JP2007176811A - Method for producing 4-nitrosodiphenylamine and 4-nitrodiphenylamine - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce 4-nitrosodiphenylamine and 4-nitrodiphenylamine at high selectivity from aniline and nitrobenzene. <P>SOLUTION: In the production method, aniline is reacted wit nitrobenzene in the presence of a base and a montmorillonite. As the montmorillonite, one having a sodium ion or an aluminum ion as an interlaminar cation or one subjected to a contact treatment with a quaternary ammonium compound is used preferably. As the base, an alkali metal hydroxide is used preferably. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a process for producing 4-nitrosodiphenylamine and 4-nitrodiphenylamine from aniline and nitrobenzene. Both 4-nitrosodiphenylamine and 4-nitrodiphenylamine can be converted to 4-aminodiphenylamine by hydrogenation. By alkylating this 4-aminodiphenylamine, it is useful as an antioxidant for natural rubber and synthetic rubber. 4-Alkylaminodiphenylamine can be obtained. 4-Nitrosodiphenylamine and 4-nitrodiphenylamine are also useful as raw materials for azo dyes.

  As a method for producing 4-nitrosodiphenylamine and 4-nitrodiphenylamine, JP-A-6-508630 (Patent Document 1) discloses reacting aniline with nitrobenzene in the presence of a base. . JP 2005-515163 A (Patent Document 2) discloses reacting aniline with nitrobenzene in the presence of a quaternary ammonium compound together with a base.

Japanese National Patent Publication No. 6-508630 JP 2005-515163 A

  In the conventional method, the selectivity of 4-nitrosodiphenylamine and 4-nitrodiphenylamine is not always sufficient. Accordingly, an object of the present invention is to provide a method capable of producing 4-nitrosodiphenylamine and 4-nitrodiphenylamine with high selectivity from aniline and nitrobenzene.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by reacting aniline with nitrobenzene in the presence of a predetermined solid catalyst together with a base, and the present invention has been completed.

  That is, the present invention provides a method for producing 4-nitrosodiphenylamine and 4-nitrodiphenylamine by reacting aniline with nitrobenzene in the presence of a base and montmorillonites.

  According to the present invention, 4-nitrosodiphenylamine and 4-nitrodiphenylamine can be produced from aniline and nitrobenzene with high selectivity.

  In the present invention, aniline and nitrobenzene are used as raw materials, and the use ratio is usually 1/10 to 10/1 in terms of the molar ratio of aniline / nitrobenzene. In general, the higher the use rate of aniline, the higher the production rate of 4-nitrosodiphenylamine, and the higher the use rate of nitrobenzene, the higher the production rate of 4-nitrodiphenylamine.

  When aniline and nitrobenzene are reacted, 4-nitrosodiphenylamine and 4-nitrodiphenylamine can be produced with high selectivity by the presence of montmorillonite together with a base.

  Examples of the base include alkali metal and alkaline earth metal hydrides, hydroxides, alkoxides, etc. Among them, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferably used. The usage-amount of a base is 1-10 mol normally with respect to 1 mol of nitrobenzene, Preferably it is 2-5 mol.

  Montmorillonites are montmorillonite (narrow sense; see the following formula)

M ^{n +} _{1 / (3n)} [Si ₄ (Al _5/3 Mg _1/3 ) O ₁₀ (OH) ₂ ] ^(1/3)- · yH ₂ O

[Wherein, M ^{n +} represents an n-valent interlayer cation, and y represents a hydration number. ]

In other words, the basic structure of the layer is a 2: 1 type structure of silicate sheet / aluminate sheet / silicate sheet, and a part of aluminum in the aluminate sheet is replaced with magnesium. Thus, the layer is negatively charged, and a layered compound in which exchangeable cations exist between the layers, and can be generally represented by the following formula.

M ^{n +} _{x / n} [Si ₄ (Al _2−x Mg _x ) O ₁₀ (OH) ₂ ] ^x− · yH ₂ O

[Wherein, M ^{n +} represents an n-valent interlayer cation, x represents a number exceeding 0 and less than 2, and y represents a hydration number. ]

  Examples of interlayer cations include sodium (I) ion, magnesium (II) ion, aluminum (III) ion, potassium (I) ion, calcium (II) ion, titanium (IV) ion, iron (III) ion, copper (II) ions, zinc (II) ions, zirconium (IV) ions, and the like. Among them, montmorillonites having sodium ions or aluminum ions are preferably used as interlayer cations. In order to obtain montmorillonites having a desired interlayer cation, the montmorillonites may be subjected to ion exchange by contact treatment with a solution containing the cation, preferably an aqueous chloride solution of the cation element.

  It is also effective to contact montmorillonites with a quaternary ammonium compound or a solution thereof, preferably an aqueous solution. Thereby, highly active montmorillonites can be obtained and the conversion of aniline or nitrobenzene can be improved. Examples of the quaternary ammonium compound include quaternary ammonium chloride such as tetramethylammonium chloride, tetraethylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, methyltrioctylammonium chloride, and trilaurylmethylammonium chloride. , Quaternary ammonium bromide such as tetra-n-butylammonium bromide, benzyltributylammonium bromide, hydroxide such as tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, benzyltrimethylammonium hydroxide Examples thereof include quaternary ammonium, quaternary ammonium hydrogen sulfate such as tetrabutylammonium hydrogen sulfate, and the like. Among these, quaternary ammonium chloride is preferable, and tetraalkylammonium chloride is more preferable.

  The usage-amount of montmorillonite is 1-10000g normally with respect to 1 mol of nitrobenzene, Preferably it is 10-1000g.

  Examples of the solvent that can be used in the reaction include dimethyl sulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, tetrahydrofuran, t-butanol and the like. Of these, dimethyl sulfoxide is preferable. Alternatively, the raw material aniline or nitrobenzene may be used in excess and used as a raw material and solvent.

  The reaction temperature is usually 0 to 200 ° C, preferably 20 to 100 ° C. Moreover, reaction time is 0.1 to 24 hours normally. Increasing the reaction temperature promotes the reaction, but the selectivity of 4-nitrosodiphenylamine and 4-nitrodiphenylamine tends to decrease. Therefore, in order to improve the conversion of aniline or nitrobenzene, it is preferable to increase the reaction temperature. The reaction time should be extended.

  The post-treatment operation after the reaction is appropriately selected. For example, the reaction mixture is filtered to collect montmorillonites as a filter residue, and the filtrate is neutralized if necessary, and then distilled, distributed, crystallized, etc. The separation and purification operation may be performed. The collected montmorillonites can be reused.

  Examples of the present invention will be shown below, but the present invention is not limited thereto.

  Nitrobenzene, 4-nitrosodiphenylamine and 4-nitrodiphenylamine were analyzed by high performance liquid chromatography. The conversion of nitrobenzene, the selectivity of 4-nitrosodiphenylamine and the selectivity of 4-nitrodiphenylamine are the number of moles of nitrobenzene used. Where X is X, the number of moles of unreacted nitrobenzene is Y, the number of moles of 4-nitrosodiphenylamine produced is Z1, and the number of moles of 4-nitrodiphenylamine is Z2.

Nitrobenzene conversion rate (%) = [(XY) / X] × 100
Selectivity of 4-nitrosodiphenylamine (%) = [Z1 / (XY)] × 100
Selectivity of 4-nitrodiphenylamine (%) = [Z2 / (XY)] × 100

  The following were used as montmorillonites.

[Montmorillonites (A)]
Montmorillonite [Na ⁺ _1/3 [Si ₄ (Al _5/3 Mg _1/3 ) O ₁₀ (OH) ₂ ] ^(1/3)- · yH ₂ O] having a sodium ion as an interlayer cation [Kinimine] "Kunipia" from Kogyo Co., Ltd.] was used as montmorillonites (A).

[Montmorillonites (B)]
To a 300 mL three-necked flask, 100 mL of 0.5 mol / L tetramethylammonium chloride aqueous solution and 10.50 g of montmorillonite (A) were added and stirred at room temperature for 24 hours. The obtained slurry was filtered, and the solid residue was washed with water and dried. The dried product thus obtained was used as montmorillonites (B).

[Montmorillonites (C)]
To a 500 mL three-necked flask, 200 mL of 0.033 mol / L aluminum chloride aqueous solution and 4.50 g of montmorillonite (A) were added and stirred at room temperature for 24 hours. The obtained slurry was filtered, and the solid residue was washed with water and dried. The dried product thus obtained was used as montmorillonites (C). The montmorillonites (C) have aluminum ions as interlayer cations.

Example 1
In a 50 mL three-necked flask, 0.50 g (4.0 mmol) of nitrobenzene, 2.26 g (24.2 mmol) of aniline, 0.79 g (12.0 mmol) of potassium hydroxide, 2.00 g of montmorillonites (A), Then, 10 mL of dimethyl sulfoxide was charged, and the reaction was carried out for 1 hour while maintaining the temperature at 60 ° C. with stirring. The reaction mixture was filtered and the filtrate was analyzed. As a result, the conversion of nitrobenzene was 29.0%, the selectivity of 4-nitrosodiphenylamine was 68.4%, the selectivity of 4-nitrodiphenylamine was 25.2% (total selection) The rate was 93.6%.

Example 2
The same operation as in Example 1 was performed except that the reaction time was 8 hours. The conversion rate of nitrobenzene was 53.1%, the selectivity of 4-nitrosodiphenylamine was 71.5%, and the selectivity of 4-nitrodiphenylamine was 21.2% (total selectivity 92.7%).

Example 3
The same operation as in Example 1 was performed except that the reaction temperature was 75 ° C. The conversion of nitrobenzene was 39.6%, the selectivity of 4-nitrosodiphenylamine was 60.8%, and the selectivity of 4-nitrodiphenylamine was 21.5% (total selectivity 82.3%).

Example 4
The same operation as in Example 1 was performed except that the reaction temperature was 90 ° C. The conversion rate of nitrobenzene was 42.5%, the selectivity of 4-nitrosodiphenylamine was 49.4%, and the selectivity of 4-nitrodiphenylamine was 17.8% (total selectivity 67.2%).

Example 5

  The same operation as in Example 1 was performed except that the montmorillonite (B) was used instead of the montmorillonite (A). The conversion rate of nitrobenzene was 49.0%, the selectivity of 4-nitrosodiphenylamine was 70.8%, and the selectivity of 4-nitrodiphenylamine was 24.4% (total selectivity 95.2%).

Example 6
The same operation as in Example 1 was performed except that the montmorillonite (B) was used instead of the montmorillonite (A) and the reaction time was 8 hours. The conversion of nitrobenzene was 80.1%, the selectivity of 4-nitrosodiphenylamine was 75.8%, and the selectivity of 4-nitrodiphenylamine was 19.1% (total selectivity 94.9%).

Example 7
The same operation as in Example 1 was performed except that the montmorillonite (C) was used instead of the montmorillonite (A). The conversion rate of nitrobenzene was 30.2%, the selectivity of 4-nitrosodiphenylamine was 81.8%, and the selectivity of 4-nitrodiphenylamine was 12.4% (total selectivity 94.2%).

Comparative Example 1
The reaction was performed in the same manner as in Example 1 except that the montmorillonite (A) was not used. As a result of analyzing the reaction mixture, the conversion rate of nitrobenzene was 58.6%, the selectivity of 4-nitrosodiphenylamine was 28.3%, the selectivity of 4-nitrodiphenylamine was 45.4% (total selectivity 73.7%) )Met.

Comparative Example 2
The reaction was conducted in the same manner as in Example 1 except that 0.45 g (4.0 mmol) of tetramethylammonium chloride was used instead of montmorillonite (A). As a result of analyzing the reaction mixture, the conversion rate of nitrobenzene was 80.7%, the selectivity of 4-nitrosodiphenylamine was 33.1%, the selectivity of 4-nitrodiphenylamine was 45.4% (total selectivity 78.5%) )Met.

Claims (7)

  A process for producing 4-nitrosodiphenylamine and 4-nitrodiphenylamine, which comprises reacting aniline and nitrobenzene in the presence of a base and montmorillonites.   The method according to claim 1, wherein the montmorillonites have sodium ions or aluminum ions as interlayer cations.   The method according to claim 1 or 2, wherein the montmorillonite is contact-treated with a quaternary ammonium compound.   4. A process according to claim 3, wherein the quaternary ammonium compound is quaternary ammonium chloride.   The method according to claim 1, wherein the base is an alkali metal hydroxide.   The method according to any one of claims 1 to 5, wherein the reaction is carried out in an organic solvent. The process according to claim 6, wherein the organic solvent is dimethyl sulfoxide.