JP3179930B2 - Method for producing aromatic nitro compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an aromatic nitro compound. More specifically, the present invention relates to a method for producing an aromatic nitro compound in high yield without requiring treatment of a large amount of waste acid.

[0002]

2. Description of the Related Art Aromatic nitro compounds are important compounds as intermediates for organic chemicals, and are generally produced using concentrated nitric acid or a mixed acid which is a mixture of concentrated nitric acid and concentrated sulfuric acid.

[0003] However, in this conventional method, a large amount of a high-concentration acid is used, so there is a danger in operation, and a large amount of expense is required for treating a large amount of waste acid. Further, it cannot be used for nitration of an aromatic compound having a substituent weak to an acid such as an ester group.

As an improved method of the above method, Japanese Patent Application Laid-Open No. Hei 4-217645 filed by the present applicant has disclosed that an aromatic compound is reacted with oxygen or air containing nitrogen oxides and ozone in the presence of an organic solvent. A method for preparing an aromatic nitro compound is described.

[0005]

The present inventors have conducted intensive studies to further improve the method disclosed in Japanese Patent Application Laid-Open No. 4-217645, and as a result, have found that aromatic compounds can be converted to nitrogen oxides in the presence of sulfur trioxide. The present inventors have found that an aromatic nitro compound can be obtained at a high yield without using oxygen or air including ozone by nitrating the compound alone or a combination of a nitrogen oxide and a protonic acid, thereby completing the present invention. As an example of nitrating an aromatic compound in the presence of sulfur trioxide, an example of reacting anthraquinone with a reduced amount of nitric acid and / or sulfuric acid is found in JP-A-49-55654.
-Nitroanthraquinone yield is only 60%.

An object of the present invention is to provide a method for producing an aromatic nitro compound with a high yield under a condition of less waste acid than the conventional method, while ensuring operational safety.

[0007]

That is, the present invention relates to a method for producing an aromatic nitro compound, which comprises reacting an aromatic compound with a nitrogen oxide as a nitrating agent in the presence of sulfur trioxide.

Hereinafter, the present invention will be described in more detail. By selecting the reaction conditions in the production method of the present invention, the target aromatic nitro compound can be obtained with high yield and selectivity.

Specific examples of the aromatic compound used as a raw material in the production method of the present invention include benzene, toluene, xylene (ortho, meta, para) and their mononitro or dinitro compounds, carbon atoms having 1 or more carbon atoms. Benzene substituted with a plurality of alkyl groups and their mononitro or dinitro compounds, halogenated benzenes such as monochlorobenzene, dichlorobenzene and trichlorobenzene and their mononitrated or dinitrated compounds, substituted with alkyl groups and halogens Benzene and their mononitrates or dinitrates, benzene substituted by alkoxy groups and their mononitrates or dinitrates, benzenes substituted by carbonyl and cyano groups and their mononitrates or dinitrates Benzoic acid and its derivatives, phenol esters, phenylacetic acid esters, naphthol esters, naphthalene and its derivatives, anthracene and its derivatives, anthraquinone and its derivatives, pyrene and its derivatives, alkyl groups, alkoxy groups, or halogens Acetanilide derivative, pyridine, α-picoline, β-picoline,
-Ethylpyridine and the like.

The sulfur trioxide used as a catalyst in the present invention is
It may be liquid or solid at room temperature.

The amount of the catalyst used is from 10 to 500 mol%, preferably from 20 to 300 mol%, based on the aromatic compound as the raw material.
It is.

As the nitrogen oxide used in the present invention, dinitrogen tetroxide, nitrogen dioxide, nitrogen monoxide and the like are used, and these may be used as a mixture. The amount of the nitrogen oxide used is 10 to 500 mol%, preferably 30 to 300 mol%, based on the aromatic compound as the raw material.

Furthermore, in the present invention, the reaction is promoted by adding a protonic acid. Examples of the protic acid include inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, chlorosulfonic acid, and sulfamic acid, and organic acids such as methanesulfonic acid, ethanesulfonic acid, and trifluoromethanesulfonic acid. At least one member selected from the group consisting of: Of these, nitric acid and sulfuric acid are particularly preferred. The amount of the protonic acid used is 10 to 500 mol% based on the aromatic compound as the raw material.

The use of a solvent for the nitration of the aromatic compound is preferred in terms of the yield of the aromatic nitro compound and safety. Examples of the solvent include those that do not undergo nitration under the reaction conditions of the present invention, for example, organic solvents such as halogenated aliphatic compounds, sulfolane, and nitromethane, and nitrous oxide, a nitrating agent that is liquid at the reaction temperature. Can be Of these, particularly preferred are halogenated aliphatic compounds, specifically, methylene chloride, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane. , 1,1,2,2-
Tetrachloroethane, pentachloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,2,2
3-trichloropropane, 1,1,2,3-tetrachloropropane, 1,1,3,3-tetrachloropropane,
1,1,1,2,2,3,3-heptachlorpropane,
1,1,1,2,3,3,3-heptachlorpropane,
Examples thereof include 1,2-dichlorobutane and 1,4-dichlorobutane. Of these, particularly preferred are methylene chloride, 1,2-dichloroethane and the like. These may be used alone or in combination of one or more.

The amount of the solvent to be used is 1 to 50 times by weight, preferably 3 to 20 times by weight, relative to the aromatic compound as a raw material.

Further, since this reaction is a suspension reaction, the reaction can be promoted by adding a surfactant. Examples of the surfactant include various alkyl sulfosuccinates represented by sodium di (2-ethylhexyl) sulfosuccinate (alias: dioctyl sodium sulfosuccinate);
Examples thereof include polyoxyethylene alkyl allyl ethers represented by polyoxyethylene nonylphenyl ether (trade name: Nonal 210; Toho Chemical), and quaternary salts represented by tetrabutylammonium bromide.
Among them, the effect of the alkyl sulfosuccinate is particularly large.

The reaction is carried out as follows. First, sulfur trioxide is added to a reactor charged with an aromatic compound and, if necessary, an organic solvent at a predetermined temperature while stirring. Subsequently, gaseous or liquid nitrogen oxides are added with stirring.

The aromatic compound may be added to the mixed solution of sulfur trioxide and the solvent after nitrogen oxides are added in advance.

In this reaction, nitrogen oxide alone is converted at a high selectivity in the presence of sulfur trioxide, but the reaction is promoted by further adding a protonic acid.

The reaction temperature is usually preferably in the range of -20 ° C. to around room temperature, but when a solvent is used, it can be heated to the boiling point of the solvent at normal pressure or under pressure. Generally, as the reaction temperature increases, the reaction rate increases, but the by-products tend to increase.

The reaction time is determined by analyzing and grasping the remaining amount of the aromatic compound as a raw material in the reaction product, and is usually preferably 2 hours to 20 hours.

After the reaction, if necessary, the reaction solution is neutralized.
The purity of the target product can be efficiently increased by ordinary methods such as washing, distillation, and crystallization.

[0023]

The present invention will be described in more detail with reference to the following examples.

Example 1 5.2 g (25 mmol) of anthraquinone was suspended in 52 g of 1,2-dichloroethane (EDC), and 4 g of sulfur trioxide was added dropwise with stirring at 5 ° C. Subsequently, nitrogen dioxide gas was blown in at a flow rate of 100 mmol / hour in terms of nitrous oxide for 15 minutes. 94% in the mixture
3.4 g of nitric acid was added dropwise. Then gradually the room temperature (23
(C) while continuing to stir for 3 hours. The suspension at the third hour was analyzed by liquid chromatography, and as a result, the following composition was obtained.

Composition ratio (%) Anthraquinone (unreacted component) 2.8 1-Nitroanthraquinone 83.9 2-Nitroanthraquinone 7.1 Dinitroanthraquinone 5.8 Subsequently, 20 ml of water was added to stop the reaction. Thereafter, the filtration was performed as it was. The cake was washed with water and dried to obtain 5.1 g of crystals of 1-nitroanthraquinone. As a result of analyzing the crystals, the purity was 94.1%.
(75.9% yield).

Further, the EDC layer and the aqueous layer of the filtrate were separated,
The DC layer was washed with water, concentrated and dried to obtain 1.4 g of crystals. As a result of analyzing the crystals in the same manner, the 1-nitroanthraquinone content was 34.9% (yield 7.7%).

Example 2 5.2 g (25 mmol) of anthraquinone was suspended in 52 g of 1,2-dichloroethane (EDC), and 4 g of sulfur trioxide was added dropwise while stirring at 5 ° C. Subsequently, nitrogen dioxide gas was blown in at a flow rate of 100 mmol / hour in terms of nitrous oxide for 30 minutes. Then gradually the room temperature (25
(° C.) while stirring was continued for 6 hours. The suspension at 6 hours was analyzed by liquid chromatography to find that the composition was as follows.

Composition ratio (%) Anthraquinone (unreacted component) 23.4 1-Nitroanthraquinone 66.2 2-Nitroanthraquinone 6.9 Dinitroanthraquinone 3.5 Example 3 Anthraquinone in 26 g of 1,2-dichloroethane (EDC) 2.6 g (12.5 mmol) was suspended, and 3.3 g of 60% fuming sulfuric acid was added dropwise while stirring at 5 ° C. Subsequently, 2.3 g of liquid nitrogen dioxide (dinitrogen tetroxide) was added dropwise. Then, gradually return to room temperature (20 ° C.) for 10 minutes.
Stirring was continued for hours. The suspension at 10 hours was analyzed by liquid chromatography, and as a result, the suspension had the following composition.

Composition ratio (%) Anthraquinone (unreacted component) 6.7 1-Nitroanthraquinone 81.0 2-Nitroanthraquinone 8.5 Dinitroanthraquinone 3.8 Example 4 In Example 3, further 94% nitric acid The procedure was exactly the same except that 0.84 g was added and the reaction time was 7 hours.
The suspension at 7 hours was analyzed by liquid chromatography to find that the composition was as follows.

Composition ratio (%) Anthraquinone (unreacted portion) 4.2 1-Nitroanthraquinone 82.0 2-Nitroanthraquinone 7.3 Dinitroanthraquinone 6.5 Example 5 1,2-Dichloroethane (EDC) 26 g of anthraquinone 2.6 g (12.5 mmol) was suspended, and 1.4 g of sulfur trioxide was added dropwise while stirring at 5 ° C. Subsequently, 1.4 g of liquid nitrogen dioxide (dinitrogen tetroxide) was added dropwise. Further, 0.84 g of 94% nitric acid was added dropwise to the mixture, and stirring was continued at 5 ° C. for 7 hours and 30 minutes. The suspension at 7 hours and 30 minutes was analyzed by liquid chromatography and was found to have the following composition.

Composition ratio (%) Anthraquinone (unreacted component) 2.6 1-Nitroanthraquinone 86.6 2-Nitroanthraquinone 5.9 Dinitroanthraquinone 4.8 Example 6 1,2-Dichloroethane (EDC) 26 g of anthraquinone 2.6 g (12.5 mmol) were suspended, and 1 g of sulfur trioxide was added dropwise while stirring at 5 ° C. Subsequently, 1.2 g of liquid nitrogen dioxide (dinitrogen tetroxide) was added dropwise. 9 more
0.84 g of 4% nitric acid was added, and stirring was continued for 3 hours while gradually returning to room temperature (22 ° C.). The suspension at the third hour was analyzed by liquid chromatography, and as a result, the following composition was obtained.

Composition ratio (%) Anthraquinone (unreacted component) 21.4 1-nitroanthraquinone 70.0 2-nitroanthraquinone 6.7 dinitroanthraquinone 1.9 Example 7 To 10 g of liquid nitrogen dioxide (dinitrogen tetroxide) 2.6 g (12.5 mmol) of anthraquinone was suspended, and 1 g of sulfur trioxide was added dropwise while stirring at 5 ° C. Room temperature (1
(8 ° C.) while stirring was continued for 7 hours and 30 minutes. The suspension at 7 hours and 30 minutes was analyzed by liquid chromatography and was found to have the following composition.

Composition ratio (%) Anthraquinone (unreacted component) 56.4 1-Nitroanthraquinone 39.4 2-Nitroanthraquinone 2.9 Dinitroanthraquinone 1.3 Example 8 1,2-Dichloroethane (EDC) 26 g of anthraquinone 2.6 g (12.5 mmol) were suspended, and 1 g of sulfur trioxide was added dropwise while stirring at 5 ° C. Subsequently, 1.2 g of liquid nitrogen dioxide (dinitrogen tetroxide) was added dropwise. Further, 1.2 g of methanesulfonic acid was added and gradually added to room temperature (20
(° C.) while stirring was continued for 2 hours. The suspension at the second hour was analyzed by liquid chromatography, and as a result, the following composition was obtained.

Composition ratio (%) Anthraquinone (unreacted component) 41.6 1-Nitroanthraquinone 49.2 2-Nitroanthraquinone 5.5 Dinitroanthraquinone 3.7 Example 9 78 g of 1,2-dichloroethane (EDC) below freezing,
While stirring, 4.1 g of crystalline sulfur trioxide was added. Subsequently, 7.8 g (37.5 mmol) of anthraquinone were added. Further, 4 g of liquid nitrogen dioxide (dinitrogen tetroxide) was added dropwise. After stirring for 15 minutes, 94% nitric acid was added to the mixture.
5 g was added dropwise. Thereafter, stirring was continued at 3 ° C. for 10 hours.
The suspension at 10 hours was analyzed by liquid chromatography, and as a result, the suspension had the following composition.

Composition ratio (%) Anthraquinone (unreacted component) 3.9 1-nitroanthraquinone 86.6 2-nitroanthraquinone 5.8 dinitroanthraquinone 3.7 Subsequently, 20 ml of water was added to stop the reaction. Thereafter, the filtration was performed as it was. The cake was washed with water and dried to obtain 8.5 g of 1-nitroanthraquinone crystals. As a result of analyzing the crystals, the purity was 91.2%.
(81.5% yield).

Further, the EDC layer and the aqueous layer of the filtrate were separated,
The DC layer was washed with water, concentrated and dried to obtain 1.6 g of crystals. As a result of analyzing the crystals in the same manner, the 1-nitroanthraquinone content was 29.5% (yield 5%).

Example 10 To 78 g of 1,2-dichloroethane (EDC) was added ice-cooled
While stirring, 4.3 g of crystalline sulfur trioxide was added. Subsequently, 7.8 g (37.5 mmol) of anthraquinone were added. Further, 4.2 g of liquid nitrogen dioxide (dinitrogen tetroxide) was added dropwise. After stirring for 15 minutes, 2.5 g of 94% nitric acid was added dropwise to the mixture. Thereafter, stirring was continued at 10 ° C. for 8 hours. The suspension at 8 hours was analyzed by liquid chromatography to find that the composition was as follows.

Composition ratio (%) Anthraquinone (unreacted component) 1.8 1-Nitroanthraquinone 86.9 2-Nitroanthraquinone 6.9 Dinitroanthraquinone 4.4 Example 11 1,78 g of 1,2-dichloroethane (EDC) below freezing,
While stirring, 4.1 g of crystalline sulfur trioxide was added. Subsequently, 7.8 g (37.5 mmol) of anthraquinone were added. Further, 4 g of liquid nitrogen dioxide (dinitrogen tetroxide) was added dropwise. After stirring for 15 minutes, 0.17 g of sodium di (2-ethylhexyl) sulfosuccinate was added as a surfactant, and 2.5 g of 94% nitric acid was added dropwise to the mixture. Thereafter, stirring was continued at 7 ° C. for 4 hours. The suspension at the 4th hour was analyzed by liquid chromatography to find that the composition was as follows.

Composition ratio (%) Anthraquinone (unreacted component) 4.4 1-Nitroanthraquinone 85.3 2-Nitroanthraquinone 7.1 Dinitroanthraquinone 3.2 Example 12 1,47-g of 1,2-dichloroethane (EDC) below freezing,
While stirring, 4.1 g of crystalline sulfur trioxide was added. Subsequently, 7.8 g (37.5 mmol) of anthraquinone were added. Further, 4 g of liquid nitrogen dioxide (dinitrogen tetroxide) was added dropwise. After stirring for 15 minutes, 0.17 g of sodium di (2-ethylhexyl) sulfosuccinate was added as a surfactant, and 2.5 g of 94% nitric acid was added dropwise to the mixture. Thereafter, stirring was continued at 10 ° C. for 4 hours and 30 minutes. 4
The suspension at 30 minutes was analyzed by liquid chromatography and was found to have the following composition.

Composition ratio (%) Anthraquinone (unreacted portion) 4.1 1-Nitroanthraquinone 84.7 2-Nitroanthraquinone 7.1 Dinitroanthraquinone 4.1

[0041]

According to the present invention, the aromatic compound is nitrated with nitrogen oxide alone or in combination with nitrogen oxide and protonic acid in the presence of sulfur trioxide, thereby ensuring safety in operation and eliminating the conventional method. A method for obtaining an aromatic compound in a high yield under a condition with a small amount of acid was established.

──────────────────────────────────────────────────続 き Continued on the front page (72) Isao Hashiba, Inventor 722-1, Tsuboi-cho, Funabashi-shi, Chiba Nissan Kagaku Kogyo Co., Ltd. (72) Inventor Makoto Ishikawa 722-1, Tsuboi-cho, Funabashi-shi, Chiba (72) Inventor Fumio Suzuki 722-1, Tsuboi-cho, Funabashi-shi, Chiba Nissan Kagaku Kogyo Co., Ltd. Central Research Laboratory (56) References JP-A-58-81442 (JP, A) JP-A-61-120643 (JP, A) JP-A-6-179639 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 201/08 C07C 205/47 B01J 27/04 C07B 61 / 00 300 C07B 43/02

Claims (5)

(57) [Claims] 1. A method for producing an aromatic nitro compound, comprising reacting an aromatic compound in the presence of sulfur trioxide with a nitrogen oxide as a nitrating agent in a solvent . 2. The method for producing an aromatic nitro compound according to claim 1, wherein a protonic acid is added when the nitrogen oxide is reacted as a nitrating agent in the presence of sulfur trioxide. 3. The method of claim 1, wherein the protonic acid is nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid,
The method for producing an aromatic nitro compound according to claim 2, wherein the method is at least one selected from methanesulfonic acid and halogenated methanesulfonic acid. Wherein the solvent is a halogenated aliphatic compound, sulfolane, process for producing an aromatic nitro compound according to any one of claims 1 to 3 is at least one selected from dinitrogen tetroxide. 5. The method of claim 1 or the aromatic nitro compound according to any one of claims 4 nitration is carried out in the presence of a surfactant.