DE1192349B - Process for the production of Kuepen dyes of the benzanthrone series - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

German class: 22 b - 3/09

Number: 1192 349

File number: F 32056IV c / 22 b

Filing date: September 6, 1960

Opening day: May 6, 1965

It is known that Bz-l-benzanthronyl- (l-anthraquinonyl) -amine or its derivatives with alkaline To treat condensation agents (see. German Patent 212 471). Furthermore, in the German Patent specifications 520 876, 522 970 and 844 781 described that one of dyes in the 4- or 5-position of the anthraquinonyl radical contain a free amino group, by acylation of this group, z. B. obtained with benzoyl chloride, olive green dyes. These dyes can also be removed directly the corresponding 4- or 5-acylamino-l-anthraquinonyl (bz-l-benzanthronyl) amines, z. B. produce aniline by treatment with sodium anilide (cf. French patent 697 231).

It has now been found that new vat dyes are obtained if Bz-1-benzanthronyl- (l-anthraquinonyl) amines, which are substituted in the 4-position of the benzanthrone, treated with condensing agents.

The Bz-1-benzanthronyl- (l -anthraquinonyl) -amines can be obtained by adding 1-haloanthraquinone, which is optionally in the 5-position is further substituted by halogen, according to conventional methods in the Converted benzanthrone and this then by further halogenation in the corresponding Bz-1,4 Dihalobenzanthrone transferred. With this Benz

Cl

Process for the production of vat dyes of the benzanthrone series

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Klaus Wunderlich,

Dr. Hans-Samuel Bien, Leverkusen;

Fritz Baumann, Opladen

anthrone, the halogen in the 4-position is surprisingly extremely easy to break through to exchange other substituents, so that in a simple manner amino and substituted amino groups, such as acylamino, arylamino or aminoanthraquinonyl groups, or cyano or carbonamide groups can be introduced. Such substituents can also be used together with the neighboring C atoms in the 3- or 10-position of the benzanthrone Form rings. Examples of such new benzanthrones are

Cl

C = O

From these benzanthrones substituted in the 4-position, those in the Bz-1-position can be replaced by a Anthraquinonylamino group-substituted derivatives by known processes by an anthrimide melt with ■ 1-aminoanthraquinone, which optionally contains further substituents, can be obtained.

The treatment of the Bz-l-benzanthronyl- (l-anthraquinonyl) -amines can be done with acidic as well as with alkaline condensation agents. Examples of such condensing agents are alcoholic potash, pyridine — AlCl ₃ , sodium anilide — aniline, ethanolamine — potassium hydroxide, sulfuric acid or AlCl ₃ —SO ₂ —NaCl.

The olive-green to green dyes obtained according to the invention have good to very good fastness properties. Particularly noteworthy is the excellent one

509 568026

3 4

Lightfastness. Such dyes will preferably melt after crystallization from dimethylformamide

used, which are in the 4-position of benzanthrone at 272 to 274 ° C and dissolve in sulfuric acid in

an acylamino group, e.g. B. a benzoylamino thin layer with blue, in a thick layer with

group, own. purple red color.

Compared to the known dyes that can 5 Das Bz-l-bromo-4-amino-8-chlorobenzanthrone

Acylamino group not in the 4-position of the Benz- also directly from the Bz-l ^ -Dibromo-S-chloro-benz-

anthrons, but wear on the anthraquinonyl residue, anthrone through conversion with ammonia in nitrobenzene

The dyes according to the invention obtained are distinguished at 210 ⁰ C obtained

substances through a much clearer shade. Invention _,, _,. ",,,,," ~

dyes which can be prepared according to the present invention, which are in the 4- or 10 Bz-l-bromo ^ -cyan-S-chlorobenzanthrone (IV)

5-position of the anthraquinonyl radical further Substi- 12 g of Bz-1,4-dibromo-8-chlorobenzanthrone (I) are

tuenten, z. B. contain other acylamino groups, together with 5 g of copper (I) cyanide in 75 g of dimethyl

have strong, very yellowish green tones. formamid V heated to 80 to 90 ° C for _{2 hours.} That

Compared to the US patents, the reaction product is sucked off cold, with dimethyl

2,820,790 and 1,845,469 known dyes signed 15 formamide and alcohol and washed with dilute

NEN the dyes according to the invention boiled out by a nitric acid. The light yellow needles of the

much clearer nuance. Bz-l-bromo-4-cyano-8-chloro-benzanthrons are used in

The preparation of the intermediates that result in almost quantitative yield. They are breaking up

Structure of the dyes according to the invention used in sulfuric acid with an orange-brown color and

is done in the following 20 melt at 320 to 322 ° C.

Way. These intermediate dye products are represented by _, ^. , ".,

Roman numerals referred to on the Her- Bz-l-Brom- ^ carboxy-S-chloro-benzanthron (V)

position of the dyes according to the invention referenced 68 g of Bz-l-bromo-4-cyano-8-chlorobenzanthrone (IV)

will. are in 775 g of 82% sulfuric acid at 100 ^° C.

Bz-1,4-dibromo-8-chlorobenzanthrone (I) ^{25 ϊη} ?? ^ ¹ \ ^v0 £. ^{l U} \ ^{2 Stui} \ i ^{n verse} . ^ J? ^ J ³¹ '

or Bz-l-bromine- ^ S-dichlorobenzanthrone closing drop in water, the carbon

acid precipitated in the form of light yellow needles. These

The Bz-l ^ dibromo-S-chloro-benzanthrone is sucked off, washed neutral and dried,

obtained in the following way:!, S-dichloro-anthraquinone The yield is almost quantitative. The Bz-1-bromine

is by conventional methods about the corresponding 30 4-carboxy-8-chlorobenzanthrone melts above

Anthrone in the 4,8-dichlorobenzanthrone (greenish - 300 ° C and dissolves in sulfuric acid with violet

yellow needles; Melting point: 176 to 178 ° C [from paint.

Nitrobenzene]) converted by brominating this Bz-l-bromo-8-chlorobenzanthrone

Compound m nitrobenzene, the yellow needles become 4-carboxylic acid chloride (VI)
des Bz-l ^ dibromo-S-chloro-benzanthrons obtained, the 35

dissolve in sulfuric acid with a red-violet color and 21 g of bromo-chloro-benzanthrone-carboxylic acid (V)

at 220 to 221 ° C or after crystallization from nitro are in 85 g of nitrobenzene by adding 25 g

Melt benzene at 225 to 226 ^{° C.} Thionyl chloride and 0.5 g of pyridine can be used just as well at 12O ⁰ C within

for the syntheses described, that of 2 hours is also converted into their acid chloride. the

Use Bz-l-bromine-4,8-dichloro-benzanthrone, the 40 green-yellow needles will come off after cooling.

sucked by bromination of the 4,8-dichlorobenzanthrone, washed and dried,

in a chloroacetic acid-hydrochloric acid mixture obtained by reacting the chloride VI with 1 mol

(yellow needles; melting point: 216 to 217 ° C). 1-Amino-anthraquinone is obtained in yellow needles

_,, _,, amide VII, which is recrystallized from quinoline

_{Can be} Bz-l-bromo-4-p-toluolsulfamido- _{45 Siert It dissolves in pivoting} f i _{e with acid}

8-chloro-benzanthrone (II) blue-green in color.

In a melt of 100 g of p-toluenesulfamide, _n . .,. _{_ ,,,} .,, ττ ΤΤ τλ

0.4 g copper acetate and 32 g anhydrous sodium Bz-l-bromo- ^ amlino-S-chlorobenzanthrone (VIII)

acetate, 50 g of Bz-1,4-dibromo-A mixture of 30 g of Bz-1,4-dibromo-8-chloro-8-chlorobenzanthrone (I) are introduced at about 150.degree. After about VaStün- 50 benzanthrone (I) 30 g of aniline, 15 g of anhydrous Nadigem heating at 170 ⁰ C is triumacetat the melt after and 110 g of nitrobenzene is diluted under re-cooling to about 110 ⁰ C with glacial acetic acid and river about Va hour heated to boiling. After the boiled. The yellow product is filtered off with suction while cooling, the reaction product is filtered off with suction, washed with glacial acetic acid, alcohol and plenty of hot water, washed a little nitrobenzene and alcohol and dried with and. The Bz-1-bromo-4-p-toluenesulfamido-55 boiled water. The orange-red needles of 8-chloro-benzanthrone are obtained in almost quantitative quantities. Almost quantitative yields obtained from dimethylformamide crystallized, they dissolve, the yellow needles melt at 248 to 250 ^° C. and in sulfuric acid with an orange color and melt in sulfuric acid with a red-violet color. at 228 to 229 ° C. From dimethylformamide or

_π , _. · Ο ^,,,,, _TTT , 6o nitrobenzene can easily be recrystallized.

Bz-l-bromo-4-amino-8-chlorobenzanthrone (III)

30 g of the sulfamide compound are in 370 g of Bz-1-bromo-8-chloro-benzanthronyl-

Dissolved sulfuric acid and about 1 hour at 30 to ⁴ '* -antnrachinonylimid (IX)

40 ⁰ C stirred. Then the solution is poured onto ice. A mixture of 8.5 g of Bz-l ^ -dibromo-S-chloro-The orange-yellow precipitate is suctioned off and 65 benzanthrone (I) 4.6 g of 1-amino-anthraquinone, 0.2 g

washed with hot water and alcohol. The copper acetate, 7.0 g of anhydrous potassium carbonate and

Bz-1-bromo ^ -amino-S-chlorobenzanthrone is boiled in almost 60 g of nitrobenzene for ¹ _1/2 to 1 1/2 hours

obtained in quantitative yield. The yellow needles are heated. After cooling down, the product is

5 6

sucked, with acetic anhydride and alcohol, 6.3 g of the from Bz-l-bromo ^ -anilino-S-chloro-benz-

wash and boil with dilute hydrochloric acid. anthrone and 1-aminoanthraquinone obtained

The in-the 4 position by exchanging located thrimids be at 100 ⁰ C in a melt of 15 g

The red-brown anthrimide formed by bromine atoms dissolves potassium hydroxide and 25 g of ethanolamine are introduced.

in sulfuric acid with a brownish red color. 5 After 3 hours of heating at 110 to 120 ⁰ C, the

^, _ ""., .1O _{11 ,, ΛΛ poured} melt onto water and blow through

Bz-1-bromine - ^ - benzacndon-S-chlorobenzanthrone (X) _{is oxidized by air. The} green dye is removed.

A mixture of 48 g of Bz-l ^ -dibromo-S-chlorine sucks and washed neutral; he dyes cotton

benzanthron (I) 48 g anthranilic acid methyl ester, 40 g olive vat in strong olive green tones. In Sweden

anhydrous sodium acetate, 0.5 g copper acetate and io feic acid, it dissolves with a green color. 240 g of nitrobenzene is 1 to 2 hours at 19O ⁰ C

heated. The bromine is in the 4-position against the example ^

Anthranilic acid methyl ester exchanged. After a mixture of 17.6 g of the anilino-benzanthrone

When they cool, the orange-red needles are sucked off (VIII), 10.5 g of l-amino-5-benzoylamino-anthraquinone,

and washed with alcohol. After boiling 15 17 g of anhydrous potassium carbonate, 0.5 g of copper acetate

and washing the ester (Xa) with water is obtained and 360 g of nitrobenzene is heated to the boil. To

the product in almost quantitative yield. about an hour, 3.5 g of l-amino-5-ben-

50 g of the ester (Xa) are at 170 ⁰ C in 600 zoylamino-anthraquinone g subsequently added. Stir in more polyphosphoric acid. The mixture is Vasttmdiger R _ea ktionsdauer keeping the product for the time being at 17O ⁰ C, filtered with suction, the purple 20 8O ⁰ C until, with nitrobenzene and alcohol of a sample in sulfuric acid geFarbe no longer wash supply and boiled out with dilute hydrochloric acid changes (about 1 hour). It is then poured onto ice. The dark red-brown crystals of the anthrimide are boiled, filtered off with suction and washed neutral. The obtained in very good yield and dissolve in acridon falls after recrystallization from nitro-sulfuric acid with an olive color, benzene in dark red needles, the yield 25 36 g of sodium in 300 g of aniline with addition is almost quantitative. of 0.5 g copper powder and passing stick through. -I _1-solved at 160 ⁰ C. Be at 130 ⁰ C 21 in the melt thus obtained in Example 1 g of 4-anilino-l-Bz bromine from

A mixture of 5.7 g of the anthrimide (IX), 8-chlorobenzanthrone and l-amino-5-benzoylamino-2.3 g of 1-amino-anthraquinone, 0.2 g of copper acetate, 5 g of 30 anthraquinone obtained anthrimide entered and anhydrous potassium carbonate and 60 g of nitrobenzene at 140 to 150 ⁰ C for 3 hours. The umw is heated to the boil for several hours. After reduction mixture is a mixture of ice and cooling to 100 ⁰ C, the product is filtered off, poured hydrochloric acid and washed the product after Aufmit acetic anhydride and ethanol and filtered off with suction and washed neutral cooking. The obtained is boiled with dilute hydrochloric acid. The resulting 35 th dye can be dissolved in sulfuric acid by pouring over and given dark red-brown anthrimide, if still by boiling with dimethylformamide with a Corinthian color. getting cleaned. He dyes trees from an olive-green vat

This anthrimide can also be made from wool in strong yellowish olive-green tones; in

the sulfuric acid obtained from Bz-l, 4,8-trihalogen-benzanthrone, it dissolves with a green color,

will. 40. . ₁

11 g of the anthrone (I) and 2 moles of 1-amino-anthraquinone obtained from 1 mole of Bz-l ^ -dibromo-S-chloro-benz- Example 4 A mixture of 23 g of the acridone (X), 11.5 g of ten anthrimide be in a melt of 20 g of 1-amino-anthraquinone, 25 g of potassium carbonate and potassium hydroxide and 35 g of ethanolamine at 100 ⁰ C 5 g of potassium acetate and 0.5 g of cuprous chloride is added and stirred for 3 hours at 130 ⁰ C. The 45 ¹ I heated to boiling for _{2 to 1 hour.} After cooling, the melt is poured onto ice and the red-brown needles of the anthrimide are oxidized from the air by blowing through them. The dark olive dye is sucked off, sucked off with acetic anhydride and alcohol and washed neutral; if necessary, he can be washed and boiled with dilute hydrochloric acid, cleaned by boiling with dimethylformamide and the anthrimide dissolves in sulfuric acid with olive quinoline. He dyes tree from a gray vat.

wool in greenish olive tones and dissolves in 8 g of potassium hydroxide and 3 g of potassium acetate, water-sulfuric acid with an olive-green color. free, be locked with 20 g of isobutanol at 80 to 100 ⁰ C ". . stir until a clear melt is obtained. Then Example 2 are 4.5 g of Bz-l-bromo - ^ - benzacridone-A mixture of 7 g of Bz-l-bromo-4-anilino-8-chloro-55 8-chlorobenzanthrone and 1-amino anthraquinone erbenzanthron (VIII), 2.0 g 1-amino-anthraquinone, registered anthrimide maintained and the temperature, 4 g of anhydrous potassium carbonate, 2 g of anhydrous increased to 130 ⁰ C. After 3 hours, the sodium acetate, 0.1 g of copper acetate and 50 g of nitro melt are added to water and the reaction benzene is heated to the boil. Within this product at 6O ⁰ C by blowing air oxy-hour a further 2 g of 1-amino-anthraquinone be diert in 60th The dye obtained in this way dyes cotton in small portions. After a 3 to olive vat in olive tones. The product will take 5 hours to implement. . Sucked ^{off 8O 0} C, washed with acetic anhydride and alcohol, for example, and boiled with dilute hydrochloric acid. 15 g of the anthrimide described in Example 4. After washing until neutral, and drying will be the 65 ig ^he obtained in 350 g of 85% sulfuric acid, about ¹ L ^of ₂ hours reddish brown anthrimide in very good yield. heated to 110 ° C. The reaction mixture is dissolved in sulfuric acid with brown ice, filtered off with suction, washed neutral and turned red-brown in color. dries. The brown dye dissolves in sulfur

7 8

acid with an olive green color and dyes cotton from 60.5 g of Bz-l-bromine ^ -benzoylamino-S-chlorobenzan red-brown vat in real brown tones of very throne, 40 g of potassium carbonate (anhydrous), 1 g of copper good to excellent lightfastness. acetate, 26 g of 1-amino-anthraquinone and 600 g of nitro. . benzene are heated to the boil for about 1 hour. Example ₅ After adding another 5 g of 1-amino-anthraquinone

In a mixture of 60 g of aluminum chloride and after a total of about 2 to 3 hours, Um-10 g of sodium chloride, sulfur dioxide is sucked off with a settling time at 120 ° C. The product will Stirring initiated until a clear melt is obtained with nitrobenzene, acetic anhydride and alcohol. Now 12.5 g of the anthrimide are washed in and boiled with dilute hydrochloric acid, carry, the analogous to Example 4 by reaction io The red-brown anthrimide dissolves in sulfuric acid desAcridonsPOmitl-Amino-S-benzoylamino-anthra- with olive green color and can be converted from quinoline to umquinone instead of 1-amino-anthraquinone obtained crystallize.

will. The temperature is kept at 100 ^° C. for 1 hour. In 600 g of aniline are kept at 160 ^° C. under nitrogen, then the melt is poured onto ice, and 72 g of sodium hydroxide solution are made alkaline with and addition of 0.4 g of copper powder and for some time at 15 solves. 8O ⁰ C is stirred at 120 ⁰ C in the melt obtained. The product is filtered off, washed thoroughly 43 g of the Bz-1-bromine ^ -benzoylamino-S-chloro-benzene and dried. The brown anthrone and 1-amino-anthraquinone obtained in this way dissolve in sulfuric acid with corinthian thrimids added. The temperature is now internal color and dyes cotton from a brown vat in a half four hours slowly increased to 16O ⁰ C. The real red-brown tones. 20 melt is based on a mixture of hydrochloric acid and. Put ice, boil, suck off and wash neutral ge-Example 7. The moist filter material is diluted in

A mixture of 9.3 g of Bz-l-bromine ^ cyan-S-chlorine sodium hydroxide solution was suspended. The leuco connection will

benzanthrone (IV), 5.8 g 1-amino-anthraquinone, 12 g oxidized by introducing air at about 6O ⁰ C. The anhydrous potassium carbonate and 4 g of anhydrous potassium dye are filtered off with suction and washed until neutral. He

Umacetat, 0.2 g of copper acetate and 100 g of nitrobenzene can be passed through by Umküpen and if necessary

is heated to boiling for about 1 hour while stirring. Boil with dimethylformamide and crystallize

After cooling to 80 ° C, it is suctioned off. The purify from quinoline. The dark green dye dissolves

dark red crystals become green with nitrobenzene and turn green in sulfuric acid Ethanol washed and with dilute hydrochloric acid from 30 cotton from a blue-gray vat in strong green

cooked. The anthrimide is thus in very good shades of good fastness properties and excellent

Prey received, it dissolves in sulfuric acid with olive lightfastness.

green color and can be recrystallized from quinoline. When using Bz-l-bromo-4- (p-methoxy-

sate. benzoylamino) -8-chlorobenzanthrone instead of

5 g of the anthrimide obtained from Bz-l-bromo-4-cyano-8-chloro-benzanthrone 35 Bz-l-bromo ^ -benzoylamino-S-chloro-benzanthrone and 1-amino-anthraquinone obtained a similar dye. The reaction is carried out at 100 ° C in a melt of 10 g potassium product from 2 mol Bz-1-bromo-4-benzoylamino-8-chk> rhydroxyd, 5 g potassium acetate and 20 g isobutanol monobenzanthrone and 1 mol isophthalic acid dichloride and 3 Stirred at 120 to 130 ^° C. for hours. using the above process, likewise a green vat-After stirring into water, the product 40 is oxidized by blowing air through it, dye of the same good fastness properties. The dye _. -in is suctioned off and washed neutral. It dyes rs e 1 s ρ 1 e cotton from a brown vat in strong olive tones Analogous to that described in example 8, paragraph 3, from excellent to excellent lightfastness and process, the red-brown anthrimide (dissolves in sulfuric acid with an olive green color. 45 color in sulfuric acid : yellowish olive green). -ίο converts the conversion of l-amino-5-benzoyl example 8 amino-anthraquinone in place of 1-amino-anthra-

In a mixture of 25 g of Bz-1-bromo-4-aminoquinone according to Example 8, paragraph 3, is obtained. 8-chloro-benzanthrone (III) and 220 g of nitrobenzene The dye which, after crystallization from 12 g of benzoyl chloride are added dropwise at 130 ⁰ C. 5 ° quinoline in the form of olive needles is obtained and after about Istündigem heating to 130 ° C, the dissolves in sulfuric acid with gelbstichiggrüner color, increased temperature for a short time to 190 ⁰ C. After dyeing cotton from a blue vat in strong, somewhat cooling, the product is filtered off with suction and washed with dull yellow-green tones of very good general little nitrobenzene and alcohol. The fastness properties and excellent light fastness, yellow needles of Bz-l-bromine ^ -benzoylamino-S-chloro-55

Benzanthrons melt after the crystallization from Example 10 nitrobenzene at 270 to 27 ° C and dissolve in

Sulfuric acid in a thin layer with olive green, in After that in Example 8, paragraph 3, described

thick layer with red color. The yield is almost method if the corinth colored anthrimide is used

quantitatively. 60 (solution color in sulfuric acid: yellowish olive

Instead of benzoyl chloride, the green) can be converted, which is produced by the conversion of 1-amino

The most varied of carboxylic acid chlorides are used 4-benzoylamino-anthraquinone instead of 1-amino

the, z. B. alkyl benzoic acid chlorides, alkoxy-benzoic anthraquinone according to Example 8, paragraph 2, is obtained,

acid chlorides, halo-benzoic acid chlorides, dialkyl- The dye that comes out after crystallization

sulfamido-benzoic acid chlorides, naphthoic acid chlo- 65 quinoline in the form of olive-green needles and

ride, anthraquinonyl carboxylic acid chlorides, aryldicar- dissolves in sulfuric acid with a yellowish green color,

acid chlorides (e.g. isophthalic acid dichloride) or dyes cotton in strong yellow-green tones of

Benzthiazolecarboxylic acid chlorides. excellent lightfastness.

Example 11

A mixture of 5.2 g of Bz-1-bromo-4-p-toluenesulfamido-8-chlorobenzanthrone (II), 5 g of anhydrous potassium carbonate, 2 g of anhydrous potassium acetate, 2.5 g of 1-amino-anthraquinone and 50 g of nitrobenzene Heated to the boil for about 1 1/2 to 2 hours. Then it will be the reaction product sucked off at 150 ° C, washed with nitrobenzene and alcohol and diluted with Boiled hydrochloric acid. After suctioning off, washing neutral and drying, the anthrimide is in very good yield obtained. The red-brown needles dissolve in sulfuric acid with dark green ones Colour.

As described in Example 8, paragraph 3, the anthrimide obtained from Bz-1-bromo-4-p- ^{toluene-sulf c} amido-8-chloro-benzanthrone and 1-amino-anthraquinone is converted. The dye obtained, which is obtained in the form of dark green needles after crystallization from quinoline and dissolves in sulfuric acid with a green color, dyes cotton from a gray-blue vat in strong green tones.

Example 12

A mixture of 72 g of Bz-1-bromo-4-amino-8-chlorobenzanthrone (III), 40 g of anhydrous potassium carbonate, 2 g of copper acetate, 30 g of 1-amino-anthraquinone and 600 g of nitrobenzene is heated to the boil. After about IV2 hours another 16 g of 1-amino-anthraquinone are appended, and after about 2 V ₂ hours, the reaction product is filtered off at 6O ⁰ C, washed with nitrobenzene, acetic anhydride and alcohol and boiled out with dilute hydrochloric acid. After washing neutral and drying, the red-brown anthrimide is obtained in very good yield; it dissolves in sulfuric acid with a corinthian color.

8 gdes from Bz-1-bromo-4-amino-8-chlorobenzanthrone and 1-amino-anthraquinone obtained anthrimides are at 100 ° C in a melt of 15 g of potassium hydroxide and entered 30 g of ethanolamine. After 3 hours of heating at 130 ° C, the melt increases Added ice and the leuco compound obtained is oxidized by a stream of air. The dye is suctioned off and washed neutral. The dark olive green dye dissolves in sulfuric acid with olive green Color and dye cotton in bold olive green tones.

Example 13

A mixture of 35 g of Bz-l-bromo-4-amino-8-chloro-benzanthrone, 35 g of 2-phenyl-4-chloro-6,7-phthaloyl-quinazoline, 1 g of anhydrous ferric chloride and 540 g of nitrobenzene is heated to the boil. The reaction starts immediately with evolution of hydrochloric acid. After some time, the product is filtered off with suction at 180 ° C., with nitrobenzene, alcohol and hot water washed and dried. The orange-yellow needles of the reaction product are in very good yield obtained and dissolve in sulfuric acid with an orange-red color.

A mixture of 17 g of the compound described above, 10 g of anhydrous potassium carbonate, 0.5 g Copper acetate, 6 g of 1-amino-anthraquinone and 360 g of nitrobenzene are heated to the boil for several hours. The reaction product is filtered off with suction at 150 ° C., washed with nitrobenzene and alcohol and boiled with dilute hydrochloric acid. After vacuuming, neutral washing and drying, the Anthrimide obtained in very good yield. The red-brown needles dissolve in sulfuric acid olive color and can, if necessary, be cleaned by boiling with quinoline.

Analogous to the process described in example 8, paragraph 3, this is carried out by the following reactions of Bz-l-bromo-4-amino-8-chlorobenzanthrone with 2-phenyl-4-chloro-6,7-phthaloyl-quinazoline and 1-amino-anthraquinone obtained anthrimide converted. The dark olive green dye obtained in this way, which is in Sulfuric acid dissolves with a green color, dyes cotton from a blue vat in strong yellowish green tones of good fastness properties.

Claims (1)

Claim: Process for the production of vat dyes of the benzanthrone series, characterized in that that one Bz-l-benzanthronyl- (l-anthraquinonyl) amines, which are in the 4-position of the Benzanthrones are substituted, treated with condensing agents. Considered publications:
U.S. Patent Nos. 1,845,469, 2,820,790. When the application was announced, a coloring table with explanations was laid out.