DE2202833A1 - PROCESS FOR THE PRODUCTION OF DIAMINO ALPHA, ALPHA'-DIANTHRACHINONYLENE - Google Patents

Description

Our symbols: OZ; ' ■ - / - ■' ■) Noe / Fe 6700 Ludwigshafen, den,. 'Υ.ΐ, ΐ /, ν ¹

-dianthraohinonylenes

The invention relates to a process for the preparation of diamino A, oC ¹ dianthraohinonylenes, the amino groups of which are in one of the free 06 positions of the anthraquinone nucleus.

OC, cC '-Diamino-1,1'-dianthraquinonyls are already known and are valuable pigments that are used for coloring Lacquers, plastic masses and for the production of printing inks are used.

The known processes for the production of the oil, ^ i '-Diamino-1,1'-dianthraquinonyls start from 1-chloroanthraquinones which carry an acyl-tmino group in one of the remaining 06-positions »This 1-chloro compound becomes in the presence of copper condensed in the so-called Ullmann reaction to bis- d, * L '-acylamino-1,1 »-dianthraquinonylene and the bisacylamino compound is converted into the corresponding cd, * £' -diamino-1,1 '-dianthraquinonyls by saponification (DT -PS 1 186 968).

Furthermore, from DT-OS 1 493 545, DT-OS 1 643 280 and DT-AS 1 205 215 processes are known by which 4.4 ^1- diamino-1,1'-dianthraquinonyl compounds are obtained in particular.

It has now been found that diamino- οί, * C 'dianthraquinonyls of the formula

(R)

(R)

X ¹ 0 X '

568/71

309830/1 0 2 Λ

-2-

in which one X and X · one primary amino group and the remaining X and X ¹ hydrogen or hydroxyl, η the values O, 1 or 2 and

R for the case η ■■ - ■■ 1 a carbon ^ mido group or an N-alkylcarbonamido group with \ to 4 carbon atoms in the alkyl radical, or for the case η = 2 an o-dicarboximide group whose nitrogen atom is an alkyl group with 1 to 4 Can carry carbon atoms or a phenyl group, and where one X and X * together with the carbon atom of the adjacent) C = 0 group can form a condensed six-membered carbocyclic or a condensed five- or six-membered heterocyclic ring, in more advantageous Way, if dichloro t /., TV »-dianthraohinonyle of the above formula, in which one X and X * ^{mean chlorine and the other X, X f} , hydrogen or hydroxyl and R and η have the meaning given above, with at least 2 moles of a sulfonic acid amide per mole of dichloro- ^, '·' - '-dianthraquinonyl in the presence of an acid acceptor and copper, copper-I salts, copper-II salts or mixtures thereof and the sulfonamide groups in the reaction product with strong acids v soaped.

The process according to the invention provides diamino-X, ti'-dianthraquinonyls in high yield and at the same time high purity.

For the preparation of the diamino oi, oC »-dianthraquinonyls of the formula I come as starting materials z. B. 4,4'-dichloro-1,1'-dianthraquinonyl, 5,5'-PiCbJLOr-I, i'-dianthraquinonyl, 8,8 · dichloro-1,1 · -dianthraquinonyl, A , 4 * -dichlor -1,1 * -dianthraquinony 1-6,7,6 », T'-tetracarbonic acid-bis-imide, 4,4'-dichloro-1,1'-

o.Tto », T'-tetracarboxylic acid-bis-N-methylimide, -I, 1 ^f -dianthraquinonyl-6,7,6 ', 7'-tetracarboxylic acid bis-H-phenylimide, 4,4 * -dichloro-1,1 · -Di ^ nthraquinonyl-2,3,2 ·, 3'-tetracarboxylic acid bis-imide, 4,4 * -dichloro-1,1 '-dianthraquinonyl-2,3,2 * ^' - tetracarboxylic acid bis-N-phenylimide , 4,4 ^f -Dichlor-1,1 · - dianthraquinonyl-3,3 ^f -dicarboxylic acid-bis-anilide and the dichloro- ^, «^ '- dianthraquinonyls of the formulas

-3- 309830 / 102A

Cl

Cl

O Il

H N 'ι Cl

11

I.

Cl 'ν NH

It

HO O Cl HO O YYY

N "" N.

1 ο

O, '

Cl

Ί ί

S- N Cl

• ν

Cl N-S under consideration,

and

HN-N Cl J Jl, λ

LiL

YY,

Cl N - NH

As dichloro ^, <^ '-dianthraquinonyl compounds, from which
Particularly valuable pigment dyes are particularly suitable in which the chlorine atom is in the 4-position to the dianthraquinonyl compound. So are
4,4 * -Dichlor-1,1'-dianthraquinonyl and the compounds of the formulas

BAD CRiGlN ¹ AL

309830/1024

T, 1

If ^ N Cl f Il I

O "rS 1 Li O I .U

Cl N. N

S. -N O Cl
ι 0 I ^ ί Ί ι
if H. - S. S " Ii ' N Ί " Cl

HN-N Cl J Ii j

and

ύ π ν

01 N-NH

as starting materials for the process of the invention in particular "preferred

The sulfonic acid amides are aromatic and aliphatic Sulfonic acids, such as o- or p-toluenesulfonic acid amide, Benzenesulfonic acid amide, methanesulfonic acid amide or ethanesulfonic acid amide into consideration.

The implementation of the dichloro £, <^ »-dianthraquinonyls with the Sulphonic acid amide is carried out in the usual manner " It is expedient to work in an inert and high-boiling solvent in the presence of an acid acceptor and in Presence of copper, copper-I salts, copper-II salts or Mixtures thereof as a catalyst.

As high-boiling and inert solvents, for. B. trichlorobenzene, Naphthalene, methylnaphthalenes, chloronaphthalene, ohinoline, preferably N-methylpyrrolidone, nitrobenzene or Mixtures of these into consideration. The amount of solvent is to be measured in such a way that the rea, ktlo, nsmischu, ng before, during and after the reaction can be mixed by stirring. In general one uses the 3 to 30, preferably the 5 to 15 times the amount by weight of solvent, based on the di-

309 8 30 / 102A bad OHiGiKAL ~ ⁵ ~

-5- (..ζ. CiY} h \

chlorine- sL _f 06 '-dianthraquinonyl. The use of larger amounts of solvent is not harmful and has no advantage over the stated amounts of solvent, apart from the disadvantage that in this case larger amounts of solvent have to be worked up.

Suitable acid acceptors for the process of the invention are the alkali and alkaline earth salts of weak acids, z. B. Sodium Acetate, Potassium Acetate, Sodium Propionate, Potassium Propionate, Sodium formate, potassium formate, barium acetate, calcium acetate, Sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate. Sodium acetate, potassium acetate, Potassium carbonate or mixtures thereof are used.

The addition of copper, cuprous salt and / or copper-II-salt accelerates the reaction between the dichloro- & · ^ '-dianthrachinonyl and the sulfonamide. Without the addition of copper or copper ions, the reaction takes place only very slowly, so that in the absence of copper and / or copper ions practically no conversion in the desired sense and, above all, by-products are obtained.

The amount of addition of copper, copper-I salts and / or Copper (II) salts is expediently 0.1 to 2.0 wt .- #, based on dichloro - <*, eC · -dianthraquinonyl.

The reaction is generally carried out at temperatures above 150 ⁰ G, wherein the temperature to above, except by the boiling point of the solvent used - if one does not want to work under pressure -, dichloro- used primarily by the thermal stability of the ala starting materials ⁰ S ^ ^1- dianthraquinonyls and the Bissulfonamido- vl, et '-dianthraquinonyls formed during the reaction is determined.

Advantageously, therefore, preferably performs the reaction at temperatures between 150 and 250 ⁰ G, 170-220 ^0C. If the temperature range mentioned is used, the reaction generally ends after 2 to 24 hours. The reaction is over when no or only traces of chlorine can be detected in a processed sample.

309830/1024 -6-

-6- OZ --Ι -j ^

The obtained Bi ^ -sulfonamide »- *, ° i • -dianthraquinonyl, the also referred to as implementation product, can be directly from the mother liquor is separated off by filtration, decanting or centrifugation, or the reaction product is separated off by washing freed from the solvent used in the reaction with a water-miscible solvent and the residue then washed with plenty of water. The isolated reaction product kmin from the solvent also by distillation with Be freed steam, the reaction product is then isolated from the aqueous phase.

However, the entire reaction mixture can also be worked up by distillation with steam, the reaction product then being added to the aqueous residue of the steam distillation is isolated.

In the event that the reaction to the bis-sulfonamido-Ot, od_ carries out dianthraquinonyl in quinoline or another basic high-boiling solvent, the reaction mixture can also be poured into aqueous, dilute mineral acid be freed from the solvent. The reaction product which has precipitated is then isolated in a customary manner. That The reaction product is dried and ground after washing.

To saponify the sulfonamide groups, the reaction product is advantageously introduced ^{into the strong acid at from 0 °} C. to room temperature and advantageously stirred ^{at from 0 °} C. to 30 ^{° C.} The saponification is completed shortly after it has been introduced into the sulfuric acid and the diamino-afc, "t * -dianthraquinonyl can be isolated from the acid in a manner known per se.

In addition to concentrated phosphoric acid, trichloroacetic acid and above all 98 to 88% strength by weight sulfuric acid are used as strong acids into consideration.

The amount of acid is not critical if the mixture is stirrable. In the case of sulfuric acid, one generally uses based on the reaction product, 5 to 20 times the amount.

309830/1024 -7-

-7- υ. 7. τ ψ \: _}

When the saponification is complete, the acid solution is poured onto water or ice / water and the diamino-, '' -dianthraquinonyl is separated from the acidic aqueous phase and washed neutral.

When sulfuric acid is used as the dilution medium, the diaraino-1,1'-dianthraquinonyls ClI) obtained can be precipitated as sulfate fractionated by the metered addition of diluents, preferably water, and thus separated from impurities and possible by-products.

The precipitated sulphate of diamino · "'' -dianthrachinonyls is separated, washed with sulfuric acid the same concentration and the sulfate Major & h Add hydrolyzed in plenty of water, the diamino * preserved. '-, ■' -dianthrachinonyl then with warm V / ater neutrally washed.

Depending on the intended use, the intended or necessary finishing operation, the di traino- <■ · ',' dianthraquinonyl in the form of the aqueous pressed material is further processed or dried.

The ^{diamino- (} ', ^rt dianthrachmonyls obtained by the process of the invention are outstandingly suitable as pigments.

Compared to the prior art process, the process of the invention has the advantage that the dichloro ^ ', ·' -dianthraquinonyls of the formula I, in which one X and X * mean chlorine, are required as starting materials, in a simple and rapid reaction can be obtained from the 'v-dichloroanthraquinone derivatives in high space-time yield .

Another advantage of the process of the invention is that the bis-sulfonic acid ^{amido - Y, *%} mianthraquinonyls are saponified quantitatively by strong acids such as sulfuric acid already at ⁰ ° C. to room temperature in a short time, while according to the prior art processes Technology the bisacylamino-1, V'-dianthraquinonyls in concentrated sulfuric acid at above 100 ° C must be expected.

3098 3-0 / 1024

-8- O.Z. 27

So becomes ζ. B. according to the information in DT-PS 1 186 968, Example 1 d is 4,4'-dibenzoyl-1,1'-dianthraquinonyl heated ^{to 110 0 C for saponification in wt .- # iger sulfuric acid.} In contrast, the corresponding 4,4'-bis-p-toluenesulfonamido-1,1'-dianthraquinonyl with the gl <
saponified a few minutes.

anthraquinonyl with the same agent already at 0 C in

The following exemplary embodiments are intended to continue the process explain. The parts and percentages given below relate to weight.

example 1

a) 241.5 parts of 4,4'-dichloro-1,1'-dianthraquinonyl, 300 parts of p-toluenesulfamide, 160 parts of anhydrous potassium acetate and 2 parts of copper (II) acetate are introduced into 2400 parts of dehydrated nitrobenzene. The mixture is stirred for 10 hours at 200 ^° C. and the nitrobenzene is then removed by steam distillation. The suspension that remains is filtered off with suction while hot and washed with hot water. After drying, 376 parts of yellow-brown 4,4'-BiS-p-toluenesulfonamino-1,1'-dianthraquinonyl are obtained.

b) The product obtained under a) is introduced into 4000 parts of 96% sulfuric acid at room temperature and stirred until it is completely dissolved. 2250 parts of water are then added dropwise over the course of 2 hours, the dye crystallizing out as a sulfuric acid salt. The yellow crystals are filtered off with suction on a glass frit and they are washed with 1100 parts of 61.5% sulfuric acid. Then, the sulfuric acid salt is decomposed by pouring water, the "dyeing turns to dark red. Then is washed so long with hot water, until in the end no sulfuric acid is more naehsJuweisen and dries the filtered under reduced pressure at 50 ⁰ C. This gives 193 parts of pure 4,4'-DIaAInO-1, 1'-dianthraquinonyl in the form of a dark red powder.

-9- 3 098 30 / tO24

-9- O.Z. 2γ

Example 2

a) A mixture of 3000 parts of dehydrated nitrobenzene, 250 parts of N-methylpyrrolidone, 241.5 parts of 5,5'-dichloro 1,1'-dianthraquinonyl, 300 parts of p-toluenesulfonamide, 160 parts of potassium carbonate and 5 parts of copper (II) acetate is stirred at 200 ⁰ C for 20 hours. After cooling, the crystal slurry is suctioned off and washed with ethanol. The product is then boiled with water to remove excess p-toluene-remove, and dried at 100 ⁰ C. 321 parts of yellow 5,5 * -bis-p-toluenesulfonamino-1,1'-dianthraquinonyl are obtained.

b) The product obtained according to a) is introduced into 3000 parts of 96% sulfuric acid at room temperature. After everything has dissolved, the 5,5 * -diamino-1,1'-dianthraquinonyl is deposited as sulfuric acid salt by adding dropwise 1320 parts of water, which is filtered off with suction through a glass frit and washed with 1000 parts of 65% sulfuric acid. The separated sulfate is then added to 3000 parts of water at 50 ⁰ O, wherein the color changes to red. The mixture is stirred for 30 minutes, filtered off with suction and washed neutral with warm water. After drying at 50 ⁰ C under reduced pressure, 172 parts is obtained 5,5'-DIaInInO-1,1 • -dianthrachinonyl in the form of a red powder.

Analogously to the procedures described in Examples 1 or 2, the following ¹ X, <* »-Diamino-V'-dianthraquinonyls are obtained from the corresponding dichloro- ^: i, K'-dianthraquinonyls:

Example designation colors

8,8'-DIaHiInO-1,1'-dianthraquinonyl yellowish

Red

^{4,4-diamino-l} 5,8,5 ', 8 ^l -tetrahydroxy-1,1 ^f - violet dianthraquinonyl

4,4 * -Diamino-1,1'-dianthraquinonyl-6,7, bluish tint 6 · ^ • -tetracarboxylic acid-bis-methylimide red

6 4,4 ^f -Diamino-1,1'-dianthraquinonyls, 3, red-

2 »^ '- tetracarboxylic acid-bis-anilide violet

8,8'-diamino-5,5-dibenzanthronyl red

8 8,8 · -Dinmino-5,5'-dianthrapyridonyl red

3Ö9830 / 102

-10-

-10- O.Z. 27

Example 9

In 1650 parts of quinoline, 241.5 parts of 4.4 ' dianthraquinonyl, 300 parts of a mixture of ο- and p-toluenesulfonic acid amide, 160 parts of anhydrous potassium acetate and 0.1 part of copper-I-bromide entered. The mix will Stirred at 220 to 225 ° C. for 4 hours. After cooling, the reaction mixture is poured into an excess of aqueous hydrochloric acid poured. The precipitated bis-p (o) -toluenesulfonic acid amide is filtered off with suction, washed neutral with water and then dried. Yield: 358 parts of 4,4'-bis-toluenesulfonamido-1,1'-dianthraquinonyl.

The saponification to 4,4'-diamino-1,1'-dianthraquinonyl takes place as described in Example 1 under b).

-11- 309830 / T024

Claims (9)

-11- O.Z. 27 claims 1. Process for the production of diamino- <x, oC '-dianthraquinonylene the formula X ¹ 0 X ' in which one each of X and X ^{1 is} a primary amino group and the remaining X and X ^{1 are} hydrogen or hydroxyl, η the values 0, 1 or 2 and R for the case η = 1 a carbonamido group or an N-alkylcarbonamido group with 1 "to 4 carbon atoms in the alkyl radical, or for the case η = 2 an o-dicarboximide group whose nitrogen atom is an alkyl group with 1 to 4 carbon atoms or a Can carry a phenyl group, and where one X and X 'together with the carbon atom of the adjacent> C = OG group can form a condensed six-membered carbocyclic or a condensed five- or six-membered heterocyclic ring, characterized in that dichloro ol, t * »-dianthraquinonyls of the above formula, in which one each of X and X ^{1 is} chlorine and the other X, X · hydrogen or hydroxyl and R and η have the meaning given above, with at least 2 moles of a sulfonic acid amide per mole of dichloro otmianthraquinonyl in the presence of an acid acceptor and copper, copper (I) salts, copper (II) salts or mixtures thereof and the sulfonamide group saponified with strong acids in the reaction product. Process according to claim 1, characterized in that the dichloro-Qi, ^ '-dianthraquinonyl compounds 4,4'-dichloro-1, 1-dianthraquinonyl, 8,8'-dichloro-5,5'-dibenzanthronyl, 8.8 -Ώ1οΙι1θΓ-5,5'-άΐ / ~ 1 (N), 9,1 '(N), 9 ^f _7-anthrapyridonyl, 8.8 · dichloro-5,5 * -dianthrapyrimidyl, 8.8 ^f -dichlor -5,5'-di-O.9 (N) »1 ^f ^ '(Nj-isothiazolanthronyl or 8.8 ^l -dichloro-5.5 ^t - di-pyrazoloanthronyl used. ίο ■ 309830/102 A " ¹² " -12- O.Z. 27 3. The method according to claim 1, characterized in that the dichloro-Λ, oc »-dianthraquinonyls are reacted with aromatic sulfonic acid amides. 4. The method according to claim 1 or 2, characterized in that the sulfonic acid amide used is ο- or p-toluenesulfonic acid amide, benzenesulfonic acid amide or mixtures thereof. 5. The method according to claim 1, 2 or 3, characterized in that the acid acceptor used is alkali metal or alkaline earth metal salts of weak acids. 6. The method according to claim 5, characterized in that the acid acceptors used are sodium acetate, potassium acetate, potassium carbonate or mixtures thereof. 7. The method according to spoke 1 Ms 3, characterized in that the reaction product is saponified in sulfuric acid. 8. The method according to claim 4, characterized in that 88 to 96 wt .- ^ strength sulfuric acid is used. 9. Process according to claims 4 or 5, characterized in that the saponification is carried out at 0 to 30 ^° C. Badische Anilinft Soda-Fabrik AG 309830/1024