JPS6055057B2 - Method for producing anthrimides or anthraquinonylaminobenzanthrones - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an aminoanthraquinone and a halogenanthraquinone or a monohalogenbenzanthrone or a dihalogenbenzanthrone in the coexistence of a copper-based catalyst and an acid binder in an aqueous medium containing an inert organic solvent. The present invention relates to a method for producing anthrimides or anthraquinonylaminobenzanthrones by reaction.

Anthrimides or anthraquinonylaminobenzanthrones are important intermediates for vat dyes. Conventionally, they are made with aminoanthraquinones in the presence of a copper-based catalyst and an acid binder in a high-boiling organic solvent such as nitrobenzene or naphthalene. It has been produced by the Ullmann reaction with halogenanthraquinones or halogenobenzanthrones. In condensation reactions in high-boiling organic solvents, a large amount of solvent is used, and there is a large loss of solvent due to evaporation during the reaction or post-treatment. It is extremely difficult and troublesome to separate.

Moreover, these commonly used high-boiling organic solvents are flammable and toxic, and it is not desirable to handle them in large quantities. In order to improve the drawbacks of the conventional method, a method that does not use high-boiling organic solvents has been proposed (U.S. Pat. No. 24
However, in this method, the reaction does not proceed satisfactorily, and the reaction product contains undesirable salts.

A method using water instead of a high-boiling organic solvent has also been proposed (US Pat. No. 3,040,063), but even if the raw material is sufficiently atomized, some unreacted substances remain and the resulting product is The quality of the dyes derived from the products obtained is inferior to that of conventional methods.

In order to improve the drawbacks of known production methods, the present inventors conducted extensive research and discovered that when a small amount of an inert organic solvent is added to an aqueous solvent to carry out the condensation reaction, the reaction proceeds extremely smoothly. reached. Namely, anthrimide is produced by condensing aminoanthraquinones and halogenated anthraquinones or halogenobenzanthrones in a solvent consisting of water and an inert organic solvent in the presence of a copper-based catalyst and an acid binder at high temperature using a closed reactor. The present invention provides a method for producing anthraquinonylaminobenzanthrones or anthraquinonylaminobenzanthrones. The aminoanthraquinones used in the present invention include aminoanthraquinones such as 1-aminoanthraquinone, 1,4-diaminoanthraquinone, and 1,5-diaminoanthraquinone, and the halogenanthraquinones include 1-chloroanthraquinone, 1-bromoanthraquinone, and the like. anthraquinone, 1,5-diic leanthraquinone, 1
, 6-(or 1,7-)dichloroanthraquinone, 1,
There are halogenanthraquinones such as 4,5,8-tetrachloroanthraquinone, and halogenbenzanthrones include 3-chlorobenzanthrone, 3-prombenzanthrone, 3,9-dichlorobenzanthrone, 3, 9
- diprombenzanthrone, etc.

These raw materials may be pulverized and used in the presence or absence of a dispersant, but this is usually not necessary. Moreover, it is not necessary to use a dried product. The condensation reaction of the present invention is 1
from 70°C to 25Cf'C, preferably from 190°C to 25Cf'C.
Perform at 30°C.

The amount of water used is 1.5 to 1, preferably 2 to 5 times the total amount of aminoanthraquinones and halogenanthraquinones or halogenobenzanthrones. The amount of the inert organic solvent used in combination with water is such that the amount of inert solvent in the aqueous medium is 5 to 2%. If the amount of inert solvent is larger than this, there will be a large solvent loss in the solvent removal and recovery process, for example, by solvent evaporation, and a large amount of steam will be required in steam distillation. If the amount is less than this, some unreacted substances will remain, blocking of the reactants will occur, and the quality will be poor. Inert organic solvents are those that are not substantially changed during the condensation reaction, and include nitrobenzene, nitrotoluene, toluene, xylene, mesitylene, ethylbenzene, halogenated benzenes, or aromatic hydrocarbon solvents such as naphthalene, methanol, etc. Examples include alcohols such as , ethanol, propanol, butanol, ethylene glycol, propylene glycol, dipropylene glycol, and triethylene glycol, but aromatic hydrocarbon solvents are particularly preferred.

Copper-based catalysts include copper powder, copper acetate, copper carbonate hydroxide (basic copper carbonate), copper carbonate, copper chloride, copper oxide (I-valent or ■-valent), etc., and acid binders include sodium carbonate. , potassium carbonate, calcium carbonate, magnesium oxide, calcium oxide, sodium acetate, etc. can be used. In the present invention, the condensation reaction is carried out using a closed container, but after the completion of the reaction,
Since the organic solvent can be recovered at the same time as depressurization, a special device for organic solvent recovery is not required.

As described above, the present invention can reduce the amount of organic solvent used, is advantageous in terms of equipment and environmental hygiene, and can produce high-quality anthrimides or anthraquinonylaminobenzanthrones, which can be further derived into dyes. High quality dyes can be obtained.

The present invention will be explained below with reference to Examples.

Example 1 Preparation of 3,9-bis(1-anthraquinolylamino)benzanthrone In a 500 ml autoclave, 3,9
-Diprombenzanthrone 18.75f11-Aminoanthraquinone 21.65y1Copper acetate1.9y1Sodium carbonate 6.3f1225g of water and 25g of nitrobenzene
was added, and the mixture was stirred at 215°C for 2 hours (pressure was 20-25k9/Clt).

At the same time as the pressure was released, nitrobenzene was distilled off, and the mixture was further heated and stirred to make it weakly acidic with sulfuric acid.
Anthraquinonylamino)benzanthrone 32.1y was obtained (bromine content 0.58%).

Similar results were obtained when cupric oxide was used instead of copper acetate.

This product is subjected to a ring-closing reaction to produce high quality C.I. I. VatB
I got luck25. Example 23 - Preparation of (1-anthraquinonylamino)benzanthrone In a 1e autoclave, 3-prombenzanthrone 56.5y1 1-aminoanthraquinone 38.8y1 cupric oxide 3.7y1
11y of sodium carbonate, 468y of water, and 52y of triethylene glycol were added, and the mixture was stirred at 205°C for 9 hours.

After cooling and releasing the pressure, the mixture was made weakly acidic with sulfuric acid, heated and stirred, and then vacuumed separately to obtain 81.9y of 3-(1-anthraquinonylamino)benzanthrone (bromine content 0.21%).
).

Similar results were obtained using nitrobenzene instead of triethylene glycol.

This product is subjected to a ring-closing reaction to produce high quality C.I. I. ■AtG
I got reen3.

Example 3 Preparation of 1,4-bis(1-anthraquinonylamino)anthraquinone In a 500 ml autoclave, 1,4
-Diaminoanthraquinone 15.7fI11-Chloranthraquinone 33.7y1 Basic copper carbonate (monohydrate)2.
70y1 magnesium oxide 3.0y1 water 212y and O
- dichlorobenzene 24y was added, and the mixture was heated to 195
℃ for 24 hours with stirring (pressure 13-17k9/Cf
l).

At the same time as the pressure was released, 0-dichlorobenzene was distilled off, acidified with sulfuric acid, heated and stirred, separated under suction, and 1,4-bis(1-
Anthraquinonylamino)anthraquinone 43.0f was obtained (chlorine content 0.15%). This product is subjected to a ring-closing reaction to produce high quality C.I. I. VatBrOwnl was obtained.

Comparative Example 3,9-bis(1-anthraquinonylamino)benzanthrone In a 500 ml autoclave, 3,9
-Diprombenzatron 18.75y11-Aminoanthraquinone 21.65f1 Copper acetate 1.9f Sodium carbonate 6.3f and water 250y were added, and this mixture was heated to 21
It was heated and stirred at 5°C for 2 minutes (pressure 24-28 kg/c!).
i).

Claims (1)

[Claims] 1. Aminoanthraquinone and halogenanthraquinone or monohalogenobenzanthrone or dihalogenobenzanthrone in an aqueous medium containing 5 to 20% by weight of an inert organic solvent in the coexistence of a copper-based catalyst and an acid binder, A method for producing anthrimides or anthraquinonylaminobenzanthrones, which comprises carrying out a heat reaction under pressure.