CN112194584A - Method for preparing 4-nitrosoaniline and 4-nitroaniline - Google Patents
Method for preparing 4-nitrosoaniline and 4-nitroaniline Download PDFInfo
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- CN112194584A CN112194584A CN202010983207.0A CN202010983207A CN112194584A CN 112194584 A CN112194584 A CN 112194584A CN 202010983207 A CN202010983207 A CN 202010983207A CN 112194584 A CN112194584 A CN 112194584A
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Abstract
The invention discloses a method for preparing 4-nitrosoaniline and 4-nitroaniline by reacting nitrobenzene and ammonia under the action of a catalyst, which has the advantages of high conversion rate, good selectivity and environmental friendliness. In addition, the application also provides a method for preparing p-phenylenediamine by reducing 4-nitrosoaniline and 4-nitroaniline, which has high yield and does not need separation and purification.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a method for preparing 4-nitrosoaniline and 4-nitroaniline by reacting nitrobenzene and ammonia under the action of a catalyst.
Background
The 4-nitrosoaniline is mainly used for preparing p-phenylenediamine, which is a widely applied chemical intermediate, can be used for preparing azo dyes, fur coloring agents, antioxidants and photo developers, and can be particularly used as a raw material of aramid fibers and rubber auxiliaries.
There are two main methods for preparing 4-nitrosoaniline. The first is the synthesis of N-nitrosoaniline from aniline and sodium nitrite, followed by the preparation of 4-nitrosoaniline by Fischer-Tropsch rearrangement. The disadvantage of this process is that the denitrosation takes place during the Fischer-Tropsch rearrangement and that large amounts of nitroso compounds are produced which contain environmentally harmful nitroso compounds. The second method is to prepare 4-nitrosoaniline by reacting p-nitrosophenol with ammonia or ammonium chloride. The disadvantage of this process is that the yield of 4-nitrosoaniline is too low.
In addition, U.S. Pat. No. 6,98001 discloses a process for preparing 4-nitrosoanilines, which comprises reacting urea with nitrobenzene in the presence of a base to give 4-nitrosoaniline and 4-nitroaniline. Since urea reacts with nitrobenzene, a large amount of urea is consumed in order to avoid the formation of 4, 4' -dinitrodiphenylamine.
Disclosure of Invention
The inventors have completed the present application in order to overcome the above-described disadvantages. The application provides a novel method for preparing 4-nitrosoaniline and 4-nitroaniline by reacting nitrobenzene and ammonia under the action of a catalyst, and the method has the advantages of high conversion rate, good selectivity and environmental friendliness.
The invention has the problems of low reaction conversion rate, poor selectivity and environmental pollution in the prior art, and the inventor unexpectedly finds that nitrobenzene reacts with ammonia under the action of a catalyst to generate 4-nitrosoaniline and 4-nitroaniline, the reaction has high selectivity, no ortho-position or meta-position product is generated, and the yield is high.
Accordingly, in one aspect, the present application relates to a process for preparing 4-nitrosoaniline and 4-nitroaniline comprising: nitrobenzene reacts with ammonia in an organic solvent in the presence of a catalyst to give 4-nitrosoaniline and 4-nitroaniline.
The catalyst used in the present application is a mixture of a base and an amide or a base, preferably a mixture of a base and an amide.
The amides include, but are not limited to, substituted benzamides, substituted aliphatic amides, diamides.
The substituted benzamide refers to benzamide containing one or more substituents on the benzene ring, wherein the substituents are independently selected from hydrogen, halogen, nitro, amine group, alkoxy, sulfonate group, sulfonic group, hydroxyl, aldehyde group, carboxyl and alkyl, aryl and aralkyl containing at least one amine group.
Examples of substituted benzamides useful in the present invention include, but are not limited to, one of benzamide, 4-methylbenzamide, 4-methoxybenzamide, 4-chlorobenzamide, 2-methylbenzamide, 4-nitrobenzamide, 4-aminobenzamide, or combinations thereof.
The substituted aliphatic amide is represented by formula (I). The structural formula of formula (I) is as follows:
wherein n is 0 or 1, R is selected from the group consisting of alkyl, aralkyl, alkenyl, aralkenyl, cycloalkyl, and cycloalkenyl, and X is selected from the group consisting of hydrogen, halogen, nitro, amine, alkoxy, sulfonate, hydroxyl, aldehyde, carboxyl, and alkyl, aryl, and aralkyl groups containing at least one amine group.
Examples of substituted aliphatic amides useful in the present invention include, but are not limited to, one of isobutyramide, urea, acetamide, propionamide, or combinations thereof.
The diamide is represented by the formula (II). The structural formula of formula (II) is as follows:
wherein R1 and R2 are independently selected from aryl, aliphatic and direct bonds, A is selected from-SO 2-, -O-, -S-,
and a direct bond.
The diamide used in the present invention includes, but is not limited to, one of adipamide, oxamide, terephthalamide, 4' -biphenyldicarboxamide or a combination thereof.
Wherein the base used is an organic or inorganic base or a mixture thereof. Inorganic bases include, but are not limited to, for example, alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide; alkaline earth metal hydroxides, such as calcium hydroxide. As the inorganic base, one compound may be used alone, or a mixture thereof may be used. Organic bases include, but are not limited to, for example, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium propoxide, potassium ethoxide, potassium tert-butoxide; tetra-substituted amine hydroxide. As regards tetra-substituted ammonium hydroxides, each substituent is chosen from alkyl, aryl, aralkyl groups, preferably containing from 1 to 18 carbon atoms, more preferably tetraalkylammonium hydroxides, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltributylammonium hydroxide, methyltripropylammonium hydroxide, methyltriethylammonium hydroxide, trimethylbenzylammonium hydroxide, N, N, N-trimethylphenylammonium hydroxide, particularly preferably tetramethylammonium hydroxide. For product selectivity and conversion, the base is preferably tetramethylammonium hydroxide.
The molar ratio of the nitrobenzene to the condensation catalyst is 1: 1-1: 0.2. Further, when the condensation catalyst is alkali and amide, the molar ratio of nitrobenzene to condensation catalyst is 1: 1-1: 0.2, preferably 1: 0.9-1: 0.5, wherein the molar ratio of alkali to amide is 1: 1-1.5: 1; when the condensation catalyst is alkali, the molar ratio of the nitrobenzene to the condensation catalyst is 1: 1-1: 0.5, preferably 1: 0.9-1: 0.7.
Optionally, a phase transfer catalyst, such as quaternary ammonium salt, quaternary ammonium base, quaternary phosphonium salt, polyethylene glycol dialkyl ether, pyridine, cyclic crown ether, etc., is added to the reaction system. They may be used alone or in combination. Quaternary ammonium salts, crown ethers are preferred. The quaternary ammonium salt is preferably benzyltriethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, benzyltrimethylammonium chloride, benzyltributylammonium chloride, tetramethylammonium chloride, tetrabutylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, benzyltrimethylammonium bromide, benzyltriethylammonium bromide, benzyltributylammonium bromide, tetramethylammonium bromide, more preferably tetrabutylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride.
In the preparation method of the present invention, the organic solvent includes, but is not limited to, for example, dimethyl sulfoxide, dimethylformamide, ethylene glycol, methanol, N-methylpyrrolidone, and preferably dimethyl sulfoxide. The solvents may be used alone or in combination, and are not limited to the above. The weight ratio of the organic solvent to the nitrobenzene is 45: 1-6: 1, preferably 18: 1-12: 1.
The molar ratio of nitrobenzene to ammonia is preferably 1:1.5 to 1:4, more preferably 1:1.8 to 1: 2.5.
The reaction temperature of the method is preferably 25-100 ℃, and more preferably 80-90 ℃. If the reaction temperature is too low, the reaction rate is slow; the reaction temperature is too high, and the by-products are increased, resulting in a decrease in the yield of 4-nitrosoaniline and 4-nitroaniline.
The reaction pressure of the invention is 0.15-3 MPa, preferably 0.15-1 MPa.
The yield is significantly affected by the water produced during the reaction. In order to remove moisture generated at the start of the reaction or during the reaction from the reaction solution, vacuum distillation or the use of a drying agent may be performed to increase the yield of the reaction. Substances used as the drying agent include, but are not limited to, anhydrous sodium carbonate, anhydrous sodium sulfate, anhydrous magnesium sulfate, calcium oxide, calcium chloride, potassium hydroxide, sodium hydroxide, molecular sieves, and anhydrous alumina. They may be used alone or in combination.
The reaction needs to be carried out in an oxygen-containing atmosphere, such as oxygen or air. This avoids the formation of azoxybenzene, azobenzene and the like as by-products.
The reaction time of the present invention is determined by monitoring the content of nitrobenzene, and generally takes 30 minutes to 8 hours, preferably 40 minutes to 3 hours.
The term "halogen" is selected from fluorine, chlorine, bromine, iodine.
The term "alkoxy" refers to alkoxy groups containing 1 to 6 carbon atoms. Alkoxy groups may be substituted or unsubstituted, and when substituted, substituents may be substituted at any available point of attachment, independently optionally substituted with one or more substituents selected from halogen, alkyl, haloalkyl, alkoxy, hydroxy, nitro.
The term "sulfonate group" includes alkyl sulfonates, aryl sulfonates, aralkyl sulfonates.
The term "alkyl" refers to an alkyl group containing 1 to 6 carbon atoms. Alkyl groups may be substituted or unsubstituted, and when substituted, substituents may be substituted at any available point of attachment, independently optionally substituted with one or more substituents selected from halogen, alkyl, haloalkyl, alkoxy, hydroxy, nitro.
The term "aryl" is a 6 to 14 membered all carbon monocyclic ring or fused polycyclic ring with a conjugated pi-electron system, preferably an all carbon monocyclic ring, such as phenyl. Aryl groups may be substituted or unsubstituted, and when substituted, substituents may be substituted at any available point of attachment, independently optionally substituted with one or more substituents selected from halogen, alkyl, alkoxy, amino, nitro, cyano.
The term "aralkyl" refers to an alkyl-substituted aryl group.
The term "alkenyl" refers to a chain alkenyl group containing 1 to 6 carbon atoms. Alkenyl groups may be substituted or unsubstituted, and when substituted, substituents may be substituted at any available point of attachment, independently optionally substituted with one or more substituents selected from halogen, alkyl, haloalkyl, alkoxy, hydroxy, nitro.
The term "aralkenyl" refers to an aryl group having a chain alkenyl group of 1 to 6 carbon atoms. Alkenyl groups may be substituted or unsubstituted, and when substituted, substituents may be substituted at any available point of attachment, independently optionally substituted with one or more substituents selected from halogen, alkyl, haloalkyl, alkoxy, hydroxy, nitro.
The term "cycloalkyl" refers to a monocyclic alkyl group containing 3 to 6 carbon atoms.
The term "cycloalkenyl" refers to a monocyclic alkenyl group containing 3 to 6 carbon atoms.
Compared with the prior art, the method for preparing the 4-nitrosoaniline and the 4-nitroaniline has the following beneficial effects:
the method for preparing 4-nitrosoaniline and 4-nitroaniline provided by the application is a brand-new reaction, and has never been reported; nitrobenzene reacts with ammonia under the action of a catalyst to generate 4-nitrosoaniline and 4-nitroaniline, the reaction has high selectivity, no ortho-position or meta-position product is generated, and the conversion rate is high; in addition, the raw materials of nitrobenzene and ammonia are low in price, so that the synthesis cost is low; in addition, no substances harmful to the environment are generated in the reaction process, and the pollution to the environment is reduced.
Detailed Description
The gas chromatographs used in the examples were: agilent 7820A GC. When the measurement is carried out by manual sample injection, the skilled person can understand that the error caused by manual operation is also within an acceptable range. The products in the following examples were identified by gas chromatography and quantitatively analyzed.
Example 1
Firstly, compressed air is used for blowing an empty pressure kettle, then 7.44 g of nitrobenzene, 120 g of dimethyl sulfoxide, 2.2 g of tetramethyl ammonium hydroxide pentahydrate, 10.6 g of drying agent calcium oxide and 1.2 g of benzyl trimethyl ammonium chloride are added into the kettle, then the pressure kettle is sealed, 1.63 g of liquid ammonia is filled into the pressure kettle, the pressure in the kettle reaches 1.6 MPa, the kettle is stirred for 10 minutes under the pressure, and the volume concentration of ammonia in gas phase in the kettle is measured to be 12%. The reaction mixture was heated to 80 ℃ with stirring and reacted at this temperature for 7 hours. After the reaction, the autoclave was vented, cooled, the reaction mixture was weighed and sampled for gas chromatography, and the yield of 4-nitrosoaniline calculated as nitrobenzene was 56.4% and the yield of 4-nitroaniline was 42.3% were calculated.
Example 2
Blowing an empty pressure kettle by using compressed oxygen, adding 7.44 g of nitrobenzene, 240 g of N, N-dimethylformamide, 1.94 g of sodium methoxide and 50 g of anhydrous magnesium sulfate serving as a drying agent into the kettle, then sealing the pressure kettle, filling 4 g of liquid ammonia into the pressure kettle, enabling the pressure in the kettle to reach 2 MPa, and stirring the pressure for 10 minutes under the pressure, wherein the volume concentration of ammonia in a gas phase in the kettle is measured to be 85%. The reaction mixture was heated to 96 ℃ with stirring and reacted at this temperature for 7 hours. After the reaction, the autoclave was vented, cooled, the reaction mixture was weighed and sampled for gas chromatography, and the yield of 4-nitrosoaniline calculated as nitrobenzene was 54.7% and the yield of 4-nitroaniline was 43.7%.
Example 3
Blowing an empty autoclave by using compressed oxygen, adding 7.44 g of nitrobenzene, 51 g of N-methyl pyrrolidone, 3.36 g of potassium hydroxide, 63.6 g of anhydrous sodium carbonate serving as a drying agent and 3.5 g of tetramethylammonium bromide into the autoclave, then sealing the autoclave, filling 2.45 g of liquid ammonia into the autoclave, enabling the pressure in the autoclave to reach 1.7 MPa, and stirring the autoclave for 10 minutes under the pressure, thereby obtaining that the volume concentration of ammonia in a gas phase in the autoclave is 67%. The reaction mixture was heated to 100 ℃ with stirring and reacted at this temperature for 7 hours. After the reaction, the autoclave was vented, cooled, the reaction mixture was weighed and sampled for gas chromatography, and the yield of 4-nitrosoaniline calculated as nitrobenzene was 54.7% and the yield of 4-nitroaniline was 43.7%.
Example 4
Firstly, compressed air is used for blowing an empty pressure kettle, then 7.44 g of nitrobenzene, 90 g of dimethyl sulfoxide, 1.8 g of urea, 5.43 g of tetramethyl ammonium hydroxide pentahydrate, 50 g of anhydrous sodium sulfate serving as a drying agent and 4 g of tetraethyl ammonium bromide are added into the kettle, then the pressure kettle is sealed and filled with 3.2 g of liquid ammonia, the pressure in the kettle reaches 2.5 MPa, and the kettle is stirred for 10 minutes under the pressure, and the volume concentration of ammonia in a gas phase in the kettle is measured to be 35%. The reaction mixture was heated to 100 ℃ with stirring and reacted at this temperature for 7 hours. After the reaction, the autoclave was vented, cooled, the reaction mixture was weighed and sampled for gas chromatography, and the yield of 4-nitrosoaniline calculated as nitrobenzene was 54.8% and the yield of 4-nitroaniline was 43.5%.
Examples 5 to 9
The reaction was carried out under the same conditions as in example 4 except that the type and amount of the amide were changed, and the results are as follows:
examples 10 to 12
The reaction was carried out under the same conditions as in example 4 except that the molar ratio of liquid ammonia to nitrobenzene in each reaction was changed, and the results are shown below.
Examples 13 to 16
The reaction was carried out under the same conditions as in example 4 except that the reaction temperature and pressure of each reaction were changed, and the results are shown below.
Examples 16 to 18
The reaction was carried out under the same conditions as in example 4 except that the moisture content of the system of each reaction was changed, and the results are shown below.
| Examples | Moisture system content and desiccant | Yield of 4-nitrosobenzene | Yield of 4-nitrobenzene |
| 16 | Vacuum distillation | 56.2 | 43.1 |
| 17 | Without the use of a desiccant | 40.1 | 30.2 |
| 18 | Sodium carbonate as drying agent | 55.3 | 43.1 |
Examples 19 to 21
The reaction was carried out under the same conditions as in example 4 except that the gas atmosphere in each reaction system was changed, and the results are shown below.
| Examples | Gas atmosphere of each reaction System | Yield of 4-nitrosobenzene | Yield of 4-nitrobenzene |
| 19 | Air (a) | 55.2 | 43.6 |
| 20 | Oxygen gas | 55.4 | 42.8 |
| 21 | Nitrogen gas | 20.1 | 15.8 |
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the invention is not limited to the embodiments described above, which are described in the specification only to illustrate the principles of the invention. The invention also includes insubstantial variations and modifications of the invention as would be understood by those skilled in the art without departing from the spirit of the invention as disclosed in the claims.
Claims (24)
1. A process for preparing 4-nitrosoaniline and 4-nitroaniline comprising: nitrobenzene reacts with ammonia in an organic solvent in the presence of a catalyst to give 4-nitrosoaniline and 4-nitroaniline.
2. A process for the preparation of para-phenylenediamine according to claim 1, wherein the condensation catalyst is a base or a base and an amide.
3. A process for preparing p-phenylenediamine according to claim 1 or 2, characterized in that the base is an alkali metal hydride, an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal alkoxide, a tetra-substituted ammonium hydroxide, preferably a tetra-substituted ammonium hydroxide.
4. A process for preparing a para-phenylenediamine according to claim 3, characterized in that the tetra-substituted ammonium hydroxide is a tetraalkylammonium hydroxide, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltributylammonium hydroxide, methyltripropylammonium hydroxide, methyltriethylammonium hydroxide, trimethylbenzylammonium hydroxide, N-trimethylphenylammonium hydroxide, preferably tetramethylammonium hydroxide.
5. A process for the preparation of para-phenylenediamine according to claim 2, characterized in that said amide includes, but is not limited to, substituted benzamides, substituted aliphatic amides, diamides.
6. A process for preparing p-phenylenediamine according to claim 5, wherein said substituted benzamide substituents are independently selected from the group consisting of hydrogen, halogen, nitro, amine, alkoxy, sulfonate, hydroxyl, aldehyde, carboxyl, and alkyl, aryl, and aralkyl groups containing at least one amine group.
7. A process for preparing p-phenylenediamine according to claim 6, wherein said substituted phenylamide is selected from the group consisting of benzamide, 4-methylbenzamide, 4-methoxybenzamide, 4-chlorobenzamide, 2-methylbenzamide, 4-nitrobenzamide, 4-aminobenzamide, and combinations thereof.
8. A process for producing p-phenylenediamine according to claim 5, characterized in that said substituted aliphatic amide is represented by the following formula:
wherein n is 0 or 1, R is selected from the group consisting of alkyl, aralkyl, alkenyl, aralkenyl, cycloalkyl, and cycloalkenyl, and X is selected from the group consisting of hydrogen, halogen, nitro, amine, alkoxy, sulfonate, hydroxyl, aldehyde, carboxyl, and alkyl, aryl, and aralkyl groups containing at least one amine group.
9. A process for preparing p-phenylenediamine according to claim 8, wherein said substituted aliphatic amide is selected from the group consisting of isobutyramide, urea, acetamide, propionamide, and combinations thereof.
10. A process for preparing p-phenylenediamine according to claim 5, wherein said diamide is selected from the group consisting of one of a diamide, oxamide, terephthalamide, 4' -biphenyldicarboxamide and combinations thereof.
11. A process for preparing p-phenylenediamine according to claim 1, characterized in that said organic solvent is dimethylsulfoxide, N-dimethylformamide, ethylene glycol, methanol, N-methylpyrrolidone, preferably dimethylsulfoxide.
12. The process for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein a phase transfer catalyst is added.
13. The method of claim 12, wherein the phase transfer catalyst is at least one selected from the group consisting of quaternary ammonium salts, quaternary ammonium bases, quaternary phosphonium salts, polyethylene glycols, dialkyl ethers of polyethylene glycols, pyridines, and cyclic crown ethers.
14. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 13, wherein the quaternary ammonium salt is selected from benzyltriethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, benzyltrimethylammonium chloride, benzyltributylammonium chloride, tetramethylammonium chloride, tetrabutylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, benzyltrimethylammonium bromide, benzyltriethylammonium bromide, benzyltributylammonium bromide or tetramethylammonium bromide, preferably tetrabutylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, more preferably tetrabutylammonium bromide.
15. The method for producing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein the molar ratio of nitrobenzene to catalyst is 1:1 to 1: 0.2.
16. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein the catalyst is alkali, and the molar ratio of nitrobenzene to catalyst is 1:1 to 1:0.5, preferably 1:0.9 to 1: 0.7.
17. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein when the catalyst is alkali and amide, the molar ratio of nitrobenzene and condensation catalyst is 1:1 to 1:0.2, preferably 1:0.9 to 1:0.5, and the molar ratio of alkali and amide is 1:1 to 1.5: 1.
18. The method for producing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein the weight ratio of the organic solvent to nitrobenzene is in the range of 45:1 to 6:1, preferably 18:1 to 12: 1.
19. The process for producing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein the molar ratio of nitrobenzene to ammonia is preferably 1:1.5 to 1:4, more preferably 1:1.8 to 1: 2.5.
20. The method for producing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein the reaction temperature is 25 to 100 ℃, preferably 80 to 90 ℃.
21. The method for producing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein the reaction pressure is 0.15 to 3 MPa.
22. The process for producing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein the water is removed by vacuum distillation or by using a drying agent.
23. The method of claim 22, wherein the drying agent is at least one selected from the group consisting of anhydrous calcium carbonate, anhydrous sodium sulfate, anhydrous magnesium sulfate, calcium oxide, calcium chloride, potassium hydroxide, sodium hydroxide, molecular sieves, and anhydrous aluminum oxide.
24. The method for producing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein the reaction is carried out in an oxygen atmosphere or air.
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| EP0695739A1 (en) * | 1994-08-02 | 1996-02-07 | Bayer Ag | Process for the preparation of nitro-substituted arylamides and arylamines |
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