JPS5844656B2 - 1- Aminoanthraquinone luino - Google Patents

Description

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

To be more specific, the present invention provides a method for preparing 5-nitro-1,4゜4a,9a-tetrahydroanthraquinones represented by the following general formula (4) in the presence of a basic compound by the following general formula (B
), and then the l-hydroxylaminoanthraquinones are reduced to convert them into l-aminoanthraquinones represented by the general formula (○). This relates to a method of manufacturing a class of products.

(In the above formulas (4), a3) and (C), R1 and R2 represent hydrogen or a methyl group.

) Aminoanthraquinones are compounds that have a wide range of uses as intermediates for dyes and pigments, and l-aminoanthraquinone is particularly known as an industrially important intermediate compound.

This l-aminoanthraquinone has conventionally been produced by the following method.

1) A method of aminating l-anthraquinone sulfonic acid obtained by sulfonating anthraquinone as a raw material.

2) A method of nitrating anthraquinone and reducing the obtained l-nitroanthraquinone.

However, these methods have drawbacks as described below.

In other words, method 1) uses a mercury compound during the sulfonation reaction, and if this mercury is not recovered sufficiently, it will leak into wastewater or be mixed into products, resulting in significant contamination of the biological environment. .

Furthermore, in the method 2), it is impossible to avoid contamination of the product with dinitro compounds as a by-product and the complication of the purification process.

The present invention provides a method for producing highly pure 1-aminoanthraquinone containing almost no by-products, and an object of the present invention is to provide a novel method for producing 1-aminoanthraquinone using safe and easy reaction operations.

The present invention uses 5-nitro-1°4.4a as a starting material.
, 9a-tetrahydroanthraquinones, specifically 5-nitro-1°4.4a, 9a-tetrahydroanthraquinone, 2- or 3-methyl-5
-nitro-1,4°4a,9a-tetrahydroanthraquinone and 2,3-dimethyl-5-nitro-1,4,
4a.

9a-Tetrahydroanthraquinone.

These compounds are substances that can be easily obtained quantitatively by adding butadiene to 5-nitro-1,4-naphthoquinone, especially 5-nitro-1,4,4a,
9a-Tetrahydroanthraquinone is an important compound as a starting material.

The first step reaction adopted by the present invention is 5-nitro1.
4.1- from 4a,9a-tetrahydroanthraquinone
This is a method for obtaining hydroxylaminoanthraquinones, and allows the reaction represented by the following formula (1) to be carried out with high selectivity.

(In the above formula [I], R1 and R2 represent hydrogen or a methyl group.

) The reaction of the above formula (1) is carried out in the presence of a basic compound, and this basic compound may be used in an amount sufficient to keep the reaction system basic.

Further, the basic compound that can be used may be one that is generally recognized as a basic substance, and specific examples include the following.

■) Groups 1a, 1b, 11a and n of the periodic table
Oxides, hydroxides and salts of group b metals with weak acids, such as magnesium oxide, calcium oxide, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium acetate, sodium oxalate, sodium sulfite, phosphorus. Acid-sodium hydrogen, potassium phosphate, potassium permanganate, sodium chromate, sodium sulfide, sodium methylate, sodium phenolate,
Tetrasodium ethylenediaminetetraacetate, sodium polysulfide, sodium hydrosulfide 2) Ammonia, ammonium carbonate and ammonia complex salts 3) Primary amines, secondary amines, tertiary amines, quaternary amine hydroxides and their Sendai nitrogen bases compounds such as n-butylamine, ethanolamine, ethylenediamine, piperazine, morpoline, di-n-butylamine, jetanolamine, benzylmethylamine, tri-n-butylamine, pyridine, triethanolamine, i, s-cyasabicyclo(5, 4,0) Undecene-
7. Benzyltrimethylammonium hydroxide, tetra-n-butylammonium hydroxide, urea, thiourea, methyl ester of glycine, especially in the method of the present invention, alkali metal hydroxides, carbonates, bicarbonates, sulfides or ammonia, alkylamine, urea, pyridine, and quaternary ammonium hydroxide are preferably used, and the amount is enough to keep the reaction system basic, specifically 0.01 part by weight per 100 parts by weight of the starting material. that's all,
In particular, in the case of a strong base, it is preferably used in an amount of 0.01 to 5 parts by weight, and in other cases, it is preferably used in a range of 5 to 30 parts by weight.

Moreover, when using a liquid amine compound, it is also possible to use a solvent amount.

The reaction of the above formula (1) is carried out in a liquid phase, and any compound that is relatively stable in an oxidizing or reducing atmosphere can be used as the solvent.

Particularly preferred solvents include water, methanol, ethanol, impropertool, butanol, ethylene glycol monomethyl ether, ethylene glycol heptanoethyl ether, ethylene glycol, benzene, toluene, xylene, ligroin, acetone, tetrahydrofuran, dimethylformamide, Mention may be made of dimethyl sulfoxide and pyridine.

Further, these solvents may be used alone or in the form of a mixture.

In the reaction [■] above, the raw material 5-nitro-
It is not necessary to completely dissolve the 1,4,4a,9a-tetrahydroanthraquinones in the solvent, and the reaction proceeds even in a suspended state.

In addition, in order to efficiently separate the product hydroxylaminoanthraquinones as a solid, it is preferable to reduce the solubility of the hydroxylaminoanthraquinones. It is best to add these afterwards to lower the solubility.

The amount of solvent used in this reaction is 5-nitro-1 of the raw material.
, 4,4a,9a-tetrahydroanthraquinones in terms of weight times from 1 to 100 times, preferably from 5 to 20 times.

This reaction is carried out at 0 to 200°C, preferably at 30 to 15°C.
The reaction temperature is 0°C and the reaction time is 20~20°C even in a suspended state.
Although the reaction is completed in 120 minutes, the reaction conditions are appropriately determined depending on the type and amount of the solvent and basic compound used.

For example, it is known that when dimethylformamide or dimethyl sulfoxide is used as a solvent, the reaction can be completed in a very short time even at a temperature of 600C in the presence of a strong base such as sodium hydroxide (see below for implementation). See example.

). It has thus been found that 1-hydroxylaminoanthraquinones can be obtained stably and quantitatively in high yield.

Next, in the present invention, the l-hydroxylaminoanthraquinones are reduced by various reduction methods to obtain l-hydroxylaminoanthraquinones.
- Provides a method for producing aminoanthraquinones.

The following three methods are arbitrarily selected for the second stage reduction reaction employed in the present invention.

1) A combination of a basic substance and a reducing substance or reduction with a basic reducing substance.

2) Reduction by a combination of acidic substances and metals.

3) Catalytic hydrogen reduction.

When method 1) is adopted, it is carried out as follows.

First, as the reducing substance used, any compound that has been conventionally recognized to have a reducing power capable of reducing a nitro compound to an amino compound can be used.

Specifically, hydrogen sulfide, hydrosulfides such as sodium bisulfide, potassium bisulfide, ammonium bisulfide, etc., sulfides such as sodium sulfide, potassium sulfide, ammonium sulfide, etc., disulfides and polysulfides such as sodium disulfide, In addition to sulfur-containing compounds such as sodium polysulfide, ammonium disulfide, and ammonium polysulfide, ammonia, elemental sulfur, metallic zinc, metallic iron, metallic aluminum, metallic magnesium, metallic nickel, hydrogen activated by catalysts, sugars, etc. Examples include glucose, fructose, sucrose and maltose, paraformaldehyde, oxalic acid and its salts, formic acid and its salts, ascorbic acid and its salts.

When carrying out the process industrially, hydrogen sulfide, ammonium sulfide, sodium hexasulfide, sodium disulfide, ammonia, elemental sulfur and metallic zinc are particularly effectively used as reducing agents.

It is preferable to use these reducing agents in an amount equal to or greater than that required for reducing the raw material 1-hydroxylaminoanthraquinones to complete the reaction, and the excess reducing agent can be recovered after the reaction and recycled, but it is usually It is advantageous to use a redox equivalent in the range of 2 to 6 per mole of raw material.

This method 1) requires the presence of a basic compound.

As the above-mentioned reducing agent, a compound having basicity can be used alone as it is, but when using a neutral or acidic reducing agent, a sufficient amount of the basic compound to make the reaction system basic, i.e. , oxides, hydroxides, salts with weak acids of elements of Group 1a and Group Ⅰa of the periodic table, ammonia, primary amines, secondary amines, tertiary amines, quaternary ammonium Salt hydroxides, their Shinkin nitrogen basic compounds, etc. may be used.

This method 1) may be carried out in a liquid phase, or the solvent used may be a stable compound that not only does not react with the starting materials but also does not react with the final product and is not adversely affected by the reduction reaction.

Specifically, water, methanol, ethanol, isopropanol, butanol, ethylene glycol 7-methyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol 7-methyl ether, diethylene glycol monoethyl ether, dioxane, tetrahydrofuran, ethanolamine, Single or mixed solvents such as pyridine, benzene, toluene, xylene, chlorobenzene, anisole, and phenethole can be used.

The reaction does not need to be carried out with the raw material compounds completely dissolved, and may be carried out in a suspended state.

Furthermore, the reaction solution does not need to be homogeneous; even if it is non-uniform, the reaction proceeds smoothly.

The amount of solvent to be used is advantageously 1 to 100 times, preferably 5 to 30 times, the weight of the 1-hydroxylaminoanthraquinone.

The reduction reaction by this method is carried out at a temperature maintained at 30 to 200°C, preferably 50 to 110°C, and 1 to 200°C.
Complete in 20 hours.

Furthermore, 5-nitro-1°4.4 which is used as a starting material in the present invention
It is also possible to directly add a reducing agent and a basic compound or a basic reducing agent to the reaction mixture obtained by converting a,9a-tetrahydroanthraquinones to 1-hydroxylaminoanthraquinones to reduce them to l-aminoanthraquinones. It is.

Also, further 5-nitro 1.4.4a. Even when 9a-tetrahydroanthraquinones are reacted with a base in the presence of a reducing agent (or a basic reducing agent), the formula CI
It has also been found that the conversion to l-hydroxylaminoanthraquinones represented by 1, which is an intermediate product, by reacting in the presence of a
It has also become clear that it is advantageous to directly reduce -hydroxylaminoanthraquinones to l-aminoanthraquinones without separating them.

The l-aminoanthraquinones obtained are separated by conventional methods.

Next, a case will be described in which 2) method of reduction using acid and metal is adopted as the reduction method.

1-hydroxylaminoanthraquinones can be reduced using metals such as iron, zinc, magnesium, aluminum, nickel, tin, copper, and mineral acids such as sulfuric acid or hydrochloric acid, or organic acids such as formic acid or acetic acid.

In addition to the above acids or their aqueous solutions, the reaction medium includes methanol, ethanol, isopropanol, phthanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, The use of diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, dioxane, tetrahydrofuran, etc. gives favorable results.

The amount of metal used as a reducing agent is 2 to 6 per mole of raw material.
A redox equivalent is preferred, and a larger amount may be used.

The acids used are not only consumed as metal salts, but also used to maintain acidity or, in some cases, as solvents.

The use of an organic solvent is preferable because it has the effect of making the reaction proceed smoothly and can reduce the amount of acid used as a solvent.

The amount of the reaction medium to be used is advantageously 4 to 100 times, preferably 10 to 40 times the weight of the raw materials.

The reaction temperature is 50-150°C, preferably 60-110°C.
The reaction is carried out at a temperature range of 1 to 20 hours.

Completion of the reaction is determined by confirming the disappearance of hydroxylaminoanthraquinone by chromatographic methods.

The aminoanthraquinone thus obtained is separated by a conventional method.

Next, we will discuss the case of 3) catalytic hydrogen reduction as the third reduction method. A solid hydrogenation catalyst is present in an inert organic solvent in which l-hydroxylaminoanthraquinones are easily dissolved when heated. At least it is reduced using hydrogen gas to obtain l-aminoanthraquinones.

As catalysts, noble metals such as palladium, platinum, ruthenium or rhodium may be used with or without a support material, and iron or nickel may also be used with or without a support material, for example in the form of Raney nickel. .

Suitable inert organic solvents are selected that not only do not react with the starting materials, but also do not react with the final products and are not adversely affected by the catalytic hydrogenation reaction. Specifically, the following are preferred: be.

Aliphatic cyclic ethers, such as dioxane, tetrahydrofuran; glycol ethers, such as ethylene glycol, diethylene glycol or triethylene glycol, and mono- or di-ethers of aliphatic alcohols having 1 to 4 carbon atoms, % ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether; acetic acid esters of glycols and glycol ethers such as ethylene glycol monoacetate, ethylene glycol diacetate or ethylene glycol monomethyl Acetic ester of ether; it is advantageous to use as little amount of anisole or phenethole solvent as possible, but use an amount sufficient to dissolve the product l-aminoanthraquinones and separate the remaining catalyst when heated. It is necessary to
Usually 3 to 1-hydroxylaminoanthraquinone
It is used in an amount of ~100 times by weight, preferably 5 to 50 times by weight.

The reaction is carried out at a temperature of 0-200°C, preferably 20-150°C.

The hydrogen partial pressure is carried out at an absolute pressure of 0.5 to 40 kg/cti, preferably 1 to 4 kg/cti.

The amount of catalyst used is 0.0 per hydroxylamino compound.
5-30% by weight, preferably 1-10% by weight,
A larger amount may be used.

Completion of the reaction can be determined from the amount of hydrogen consumed.

It can also be determined by confirming the disappearance of the hydroxylamino compound by chromatography.

Although the reaction varies depending on reaction conditions such as hydrogen partial pressure and temperature during the reaction, it is usually completed in 1 to 20 hours.

According to the above, an industrially advantageous method of continuously carrying out the reaction according to formula [1] and the subsequent reduction reaction can give good results very smoothly if the same solvent is used. It is clear that, in particular, as a reduction method, a combination of a basic substance and a reducing substance shown in the term 0 or a method using a substance having basicity and reducing properties is adopted, since the formula CI in the first stage is It can be seen that the combination of soil volume with the reaction of ) is also a preferred embodiment.

The present invention will be explained in more detail by showing examples below.

In the following description, unless otherwise specified, "part" means part by weight, and "1%" means percent by weight.

Example 1 50 parts of 5-nitro-1,4,4a,9a-tetrahydroanthraquinone was added to 20 parts of ethyl cellosolve, and 0.3% aqueous sodium hydroxide solution 2 was added at 60°C with stirring.
0 part was added and reacted with stirring for 1 hour to convert it to 1-hydroxylaminoanthraquinone.

Then, 20% of a 6% aqueous sodium sulfide solution was added to the reaction mixture.
The mixture was reacted at 95-100°C for 2 hours, cooled to 25°C and filtered.

After washing the furnace slag with water, it was dried to obtain 4.2 parts of 1-aminoanthraquinone.

The purity of l-aminoanthraquinone was 98%.

Example 2 5.0 parts of 5-nitro-1,4,4a,9a-tetrahydroanthraquinone was added to 70 parts of methanol in which 0.1 part of sodium hydroxide was dissolved, and the mixture was reacted with stirring at 600C for 1 hour. .

Furthermore, add 15 parts of 15% hydrochloric acid to the reaction mixture and add 70 parts of 15% hydrochloric acid.
The mixture was heated to 0.degree. C., and 1.6 parts of powdered metal zinc was added little by little over 1 hour.

Thereafter, the temperature was maintained at 70°C for 3 hours, and then cooled to 25°C.

After finishing the reaction mixture, the slag was washed and dried, and the purity was 94%.
4.3 parts of 1-aminoanthraquinone were obtained.

Example 3 5.0 parts of 5-nitro-1,4,4a,9a-tetrahydroanthraquinone was added to 100 parts of ethylene glycol monomethyl ether, and while stirring, 0.5 parts of ammonia gas was added.
After 0.25 parts of Raney nickel was added, the mixture was reacted at 70° C. for 1 hour to convert into l-hydroxylaminoanthraquinone.

Next, 0.04 parts/hour of hydrogen gas was added to 1 kg/h while stirring.
cI? After continuing the reaction by keeping it at 80°C for 4 hours while introducing it under pressure of L, the hydrogen gas was stopped, and the hydrogen gas was replaced with nitrogen gas, and then the reaction mixture was heated to 100°C and the reaction mixture was filtered while hot. The catalyst was then separated as slag.

While maintaining the filtrate at 80°C, 100 parts of stirred sewage water was added thereto, and the mixture was cooled to 25°C to precipitate crystals.

The slag was washed with water and then dried to obtain 4.0 parts of 1-aminoanthraquinone with a purity of 97%.

Example 4 10.0 parts of 5-nitro-1,4,4a,9a-tetrahydroanthraquinone was added to 140 parts of methanol, 0.2 part of sodium hydroxide was added with stirring, and the mixture was kept at 60°C for 1 hour. The reaction mixture was cooled to 25°C, the reaction mixture was filtered, and the slag was washed with water and then dried under reduced pressure to obtain 8.4 parts of 1-hydroxylaminoanthraquinone.

50 parts of the obtained l-hydroxylaminoanthraquinone was added to a mixed solution consisting of 20 parts of ethylene glycol monomethyl ether and 20 parts of water, and heated to 60°C under stirring (after adding 10 parts of a 10% sodium sulfide aqueous solution with a trowel, After being maintained at ~100°C for 3 hours, it was cooled to 25°C and the reaction mixture was filtered.

The F residue was washed with water and dried to obtain 44 parts of 1-aminoanthraquinone.

The purity of 1-aminoanthraquinone was 99.5%.

Example 5 50 parts of l-hydroxylaminoanthraquinone obtained in the same manner as in Example 4 was mixed with 40 parts of ethyl alcohol and water i.
o parts and 3 parts of sulfuric acid, and stirred for 80 minutes.
The mixture was heated to .degree. C., 17 parts of ribbon metal iron was added over a period of about 1 hour, the mixture was kept at 80.degree. C. for 3 hours to react, and then cooled to 25.degree.

The reaction mixture was separated into a furnace, and the furnace slag was washed with water and then dissolved in dimethylformamide and passed through again to separate the remaining metallic iron.

Dimethylformamide was distilled off under reduced pressure to obtain 4.3 parts of 1-aminoanthraquinone with a purity of 92%.

Example 6 5.0 parts of l-hydroxylaminoanthraquinone obtained in the same manner as in Example 4 and 0.25 parts of Raney nickel were added to 100 parts of ethyl cellosolve.

While introducing hydrogen gas at a rate of 0.04 parts/hour into the reaction solution while stirring, the temperature was raised to 80°C in 30 minutes, and after the reaction was continued at 80°C for 4 hours, the hydrogen gas was stopped and nitrogen gas was introduced into the reaction solution. Replaced with hydrogen gas.

Next, the reaction mixture was heated to 100°C, the reaction mixture was filtered while hot, the catalyst was separated as slag, and the p liquid was heated to 80°C.
While maintaining the temperature at °C, 100 parts of stirring sewage water was added to precipitate crystals.

This slurry liquid was then cooled to room temperature and filtered.

The furnace slag was washed with 5 parts of methanol and then dried to obtain 4.2 parts of l-aminoanthraquinone.

The purity of this l-aminoanthraquinone was 97%.

Example 7 50 parts of 5-nitro-1,4,4a,9a-tetrahydroanthraquinone was added to 50 parts of pyridine and held at 60°C for 1 hour with stirring to form hydroxylaminoanthraquinone, then the temperature was lowered with stirring. 90'C
0.72 parts of hydrogen sulfide gas for 2 hours at this temperature.
The time passed.

The reaction mixture was cooled to 25°C and 50 parts of water was added to precipitate crystals.

The crystals were separated from the furnace, washed with warm water, and dried under reduced pressure.
-4.0 parts of aminoanthraquinone was obtained.

Example 8 5-nitro-2,3-dimethyl-1,4,4a.

9a-50 parts of tetrahydroanthraquinone to 10 parts of water
0 parts were mixed, 20 parts of a 10% aqueous sodium sulfide solution was added at 90°C with stirring, and the mixture was maintained at 90 to 95°C for 1 hour.

The crystals were then cooled to 25°C, separated in a furnace, washed with water, and dried under reduced pressure to yield 4.5 parts of 5-amino-2,3-dimethylanthraquinone with a melting point of 222°C.

Claims (1)

[Scope of Claims] 1 5-nitro-1,4゜4a,9a-tetrahydroanthraquinones represented by the following general formula (4) are converted into 1-ditro-1,4゜4a,9a-tetrahydroanthraquinones represented by the following general formula (B) in the presence of a basic compound. 1-aminoanthraquinones, characterized by converting them into humanized xylaminoanthraquinones, and further reducing the obtained 1-hydroxylaminoanthraquinones to convert them into 1-aminoanthraquinones represented by the general formula (O). Production method. (However, the method of reducing l-hydroxylaminoanthraquinones using a hydrogenation catalyst in an aqueous medium is excluded.) (In the above formulas (4), (B) and (○, R1 and R2 are hydrogen or (Represents a methyl group.)