JPS6033381B2 - Method for producing purified 1-aminoanthraquinone - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing purified 1-aminoanthraquinone.

More specifically, 1-nitroanthraquinone including dinitroanthraquinones or 1-aminoanthraquinone including diaminoanthraquinones is hydrogenated in water or a mixed solvent of water and an organic solvent using a hydrogenation catalyst in the presence of a base. to reduce to 1-aminoanthraquinone and diaminoanthrahydroquinone, separate the catalyst from the air hydrogenation reaction solution, add 1-aminoanthraquinone to the reaction solution and stir, and then remove impurities. ,or,(
B) A method for producing purified 1-aminoanthraquinone by adding 1-aminoanthraquinone to a hydrogenation reaction solution, stirring, removing insoluble matter, and further oxidizing. 1-aminoanthraquinone can be obtained by reducing 1-nitroanthraquinone in a conventional manner.

However, when 1-nitroanthraquinone is produced by nitration of anthraquinone, in addition to 1-nitroanthraquinone, 2-nitroanthraquinone and various dinitroanthraquinone compounds are produced, and from this, 1-nitroanthraquinone and various dinitroanthraquinone compounds are produced.
It is extremely difficult to extract pure nitroanthraquinone. Nitration of anthraquinones in sulfuric acid usually yields products containing only 60-75% 1-nitroanthraquinone. Even if this product is reduced to aminoanthraquinone, it cannot be used directly as an intermediate for dye synthesis. Therefore, purification with nitroanthraquinone or aminoanthraquinone is necessary.
Various purification methods using nitroanthraquinone have been attempted. Examples include treatment with sulfite, treatment with an organic solvent (dimethylformamide, etc.), treatment with a base, and the like. However, even with these purification methods, it is difficult to obtain highly pure 1-nitroanthraquinone, or
Or the purification yield of 1-nitroanthraquinone is low.

The applicant first reduced 1-nitroanthraquinones, including dinitroanthraquinones, or 1-aminoanthraquinones, including diaminoanthraquinones, to the corresponding aminoanthrahydroquinones in the presence of a base, and then partially oxidized them with air or other common oxidizing agents. discovered that highly pure 1-aminoanthraquinone could be obtained by further oxidizing the furnace solution after separating the insoluble matter (Japanese Patent Application Laid-open No. 1989-1991).
1-92828). Further, as a result of studying the above method, it was found that it is more advantageous to use 1-aminoanthraquinone in the partial oxidation step, and the present invention has been achieved.
That is, by using 1-aminoanthraquinone in the partial oxidation of aminoanthrahydroquinone, the use of an oxidizing agent as in the case of the above invention becomes unnecessary, and the added 1
-Ami/anthraquinone not only acts as a partial oxidizing agent, but is itself purified and recovered. Furthermore, when the hydrogenation reaction is carried out using a mixed solvent of water and an organic solvent, the oxidation reaction using a general oxidizing agent in the presence of a hydrogenation catalyst poses safety problems. That is, introducing air or an oxidizing agent such as hydrogen peroxide into water containing an organic solvent in the presence of a catalyst may lead to fire or explosion. However, the method of the invention eliminates this risk. Next, the method of the present invention will be further explained.

1-nitroanthraquinone including dinitroanthraquinones or 1-aminoanthraquinone including diaminoanthraquinones is hydrogenated using a hydrogenation catalyst in water or a mixed solvent of an organic solvent and water in the presence of a base to obtain the corresponding amino and Reduced to diaminoanthrahydroquinone.

After that, ■ Separate the catalyst from the hydrogenation reaction solution, then add 1-aminoanthraquinone to the reaction solution to partially oxidize the soluble diaminoanthrahydroquinones to insoluble diaminoanthraquinones, and remove the insoluble matter. Alternatively, 1-aminoanthraquinone is added to the 'B-hydrogenation reaction solution to partially oxidize soluble diaminoanthrahydroquinones to form insoluble diaminoanthraquinones and remove them together with the catalyst. , a 1-aminoanthrahydroquinone reaction solution is obtained.

It was found that highly pure 1-aminoanthraquinone could be obtained by oxidizing the 1-aminoanthrahydroquinone reaction solution thus obtained in a conventional manner. The present invention utilizes the fact that soluble diaminoanthrahydroquinone is oxidized to insoluble diaminoanthraquinone by 1-aminoanthraquinone, and the added 1-aminoanthraquinone itself is reduced to soluble 1-aminoanthrahydroquinone.

That is, it utilizes the difference in redox potential between 1-aminoanthraquinone and its hydroquinone form, and between diaminoanthraquinone and its hydroquinone form. The diaminoanthraquinones that can be removed by the present invention are 1.51, 1.81,
1,6-1,7-diaminoanthraquinone,
Removal of 1,5-diaminoanthraquinone is particularly easy. In this way, according to the invention there is no need to use common oxidizing agents for partial oxidation and the dangers associated with introducing oxidizing agents into the reaction medium consisting of organic solvent and water in the presence of a catalyst. can be avoided, greatly improving safety.

Furthermore, 1-aminoanthraquinone added as a partial oxidizing agent is recovered together with the purified product and no loss occurs. The 1-1-nitroanthraquinone including dinitroanthraquinones or the 1-1-aminoanthraquinone including diaminoanthraquinones used in the present invention can be synthesized by various known methods.

The hydrogenation of the present invention can be carried out by a conventional method under normal pressure or increased pressure. For example, a reactor equipped with a stirrer and a hydrogen blowing tube is charged with crude 1-nitroanthraquinone or crude 1-aminoanthraquinone, water or a mixed solvent of water and an organic solvent, an inorganic or organic base, and a catalyst, and the mixture is stirred at a predetermined temperature. However, in addition to the normal pressure method in which the reaction is carried out by blowing hydrogen into the reactor, it is also possible to employ a pressurized method in which the raw materials are placed in a pressure-resistant container, hydrogen is introduced therein, and the reaction is carried out by stirring or shaking. The base used in the present invention may be either inorganic or organic, and of course may be a mixture.

It makes 1-aminoanthrahydroquinone soluble in water or a mixed solvent of organic solvent and water, and any essentially inert base can be used.

Organic bases include diethylamide, morpholine, . Piveridine, ethanolamine, etc. are suitable, but those that are industrially advantageous include hydroxides, oxides, carbonates, acetates of alkali metals or alkali metals, which are inorganic bases, and phosphoric acid. I can give you salt. It is preferable to use a hydroxide in a molar ratio of 2/n or more (n is the valence of an alkali metal or alkaline earth metal) to crude 1-nitroanthraquinone or crude 1-aminoanthraquinone. Among them, hydroxides and oxides are particularly advantageous. The base may be added at any stage before the partial oxidation reaction, but it is most preferable to add the base from the start of the reduction reaction. The appropriate amount of solvent to be used is 5 to 100 times the amount of crude 1-nitroanthraquinone or crude 1-aminoanthraquinone. Organic solvents used with water include:
Any substance that is inert during the hydrogenation reaction may be used, including methanol, ethanol, and n-fluoride. . Preferred are those that are well soluble in water, such as /g/g/ol, isopro/benol, butanol, dioxane, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. It is also possible to add a surfactant, which does not adversely affect the hydrogenation, but it is usually not necessary. As the hydrogenation catalyst used in the present invention, a hydrogenation catalyst commonly used for catalytic hydrogenation of quinone to produce hydroquinone can be used.

For example, palladium, platinum, ruthenium, rhodium,
Catalysts containing metals such as nickel, cobalt, copper, iron, or mixtures thereof as active ingredients can be used. In particular, one type of metal compound selected from the group consisting of noble metal catalysts supported on carbon, alumina silica gel, etc., and oxides, carbonates, and hydroxides of noble metal catalysts and metals in group 8, period 5 of the periodic table. Catalysts or mixtures of catalysts deposited on an inert support are used. The amount of catalyst used varies depending on the reaction conditions and the type of catalyst, but for example, when carrying out the reaction using a supported palladium catalyst, 10 parts of crude 1-nitroanthraquinone or crude 1-aminoanthraquinone and 0 parts of palladium metal are used. .01 None, 1. The following countries are appropriate. Reaction conditions include reaction temperature oo to 1
60 qo, preferably 100 to 8,000 qo, and the reaction pressure is preferably in the range of normal pressure to 100 kg/kg, but this reaction also proceeds under conditions of room temperature and normal pressure.

If the reaction temperature is too high, undesirable side reactants are likely to be produced. It is not necessary to carry out the hydrogenation reduction reaction of crude 1-nitroanthraquinone or crude 1-aminoanthraquinone until 1-aminoanthrahydroquinone and diaminoanthrahydroquinone are completely produced.

The crude 1-nitroanthraquinone used in the present invention may contain 2-nitroanthraquinone and anthraquinone in addition to dinitroanthraquinone, and the crude 1-aminoanthraquinone may contain diaminoanthraquinones as well as diaminoanthraquinones.
It may contain anthraquinone and 2-aminoanthraquinone.

In this case, a suitable purification method may be used in combination after the present invention. The 1-aminoanthraquinone added to the hydrogenation reaction solution does not need to be purified, and the amount used is based on the crude 1-aminoanthraquinone in the raw material.
Although it varies depending on the content of dinitroanthraquinone or diaminoanthraquinone in nitroanthraquinone or crude 1-aminoanthraquinone, if the amount of 1-aminoanthraquinone added is too small, purification will be incomplete, and if it is too large, the excess will be treated as insoluble matter. removed.

Of course, this can be recovered. 1-aminoanthraquinone 0 compared to diaminoanthrahydroquinone that is usually mixed in
．． A molar ratio of 1 to 5 times, preferably 0.5 to 2 times, is used. Diaminoanthrahydroquinone in the hydrogenation reaction solution is 1
The 1-aminoanthrahydroquinone reaction solution, which has been partially oxidized with monoaminoanthraquinone and then removed from insoluble matter, is easily oxidized to 1-aminoanthraquinone by air or a common oxidizing agent such as peroxide.

The 1-aminoanthraquinone obtained by the present invention has good quality and yield, and is of sufficient value as a dye intermediate.

The feature of the present invention is that 1-aminoanthraquinone can be purified extremely simply and safely, and it is easy to implement industrially. Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 Into a 300' glass reactor, 5.00 g of crude 1-aminoanthraquinone (purity 92%, containing 5% 1,5-diaminoanthraquinone, 2% 1,8-diaminoanthraquinone), 50% Inpropyl alcohol water 100 hours, caustic soda 1.66 hours and 5% palladium on carbon 0
．． After adding 209 and replacing the system with hydrogen, 30oo
Hydrogenation was carried out while stirring.

The reaction was stopped when 0.0221 mol of hydrogen was absorbed, and the hydrogen in the reactor was replaced with nitrogen. 1- under nitrogen aeration
Add 0.33 ml of aminoanthraquinone, 1 in 30 qo
The mixture was stirred for a period of time, and the deposited precipitate was separated in the furnace together with the catalyst. The furnace liquid was oxidized with air, and the precipitated crystals were filtered, washed with water, and dried to obtain 4.80 g of 1-aminoanthraquinone. This product had a purity of 98% and contained significant amounts of 1,5-diaminoanthraquinone and 1,8-diaminoanthraquinone. The yield in terms of purity (including 1-aminoanthraquinone used to remove diaminoanthraquinone, the same applies hereinafter) was 95.4%. Example 2 Crude 1-nitroanthraquinone (purity 94%, containing 5% 1,5-dinitroanthraquinone and 1% 1,8-dinitroanthraquinone) was placed in a glass reactor with a content of 300.
At 5.00 pm, 100 ml of 50% methanol water, 2.00 ml of caustic soda, and 0.50 ml of 5% palladium carbon were added, and after purging the system with hydrogen, hydrogenation was carried out with stirring at 20 qo.

The reaction was stopped when 0.0814 mol of hydrogen was absorbed, and the hydrogen in the reactor was replaced with nitrogen. 1- under nitrogen aeration
Add 0.23 ml of aminoanthraquinone, 1 in 30 qo
The mixture was stirred for a period of time, and the deposited precipitate was separated in the furnace together with the catalyst. The furnace liquid was oxidized with air, and the precipitated crystals were filtered through the furnace, washed with water, and dried to obtain 4.22% of 1-aminoanthraquinone (purity 98%).
) was obtained. The yield of 1-aminoanthraquinone was 94.6%.
Met.

Example 3 In the same manner as in Example 1, 5.00 g of 1-aminoanthraquinone (purity 97.5%, 1.5% of 1,5-diaminoanthraquinone, 1.0% of 1,8-diaminoanthraquinone) was used. Hydrogenation was carried out.

Claims (1)

[Claims] 1. 1-nitroanthraquinone containing dinitroanthraquinones or 1-aminoanthraquinone containing diaminoanthraquinones is produced in water or a mixed solvent of water and an organic solvent using a hydrogenation catalyst in the presence of a base. (A) Separate the catalyst from the hydrogenation reaction solution, add 1-aminoanthraquinone to the reaction solution, stir, and remove insoluble matter. or (B) 1-aminoanthraquinone is added to the hydrogenation reaction solution, stirred, and then insoluble materials are removed. A method for producing purified 1-aminoanthraquinone, which comprises further oxidation.