JP3020415B2 - Method for producing aminobenzanthrones - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing aminobenzanthrones from halogenobenzanthrones.

[0002]

2. Description of the Related Art As a conventional method for synthesizing aminobenzanthrones, the following method is known. A method in which benzanthrone is nitrated and then reduced by reducing the nitro group (DE 198507, DE 204905, DE 210565, etc.). Benzanthrone is brominated and then nitrated to give 3
-Bromo-9-nitrobenzanthrone, which is then reacted with an aromatic sulfonamide to give 3-arylsulfonylamino-9-nitrobenzanthrone. Further, a method of obtaining 3,9-diaminobenzanthrone by reduction and hydrolysis (U.S. Pat. No. 2,821,533).

[0003]

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[Where Ar represents an aryl group. A method in which halogenobenzanthrone is obtained by adding amino to perform amino substitution in the presence of a copper catalyst (Japanese Patent Application Laid-Open No. 2-243662). However, in the method (1), there are many by-products in the nitration reaction, complicated purification is required to obtain high-purity nitrobenzanthrones, the yield is low, and
Since the nitro compound, which is an intermediate, causes dermatitis damage, it has to be produced industrially in completely closed equipment, and there are many problems such as the need for expensive equipment.
The method is very long and has many by-products at each stage, so that it is extremely difficult to carry out the method industrially. Further, the intermediates 3-bromo-9-nitrobenzanthrone and 3-arylsulfonylamino-9-
Similar to nitrobenzanthrone, nitrobenzanthrone has a problem of strong dermatitis damage and a problem of treating a large amount of waste acid generated during hydrolysis of 3-arylsulfonylamino-9-aminobenzanthrone. This is an extremely unattractive method. On the other hand, the method has a feature that the process is short and no dermatitis disorder is caused due to the absence of an intermediate. However, in the method (1), the reaction temperature must be 150-250 ° C., which is extremely high for industrial implementation, and the reaction time is extremely long, 15-20 hours, so that a large amount of energy loss is inevitable. Further, when an additional test was actually performed, it was confirmed that the reaction was not completed even after the reaction at 150 ° C. for 20 hours.

[0005]

SUMMARY OF THE INVENTION The present invention solves these problems of the prior art, that is, the production of a large amount of by-products, the safety of handling intermediates, the complexity of the process, and the like. An object of the present invention is to provide a method for obtaining a good and high-purity aminobenzanthrone.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on a novel method for producing aminobenzanthrones which can be used in place of the above-mentioned conventional method, and as a result, have found an excellent method having extremely industrial value. The invention has been found.

That is, the present invention provides a process for producing aminobenzanthrones, wherein an amide compound is used as a solvent when halogenobenzanthrone is substituted with ammonia in the presence of a copper catalyst. Is the way.

Hereinafter, the present invention will be described in detail. The halogenobenzanthrones used as starting materials in the present invention are specifically 3-chlorobenzanthrone, 3-bromobenzanthrone, 3-iodobenzanthrone, 3,9-
Dichlorobenzanthrone, 3,9-dibromobenzanthrone, 3,9-diiodobenzanthrone and the like,
Particularly, 3-bromobenzanthrone and 3,9-dibromobenzanthrone are preferred.

The copper catalyst used in the method of the present invention includes electrolytic copper powder, cuprous oxide, cupric oxide, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, Examples thereof include copper metal such as cuprous iodide, copper acetate, and copper sulfate, and copper salts. Particularly, electrolytic copper powder and cupric oxide are preferable.

[0010] The amount of the catalyst used in the method of the present invention is based on 1 mole of the halogenobenzanthrone as a raw material.
Usually 0.0001 to 0.5 mol is good, especially 0.001.
~ 0.3 mol is preferred. Further, iodine may be added as a co-catalyst. The amount used is halogeno benzhanthrone 1
Usually, 0.000001 to 0.001 mol is sufficient with respect to the mol, and preferably 0.00001 to 0.1 mol.
01 mol.

Examples of the amide compound used as a solvent in the method of the present invention include, for example, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, 1,3-
Examples thereof include dibutyl-2-imidazolidinone, 1,3,6-trimethylhexahydro-1,3,6-triazocin-2-one, N, N-dimethylformamide, and N, N-dimethylacetamide. Preferably, 1,3-dimethyl-2-imidazolidinone and N-methyl-2-pyrrolidone are used, and particularly preferably, 1,3-dimethyl-2-pyrrolidone is used.
Use imidazolidinone.

The amount of the solvent to be used is generally 0.5 to 50 parts by weight, preferably 1 to 5 parts by weight, per 1 part by weight of the raw material, halogenobenzanthrone. Further, if necessary, water may be added to the amide compound. The amount of water to be added is usually 0.01 to 1 with respect to 1 part by weight of the amide compound.
00 parts by weight, preferably 0.1 to 10 parts by weight.

As the ammonia used in the method of the present invention, ammonia gas is dissolved in a solvent and used, or liquid ammonia or an aqueous ammonia solution is used.

The amount of ammonia used is usually at least 2 moles, preferably at least 4 moles, per mole of the halogenobenzanthrone. When an aqueous ammonia solution is used, its concentration may be 5% by weight or more, but preferably 15% by weight or more.

Further, in the method of the present invention, potassium acetate, ammonium acetate or the like may be added as an additive in order to capture hydrogen halide generated during the reaction.

The reaction is usually carried out at a temperature in the range of 80 to 180 ° C., preferably in the range of 100 to 150 ° C. The reaction is usually performed for 1 hour or more, preferably for 3 to 10 hours.

The reaction pressure depends on the amount of ammonia and the reaction temperature, but is usually in the range of about 1 to 100 kg / cm ² .

The aminobenzanthrones obtained by these operations are separated as crude crystals by filtering the reaction solution as it is or by adding an acid and filtering. Subsequently, a copper removal treatment is performed to obtain high-purity aminobenzanthrones in good yield.

The type of acid added before filtration is not particularly limited, but preferred examples thereof include sulfuric acid, hydrochloric acid, phosphoric acid,
Examples include inorganic acids such as boric acid and organic acids such as acetic acid. Particularly preferably, sulfuric acid is used.

The copper removal treatment includes a method in which crude crystals of aminobenzanthrones are dissolved in sulfuric acid, discharged into water, filtered, washed with water, and the copper catalyst is removed.

The concentration of sulfuric acid used at that time is usually 70
% Or more, preferably 90% or more. The amount of sulfuric acid used is 1 to 100 parts by weight, preferably 3 to 10 parts by weight, based on 1 part by weight of the crude crystals.

As another method of copper removal treatment, crude crystals of aminobenzanthrones are dissolved in an amide-based solvent or a mixed solvent of an amide-based solvent and water, and then filtered to remove the copper catalyst as a waste filter cake. Method.

The amide solvents used for dissolving the crude crystals in the copper removal treatment include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3
-Dimethyl-2-imidazolidinone, N-methyl-2-
And pyrrolidone. Preferably, N, N-dimethylformamide and 1,3-dimethyl-2-imidazolidinone are used. The ratio of the mixed solvent is usually one in which 0.7 parts by weight or less of water is added to 1 part by weight of the amide solvent. Preferably, an N, N-dimethylformamide aqueous solution having a concentration of 60% or more or N, N-dimethylformamide is used.

When it is necessary to further increase the purity in order to use it as an intermediate such as an organic photoelectric material, recrystallization with an organic solvent may be performed. Examples of the organic solvent include dimethylformamide, N, N-dimethylacetamide,
Examples thereof include 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, toluene, xylene, monochlorobenzene, and dichlorobenzene.

[0025]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
All "parts" here represent parts by weight.

Example 1 In a stainless steel autoclave reactor equipped with a stirrer, 1400 parts of 25% by weight ammonia water, 400 parts of 3,9-dibromobenzanthrone, 2000 parts of 1,3-dimethyl-2-imidazolidinone, 20 parts of potassium acetate Parts, 16 parts of cupric oxide as a catalyst, and heated to 150 ° C.
It was kept warm for 0 hours. Thereafter, the mixture was cooled to room temperature, 1500 parts of a 20% aqueous sulfuric acid solution was added, and the mixture was filtered and washed with water to obtain 646 parts of crude crystals (dryness: 38.9%). Next, 2460 parts of N, N-dimethylformamide and 348 parts of water were added, and 7
It was kept at 0 ° C. for 1 hour. Thereafter, 120 parts of activated carbon and 120 parts of celite were added, and the mixture was filtered at 70 ° C. and the filtrate was collected. The filtrate was added to 7200 parts of water, and the precipitated crystals were filtered, washed with water and dried, and 3,9-diaminobenzanthrone 2
27 parts (85% yield) were obtained. Analysis by high performance liquid chromatography revealed a purity of 93%.

Example 2 In a stainless steel autoclave reactor equipped with a stirrer, 1,3
2000 parts of dimethyl-2-imidazolidinone and 9 parts of water
Charge 30 parts, then blow in ammonia gas,
It was prepared to contain 13% by weight ammonia. Further, 500 parts of 3,9-dibromobenzanthrone, 26 parts of potassium acetate, and 15 parts of electrolytic copper powder as a catalyst were charged.
The temperature was raised to 0 ° C. and kept at the same temperature for 2 hours. Thereafter, the mixture was cooled to room temperature, 6000 parts of 5% sulfuric acid aqueous solution was added, and the mixture was filtered and washed with a 1% aqueous sodium hydroxide solution to obtain 793 parts of crude crystals (dry matter: 41.0%). Next, 1600 parts of N, N-dimethylformamide was added, and the mixture was kept at 80 ° C. for 1 hour. Thereafter, the mixture was filtered at 80 ° C. and the filtrate was collected. The filtrate was added to 7,500 parts of water, and the precipitated crystals were filtered, washed with water and dried to obtain 305 parts of 3,9-diaminobenzanthrone (yield 91%). The purity was 97% as analyzed by high performance liquid chromatography.

Example 3 In a stainless steel autoclave reactor equipped with a stirrer, 1,3
1500 parts of dimethyl-2-imidazolidinone,
500 parts of 9-dibromobenzanthrone, 12 parts of ammonium acetate, 52 parts of copper sulfate pentahydrate as a catalyst, and 136 parts of liquid ammonia were charged.
The temperature was raised to 30 ° C. and kept at the same temperature for 5 hours. Thereafter, the mixture was cooled to room temperature, 5000 parts of 10% aqueous sulfuric acid was added, and the mixture was filtered to obtain 776 parts of crude crystals (dry content: 40.6%). Then, it was dissolved in 4500 parts of 98% sulfuric acid, and the glass filter was used.
After filtration using, the filtrate was discharged into 50,000 parts of water.
The precipitated crystals were filtered, washed with a 1% aqueous solution of sodium hydroxide and water, and dried to obtain 295 parts of 3,9-diaminobenzanthrone (yield: 88%). Purity was 96% as analyzed by high performance liquid chromatography.

Example 4 1250 parts of 28% by weight aqueous ammonia, 500 parts of 3,9-diiodobenzanthrone and N-methyl-2-pyrrolidone 225 were placed in a stainless steel autoclave reactor equipped with a stirrer.
0 parts and 45 parts of copper acetate as a catalyst were charged and heated to 100 ° C., and kept at the same temperature for 1 hour. Thereafter, the mixture was cooled to room temperature, 6000 parts of 25% acetic acid aqueous solution was added, and the mixture was filtered and washed with a 1% aqueous sodium hydroxide solution to obtain crude crystals (drying content: 36%).
2%) 690 parts were obtained. Then, the crude crystals were treated with 98% sulfuric acid 6
The resulting mixture was dissolved in 500 parts, filtered off using a glass filter, and the filtrate was discharged into 50,000 parts of water. The precipitated crystals were filtered, washed with a 1% aqueous sodium hydroxide solution and water, and dried to obtain 248 parts of 3,9-diaminobenzanthrone (yield 92%). Analysis by high performance liquid chromatography revealed a purity of 91%.

EXAMPLE 5 A stainless steel autoclave reactor equipped with a stirrer was charged with 1,3
Dimethyl-2-imidazolidinone (1800 parts) was charged, and then ammonia gas was blown into the mixture to adjust to contain 5% by weight of ammonia. Further, 300 parts of 3,9-dichlorobenzanthrone, 10 parts of potassium acetate, and 60 parts of copper (I) iodide were charged as a catalyst, the temperature was raised to 180 ° C., and the temperature was maintained at the same temperature for 8 hours. Thereafter, the mixture was cooled to room temperature, 6000 parts of 5% aqueous sulfuric acid was added, and the mixture was filtered and washed with a 1% aqueous sodium hydroxide solution to obtain crude crystals (dry matter: 38.7).
%) 663 parts were obtained. Next, 1500 parts of N, N-dimethylformamide was added, and the mixture was kept at 80 ° C. for 1 hour. Thereafter, the mixture was filtered at 80 ° C. and the filtrate was collected. The filtrate was added to 4500 parts of water, and the precipitated crystals were filtered, washed with water and dried, and 229 parts of 3,9-diaminobenzanthrone (yield 8).
8%). Analysis by high performance liquid chromatography revealed a purity of 90%.

Example 6 In a stainless steel autoclave reactor equipped with a stirrer, 700 parts of 25% by weight aqueous ammonia, 310 parts of 3-bromobenzanthrone, 1,3-dimethyl-2-imidazolidinone 7 were added.
Then, 100 parts, 10 parts of ammonium acetate, and 5 parts of cupric chloride as a catalyst were charged and heated to 110 ° C., and kept at the same temperature for 7 hours. Then, it is cooled to room temperature, and a 20% sulfuric acid aqueous solution 1000
Was added, and the mixture was filtered and washed with water to give crude crystals (dry matter 43.1).
%) 557 parts were obtained. Next, 1820 parts of N, N-dimethylformamide and 475 parts of water were added, and the mixture was kept at 90 ° C. for 1 hour. Thereafter, 36 parts of activated carbon and 27 parts of Celite were added, and the mixture was filtered at 70 ° C. and the filtrate was collected. The filtrate was added to 7200 parts of water, and the precipitated crystals were filtered, washed with water and dried, and 213 parts of 3-aminobenzanthrone (87% yield).
I got Analysis by high performance liquid chromatography revealed a purity of 98%.

Example 7 A stainless steel autoclave reactor equipped with a stirrer was charged with 1,3
1500 parts of dimethyl-2-imidazolidinone were charged, and then ammonia gas was blown into the mixture to adjust to contain 3% by weight of ammonia. Further, 265 parts of 3-iodobenzanthrone, 5 parts of electrolytic copper powder as a catalyst, and 0.1 part of iodine were charged, heated to 90 ° C., and kept at the same temperature for 2 hours. Thereafter, the mixture is cooled to room temperature, and 5% phosphoric acid water 50
After addition of 00 parts, the mixture was filtered and washed with a 1% aqueous sodium hydroxide solution to obtain 542 parts of crude crystals (33.6% of dry matter). Next, 2000 parts of N, N-dimethylformamide was added, and the mixture was kept at 80 ° C. for 1 hour. Thereafter, the mixture was filtered at 80 ° C. and the filtrate was collected. The filtrate was added to 9600 parts of water, and the precipitated crystals were filtered, washed with water and dried to obtain 179 parts of 3-aminobenzanthrone (yield 98%). Analysis by high performance liquid chromatography revealed a purity of 98%.

Example 8 A stainless steel autoclave reactor equipped with a stirrer was charged with 1,3
-1600 parts of dimethyl-2-imidazolidinone,
265 parts of chlorobenzanthrone, 58 parts of potassium acetate,
After charging 15 parts of cupric oxide as a catalyst and further charging 136 parts of liquid ammonia, the temperature was raised to 180 ° C. and kept at the same temperature for 10 hours. Then cool to room temperature and
7000 parts of 0% boric acid water was added, and the mixture was filtered to obtain 645 parts of crude crystals (dry matter: 36.7%). Then, 98% sulfuric acid 4
After dissolving in 500 parts and filtering off using a glass filter, the filtrate was discharged into 50,000 parts of water. The precipitated crystals were filtered, washed with a 1% aqueous sodium hydroxide solution and water, and dried, and 233 parts of 3-aminobenzanthrone (yield: 95%).
%). Analysis by high performance liquid chromatography revealed a purity of 91%.

Example 9 A stainless steel autoclave reactor equipped with a stirrer was charged with N, N
-1600 parts of dimethylformamide, 289 parts of 3,9-dibromobenzanthrone, 58 parts of potassium acetate, 15 parts of cupric oxide as a catalyst, 136 parts of liquid ammonia, and then the temperature is raised to 130 ° C. Then, the mixture was kept at the same temperature for 10 hours. Then cool to room temperature, 10%
3500 parts of boric acid water were added, and the mixture was filtered to obtain 208 parts of crude crystals. Next, it was dissolved in 2080 parts of 98% sulfuric acid, filtered using a glass filter, and 1055 parts of water was added to the filtrate. The precipitated crystals were filtered, and the filter cake was washed with water and dried. This step is repeated three times, and the filter cake is dried to obtain 3,9-
50 parts of diaminobenzanthrone (26% yield) were obtained.
Analysis by high performance liquid chromatography revealed a purity of 83%.

Comparative Example 1 1,3-dimethyl-2-imidazolidinone 2 of Example 1
Except that 000 parts were not added.
The temperature was kept at 10 ° C. for 10 hours. Cool to room temperature and add 20% sulfuric acid 1
500 parts were added, filtered, washed with water and dried. The dried product was analyzed by high performance liquid chromatography and found to be 95%
Is the raw material 3,9-dibromobenzanthrone,
9-Diaminobenzanthrone was only 1%.

Comparative Example 2 1,3-Dimethyl-2-imidazolidinone 7 of Example 6
The temperature was raised to 110 ° C. in the same manner as in Example 6 except that 700 parts of toluene was used instead of 00 parts, and the temperature was kept at the same temperature for 7 hours. Then, it is cooled to room temperature, and a 20% sulfuric acid aqueous solution 1000
The mixture was filtered, washed with water and dried. When the dried product was analyzed by high performance liquid chromatography, 98% was 3-bromobenzanthrone as a raw material, and 3-aminobenzanthrone was only 0.1%.

[0037]

According to the method of the present invention, when producing aminobenzanthrones, low yields, toxicity of intermediates, complicated processes, large amounts of by-products, and severe reactions, which have been problems in the past, have hitherto been encountered. This is a practically excellent method that can solve the conditions and the like and obtain a high-purity product with a good yield.

Claims (2)

(57) [Claims] 1. The method of claim 1 wherein halogenobenzanthrone is present in the presence of a copper catalyst.
A method for producing aminobenzanthrones, wherein an amide compound is used as a solvent when ammonia is added for amino substitution. 2. The method according to claim 1, wherein the aminobenzanthrone is 3-aminobenzanthrone or 3,9-diaminobenzanthrone.