JPH05170713A - Production of anthraquinone compound - Google Patents

Abstract

PURPOSE:To synthesize an anthraquinone compound having excellent quality in high yield while suppressing the formation of by-product to an extremely low level compared with conventional process by carrying out the reaction in 1,3-dimethyl-2-imidazolidinone solvent. CONSTITUTION:The objective anthraquinone compound of formula III can be produced in high purity and yield by using 1,8-dioxy-4,5-dinitroanthraquinone of formula I and aminophenylethanol of formula II as raw materials. The problem of waste-water treatment can be solved by this process.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a compound.
More specifically, it relates to an improved process for producing anthraquinone compounds useful as disperse dyes.

[0002]

The anthraquinone compound represented by the formula (1) described below is known per se and is widely used as a blue dye excellent in leveling property and light fastness to sublimation resistance, for dyeing hydrophobic fibers. .. The following production method has been conventionally known for this compound. For example, US Pat.
No. 641,602 discloses 1,8-dioxy-4,5-dinitroanthraquinone and aminophenylethanol, for example, aromatic solvents such as nitrobenzene, pyridine and quinoline, alcohol solvents such as n-amyl alcohol and phenol. , N, N-dimethylacetamide,
A method of obtaining a compound of formula (1) by condensation in a solvent such as an N, N-dialkyl linear fatty acid amide-based solvent such as N, N-dimethylformamide has been proposed.

However, in these methods, not only a large amount of by-products are produced during the reaction, but also the reaction solution is discharged into a large amount of hydrochloric acid aqueous solution, and the precipitated crystals are separated by filtration to obtain the desired compound of the formula (1). However, insoluble impurities are simultaneously precipitated in the aqueous hydrochloric acid solution, and it is difficult to take out only the desired product with high purity, and the apparent yield is often the theoretical amount or more. In order to increase the purity of the target substance, further purification steps such as pulverization in an aqueous hydrochloric acid solution and recrystallization in an organic solvent are required. Further, since it is difficult to recover the organic solvent from the waste liquid, there are problems that a large amount of colored waste water is generated and the waste water load such as COD and BOD becomes very high.

On the other hand, as a general method, various diluents (eg, water, organic solvent, acid, alkali) are added to the reaction solution in order to selectively crystallize the target compound from the solution after the reaction. In addition, a method is known in which the solubility of a target compound is lowered and the compound is taken out.However, this method is applied to the above-mentioned U.S. Patent and an attempt is made to precipitate the target compound by using, for example, methanol as a diluent in the reaction solution. Then, since many by-products are generated, it is difficult to take out the target crystals as tar and take them out.

[0005]

The object of the present invention is to
An object of the present invention is to provide a method for obtaining an anthraquinone compound represented by the formula (1) described below with good purity and high yield using 8-dioxy-4,5-dinitroanthraquinone and aminophenylethanol as raw materials.

[0006]

The present inventors have achieved the present invention as a result of extensive studies to solve the above-mentioned conventional drawbacks. That is, the present invention uses the formula (2)

[0007]

[Chemical 4]

1,8-dioxy-4,5-dinitroanthraquinone represented by the formula (3)

[0009]

[Chemical 5]

By reacting with aminophenylethanol represented by the formula (1)

[0011]

[Chemical 6]

The method for producing an anthraquinone compound represented by the formula (1) is characterized in that the reaction is carried out in 1,3-dimethyl-2-imidazolidinone in obtaining the anthraquinone compound represented by the formula (1).

The present invention will be described in detail. By carrying out the condensation reaction in 1,3-dimethyl-2-imidazolidinone according to the method of the present invention, the compound represented by the formula (1), which has an extremely small amount of by-products as compared with the conventional method, can be obtained at a high yield. Can be manufactured at a rate. Furthermore, when taking out the target compound of the formula (1) from the reaction solution, for example, by adding a polar solvent such as methanol or an aqueous solution of methanol as a diluent or water to the reaction solution, Crystals of the compound of 1) can be preferentially precipitated and filtered. Therefore, by discharging into the hydrochloric acid aqueous solution as described above to produce crystals, impurities are simultaneously precipitated, and it is difficult to take out the desired compound of formula (1) with high purity, or waste liquid with a high drainage load is generated. There is no problem that it will occur. Furthermore, since the amount of diluent used is small, the colored waste liquid can be incinerated and the waste water problem can be solved.

When N, N-dimethylformamide described in the above-mentioned US patent is used instead of 1,3-dimethyl-2-imidazolidinone in the present invention, the polyester fiber is stained red and the light fastness is lowered. A lot of reddish impurities are produced, light fastness is inferior, and only dyes having extremely low value are obtained. Not only that, even if a polar solvent such as methanol or an aqueous solution of methanol or water was added to the reaction solution as a diluent, a tar product was produced and the target product could not be taken out.

In the production method of the present invention, the amount of 1,3-dimethyl-2-imidazolidinone used is 0.4 to 2 times by weight, preferably 0.5 to 1.5 times the amount of the compound of the formula (2).
It is desirable that the weight is twice. In this case, there is no upper limit, but it is economically disadvantageous to use 2 times or more by weight. In the production method of the present invention, it is preferable to dilute the reaction solution by adding methanol after the reaction and, if necessary, water to dilute the desired product, but the amount of methanol used as the diluent is 1,3-dimethyl-2- It is 1 to 15 times by weight, preferably 4 to 9 times by weight, the amount of imidazolidinone. The amount of water used is 0 to 4 times by weight, preferably 0.5 to 1,3-dimethyl-2-imidazolidinone.
~ 2 times the weight. Methanol, an aqueous solution of methanol, or water and then water are added to the reaction solution to precipitate the desired product as crystals, and the anthraquinone compound represented by the formula (1) is obtained by a method such as filtration. Then, if necessary, it can be purified by a recrystallization method or the like.

In the present invention, the compound of the formula (3) used as one of the raw materials does not have to be a dried product, and can be used in a wet cake form containing water. In this case, the water content is preferably 10% by weight or less. The compound of formula (3) may be a single compound or a mixture of positional isomers. The amount used is 1.5 to 3.5 molar ratio, preferably 2.0, relative to the compound of formula (2).
˜3.0 molar ratio. The reaction temperature is 80 to 1 under normal pressure.
The temperature is 80 ° C, preferably 100 to 160 ° C. The reaction time is 2 to 15 hours, preferably 5 to 10 hours. The compound of formula (1) obtained as described above has high purity,
Synthetic fibers such as acetate and polyester fibers are dyed in a vivid blue color and exhibit excellent light fastness and sublimation fastness.

[0017]

EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the examples, all percentages and parts are percentages and parts by weight.

Example 1 1,3-Dimethyl-2-imidazolidinone 120 parts, aminophenylethanol (o-, m-, p-mixture) 2
A cake containing 09 parts and 15 parts of water was heated and stirred at 70 ° C., and 202 parts of 1,8-dioxy-4,5-dinitroanthraquinone was added thereto at the same temperature. This is 118
C. to 122.degree. C., and heated up, and further stirred at the same temperature for 8 hours. After completion of the reaction, the mixture was cooled to 25 ° C and methanol 98
0 part and 236 parts of water were sequentially added dropwise to precipitate crystals, which were separated by filtration. After washing with water and drying, 233 parts of the desired product (yield 9
0.9%) was obtained. Chromatographic analysis of this product revealed that it contained 88.4% of the compound of formula (1) and 2.3% of reddish impurities.

Examples 2 to 4 180 parts of 1,3-dimethyl-2-imidazolidinone and 218 parts of aminophenylethanol shown in Table 1 were added to 70 parts.
The mixture was stirred at 0 ° C., and 202 parts of 1,8-dioxy-4,5-dinitroanthraquinone was added thereto at the same temperature. This was heated to 118 ° C to 122 ° C and heated, and further stirred at the same temperature for 6 hours. After completion of the reaction, the mixture was cooled to 25 ° C., 980 parts of methanol was added, 316 parts of water was then added dropwise to precipitate crystals, and thereafter the same operation as in Example 1 was carried out to obtain the results shown in Table 1.

[0020]

(Note 1) Content of compound of formula (1) by chromatographic analysis (Note 2) Content of reddish impurity by chromatographic analysis (Note 3) p-aminophenylethanol (Note 4) o-Aminophenyl ethanol (Note 5) A mixture of p-aminophenyl ethanol, o-aminophenyl ethanol and m-aminophenyl ethanol.

Comparative Example 1 A wet cake containing 180 parts of N, N-dimethylformamide, 218 parts of aminophenylethanol (o-, m-, p-mixture) and 15.6 parts of water was heated and stirred at 50 ° C. Then, 202 parts of 1,8-dioxy-4,5-dinitroanthraquinone were added thereto at the same temperature. This is 100 ℃ ~ 1
The temperature was raised to 05 ° C., and the mixture was stirred at the same temperature for 5 hours. After completion of the reaction, after cooling to 30 ° C., 3970 parts of 2%
The reaction solution was poured into an aqueous solution of sulfuric acid to precipitate crystals, and 1
After stirring for an hour, this was filtered off. Target 2 after washing with water and drying
88 parts (112% of theoretical yield) were obtained. Chromatographic analysis revealed that the content of the compound of formula (1) was 68.2%. The value of this product as a dye was extremely low, and the amount of reddish impurities was 14.7%.

[0023]

The method for obtaining the anthraquinone compound represented by the formula (1) with good purity from 1,8-dioxy-4,5-dinitroanthraquinone and aminophenylethanol as raw materials has been established. ..

Claims (1)

[Claims] 1. A formula (2): 1,8-dioxy-4,5-dinitroanthraquinone represented by the formula (3) By reacting with aminophenylethanol represented by the formula (1) The method for producing an anthraquinone compound represented by the formula (1), wherein the reaction is carried out in 1,3-dimethyl-2-imidazolidinone to obtain the anthraquinone compound represented by