.

Example 3

A mixture of 36 parts of l-amino-4-bromoanthraquinone-2-carboxylic acid, 19.5 parts of caprolactim-O-methyl ether and 200 parts of nitrobenzene is maintained for 2 hours at 100 ⁰ C. From the initially dark red solution soon red crystals separate out, the filtered off at 6O ⁰ C, then washed with nitrobenzene, and with alcohol and dried. 38.5 parts of the amidrazone, which melts at 223 to 225 ° C. with decomposition and is obtained in the form of red crystals, are obtained.

37.5 parts of this 2 - ^ - (l-amino-4-bromoanthraquinone-2 - carbonyl) - hydrazino -1 - aza -Δ ¹ - cycloheptens and 150 parts of nitrobenzene are removed with the aid of nitrogen, the water formed in the reaction Heated to 200 ° C for 1 hour. After cooling, the mixture is diluted with 150 parts of methanol. The reaction mixture is then filtered off with suction, washed with methanol and dried. 32.7 parts of the triazole which crystallizes in the form of orange-colored needles and has the following constitution are obtained:

suctioned off the reaction mixture, washed with butanol and methanol and finally with hot water. After drying, 22.1 parts of the violet-colored toluenesulfamino compound are from Melting point 340 to 342 ° C obtained.

For saponification, 19 parts of 3- (l-amino-4-toluenesulfamino-2-anthraquinonyl) -4,5-pentamethylene-1,2,4-triazole are dissolved in 300 parts of approximately 96% strength sulfuric acid with cooling and then V held at 20 to 25 ^° C. for _{2 hours.} The mixture is then poured onto ice, the blue-red solution is made ammoniacal, the blue precipitate which has separated out is filtered off with suction, washed acid-free and dried. 15 parts of a blue powder with a melting point of 291 to 292 ^° C. are obtained, which dissolves almost colorlessly in concentrated sulfuric acid. When paraformaldehyde is added, the solution in sulfuric acid turns blue. The connection has the following constitution:

N-- -N

O NH ₂ ii

(CH ₂ ) ₅

O NHo

The new dye is produced on textile material from a copolymer of 95% acrylonitrile and 5% methyl methacrylate or from polyethylene glycol terephthalate or from hexamethylene diamine adipate excellent lightfast blue colorations of very good thermal resistance.

11.1 parts of 3- (1,4-diamino-2-anthraquinonyl) -4,5-pentamethylene-1,2,4-triazole of formula IX are dissolved in 60 parts of nitrobenzene at 100 ° C and under good stirring mixed with 6 parts of dimethyl sulfate. The mixture is then stirred for a further 15 minutes. After about 12 to 15 hours while standing, the reaction material is suctioned off with nitrobenzene, then washed with dioxane and finally with ether and air-dried. You get 9.7 parts of dye in the form of brownish-red crystals that dissolve in water with a bright blue color. The connection has the following constitution:

N- -N

O NH,

O Br

N (CH ₂ ) ₅

55 NN

O NH ₂

CH /

O NH ₂

[CH ₃ OSO ₃ ] Q

VIII

60

The compound melts at 236 to 238 ° C and dissolves almost colorless in concentrated sulfuric acid.

22 parts 3 - (1 - amino - 4 - bromo - 2 - anthraquinonyl) -4.5 - Pentamethylene -1,2,4 - triazole of the formula VIII, 25.5 parts of p-toluenesulfonic acid amide, 15 parts of potassium acetate, 1 part of copper acetate and 250 parts of n-butanol are refluxed together for 6 hours heated to boiling. After it has cooled down

65 The new dye dyes fabrics made from a copolymer of 95% acrylonitrile and 5% vinyl pyridine in clear blue shades with excellent fastness properties.

Example 4

124 parts of the 3- (1-amino-4-bromo-2-anthraquinonyl) -4,5-pentamethylene-1,2,4-triazole described in Example 3, paragraph 2 of formula VIII are at 50 ° C

registered in a solution of 44 parts of boric acid in 1250 parts of 5% oleum. The temperature of the mixture is now slowly increased to 120 ^° C., bromine escaping. After 3 hours heating at 12O ⁰ C the reaction mixture is poured onto ice and made ammoniacal. The precipitated hydroxy compound is then filtered off with suction, washed free of acid and dried. There are obtained 104 parts of a purple powder which melts at 276-278 ⁰ C dissolves in dilute aqueous sodium hydroxide solution with blue-violet color. The connection has the following constitution:

N N

O NH ₂

(CH ₂ ) ₆

O OH

The new dye dyes tissue made of cellulose acetate (so-called two-and-a-half acetate fibers), polyethylene glycol terephthalate and polycaprolactam in purple tones.

7.4 parts of 3- (l-amino-4-hydroxy-2-anthraquinonyl) -4,5-pentamethylene-l, 2,4-triazole of the formula XI are dissolved in 300 parts of dry xylene at boiling point and with a solution of 3.9 parts of dimethyl sulfate mixed in 15 parts of xylene. After IV ₂ hours of boiling, the mixture is allowed to cool and the xylene is poured from the viscous violet mass adhering to the vessel wall. This mass slowly solidifies when rubbed with fresh xylene. The reaction material is then suctioned off, washed with dioxane and then with ether and dried in the air. 11.7 parts of dye are obtained in the form of a dark purple powder which dissolves in water with a purple color. The new dye in the formula

-N

O NH ₂

O OH

[CH ₃ OSO ₃ ] ⁰

XII

dyes textiles made of polyacrylonitrile in violet tones. Example 5

8.7 parts of 3- (1-amino-4-bromo-2-anthraquinonyl) -4,5-pentamethylene-1,2,4-triazole of the formula VIII described in Example 3, paragraph 2, 2.6 parts 1-methyl-4-mercaptobenzene and 1.2 parts of powdered potassium hydroxide are heated to the boil together in 90 parts of ethanol for one and a half hours. The color of the mixture changes from red to purple. The crystals which separate out after the reaction mixture has cooled down are filtered off with suction, washed with ethanol and then with water. After drying 10.1 parts of the reaction material is obtained in the form of purple crystals, melting at 228 to 23O ⁰ C. The new compound with a brownish-yellow color dissolves in concentrated sulfuric acid,

ίο

which turns blue-green on the addition of paraformaldehyde. It has the following constitution:

N-

XIII

and dyes fabrics made from polycaprolactam and polyethylene glycol terephthalate in purple tones.

7.2 parts of 3- (1-amino-4- (p) -tolylmercapto-2-anthraquinonyl) -4,5-pentamethylene-1,2,4-triazole of formula XIII are dissolved in 150 parts of boiling xylene and with the solution of 3 parts of dimethyl sulfate in 15 parts of xylene were stirred. After extensive heating The reaction mixture is allowed to cool to the boil and the somewhat greasy reaction material is separated through Decant from the mother liquor. After repeated trituration with xylene, it now solidifies The dye which has become sucked off, washed with ether and dried under reduced pressure. Man receives 8.7 parts of dye in the form of a violet powder. The new dye in the formula

H _a C

[CH ₃ OSO ₃ ] ^ξ

XIV

dyes textiles made of wool or polyacrylonitrile in violet tones.

Example 6

8.7 parts of 3- (l-amino-4-bromo-2-anthraquinonyl) -4,5-pentamethylene-1,2,4-triazole of the formula VIII, described in Example 3, paragraph 2, 3.2 parts methyl iso-thiuroniumsulfat and n-butanol, 4 parts of powdered potassium hydroxide in 70 parts are heated I ¹ I ₂ hours under reflux cooling to boiling. A color change from red to purple is observed. After the mixture has cooled, the reaction material is filtered off with suction, washed with methanol and water and dried. 6.8 parts of the compound of the formula are obtained

N N

O NH

(CH ₂ ) ₅

in the form of bluish-red crystals starting at 269 to

309 688/224

Melt 271 ° C and dye polycaprolactam fabric purple. The new connection dissolves in concentrated sulfuric acid with a pale red color, due to the addition of paraformaldehyde to green turns over.

6 parts of 3- (1-amino-4-methylmercapto-2-anthraquinonyl) -4,5-pentamethylene-1,2,4-triazole of the formula XV are dissolved in 1000 parts of boiling xylene. A solution of 4 parts of dimethyl sulfate is added to this solution entered in 20 parts of xylene in small proportions. The mixture is now heated for about an hour Boil. The viscous oily reaction material is separated off by decanting after the mixture has cooled down and washed repeatedly with xylene. It slowly solidifies. Then the good is sucked off, with Washed with ether and dried under reduced pressure.

8.0 parts of dye are obtained in the form of a dark violet powder which turns violet in water Color dissolves. The new dye is structured as follows:

melting compound which crystallizes in orange needles and has the following constitution:

N (CH ₂ ) ₅

Ii

'NH ₂

XVIII

CH?

O SCH,

[CH ₃ OSO ₃ ] ³

XVI

This dye dissolves in concentrated sulfuric acid with a light yellow color. On the addition of paraformaldehyde the color of the solution changes to red. The dye dyes textiles made from two and a half acetate or from triacetate or from polyethylene glycol terephthalate or from polycaprolactam in yellow and Textile material made from a copolymer of 95% acrylic

ao nitrile and 5% vinyl pyridine in reddish yellow tones.

7.2 parts of 3- (2-amino-3-anthraquinonyl) -4,5-penta-

methylene-l, 2,4-triazole of formula XVIII are dissolved in 100 parts of nitrobenzene at 15O ⁰ C and then stirred with 4 parts of dimethyl sulfate. Orange-colored crystals immediately precipitate out of the reaction mixture, which, after cooling, are filtered off with suction, washed with dioxane and ether and then dried. The new dye in the formula

and dyes textiles made from a copolymer of 95% acrylonitrile and 5% methyl methacrylate in purple tones.

Example 7

A mixture of 21 parts of 3-aminoanthraquinone-2-carboxylic acid, 150 parts of nitrobenzene, and 14.7 parts of caprolactim-O-methyl ether is kept 2 hours at 100 ⁰ C. The amidrazone thus formed is deposited in the form of red-brown crystals from which filtered off at 50 ⁰ C, washed with nitrobenzene and ethanol and then dried. 25.2 parts of the compound of the formula which melt ^{at 316 to 318 ° C. are obtained}

N N

;! Il r r

(CH ₂ ) ₅

\ λ "\ CH ₃ ©
NH ,.

[CH ₃ OSO ₃ ] ⁹

XIX

dissolves in water with a yellow color and dyes polyacrylonitrile fabrics in strong yellow tones.

Example 8

14 parts of l-aminoanthraquinone-2-carboxylic acid and 7.3 parts Butyrolactim-O-methyl ether are heated together in 70 parts of nitrobenzene 2 hours at 100 ⁰ C. The reaction mixture turns deep red. After cooling, the reaction material is filtered off with suction, washed with nitrobenzene and then with methanol and dried. 16 parts of coarse red crystals are obtained which melt at 230 to 23 ° C. with decomposition. The connection has the following constitution:

55 NH-NH

NH ₂

O NH ₂

co

XVII

10 parts of this amidrazone are heated in 40 parts of nitrobenzene in the manner explained in Example 1 of V ₂ hour at 200 ⁰ C. Red-yellow crystals separate from the solution, which is initially red and which clears up after a short time. After cooling, these are filtered off with suction and washed with nitrobenzene. The filter residue is then freed from the solvent using methanol and dried. _{9 parts of N (CH 2} ) ₅ at 334 to 335 ° C. are obtained

XX

15 parts of 2 - ^ - (l-aminoanthraquinone-2-carbonyl) -hydrazino-l-aza- ^ ¹ -cyclobutene of the formula XX are now in 90 parts of nitrobenzene with removal of the water formed during the reaction with the aid of nitrogen for 2 hours Held at 200 ° C. To

the new dye is suctioned off after cooling, with 50 parts of nitrobenzene are removed with removal of the

Nitrobenzene and then washed with methanol and dried. 10 parts of the triazole are obtained formula

N-

-N

O NHo

N (CH ₂ ) ₃

XXI

^{Standing water was kept at 200 °} C. for 2 hours with the aid of nitrogen. After cooling, the reaction mixture is filtered off with suction, washed with nitrobenzene and then with methanol and dried. 8.1 parts of the triazole of the following constitution are obtained:

10 O NH "

3- (1-Amino-2-anthraquinonyl) -4,5-trimethylene-1,2,4-triazole falls in the form of red, square crystals that melt at 313 ° C. It stains tissue Polyethylene glycol terephthalate and polycaprolactam in red tones.

3.3 parts of the dye of the formula XXI are dissolved in 20 parts of nitrobenzene at 150 ^° C. and mixed with 2 parts of dimethyl sulfate with thorough stirring. The mixture is then stirred for a further 15 minutes. After standing for 12 to 15 hours, the reaction mixture is filtered off with suction, washed with nitrobenzene, then with dioxane and finally with diethyl ether and dried ^{at about 85 to 95.degree.} 3 parts of dye are obtained in the form of brown-red crystals which dissolve in water with a yellow-red color. The connection has the following constitution:

N N

O NH.,,:

I c

i 'eP
H ₃ C

(CH ₂

[CH ₃ OSO ₃ ] -

XXII

The new dye dyes textiles made of polyacrylonitrile in orange tones.

Example 9

A mixture of 28 parts of 1-aminoanthraquinone-2-carboxylic acid, 22 parts Capryllactim-O-methyl ether and 180 parts of nitrobenzene is kept I ¹ I ₂ hours at 100 C ^c. From the dark red solution soon red crystals separate out, the filtered off at 6O ⁰ C, with nitrobenzene, and then washed with ethanol and dried. There are obtained 31 parts of the melt at 232-233 ⁰ C amidrazone of the following structure:

O NH,

NH-NH

CO C

N (CH ₂ ),

XXIII

10 parts of 2- β - (1 - aminoanthraquinone - 2 - carbonyl) hydrazino-1-aza-iP-cyclooctene of the formula XXIII and

45

XXIV

35

40 The 3 - (1 - amino - 2 - anthraquinonyl) - 4,5 - octamethylene-1,2,4-triazole is obtained in the form of yellow-red crystals which melt at 193 to 194 ° C. The new dye dyes fabrics made of polyethylene glycol terephthalate, polycaprolactam and polyacrylonitrile in orange tones.

7.7 parts of the dye of the formula XXIV are dissolved in 40 parts of nitrobenzene at 15O ⁰ C. 3.9 parts of dimethyl sulfate are introduced into this solution, the temperature rising somewhat. The mixture is kept at 150 ° C. for 15 minutes. After cooling, the reaction mixture is poured into 300 parts of diethyl ether, the solvent is poured off the viscous oily red deposit and the deposit is repeatedly triturated with diethyl ether. The dye, which has now solidified, is filtered off with suction, washed with diethyl ether and dried under reduced pressure. 9.2 parts of a water-soluble yellow-red powder are obtained. The new dye in the formula

N - N

O NH

[CH ₈ OSO ₈ ] '=

XXV

dyes fabrics made of polyacrylonitrile, polycaprolactam and wool in yellow-orange tones.

Example 10

3.6 parts of according to Example 1, paragraph 2, resulting dye of the formula V are dissolved in 14 parts of nitrobenzene at 15O ⁰ C. 2 parts of benzyl chloride are then introduced into the solution and the mixture is kept at 150 ^° C. for 2 hours. The reaction mixture brightens up somewhat in the process. It is allowed to cool, the mixture is poured into 100 parts of diethyl ether, the crystals which have separated out are filtered off with suction, washed well with diethyl ether and the filter residue is dried at 40 to 50 ^° C. 5 parts of a readily soluble in water are obtained

orange connection that corresponds to the following structure:

O NH ₂

χ ι

Il ο

N N

| i j

C C
■■ -, "V

N (CH ₂ ) ₆

I.
CH ₂

XXVI

The new dye dyes polyacrylonitrile fabrics in orange tones.

Claims (1)

PATENT CLAIM: Process for the preparation of dyes of the anthraquinone series, characterized in that anthraquinone-2-carboxylic acid hydrazides, which can carry one or more substituents and / or can contain an attached carbocyclic or heterocyclic ring, with cyclic imino ethers containing 3 to 7 carbon atoms as ring members have, to amidrazones of the general formula NH-NH i
CO, C (CH ₂ ) _n O I converts this under intramolecular water removal cleavage in 4,5-polymethylene-1,2,4-triazoles of the general formula »Ν- ¹ J 3 N- ' \ -7 transferred, if necessary in the anthraquinone nucleus in the 1-position reduced or Bromine atoms in the 4-position are converted into amino, hydroxyl or mercapto groups and if necessary, the compounds of the general formula II with alkylating agents to form compounds the general formula ¹ I.
3C Ni i! CL X © [Yf III converts, where X is an optionally substituted low molecular weight alkyl radical, [Y] ^? is an anionic radical and η is an integer from 3 to 7 and A stands for an anthraquinonyl radical which can carry one or more substituents and / or may contain attached carbocyclic or heterocyclic rings. Considered publications:
U.S. Patent Nos. 2,884,424, 2,898,343. When the application was announced, four staining tables were laid out.