JPH02311445A - Production of 1-nitroanthraquinones - Google Patents

Abstract

PURPOSE:To obtain the subject compound in high selectivity, yield and purity with simple operation under mild reaction condition by reacting 5-nitro-1,4,4a,9a- tetrahydroanthraquinones in the presence of the basic compound and oxidizing the reaction product. CONSTITUTION:A 5-nitro-1,4,4a,9a-tetrahydroanthraquinone compound of formula I (R<1> and R<2> are H, 1 to 4C alkyl or halogen) is reacted in the presence of a metallic basic compound of group Ia, Ib, IIa, IIb, etc., of the periodic table and the obtained compound of formula II is oxidized in the presence of a metallic basic compound of group Ia, Ib, IIb, etc., of the periodic table to obtain the objective compound of formula III useful as a raw material for 1- aminoanthraquinones, intermediate for dye or pigment, etc. The basic solution left after separation of the objective compound can be recycled. The separation of the product and the treatment of waste water can easily be carried out without causing environmental pollution. The objective compound can be produced at a low cost and the present process is advantageous from industrial viewpoint.

Description

Detailed Description of the Invention [Industrial Application WJ] The present invention relates to a method for producing 1-nitroanthraquinones. To explain in more detail, the following general formula (A)
5-nitro-1,4,4a,9a-tetrahydroanthraquinones represented by are converted into 1-hydroxylaminoanthraquinones represented by the following general formula (B) in the presence of a basic compound, and then oxidized. The present invention relates to a method for producing 1-nitroanthraquinones represented by the following general formula (C), in which 1-nitroanthraquinones are recycled. Furthermore, oxidizing 1-nitronaphthalene to obtain 5-nitro-1,4-naphthoquinone,
Next, 1,3-butadiene represented by the following general formula (D) is subjected to a Diels-Alder reaction to obtain the general formula (A).
The present invention relates to a method for producing the above-mentioned 1-nitroanthraquinones, which comprises obtaining 5-nitro-1°4.4a,9a-tetrahydroanthraquinones shown in ) and using this as a raw material.

(In the above formulas (A), (B), (C) and (D), R1 and RZ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and halo.

Represents one type selected from Gen atoms. ) 1-Nitroanthraquinones are compounds that have a wide range of uses, such as as raw materials for 1-aminoanthraquinones and as intermediates for dyes and pigments. Among these, 1-nitroanthraquinone is an industrially important intermediate. known as a compound.

[Prior Art] As a method for producing 1-nitroanthraquinone, a well-known method is to nitrate anthraquinone with concentrated nitric acid or a mixed acid (Japanese Patent Application Laid-open No. 5430/1983).
Japanese Patent Publication No. 57-193426, Publication No. 57-51377
No., Special Publication No. 58-35498, Special Publication No. 61-5213
7 publications). However, 1-nitroanthraquinone obtained by such a method contains a large amount of by-products such as 2-nitro and dinitro, and the purity of 1-nitroanthraquinone is at most 80% or less. Therefore, in order to obtain high-purity 1-nitroanthraquinone, which is used as an intermediate for dyes, further purification is required, but ordinary separation and purification methods such as distillation, recrystallization, and extraction eliminate these by-products. Living organisms are difficult to isolate and purify on an industrial scale. Furthermore, these methods use a large amount of sulfuric acid and nitric acid, and require a lot of hassle in terms of plate removal and waste liquid treatment.In addition, nitrobenzene is used as the reaction medium, and 5-nitro-1,4-naphthoquinone and 1. 3-butadiene and 1
After reacting at 00°C, it is oxidized at 180-200°C to form 1
- Method for obtaining nitroanthraquinone (French patent No. 1)
No. 486803), but it is difficult to control the reaction conditions and the yield is low.

[Problems to be Solved by the Invention] The purpose of the present invention is to eliminate the above-mentioned drawbacks that could not be solved by conventional methods, to enable reactions with good selectivity under mild reaction conditions, and to facilitate product separation, wastewater treatment, etc. The object of the present invention is to provide a method for obtaining 1-nitroanthraquinones that is easy and industrially advantageous in terms of working environment and pollution.

[Means for Solving the Problems] The present inventors have conducted intensive research to develop a method for industrially advantageously producing 1-nitroanthraquinones, and as a result, have finally completed the present invention. That is, according to the present invention, 1.4.4 g of 5-nitro of formula (A), 9a-
A process represented by formula (C) in which tetrahydroanthraquinones are converted into 1-hydroxylaminoanthraquinones of formula (B) in the presence of a basic compound, and the obtained 1-hydroxylaminoanthraquinones are oxidized for cyclic use. A novel method for producing 1-nitroanthraquinones can be provided. According to the present invention, 1-nitronaphthalene is further oxidized to 5-nitro-1,4-naphthoquinone,
Then, a Diels-Alder reaction is performed with 1,3-butadiene represented by general formula (D) to produce 5-nitro 1+ 4+ 4 a 19 B-tetrahydroanthraquinone of formula (A), and the resulting 5- Nitro-1,4,4
a, 9a-Tetrahydroanthraquinones are converted into 1-hydroxylaminoanthraquinones of formula (B) in the presence of a basic compound, and the obtained 1-hydroxylaminoanthraquinones are oxidized in the presence of a basic compound. Provided is an integrated method for producing 1-nitroanthraquinones represented by formula (C) in which 1-nitroanthraquinones of formula (C) are recycled.

According to the method of the present invention, the desired 1-nitroanthraquinones can be produced with a high yield under simple operations and mild reaction conditions.
It can be obtained with high purity and at low cost without causing environmental damage. This will be explained in detail below.

5-nitro-1+ of formula (A) used in the present invention
'L4a,9a-Tetrahydroanthraquinones are preferably highly pure. If 1-nitroanthraquinones contain impurities such as 6-nitro and dinitro, by-products such as 2-nitro and dinitro will be mixed in, which will have a negative impact on the purity and yield of the product. Not only do these impurities become toxic anthraquinone derivatives that are mixed into products, but their toxicity also becomes a problem. In this regard, 1-nitronaphthalene is oxidized to form 5-nitro-1
, 4-naphthoquinone, which was then converted into 1. of formula (D).
5-nitro-1,4,4a,9a-tetrahydroanthraquinones obtained by Diels-Alder reaction with 3-butadienes do not contain impurities such as 6-nitro and dinitro forms, and are considered suitable raw materials. I can stay. It takes K
The process of obtaining 5-nitro-1.4.4a,9a-tetrahydroanthraquinones (A) will be explained.

First, 1-nitronaphthalenes are converted into 5-nitro-1,4-
Oxidizes to naphthoquinones. Here, the raw material 1-
Nitronaphthalenes can also be obtained by nitration of naphthalenes, but this nitration has a much higher selectivity than the above-mentioned nitration of anthraquinones, so there are no problems in terms of yield or product purity, and the process is sufficient. High quality 1-nitronaphthalenes are available as starting materials (Encyclopedia of Chemical Technology).

(2nd edition, p. 704). As a method for oxidizing such 1-nitronaphthalenes, an electrolytic oxidation method is preferable from the viewpoints of selectivity, yield, and operability. There are two types of electrolytic oxidation methods: the direct electrolytic oxidation method, in which 1-nitronaphthalenes are oxidized directly on the electrode surface, and the indirect electrolytic oxidation method, in which oxidizing agent species are generated by electrode reaction and 1-nitronaphthalenes are oxidized. However, the indirect electrolytic oxidation method in particular has the advantage that highly pure 5-nitro-1,4-naphthoquinone can be obtained with high selectivity and yield under mild conditions.It also has the advantage of being easy to perform in terms of operability. In the indirect electrolytic oxidation method, the oxidant species itself is reduced by the indirect electrolytic oxidation, but this is regenerated into an oxidant by the electrolytic oxidation and recycled. The redox species that can be reused in this process are called mediators. The mediator can be selected according to the desired reaction conditions and reaction characteristics, but Ce(I
V ) / Ce (Ill), M n (III)
/Mn(II), Mn(IV)/Mn(II)
, A g (II)/A g (I), etc. are preferable in terms of selection, operability, safety, and the like. Preferred concentrations of these mediators in the acidic aqueous solution are Ce(rV), Mn(III),
0.0 when Mn(IV) or Ag(TI) is used as the main oxidizing agent. 1 to 10 mol/liter, more preferably 0.3 to 5 mol/liter, even more preferably 0
．． It is 5 to 3 mol/liter. If the concentration is too high,
The oxidizing agent may precipitate and become a slurry, or the viscosity of the solution may become unstable, resulting in insufficient stirring, which may impede the reaction. On the other hand, if the concentration is too low, it is disadvantageous because the oxidizing power decreases and the size of the reaction apparatus increases. In addition, these oxidants can be used to convert Ce(II) by indirect electrolytic oxidation reaction.
It is reduced to D, Mn(II), Ag(I), etc., which can be recovered in the acidic aqueous solution layer and regenerated by electrolytic oxidation, and then recycled for indirect electrolytic oxidation.

As a Ce (IV)/Ce (III) type redox system, Ce (IV)/Ce (III) type redox system is
seeds are used. Specific examples include a solution of cerium nitrate dissolved in an aqueous nitric acid solution, a solution of cerium methanesulfonate dissolved in an aqueous methanesulfonic acid solution, a solution of cerium carbonate dissolved in an aqueous nitric acid solution, an acetic acid solution, or an aqueous methanesulfonic acid solution, and electrolysis of these solutions. Examples include oxidized ones.

As the M n (III)/M n (II) type or Mn (IV)/Mn (II) type redox system, Mn species dissolved or suspended in an acid aqueous solution are used. Specific examples include a solution in which manganese sulfate is dissolved in an aqueous sulfuric acid solution, a solution in which manganese nitrate is dissolved in an aqueous nitric acid solution, and a solution obtained by electrolytically oxidizing these solutions.

As the Ag (TI)/Ag (I) type redox system, Ag species dissolved or suspended in an aqueous acid solution are used. Specific examples include a solution in which silver nitrate is dissolved in an aqueous nitric acid solution, a suspension in which silver oxide (TI) is added to an aqueous nitric acid solution, and a solution or suspension obtained by electrolytically oxidizing these solutions or suspensions.

The temperature of indirect electrolytic oxidation is preferably 0 to 80°C.

It is also effective and preferable to irradiate ultrasonic waves during the oxidation reaction. In the reaction, it is preferable to use an inert solvent as a mediator, such as a nonpolar aprotic solvent such as nitrobenzene, chlorobenzene, dichlorobenzene. When using Ce alone or as a main mediator, the acid used is preferably nitric acid, acetic acid,
Selected from metasulfonic acids. When Ce is used as a mediator, no slurry of cerium salt is present during reaction or electrolytic regeneration, and handling is easy.

When Mn is used alone or as the main mediator, the acid used is preferably sulfuric acid, and the acid concentration is 20 to 60 weight percent, preferably 35 to 55 weight percent. Mn(Ill) can be used in the form of a sulfuric acid solution or suspension of manganese(III) sulfate. When Ag is used as a mediator, the acid used is preferably nitric acid, and the acid concentration is 20-60% by weight, preferably 35-60% by weight.
The ratio is 50%.

Ag(II) can be used in the form of a nitric acid solution or suspension of silver(II) oxide, which also has the advantage of being in a solution state after the oxidation reaction. Electrolytic oxidation for mediator regeneration is usually carried out at the anode using an electrolytic cell with a diaphragm, but an electrolytic cell without a diaphragm may also be used.

Diels-Alder of 5-nitro-1,4-naphthoquinone and 1,3-butadiene represented by the above formula (D)
5-nitro-1,4 represented by the above formula (A) by reaction
, 4a, 9a-tetrahydroanthraquinones are prepared using a suitable solvent which dissolves 5-nitro-1,4-naphthoquinone and 1,3-butadiene. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloroethane, carbon tetrachloride, and dichlorobenzene; ethers such as ethyl ether and diphenyl ether; and esters such as dioctyl phthalate. ketones such as methyl acetate; alcohols such as methanol and ethanol; and cellosolves such as cellosolve. 5-nitro-1
, 4-naphthoquinone and 1,3-butadiene, generally at 0 to 250°C, preferably at 30 to 15°C, as in the case of other aromatic quinone compounds.
It is carried out at a temperature of 0°C. The reaction pressure depends on the solubility of 1,3-butadiene, etc., but is usually 120 kg/a.
m2 or less, more generally in the range of 0 to 20 kg/cff12. 1. The amount of 3-butadiene used is 5
The reaction is completed more quickly when the amount is in excess of -nitro-1,4-naphthoquinone, but if it is too much, it is not economical in terms of equipment, so it is preferably 1 to 20 times the mole, more preferably 1. It is carried out at 1 to 10 times the mole.

As described above, high purity 5 shown by formula (A)
-Nitro-1,4,4a,9a-tetrahydroanthraquinones are obtained and are used as suitable raw materials in the present invention. However, in the present invention, 5-nitro 1.4
．． The 4a,9a-tetrahydroanthraquinones are not limited to those produced by the method described above, but those produced by other appropriate methods can also be used.

In the present invention, 5-nitro-1,4,4a,9a-tetrahydroanthraquinones are converted into 1-hydroxylaminoanthraquinones in the presence of a basic compound. The reaction is carried out, for example, with 5-nitro-1,4,4a,9a-
This is carried out by adding the basic compound to the tetrahydroanthraquinones, preferably in a solvent, at a temperature of 0 to 200<0>C. As the basic compound, ordinary inorganic or organic basic compounds can be used, and examples thereof include the following.

1) Basic compounds of Groups Ia, Ib, Ia and FFB of the Periodic Table. Examples include oxidizing hydroxides and salts with weak acids, such as magnesium oxide, calcium oxide, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium acetate, sodium haloate, and sodium sulfite. , sodium hydrogen phosphate, potassium phosphate, potassium permanganate,
Sodium chromate, sodium sulfide, sodium methylate, sodium phenolate, tetrasodium ethylenediaminetetraacetate, sodium polysulfide, sodium hydrosulfide2) Ammonia, ammonium carbonate and ammonia complex salts3) Primary amines, secondary amines, Tertiary amines, hydroxylated quaternary amines, and their basic nitrogen basic compounds Among these, in particular, Group Ia, Group Ib of the periodic table,
Hydroxides, carbonates, and bicarbonates of Group Ia and Group IIb metals are preferably used. The amount of the basic compound that can be present may be sufficient to keep the liquid basic, but it is preferably 2 equivalents or more relative to 5-nitro-I, 4.4a, 9a-tetrahydroanthraquinone. Also,
When an aqueous solvent is used here, the produced 1-hydroxylaminoanthraquinones are well dissolved in this under basic conditions and can be supplied in the form of a solution to the next oxidation step, which has the advantage of facilitating operations. As the aqueous solvent, water, alcohols such as methanol, ethanol, isopropanol, and ethylene glycol, ethers, particularly cellosolves such as methyl cellosolve, etc. are preferable, and these are used alone or in combination.

In particular, it is preferable to use water alone or in combination with other aqueous solvents. In addition, when a non-aqueous solvent and an aqueous solvent are used together, the obtained 1-hydroxylaminoanthraquinones can be extracted into the aqueous solvent layer, and unreacted raw materials can be extracted into the non-aqueous solvent layer, so the aqueous solvent layer can be directly used for the next oxidation. It can be used in the process.

The obtained 1-hydroxylaminoanthraquinones are then oxidized to give 1-hydroxylaminoanthraquinones, preferably in the presence of a basic compound.
- into nitroanthraquinones.

There are no particular limitations on the oxidation method. For example, a gas containing molecular oxygen such as air is used as an oxidizing agent, and oxidation is preferably carried out at a temperature of 35° C. or higher. In particular, it is preferable to use air as the oxidizing agent because it is easy to handle and is advantageous in terms of cost. Oxidation can also be carried out using hydrogen peroxide or an aqueous solution thereof as an oxidizing agent. In this case, the oxidation reaction progresses more easily than in air oxidation, and oxidation can be carried out at a temperature of 20°C or higher. Also, during the reaction, the liquid temperature rises due to the reaction heat, and special external heating is not required. There are cases where it disappears, which is preferable. Furthermore, as an oxidation method, it is also possible to perform an electrolytic oxidation method and utilize oxygen generated at the anode.

The oxidation of 1-hydroxylaminoanthraquinones is preferably carried out in an aqueous solvent or an aqueous solvent containing water and another solvent. Solvents to be mixed with water include alcohols such as methanol, ethanol, isopropanol, and ethylene glycol; ethers; cellosolves such as ethylene glycol monomethyl ether;
Examples include ketones such as acetone. It is also preferable to carry out the reaction in the presence of an aromatic hydrocarbon in order to avoid problems such as increased viscosity and foaming during oxidation.

When 1-hydroxylaminoanthraquinones are oxidized in the presence of a basic compound, the 1-hydroxylaminoanthraquinones are easily dissolved, the oxidation progresses easily, and the operability is also good.

The basic compound preferably used is the above-mentioned 5-nitro 1 + 4 + 4819 a-
This is the same as described in the step of converting tetrahydroanthraquinones to 1-hydroxylaminoanthraquinones. The amount of the basic compound that can be present is also the same as described in the previous step. Note that the basic compound that can be present in this step and the basic compound that can be present in the previous step are not necessarily the same, but it is preferable that they are the same. Furthermore, it is preferable to carry out both steps in the same reaction tank, since this not only simplifies the equipment and steps but also improves the yield.

When oxidizing 1-hydroxylaminoanthraquinones, the concentration of 1-hydroxylaminoanthraquinone in the solution cannot be particularly limited, but if it is too low, the reaction tank will become large and productivity will decrease, so it should be 0% per 100 parts by weight of the solution. The amount is preferably .01 parts by weight or more. On the other hand, if it is too high, the viscosity of the liquid increases and the handling of the liquid becomes difficult, so it is preferably 50 parts by weight or less. More preferably 0.
The amount is preferably in the range of 1 to 20 parts by weight.

The 1-nitroanthraquinones thus produced are separated by filtration, centrifugation, etc., and washed as appropriate.

A product of sufficiently high quality can be obtained by simple processing such as drying. Since the basic compound is recovered as a filtrate, it can be recycled and reused. In this case, it is preferable to remove unnecessary organic compounds contained in the filtrate to prevent unnecessary reactions and reduction in product purity. This is carried out, for example, by passing the filtrate through an adsorption tower filled with an adsorbent such as activated carbon.

By carrying out the present invention in this manner, 1-nitroanthraquinones with high purity can be produced with less waste compared to conventional methods and industrially advantageous in terms of both pollution and production cost. Examples] Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

A nitric acid solution of ceric ammonium nitrate obtained by electrolytically oxidizing a nitric acid solution of K vertical ceric ammonium nitrate (
The ceric ion concentration is 2. Reflux cooling method (0 mol/liter) was placed in a glass container equipped with a stirrer and maintained at 7oC. Add to this 60% of 1-nitronaphthalene.
Add 55g and 100geX of nitrobenzene and stir to make about 6
The reaction was allowed to proceed for 0 minutes. After the reaction was completed, stirring was stopped, the reaction solution was transferred to a separating funnel, the oil layer and the aqueous layer were separated, and the aqueous layer was extracted 3@ with 150 g of nitrobenzene.

The aqueous layer was electrolytically oxidized again until the ceric ion concentration became 2-0 mol/liter, and used for the next batch of reactions. The extracted oil layer and the separated oil layer were mixed to remove 5-nitro-1,4-naphthoquinone and unreacted 1 in the total organic solution.
- As a result of quantifying nitronaphthalene by high performance liquid chromatography, 5-nitro-1,4-naphthoquinone 5
5.17 g was obtained, and 2.72 g of unreacted 1-nitronaphthalene was obtained. Therefore, the conversion rate of 1-nitronaphthalene is 95.5%, and the reaction rate is 5% per 1-nitronaphthalene.
The yield of -nitro-1,4-naphthoquinone was 81.3 mol%. The entire organic layer was concentrated at about 50°C under reduced pressure,
5-nitro-1°4-naphthoquinone was precipitated, and the precipitate after filtration was dried under reduced pressure for 2 hours, and then measured by high performance liquid chromatography to find it to be 99.2%.

Next, a mixture consisting of 10 g of the 5-nitro-1,4-naphthoquinone thus obtained, 3.3 g of 1,3-butadiene, and 40 ml of ethylene glycol monomethyl ether was heated to 50° C. for 6 hours with stirring in a 100 ml autoclave. held.

The reaction pressure was 1.2 atm for the material and 1.0 atm at the end of the reaction. Next, 60 ml of water was added to the reaction mixture, which was then cooled to 25°C. The precipitated crystals were filtered, washed with 30ml of methyl alcohol, and dried under reduced pressure to give a white product with a purity of 98%.
5-Nitro 1.4.4a.

11.9 g of 9a-tetrahydroanthraquinone was obtained.

100 g of methanol and 30 g of 5% ammonium aqueous solution were added to the obtained 5-nitro-1,4,4a,9a-tetrahydroanthraquinone Log, stirred at 60°C for 1 hour, and the resulting solution was cooled to 20°C. The crystals were filtered, washed with water, and dried under reduced pressure to obtain crystals of 1-hydroxylaminoanthraquinone.

Next, the crystals were added to 100 g of 5% sodium hydroxide solution and stirred, and the resulting solution was oxidized by passing air through the solution at 40°C for 2 hours.The resulting crystals were then filtered and washed with water.
9.83 g of nitroanthraquinone crystals were obtained. When the obtained crystals were analyzed by high performance liquid chromatography, it was found that the purity was 92.3% and that they contained 1-aminoanthraquinone as an impurity.

500 g of a 45% sulfuric acid aqueous solution (suspension) containing 1 mol/kg of Mn''' was placed in a glass container equipped with a reflux condenser and a stirring device and maintained at 60°C.

To this was added a mixture of 40 g of 1-nitronaphthalene and 60 g of nitrobenzene, and the mixture was heated at 65° C. with stirring.
Allowed time to react. After the reaction, the organic phase and the inorganic phase were separated, the inorganic phase was extracted with 60 g of nitrobenzene, and the obtained nitrobenzene phase was added to the organic phase obtained by separation after the reaction. The nitrobenzene phase thus obtained was concentrated to about half, cooled, and the precipitated crystals were separated by filtration. After washing with cold methanol, vacuum drying, purity 95°2%
5-nitro-1,4-naphthoquinone was obtained.

The sulfuric acid aqueous solution containing M n ''+ obtained after the reaction was electrolytically oxidized using a Pb electrode and used for the next reaction.
were reacted in the same manner as in Example 1 to obtain crystals of 1-hydroxylaminoanthraquinone.

Next, these crystals were added to 100 g of 5% sodium hydroxide solution and stirred, and the obtained solution was mixed with 5% hydrogen peroxide solution Log at 30°C and left to oxidize for 1 hour, and then the obtained crystals were filtered and washed with water. Crystals of 1-nitroanthraquinone9.
85g was obtained. When the obtained crystals were analyzed by high performance liquid chromatography, it was found that the purity was 94.2% and that they contained 1-aminoanthraquinone as an impurity.

5-Nitro-1+4 obtained in the same manner as in Example 1
+ 4 a, 9 a-tetrahydroanthraquinone 1
Add 500g of 10% potassium hydroxide solution to 0g,
The mixture was stirred at 0°C for 1 hour. Subsequently, in the same container, the obtained solution was oxidized at 50° C. for 1 hour by supplying a mixture of oxygen gas and air generated at the electrolytic anode using a blowing tube. Thereafter, the precipitated crystals were filtered, washed with water, and then dried under reduced pressure to obtain 9.78 g of crystals. Analysis by high performance liquid chromatography revealed that the purity of 1-nitroanthraquinone was 95.7%, and 1-aminoanthraquinone was present as an impurity. In addition, when the 1-nide α-anthraquinone obtained here was reduced at 95° C. using sodium hydrogen sulfide, 1-aminoanthraquinone with a purity of 99.2% was obtained. The filtrate obtained when 1-nitroanthraquinone was filtered was adsorbed with activated carbon, and then 5-nitro-1,
In addition to 4,4a,9a-tetrahydroanthraquinone, the same operation was repeated to obtain 9.81 g of 1-nitroanthraquinone with a purity of 96.2%.

Claims (10)

[Claims] (1) General formula (A) (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R^1 and R^2 are independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. and halogen atoms.) 5-nitro-1,4,4a,9a-tetrahydroanthraquinones represented by the general formula (B) (B) ▲Math. , chemical formulas, tables, etc. ▼ (In the above formula, R^1 and R^2 are the same as above.) 1-hydroxylaminoanthraquinones obtained by converting to 1-hydroxylaminoanthraquinones represented by General formula (C) (C) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R^1 and R^2 are the same as above.) - A method for producing nitroanthraquinones. (2) Oxidize 1-nitronaphthalene to produce 5-nitro-1
, 4-naphthoquinone was obtained, and the obtained 5-nitro-1,4
- Naphthoquinone with general formula (D) (D) ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ (In the above formula, R^1 and R^2 each independently represent one type selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom.) Diels-Alder reaction with 1,3-butadiene to produce the general formula (A) (A) ▲Mathematical formulas, chemical formulas, tables, etc.▼ .) to obtain 5-nitro-1,4,4a,9a-tetrahydroanthraquinones, and the obtained 5-nitro-1,
4,4a,9a-tetrahydroanthraquinones in the presence of a basic compound, the general formula (B) (B) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R^1 and R^2 are The general formula (C
) (C) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R^1 and R^2 are the same as above.) A method for producing 1-nitroanthraquinones shown by. (3) The method according to claim (2), wherein the oxidation of 1-nitronaphthalene is carried out by electrolytic oxidation. (4) Oxidation of 1-nitronaphthalene with Ce(IV)/C
e(III), Mn(III)/Mn(II), Mn(IV)/M
3. The method according to claim 2, wherein the method is carried out by indirect electrolytic oxidation using at least one redox system selected from n(II) and Ag(II)/Ag(I) as a mediator. (5) The basic compound is a group Ia group of the periodic table, a group Ib group,
The method according to any one of claims (1) to (4), which is a basic compound of group IIa and group IIb metal elements. (6) The method according to any one of claims (1) to (5), wherein the 1-hydroxylaminoanthraquinone of general formula (B) is oxidized in the presence of a basic compound. (7) The oxidation of 1-hydroxylaminoanthraquinones of general formula (B) is carried out according to Group Ia, Group Ib, and Group I of the periodic table.
7. The method according to claim 6, which is carried out in the presence of a basic compound of a group Ia and group IIb metal element. (8) Any one of claims (1) to (7), wherein the basic solution obtained after separating the 1-nitroanthraquinones obtained by the method described in claims (1) to (7) is recycled. Method described. (9) After removing the organic compounds contained in the basic solution after separating the 1-nitroanthraquinones,
The method according to claim (8), wherein the method is used cyclically. (10) The method according to claim (9), wherein the basic solution from which the 1-nitroanthraquinones have been separated is brought into contact with an adsorbent to remove organic compounds contained in the solution.