JPH0912519A - Production of 1-alkylamino-4-bromoanthraquinone - Google Patents

Abstract

PURPOSE: To economically and inexpensively obtain the subject compound in high purity in terms of an industrial use in high yield with causing a small amount of industrial waste by using an inorganic acid as a solvent, useful as a liquid crystal material, etc. CONSTITUTION: In reacting (A) a 1-alkylaminoanthraquinone (preferably 1- methylaminoanthraquinone) with bromine, (B) an inorganic acid is used as a solvent and preferably (C) a surfactant is added to the reaction system. Examples of component B includes 1-37wt.% aqueous solution of sulfuric acid, 1-50wt.% aqueous solution of hydrobromic acid or 1-98wt.% aqueous solution of sulfuric acid. The amount of the component B is 3-50 times as much as that of the component A. The reaction temperature is preferably 0-80 deg.C. For example, β-naphthol-based anionic surface, etc., are preferably used as the component C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing anthraquinone compounds useful as intermediates for coloring liquid crystal materials and organic polymer materials, sublimation transfer recording materials, disperse dyes and the like.

[0002]

2. Description of the Related Art Conventionally, various methods have been reported as a method for producing 1-alkylamino-4-bromoanthraquinone. Particularly regarding 1-methylamino-4-bromoanthraquinone, for example, a method using bromine with methanol as a solvent (Russian Patent No. 1330129), a method using bromine with o-dichlorobenzene or methylene chloride as a solvent (Russian Patent No. 91
No. 0580), a method of brominating with hydrobromic acid in an organic carboxylic acid (US Pat. No. 5,117,014), a method of using bromine as a solvent with methanol and nitrobenzene (UK No. 1239778), and the like.

However, since these methods use an organic compound as a solvent, they have problems such as recovery and disposal. Further, in the conventional method, a large amount of 1-alkylamino-2,4-dibromoanthraquinone was produced as a by-product, and sufficient purity could not be obtained as an intermediate.

[0004]

DISCLOSURE OF THE INVENTION The present invention reduces by-products such as 1-alkylamino-2,4-dibromoanthraquinone in producing industrially useful 1-alkylamino-4-bromoanthraquinone. In addition, it is an object of the present invention to provide an industrially advantageous method that produces less industrial waste and can be economically inexpensive.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that 1-alkylaminoanthraquinone is reacted with bromine by using an inorganic acid as a solvent and bromine. It was found that amino-4-bromoanthraquinone can be produced with high selectivity,
The present invention has been completed.

That is, according to the present invention, 1-alkylaminoanthraquinone is reacted with bromine to give 1-alkylamino-4.
-A method for producing bromoanthraquinone, which comprises using an inorganic acid as a solvent, and using an inorganic acid as a solvent in the presence of a surfactant 1-
The present invention provides a method for producing alkylamino-4-bromoanthraquinone.

Hereinafter, the present invention will be described in detail. Examples of the raw material 1-alkylaminoanthraquinone used in the present invention include 1-methylaminoanthraquinone, 1-ethylaminoanthraquinone, 1-n-propylaminoanthraquinone, 1-iso-propylaminoanthraquinone, and 1-n-butylamino. Anthraquinone, 1-is
Examples thereof include o-butylaminoanthraquinone, 1-tert-butylaminoanthraquinone, 1-pentylaminoanthraquinone, 1-hexylaminoanthraquinone, 1-cyclohexylaminoanthraquinone, 1-octylaminoanthraquinone and 1-decylaminoanthraquinone.

The inorganic acid that can be used in the present invention is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include hydrochloric acid, sulfuric acid, hydrobromic acid, hydroiodic acid, phosphoric acid and the like. Can be mentioned. These may be used alone or in combination of two or more. Preferably 1-3
7% by weight hydrochloric acid aqueous solution, 1 to 50% by weight hydrobromic acid,
It is a 1-98 wt% sulfuric acid aqueous solution. More preferably,
10-37% by weight hydrochloric acid is used.

In the method of the present invention, the amount of the inorganic acid used as a solvent is usually 1 to 50 times by weight that of 1-alkylaminoanthraquinone, and particularly 5 to 20% by weight in view of economy and product purity. Double is preferred.

Further, the present invention can accelerate the reaction and suppress the production of by-products by adding a surfactant to the solvent.

The surfactant which can be added to the reaction in the present invention is not particularly limited and may be anionic, cationic, nonionic or zwitterionic.

Preferred examples of the anionic surfactant include a reaction composition of β-naphthol, formalin and sodium bisulfite, a salt thereof, an alpha olefin sulfonic acid and a salt thereof, an alkylbenzene sulfonic acid and a salt thereof, an alkyl sulfate and Examples thereof include salts thereof, alkyl (phenyl) ether sulfates and salts thereof, sulfosuccinic acid and salts thereof, ether sulfonic acids and salts thereof, and the like.

Preferred examples of nonionic surfactants are higher alcohols, alkylphenols, polyoxyethylene alkylamine ethers, polyoxyalkylene glycols, fatty acid esters, adducts of alkylamines and epoxy compounds, polyethylene glycols. A system etc. are mentioned.

Preferred examples of the cationic surfactant include quaternary ammonium compounds. Also. Preferable examples of the zwitterionic surfactant include alkyl betaine-based, amido betaine-based, alanine-based, imidazolinium betaine-based surfactants and the like.

Specific examples of products that can be used include the products in the surfactant catalogs of Kao Corporation, Lion Corporation or Daiichi Kogyo Seiyaku Co., Ltd., and all of them can be used.

In the method of the present invention, the amount of the surfactant used depends on the kind of the surfactant, but is usually 0.001 with respect to 1 part by weight of 1-alkylaminoanthraquinone.
To 1 part by weight, preferably 0.005 to 0.01 part by weight. In addition, it is preferable to add these before dripping bromine.

The amount of bromine used in the method of the present invention is 1-
It is usually 0.5-for alkylamino anthraquinone.
The molar ratio is 1.5, and more preferably 0.9 to 1.1 in terms of yield and purity.

The method of the present invention is carried out at 0 to 80 ° C., particularly preferably 5 to 40 ° C. Although the reaction time cannot be uniquely defined depending on the reaction temperature, the type of solvent, the amount used, etc., it is generally 1 to 24 hours, particularly preferably 3 to 10 hours.

[0019]

EXAMPLES The present invention will be further described below with reference to examples. However, the present invention is not limited to the following examples. In the examples, "part" means "part by weight" and "%" means "% by weight". The purity was measured by the area ratio of the liquid chromatogram.

Example 1 23 parts of 1-methylaminoanthraquinone was added to 230 parts of a 35% hydrochloric acid aqueous solution and stirred for 1 hour. Bromine 15.
5 parts was added dropwise, and the mixture was reacted at 25 ° C. for 6 hours. The reaction solution was discharged into 690 parts of a 1% aqueous sulfite solution and neutralized with 240 parts of a 20% aqueous sodium hydroxide solution. It was filtered, washed with water, and dried. 1-methylamino-4-bromoanthraquinone 3
0.4 parts were obtained. 95% purity, 1-methylamino-2,
It was 1.0% of 4-dibromoanthraquinone.

Example 2 4.6 parts of 1-methylaminoanthraquinone was added to 92 parts of a 20% sulfuric acid aqueous solution, and the mixture was stirred for 1 hour. Bromine 3.1
Parts were added dropwise and the reaction was carried out at 25 ° C for 6 hours. After filtration and washing with water, the filter cake was sludged with 100 parts of a 1% aqueous sodium hydroxide solution, filtered, washed with water and dried. 1-methylamino-
5.8 parts of 4-bromoanthraquinone was obtained. Purity 95
%, 1-methylamino-2,4-dibromoanthraquinone was 1.0%.

Example 3 115 parts of 35% hydrochloric acid aqueous solution, 11.5 parts of 1-methylaminoanthraquinone and Demol N (manufactured by Kao Corporation;
(β-naphthol type anionic surfactant) (0.6 part) is charged, and the mixture is stirred for 1 hour. Bromine (7.8 parts) was added dropwise, and the mixture was reacted at 30 ° C. for 6 hours. The reaction solution was discharged into 690 parts of a 1% aqueous sulfite solution. It was neutralized with 240 parts of 20% aqueous sodium hydroxide solution. It was filtered, washed with water, and dried. 15.2 parts of 1-methylamino-4-bromoanthraquinone was obtained. The purity was 97% and 1-methylamino-2,4-dibromoanthraquinone was 0.5%.

Example 4 138 parts of a 20% sulfuric acid aqueous solution, 6.9 parts of 1-methylaminoanthraquinone and Demol N (Kao Corporation; β
-Naphthol-based anionic surfactant) (0.3 part) and charged for 1 hour. Bromine (3.1 parts) was added dropwise, and the mixture was reacted at 25 ° C for 6 hours. After filtration and washing with water, the filter cake was sludged with 100 parts of a 1% aqueous sodium hydroxide solution, filtered, washed with water and dried. 8.7 parts of 1-methylamino-4-bromoanthraquinone was obtained. Purity 97%, 1-methylamino-2,
It was 0.5% of 4-dibromoanthraquinone.

Example 5 11.5 parts of 1-methylaminoanthraquinone and 0.61 of Demol N (manufactured by Kao Corporation; β-naphthol type anionic surfactant) were added to 115 parts of 20% hydrobromic acid aqueous solution.
Charge part and stir for 1 hour. Add 7.8 parts of bromine,
The reaction was carried out at 30 ° C for 6 hours. 1% aqueous sulfite solution 69
The reaction solution was discharged to 0 part. 20% caustic soda solution 24
Neutralized with 0 part. It was filtered, washed with water, and dried. 15.4 parts of 1-methylamino-4-bromoanthraquinone were obtained. The purity was 97%, and 1-methylamino-2,4-dibromoanthraquinone was 0.4%.

Example 6 The same procedure as in Example 5 was repeated except that 12.9 parts of 1-methylaminoanthraquinone of Example 5 was replaced with 12.9 parts of 1-isopropylaminoanthraquinone, and 1- 17.1 parts of isopropylamino-4-bromoanthraquinone was obtained. The purity was 97%, and 1-isopropylamino-2,4-dibromoanthraquinone was 0.6%.

Example 7 1-Ethylaminoanthraquinone 1 instead of using 11.5 parts of 1-methylaminoanthraquinone of Example 5
The same process as in Example 5 was repeated except that 2.0 parts were used, and 1
-Ethylamino-4-bromoanthraquinone 15.6
Got a part. The purity was 97%, and 1-ethylamino-2,4-dibromoanthraquinone was 0.7%.

Example 8 The same procedure as in Example 4 was repeated except that 15 parts of a 5% hydrochloric acid aqueous solution and 100 parts of a 17.5% hydrobromic acid aqueous solution were used instead of the 20% sulfuric acid aqueous solution of Example 4. , 8.5 parts of 1-methylamino-4-bromoanthraquinone were obtained. Purity 96
%, 1-methylamino-2,4-dibromoanthraquinone was 0.7%.

Example 9 Example 3 was repeated except that 1.0 part of amylazine (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene alkylamine nonionic surfactant) was used in place of the demol N of Example 3. Was treated in the same manner as above to obtain 15.0 parts of 1-methylamino-4-bromoanthraquinone. The purity was 97% and 1-methylamino-2,4-dibromoanthraquinone was 0.6%.

[Embodiment 10] Instead of Demol N of Embodiment 3, Arcade T-28
Example 3 except that 2.0 parts (manufactured by Lion Corporation, monoalkylammonium-based cationic surfactant) were used.
The same treatment as in (1) gave 15.0 parts of 1-methylamino-4-bromoanthraquinone. The purity was 97% and 1-methylamino-2,4-dibromoanthraquinone was 0.6%.

Example 11 To 366 parts of 8% hydrobromic acid aqueous solution, 36 parts of 1-decylaminoanthraquinone and 1.4 parts of amylazine (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; polyoxyethylene alkylamine type nonionic surfactant). Charge, charge and stir for 1 hour. Bromine (15.7 parts) was added dropwise, and the mixture was reacted at 10 ° C for 15 hours. The reaction solution was discharged into 2000 parts of a 1% sulfite aqueous solution. It was neutralized with 500 parts of a 20% aqueous sodium hydroxide solution.
It was filtered, washed with water, and dried. 1-decylamino-4-
43.0 parts of bromoanthraquinone was obtained. Purity 93
%, 1-decylamino-2,4-dibromoanthraquinone was 1.0%.

Comparative Example 150 parts of methanol were charged with 30 parts of 1-methylaminoanthraquinone and stirred for 1 hour. Bromine (24.9 parts) was added dropwise, and the mixture was reacted at 20 ° C. for 6 hours. 50 parts of a 10% aqueous sulfite solution was added to the reaction solution. After stirring for 1 hour,
It was filtered, washed with water, and dried. 1-methylamino-4-
39.8 parts of bromoanthraquinone were obtained. Purity 89
%, 1-methylamino-2,4-dibromoanthraquinone was 7.4%.

[0032]

INDUSTRIAL APPLICABILITY According to the present invention, industrially useful high-purity 1-alkylamino-4-bromoanthraquinone can be produced in a high yield, with less industrial waste, and economically and inexpensively. it can.

Claims (7)

[Claims] 1. A method for producing 1-alkylamino-4-bromoanthraquinone by reacting 1-alkylaminoanthraquinone with bromine, wherein an inorganic acid is used as a solvent. Method for producing bromoanthraquinone. 2. A method for producing 1-alkylamino-4-bromoanthraquinone by reacting 1-alkylaminoanthraquinone with bromine, wherein an inorganic acid is used as a solvent in the presence of a surfactant. 1-
Process for producing alkylamino-4-bromoanthraquinone. 3. The method according to claim 1, wherein the inorganic acid used as the solvent is one kind or a mixture of two or more kinds selected from hydrochloric acid, sulfuric acid, hydrobromic acid, hydroiodic acid and phosphoric acid. 4. The inorganic acid used as a solvent is a 1 to 37% by weight aqueous hydrochloric acid solution, a 1 to 50% by weight aqueous hydrobromic acid solution or a 1 to 98% by weight aqueous sulfuric acid solution.
The described method. 5. The amount of inorganic acid used is 3 to 50 times by weight that of 1-alkylaminoanthraquinone.
Or the method of 2. 6. The reaction temperature is 0 to 80 ° C.
Or the method of 2. 7. The 1-alkylaminoanthraquinone is
1-Methylaminoanthraquinone, 1 or 2.
The described method.