JPS6337147B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improved process for producing anthraquinone intermediates. More specifically, the present invention relates to the general formula () [In the formula, X represents a halogen atom or a phenoxy group. ] An anthraquinone compound represented by and the general formula () By reacting dihydroxybenzene represented by the general formula () In a method for producing an anthraquinone intermediate, the reaction is carried out in an aqueous medium containing 10 to 80% by weight of dimethyl sulfoxide in the presence of an alkaline agent to obtain the hydroxyphenoxyanthraquinone compound represented by be. The compound of general formula () is known per se,
Conventionally, the following manufacturing method is known. For example, US Pat. No. 2,773,071 describes a method in which 1-amino-2-halogeno-4-hydroxyanthraquinone is heated to react with a large excess of dihydroxybenzenes at 175 to 180°C in the presence of an alkali. However, this method is not industrially advantageous because it uses a large amount of expensive dihydroxybenzene (9 to 16 times the theoretical amount) and produces many by-products. Also, British Patent No. 1212206 states that 1-amino-2
A method has been proposed in which -halogeno-4-hydroxyanthraquinone and dihydroxybenzenes are condensed in the presence of an alkali metal oxide or an alkali metal carbonate in a water-soluble basic solvent such as pyridine or picoline. However, this method requires a long time of more than 10 hours to complete the reaction, and also uses pyridine and picoline, which have a bad odor and are expensive solvents, which poses economic and environmental problems. Further, Japanese Patent Publication No. 46-32596 discloses 1-amino-2-phenoxy-4-hydroxyanthraquinone, and Japanese Patent Publication No. 48-926 discloses 1-amino-2-halogeno-4-hydroxyanthraquinone, respectively. A method is described in which dihydroxybenzenes are reacted in an aprotic polar solvent such as dimethylformamide or dimethyl sulfoxide in the presence of dimethylformamide or dimethylsulfoxide. These methods have the advantage of being able to synthesize the desired product under relatively mild conditions by using a special solvent with a high boiling point.
However, since expensive solvents are used alone,
It is inevitably disadvantageous in terms of cost, and it is difficult to recover, especially when diluting with a large amount of water, and if it is not recovered, the wastewater load such as COD and BOD becomes high, causing water quality problems. Moreover, even if it is attempted to further reduce the amount used compared to known methods due to cost considerations, it is practically difficult because the viscosity of the reaction mixture increases. As a method to avoid the use of such special solvents, Japanese Patent Application Laid-Open No. 51-45127 and Japanese Patent Application Laid-Open No. 51-45128
In this issue, a reaction solvent system is proposed in which the main components are lower alcohols, lower aliphatic ketones, or water, mixed with an inert organic solvent. Although these processes use water or an inexpensive organic solvent that is easy to recover, they are carried out at 150-160°C and under a pressure of 4-6 kg/ ^cm2 , so they require the use of a special pressure-resistant reaction vessel such as an autoclave. This poses a problem from an industrial perspective. The inventors of the present invention have conducted intensive studies on reactions to overcome the drawbacks of the conventional methods, and have discovered that a mixed solvent of dimethyl sulfoxide and water is superior in various respects, and have completed the present invention. That is, according to the method of the present invention, the content of dimethyl sulfoxide in the waste liquid is significantly reduced compared to when dimethyl sulfoxide is used alone,
It is possible to reduce the wastewater load such as COD and BOD, and there is no need for drying the raw material compounds or a pressure-resistant reaction vessel.It also produces high-quality compounds of the general formula () with fewer by-products than conventional methods. You can get it at a high rate. It is surprising that even if dimethylformamide is used instead of dimethyl sulfoxide in the present invention, there are many by-products and it is not possible to obtain the target product of satisfactory quality in a good yield. In the present invention, the content of dimethyl sulfoxide in the aqueous medium containing dimethyl sulfoxide is 10 to 80% by weight, preferably 20 to 55% by weight. Furthermore, it is desirable that the amount of dimethyl sulfoxide be 0.5 to 2 times, preferably 0.5 to 1.5 times by weight, relative to the compound of general formula (). In this case, the amount of mixed solvent is much smaller, but
The viscosity of the reaction mixture is lower than in the case of using dimethyl sulfoxide alone, and the desired product can be obtained with high productivity. In the present invention, the compound of general formula () used as a raw material does not need to be a dry product, and is advantageous in that a wet cake containing water can be used. As the anthraquinone compound of this general formula (), 1-amino-2-bromo-4-
Examples include hydroxyanthraquinone, 1-amino-2-chloro-4-hydroxyanthraquinone, and 1-amino-2-phenoxy-4-hydroxyanthraquinone. Examples of the dihydroxybenzene of general formula () include hydroquinone, resorcinol, and catechol. The amount used is 2.5 to 3.5 molar ratio, preferably 2.5 to 3.5 molar ratio to the compound of general formula ().
The molar ratio is 3.0. Examples of the alkaline agent used in the reaction include sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. The amount added is about 0.5 to 1.5 molar ratio to the compound of general formula (). The reaction temperature is 80 to 130℃ under normal pressure, preferably 100℃.
℃ to the boiling point of the reaction solution is suitable. After the reaction is completed, the crystals may be separated by cooling or by adding water. The compound of the general formula () obtained as described above has high purity, and can itself be used as a dye to dye synthetic fibers, such as acetate and polyester fibers, in vivid red, and has excellent light fastness and sublimation fastness. It is also a useful compound as a dye intermediate, and various excellent disperse dyes can be obtained using it as a raw material. The present invention will be explained below with reference to Examples. In the examples, parts are parts by weight. Example 1 40 parts of dimethyl sulfoxide, hydroquinone
41.6 parts of potassium carbonate and 17.4 parts of potassium carbonate were heated and stirred at 95 to 100°C, and at the same temperature, 40 parts of 1-amino-2-bromo-4-hydroxyanthraquinone and 36.6 parts of water were added.
The wet cake was added. This was heated to 108-110°C and further stirred at the same temperature for 15 hours. The viscosity of the reaction mixture at the same temperature was low and showed good fluidity. After the reaction was completed, 120 parts of water was added to separate the crystals, which were washed with water and dried to obtain 48.4 parts of the desired product. Chromatographic analysis of this revealed that it contained 84.3% of the compound of formula (1). Yield 93.5% Examples 2 to 5 Example 1 was carried out by changing the amounts of dimethyl sulfoxide and water used for the reaction. The same procedure was performed to obtain the results shown in the table below.

[Examples 7 to 11 of JP-A-48-926]

20 parts of dimethyl sulfoxide and 5 parts of hydroquinone
1 part and 3.5 parts of anhydrous potassium carbonate and heat to 60°C. Next, 6 parts of 1-amino-2-bromo-4-hydroxyanthraquinone was added and reacted at 100°C for 1 hour. The reaction solution was poured into 1000 parts of hot water at 60°C, and the resulting precipitate was collected by filtration, washed, and dried to obtain 6.4 parts of a product (purity 66.0%, yield 64.8%). Comparative Example 2 [Examples 1 to 6 of JP-A-48-926] 5 parts of hydroquinone in 20 parts of dimethylformamide
1 part and 3.5 parts of anhydrous potassium carbonate and heat to 60°C. Next, 6 parts of 1-amino-2-bromo-4-hydroxyanthraquinone was added and the mixture was reacted at 100°C for 1 hour. The reaction solution was poured into 1000 parts of hot water at 60°C, and the resulting precipitate was collected by filtration, washed, and dried to obtain 6.5 parts of the product of formula (1) (purity 75.5%, yield 75.0%). . Comparative example 3 40 parts of dimethylformamide, hydroquinone
41.6 parts of potassium carbonate and 17.4 parts of potassium carbonate were heated and stirred at 95 to 100°C, and a wet cake of 40 parts of 1-amino-2-bromo-4-hydroxyanthraquinone and 36.6 parts of water was added at the same temperature. This was heated to 108-110°C and further stirred at the same temperature for 5 hours. 120 parts of water was added to this to separate the crystals, washed with water and dried to obtain 36.4 parts of the desired product. Chromatographic analysis of this product revealed that it contained a large amount of purple byproducts as impurities in addition to the compound of formula (1), and its value as a dye or dye intermediate was extremely low.

Claims (1)

[Claims] 1 General formula () [In the formula, X represents a halogen atom or a phenoxy group. ] Anthraquinone compound represented by and general formula () By reacting dihydroxybenzene represented by the general formula () A method for producing an anthraquinone intermediate, which comprises carrying out the reaction in an aqueous medium containing 10 to 80% by weight of dimethyl sulfoxide in the presence of an alkaline agent to obtain the hydroxyphenoxyanthraquinone compound represented by . 2. The manufacturing method according to claim 1, wherein the reaction is carried out in an aqueous medium containing 20 to 55% by weight of dimethyl sulfoxide.