CN112194584B - Method for preparing 4-nitrosoaniline and 4-nitroaniline - Google Patents
Method for preparing 4-nitrosoaniline and 4-nitroaniline Download PDFInfo
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Abstract
The application discloses a method for preparing 4-nitrosoaniline and 4-nitroaniline by using nitrobenzene and ammonia to react under the action of a catalyst, which has high conversion rate, good selectivity and environmental protection. 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 application relates to the field of chemical synthesis, in particular to a method for preparing 4-nitrosoaniline and 4-nitroaniline by adopting nitrobenzene and ammonia to react 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 dyes, antioxidants and photographic developers, and can be particularly used as raw materials of aramid fibers and rubber additives.
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 the Fischer-Herpol rearrangement. The disadvantage of this process is that the dehitroso action occurs during the fischer-tropsch rearrangement and the nitroso compounds, which are harmful to the environment, are produced in large amounts. 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, US6198001 discloses a process for the preparation of 4-nitrosoaniline comprising 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 present application has been completed in order to overcome the above-described drawbacks. The application provides a novel method for preparing 4-nitrosoaniline and 4-nitroaniline by using nitrobenzene and ammonia to react under the action of a catalyst, which has high conversion rate, good selectivity and environmental protection.
In the prior art, the problems of low reaction conversion rate, poor selectivity and environmental pollution exist, and the inventor surprisingly discovers that nitrobenzene and ammonia react under the action of a catalyst to generate 4-nitrosoaniline and 4-nitroaniline, the selectivity of the reaction is high, products in ortho-position or meta-position are not generated, and the yield is high.
Accordingly, in one aspect the present application relates to a process for the preparation of 4-nitrosoaniline and 4-nitroaniline comprising: nitrobenzene reacts with ammonia in an organic solvent in the presence of a catalyst to obtain 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 a benzene ring, wherein the substituents are independently selected from hydrogen, halogen, nitro, amino, alkoxy, sulfonate, sulfonic acid, hydroxyl, aldehyde, carboxyl and alkyl, aryl and aralkyl containing at least one amino group.
Examples of substituted benzamides useful in the present application 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, aralkyl containing at least one amine group.
Examples of substituted aliphatic amides useful in the present application include, but are not limited to, one of isobutyramide, urea, acetamide, propionamide, or a combination thereof.
The diamide is represented by formula (II). The structural formula of the formula (II) is as follows:
wherein R1 and R2 are independently selected from aryl, aliphatic and direct bond, A is selected from-SO 2-, -O-, -S-, and,And a direct bond.
The diamides used in the present application include, but are not limited to, one of adipoamide, oxamide, terephthalamide, 4' -biphenyldicarboxamide, or a combination thereof.
Wherein the base used is an organic base or an 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. For 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 hydroxides. For tetra-substituted ammonium hydroxides, wherein each substituent is selected from alkyl, aryl, aralkyl, preferably containing 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-trimethylphenylammonium hydroxide, particularly preferably tetramethylammonium hydroxide. For selectivity and conversion of the product, 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 the 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 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 a 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 and 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 application, the organic solvent includes, but is not limited to, for example, dimethyl sulfoxide, dimethylformamide, ethylene glycol, methanol, N-methylpyrrolidone, preferably dimethyl sulfoxide. The solvent may be used alone or in combination, and is not limited to the above. The weight ratio of the organic solvent to the nitrobenzene is in the range of 45:1 to 6:1, preferably 18:1 to 12:1.
The molar ratio of nitrobenzene to ammonia is preferably 1:1.5-1:4, more preferably 1:1.8-1:2.5.
The reaction temperature of the present application is preferably 25 to 100℃and more preferably 80 to 90 ℃. If the reaction temperature is too low, the reaction rate is slow; the reaction temperature is too high, which increases by-products, resulting in reduced yields of 4-nitrosoaniline and 4-nitroaniline.
The reaction pressure of the present application is 0.15 to 3MPa, preferably 0.15 to 1MPa.
The water produced during the reaction has a significant effect on the yield. In order to remove moisture generated at the start of the reaction or during the reaction from the reaction solution, vacuum distillation may be performed or a desiccant may be used to increase the yield of the reaction. Materials used as the drying agent include anhydrous sodium carbonate, anhydrous sodium sulfate, anhydrous magnesium sulfate, calcium oxide, calcium chloride, potassium hydroxide, sodium hydroxide, molecular sieves, anhydrous aluminum oxide, but are not limited thereto. 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 by-products of azoxybenzene, azobenzene and the like.
The reaction time of the present application is determined by monitoring the nitrobenzene content, and generally it 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 an alkoxy group containing 1 to 6 carbon atoms. The alkoxy groups may be substituted or unsubstituted, and when substituted, the substituents may be substituted at any useful 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 sulfonate, aryl sulfonate, aralkyl sulfonate.
The term "alkyl" refers to an alkyl group containing 1 to 6 carbon atoms. The alkyl group may be substituted or unsubstituted, and when substituted, the substituent 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 having 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 useful 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 alkenyl groups containing 1 to 6 carbon atoms. Alkenyl groups may be substituted or unsubstituted, and when substituted, substituents may be substituted at any useful 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 containing an alkenyl group of 1 to 6 carbon atoms. Alkenyl groups may be substituted or unsubstituted, and when substituted, substituents may be substituted at any useful 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 is a brand new reaction, and is never reported; the nitrobenzene reacts with ammonia under the action of a catalyst to generate 4-nitrosoaniline and 4-nitroaniline, the selectivity of the reaction is high, the ortho-position or meta-position products are not 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, so that the pollution to the environment is reduced.
Detailed Description
The gas chromatographs used in the examples were: agilent 7820A GC. Manual sample injection is adopted in the measurement, and a person skilled in the art can understand that errors caused by manual operation are also within an acceptable range. The products in the following examples were determined by gas chromatography and quantitatively analyzed.
Example 1
The air pressure kettle is purged by compressed air, 7.44 g of nitrobenzene, 120 g of dimethyl sulfoxide and 2.2 g of tetramethyl ammonium hydroxide pentahydrate are added into the kettle, 10.6 g of desiccant calcium oxide and 1.2 g of benzyl trimethyl ammonium chloride are added into the kettle, the pressure kettle is closed, 1.63 g of liquid ammonia is filled into the kettle, the pressure in the kettle reaches 1.6 megapascals, the kettle is stirred for 10 minutes under the pressure, and the volume concentration of ammonia in the 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 depressurized, cooled, the reaction mixture was weighed and sampled for gas chromatography, and the yield of 4-nitroaniline was calculated to be 56.4% and 42.3% based on nitrobenzene.
Example 2
The empty pressure kettle is purged by compressed oxygen, 7.44 g of nitrobenzene, 240 g of N, N-dimethylformamide, 1.94 g of sodium methoxide and 50 g of anhydrous magnesium sulfate as a drying agent are added into the kettle, then the pressure kettle is closed, 4 g of liquid ammonia is filled, the pressure in the kettle reaches 2 MPa, stirring is carried out for 10 minutes under the pressure, and the volume concentration of ammonia in the 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 depressurized, cooled, the reaction mixture was weighed and sampled for gas chromatography, and the yield of 4-nitroaniline calculated as nitrobenzene was 54.7% and the yield of 4-nitroaniline was 43.7%.
Example 3
The empty pressure kettle is purged by compressed oxygen, 7.44 g of nitrobenzene, 51 g of N-methyl pyrrolidone and 3.36 g of potassium hydroxide are added into the kettle, 63.6 g of anhydrous sodium carbonate and 3.5 g of tetramethyl ammonium bromide are added into the kettle, the pressure kettle is closed, 2.45 g of liquid ammonia is filled into the kettle, the pressure in the kettle reaches 1.7 megapascals, the kettle is stirred for 10 minutes under the pressure, and the volume concentration of ammonia in the gas phase in the kettle is measured to be 67%. The reaction mixture was heated to 100℃with stirring and reacted at that temperature for 7 hours. After the reaction, the autoclave was depressurized, cooled, the reaction mixture was weighed and sampled for gas chromatography, and the yield of 4-nitroaniline calculated as nitrobenzene was 54.7% and the yield of 4-nitroaniline was 43.7%.
Example 4
The air pressure kettle is purged by compressed air, 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 as a drying agent and 4 g of tetraethylammonium bromide are added into the kettle, the pressure kettle is closed, 3.2 g of liquid ammonia is filled, the pressure in the kettle reaches 2.5 megapascals, stirring is carried out for 10 minutes under the pressure, and the volume concentration of ammonia in the gas phase in the kettle is measured to be 35%. The reaction mixture was heated to 100℃with stirring and reacted at that temperature for 7 hours. After the reaction, the autoclave was depressurized, cooled, the reaction mixture was weighed and sampled for gas chromatography, and the yield of 4-nitroaniline 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 were 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 were as follows.
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-nitrosyl benzene | Yield of 4-nitrobenzene |
| 16 | Vacuum distillation | 56.2 | 43.1 |
| 17 | Without drying agent | 40.1 | 30.2 |
| 18 | Sodium carbonate as desiccant | 55.3 | 43.1 |
Examples 19 to 21
The reaction was carried out under the same conditions as in example 4 except that the atmosphere of each reaction system was changed, and the results are shown below.
| Examples | Atmosphere of each reaction System | Yield of 4-nitrosyl benzene | Yield of 4-nitrobenzene |
| 19 | Air-conditioner | 55.2 | 43.6 |
| 20 | Oxygen gas | 55.4 | 42.8 |
| 21 | Nitrogen gas | 20.1 | 15.8 |
The foregoing describes specific embodiments of the present application. It is to be understood that the application is not limited to the above-described embodiments, which are described in the foregoing description only for the purpose of illustrating the principles of the application. Various insubstantial changes and modifications of the application can be made by those skilled in the art without departing from the spirit of the application, and such changes and modifications are intended to be within the scope of the application as claimed.
Claims (16)
1. A method of preparing 4-nitrosoaniline and 4-nitroaniline comprising: in the presence of a catalyst, nitrobenzene and ammonia react in an organic solvent to obtain 4-nitrosoaniline and 4-nitroaniline, vacuum distillation is adopted or a drying agent is used for removing water, the reaction is carried out in an oxygen atmosphere or air, the reaction temperature is 80-90 ℃, the reaction pressure is 0.15-3 MPa, the catalyst is alkali or alkali and amide, the alkali is tetramethylammonium hydroxide, sodium methoxide or potassium hydroxide, and the amide is urea, benzamide or oxamide.
2. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein the organic solvent is dimethyl sulfoxide, N-dimethylformamide, ethylene glycol, methanol, N-methylpyrrolidone.
3. The process for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein a phase transfer catalyst is added.
4. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 3, wherein the phase transfer catalyst is at least one selected from the group consisting of quaternary amine salts, quaternary amine bases, quaternary phosphonium salts, polyethylene glycols, polyethylene glycol dialkyl ethers, pyridines, cyclic crown ethers.
5. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 4, wherein the quaternary ammonium salt is selected from the group consisting of 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, and tetramethylammonium bromide.
6. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein the catalyst is a base and the molar ratio of nitrobenzene to catalyst is 1:1-1:0.5.
7. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein when the catalyst is a base and an amide, the molar ratio of nitrobenzene to catalyst is 1:1 to 1:0.2, and wherein the molar ratio of base to amide is 1:1 to 1.5:1.
8. The method for preparing 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.
9. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein the molar ratio of nitrobenzene to ammonia is 1:1.5-1:4.
10. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 1, 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.
11. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein the organic solvent is dimethyl sulfoxide.
12. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 4, wherein the quaternary ammonium salt is tetrabutylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide, cetyltrimethylammonium bromide, octadecyltrimethylammonium chloride.
13. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 4, wherein the quaternary ammonium salt is tetrabutylammonium bromide.
14. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein when the catalyst is a base and an amide, the molar ratio of nitrobenzene to catalyst is 1:0.9-1:0.5, and wherein the molar ratio of base to amide is 1:1-1.5:1.
15. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein the weight ratio of the organic solvent to nitrobenzene is in the range of 18:1 to 12:1.
16. The method for preparing 4-nitrosoaniline and 4-nitroaniline according to claim 1, wherein the molar ratio of nitrobenzene to ammonia is 1:1.8-1:2.5.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0695739A1 (en) * | 1994-08-02 | 1996-02-07 | Bayer Ag | Process for the preparation of nitro-substituted arylamides and arylamines |
| CN1458140A (en) * | 2003-05-04 | 2003-11-26 | 厦门市先端科技有限公司 | Process for preparing aniline and its derivatives |
| CN1575272A (en) * | 2001-10-31 | 2005-02-02 | 锦湖石油化学株式会社 | Method for preparing 4-nitroso-substituted aromatic amine |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0695739A1 (en) * | 1994-08-02 | 1996-02-07 | Bayer Ag | Process for the preparation of nitro-substituted arylamides and arylamines |
| CN1575272A (en) * | 2001-10-31 | 2005-02-02 | 锦湖石油化学株式会社 | Method for preparing 4-nitroso-substituted aromatic amine |
| CN1458140A (en) * | 2003-05-04 | 2003-11-26 | 厦门市先端科技有限公司 | Process for preparing aniline and its derivatives |
Non-Patent Citations (1)
| Title |
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| 杨伯涵编著.《化工生产安全基础知识实用读本》.苏州大学出版社,2017,(第第1版版),第42-43页. * |
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