CN109761824B - Method for synthesizing p-aminophenol and co-producing p-aminophenyl ether through catalytic hydrogenation - Google Patents
Method for synthesizing p-aminophenol and co-producing p-aminophenyl ether through catalytic hydrogenation Download PDFInfo
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Abstract
The invention belongs to the technical field of organic chemical industry, and relates to a method for synthesizing p-aminophenol and co-producing p-aminophenyl ether with high added value by catalytic hydrogenation, in particular to a method for preparing p-aminophenol and p-aminophenyl ether by using nitrobenzene and alcohol as raw materials through catalytic hydrogenation and rearrangement in an acidic medium, wherein the conversion rate of nitrobenzene is more than or equal to 99.5 percent, and the total yield of the p-aminophenol and the p-aminophenyl ether is more than 85 percent. The invention has the advantages of cheap and easily obtained raw materials, less production process, less waste water, easy treatment, less pollution and the like, can randomly adjust the proportion of two products according to the proportion of the nitrobenzene and the alcohol and the process change, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, and relates to a method for synthesizing p-aminophenol and co-producing p-aminophenyl ether with high added value by catalytic hydrogenation, in particular to a method for preparing p-aminophenol and p-aminophenyl ether by using nitrobenzene and alcohol as raw materials through catalytic hydrogenation and rearrangement in an acidic medium, wherein the conversion rate of nitrobenzene is more than or equal to 99.5 percent, and the total yield of the p-aminophenol and the p-aminophenyl ether is more than 85 percent. The invention has the advantages of cheap and easily obtained raw materials, less production process, less waste water, easy treatment, less pollution and the like, can randomly adjust the proportion of two products according to the proportion of the nitrobenzene and the alcohol and the process change, and is suitable for industrial production.
Background
Para-aminophenol (PAP for short) is an organic synthetic intermediate with wide application, and is widely applied to the fields of medicines (paracetamol, clofibrate vitamin B1, complexing agents nicotinamide, 6-hydroxyquinoline and the like), dyes, rubber, photography and the like. P-aminophenyl ether is an important intermediate for producing dyes, medicines, perfumes, etc., such as p-anisidine, p-phenetidine. P-phenetole is commonly used for the preparation of dyes such as c.i. acid blue 19, 83, 90, etc., c.i. basic blue 18, c.i. disperse yellow 34, 86, c.i. pigment red 123, etc.; the pharmaceutical composition is used for producing celiprolol, phenacetin, tabesin, rivanol and the like; it is also widely used as a rubber aging preventive, a food or feed preservative, and a precursor of an antioxidant.
Many reports about the synthesis research of p-aminophenol and p-aminophene at home and abroad are reported, and the main production method comprises the following steps: the p-chloronitrobenzene process and the nitrobenzene process. The p-chloronitrobenzene method takes p-nitrochlorobenzene as a raw material, the p-nitrochlorobenzene is pressurized and hydrolyzed under the alkaline condition to obtain p-nitrophenol sodium, and then the p-aminophenol is prepared by acidification and reduction; or the p-nitrochlorobenzene, methyl/ethanol and alkali liquor are subjected to alkoxylation reaction to generate p-nitrophenyl ether, and then the p-aminophenyl ether is obtained through reduction. The p-chloronitrobenzene method has the advantages of mature technology in the production of p-aminophenol and p-aminophenyl ether, but has the problems of longer synthetic route, high production cost, serious pollution and the like. The p-aminophenol prepared by the nitrobenzene hydrogenation reduction method has the advantages of low price and easy obtainment of raw materials, less production procedures, good product quality, little pollution, easy treatment of three wastes and the like, and is a process route which is environment-friendly and competitive; however, few documents are published for the synthesis of p-aminophenyl ethers by the nitrobenzene process.
Patent US2198249 (1940) discloses for the first time the hydrogenation of nitrobenzene to p-aminophenol in the presence of Pt/C catalyst, mineral acid, after which many relevant research techniques are reported in succession. Patent US4885389A discloses that in the presence of 3% Pt/C catalyst, nitrobenzene is hydrogenated at 60-100 ℃ to prepare p-aminophenol by using sulfuric acid solution containing 0.1-1% of organic acid (formic acid, acetic acid, trichloroacetic acid, etc.) as reaction medium, and the product yield reaches 83%. Patent US6403833 discloses the use of a series of single Ni catalysts and composite Ni-Pd and Ni-Pt catalysts in the hydrogenation of nitrobenzene to produce p-aminophenol in a sulphuric acid medium at a reaction temperature of 120 ℃ with selectivity to p-aminophenol up to 65%. Tanielyan, king et al, studied the hydrogenation of nitrobenzene to p-aminophenol at 80-90C, low pressure, 1.5% Pt/C catalyst, 10-15% sulfuric acid concentration, and added surfactant as a phase transfer catalyst, with better results (PAP/AN 6.7 mol). Patent CN10440040 discloses that metal Pt is loaded on solid acid as a catalyst, and p-aminophenol is prepared from nitrobenzene through catalytic hydrogenation in a neutral or weakly acidic aqueous solution, wherein the product yield reaches 17-83%; solves the problems of strong corrosivity, high requirement on equipment materials, treatment of a large amount of dilute ammonium sulfate solution as a byproduct and the like in the process of synthesizing p-aminophenol by catalytic hydrogenation of nitrobenzene by using sulfuric acid as a reaction medium.
Gao Lei et al in para-anisidine processing technology research mention that para-anisidine can be prepared from nitrobenzene under hydrogen pressure with sulfuric acid-methanol and dimethyl sulfoxide as solvents and noble metals as catalysts, and has harsh reaction conditions, difficult separation and complex subsequent treatment due to the use of high-boiling-point water-soluble organic solvents, and environmental pollution.
The above methods are all methods for preparing p-aminophenol or p-aminophenyl ether by using nitrobenzene as a main raw material, but only a single product can be produced due to different reaction processes or reaction systems; the invention is characterized in that a set of reaction device is used for synthesizing two products of p-aminophenol and p-aminophenyl ether by a one-pot method, the proportion of the two products is adjusted at will according to the proportion of the added raw materials of nitrobenzene and alcohol and the process change in the process, the invention is suitable for the requirement of the market on the products, and is suitable for industrial production.
Disclosure of Invention
The invention aims to provide a method for synthesizing p-aminophenol and co-producing p-aminophenyl ether with high added value by catalytic hydrogenation, and more particularly relates to a method for preparing p-aminophenol and p-aminophenyl ether by using nitrobenzene and alcohol as raw materials through catalytic hydrogenation and rearrangement in an acidic medium, wherein the conversion rate of nitrobenzene is more than or equal to 99.5 percent, and the total yield of the p-aminophenol and the p-aminophenyl ether is more than 85 percent. The method has the advantages of cheap and easily-obtained raw materials, less production process, less waste water, easy treatment, less pollution and the like, can randomly adjust the proportion of two products according to the proportion of the nitrobenzene and the alcohol and the process change, is suitable for the requirement of the market on the products, and is suitable for industrial production.
The invention provides a method for synthesizing p-aminophenol and co-producing p-aminophenyl ether with high added value by catalytic hydrogenation, which comprises the following steps:
putting a Pt/C catalyst, nitrobenzene, alcohol, a phase transfer catalyst and dilute sulfuric acid into a high-pressure reaction kettle, introducing nitrogen to replace air for more than 5 times, introducing hydrogen until the partial pressure of the hydrogen is 0.1-10 kgf, stirring, heating to 60-110 ℃, and reacting for 1-10 hours; after the reaction is finished, cooling to room temperature for suction filtration, recovering a catalyst filter cake, washing with deionized water, recycling, adjusting the pH of the filtrate to 7-7.5 with liquid alkali or ammonia water, and recovering unreacted methanol and byproduct aniline through atmospheric distillation until the aniline content in the kettle liquid is less than or equal to 0.1%; slowly cooling the distillation kettle liquid to be less than or equal to 0 ℃, separating out crystals, filtering to obtain a mixed product of p-aminophenol and p-aminophenyl ether, carrying out reduced pressure rectification on the mixed product to obtain a p-aminophenyl ether product, and recrystallizing the rectification kettle material in an organic or inorganic medium to obtain the p-aminophenol product.
In the step (1), the alcohol is methanol, ethanol, n-propanol, isopropanol or n-butanol, preferably methanol or ethanol.
In the step (1), the hydrogen partial pressure is preferably 0.2kgf to 6kgf, more preferably 0.5kgf to 4 kgf.
In the step (1), the reaction temperature is preferably 65-95 ℃.
In the step (1), the reaction time is preferably 2 to 6 hr.
In the step (1), the content of metal Pt in the Pt/C catalyst is 0.5-5%, and the Pt/C catalyst with the content of 1-3% is preferred.
In the step (1), the amount of the Pt/C catalyst is 0.2-8% of the weight of nitrobenzene, preferably 0.5-5%.
In the step (1), the phase transfer catalyst is a quaternary ammonium salt and PEG, such as cetyltrimethylammonium bromide, dodecyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium chloride, PEG400, PEG600, and the like, and the amount of the phase transfer catalyst is 0.3 to 5%, preferably 0.5 to 1%, of the amount of nitrobenzene.
In the step (1), the concentration of the dilute sulfuric acid is 5-30%, preferably 10-20%.
In the step (1), the molar ratio of nitrobenzene to alcohol is 1: 0 to 10, preferably 0.5 to 2.5.
In the step (1), the molar ratio of nitrobenzene to sulfuric acid is 1: 0.5 to 2, preferably 0.9 to 1.2.
In the step (3), the recrystallization medium is one or a mixture of water, methanol and ethanol.
Nitrobenzene, methanol (or ethanol) and acid are used as raw materials, the nitrobenzene is firstly subjected to catalytic hydrogenation reduction to generate phenylhydroxylamine, and then the phenylhydroxylamine is rearranged in an acidic medium to generate p-aminophenol and p-aminophene; the reaction equation is as follows:
the invention overcomes the defects of the existing synthesis method, adopts a method for synthesizing p-aminophenol and co-producing high-added-value p-aminophenyl ether by using cheap and easily-obtained raw materials, less production processes and less pollution, realizes the synthesis of two products of p-aminophenol and p-aminophenyl ether on a set of reaction device by a one-pot method, the nitrobenzene conversion rate is more than or equal to 99.5 percent, and the total yield of the p-aminophenol and the p-aminophenyl ether is more than 85 percent; according to the requirements of the market on two products, the ratio of the added raw materials of nitrobenzene and alcohol or process conditions are properly adjusted in the production process to meet the yield requirement, the increase of the ratio of the raw material of nitrobenzene is beneficial to improving the yield of p-aminophenol, the increase of the ratio of the raw material of methanol or ethanol is beneficial to improving the yield of p-aminophenyl ether, the increase of hydrogen pressure or the extension of reaction time is also beneficial to improving the yield of p-aminophenyl ether, the process is simple and flexible to control, and the method is suitable for industrial production.
Detailed Description
Example 1
75g of nitrobenzene, 478g of 15 percent sulfuric acid, 10g of methanol, 0.75g of 2 percent Pt/C catalyst and 0.75g of hexadecyl trimethyl ammonium bromide are added into a 1L high-pressure reaction kettle, nitrogen is introduced to replace air for 6 times, hydrogen is introduced until the hydrogen partial pressure is 2kgf, then the mixture is stirred and heated to 90 ℃ to react for 2 hours, the temperature is reduced, the filtration is carried out, 0.8g of catalyst wet base is recovered, and the yield of p-aminophenol, the yield of p-anisidine and the yield of byproduct aniline are respectively 76 percent, 15.5 percent and 6 percent by utilizing liquid chromatography analysis on hydrogenation filtrate.
Adjusting the pH value of the filtrate to 7-7.5 by using 25% ammonia water, distilling at normal pressure to recover unreacted methanol and byproduct aniline, and analyzing the aniline content in the kettle liquid to stop at 0.05%; slowly cooling the distillation kettle liquid to be less than or equal to 0 ℃, precipitating crystals, filtering to obtain a mixed product of para-aminophenol and para-anisidine, and carrying out reduced pressure rectification on the mixed product to obtain 11.3g of para-anisidine product, wherein the yield of the para-anisidine is 15%; the rectification residue is recrystallized in 50 percent methanol water solution to obtain 50.5g of p-aminophenol product, and the PAP yield is 75.2 percent.
Example 2
75g of nitrobenzene, 398.4g of 15 percent sulfuric acid, 40g of methanol, 0.75g of 2 percent Pt/C catalyst and 0.4g of hexadecyl trimethyl ammonium bromide are added into a 1L high-pressure reaction kettle, nitrogen is introduced to replace air for 6 times, hydrogen is introduced until the hydrogen partial pressure is 2kgf, then stirring is started and the temperature is increased to 80 ℃ to react for 4 hours, the temperature is reduced, the filtration is carried out, 0.8g of catalyst wet base is recovered, and the yield of p-aminophenol, the yield of p-anisidine and the yield of byproduct aniline are respectively 17 percent, 74.5 percent and 5 percent by utilizing liquid chromatography analysis on hydrogenation filtrate.
Adjusting the pH value of the filtrate to 7-7.5 by using 30% sodium hydroxide, distilling at normal pressure to recover unreacted methanol and byproduct aniline, and analyzing the aniline content in the kettle liquid to stop at 0.04%; slowly cooling the distillation kettle liquid to be less than or equal to 0 ℃, precipitating crystals, filtering to obtain a mixed product of p-aminophenol and p-anisidine, and carrying out reduced pressure rectification on the mixed product to obtain 55.8g of a p-anisidine product, wherein the yield of the p-anisidine is 73.9%; the rectification residue is recrystallized in 60% methanol water solution to obtain 11.1g of p-aminophenol product, and the PAP yield is 16.5%.
Example 3
75g of nitrobenzene, 597.6g of 10 percent sulfuric acid, 20g of methanol, 3g of 1 percent Pt/C catalyst and 0.55g of dodecyl trimethyl ammonium bromide are added into a 1L high-pressure reaction kettle, nitrogen is introduced to replace air for 6 times, hydrogen is introduced to the reaction kettle until the hydrogen partial pressure is 4kgf, then the reaction kettle is stirred and heated to 65 ℃ to react for 5 hours, the temperature is reduced, the filtration is carried out, 3.2g of catalyst wet base is recovered, the yield of p-aminophenol is 51.6 percent, the yield of p-anisidine is 42.5 percent and the yield of byproduct aniline is 4.5 percent by utilizing liquid chromatography analysis of hydrogenation filtrate.
Adjusting the pH value of the filtrate to 7-7.5 by using 30% ammonia water, distilling at normal pressure to recover unreacted methanol and byproduct aniline, and analyzing the aniline content in the kettle liquid to be 0.068% and stopping; slowly cooling the distillation kettle liquid to be less than or equal to 0 ℃, precipitating crystals, filtering to obtain a mixed product of p-aminophenol and p-anisidine, and carrying out reduced pressure rectification on the mixed product to obtain 31.8g of a p-anisidine product, wherein the yield of the p-anisidine is 42%; the rectification residue is recrystallized in 50 percent methanol water solution to obtain 34.3g of p-aminophenol product, and the PAP yield is 51.1 percent.
Example 4
Adding 90g of nitrobenzene, 376.5g of 20 percent sulfuric acid, 48.8g of methanol, 3 percent Pt/C catalyst and 0.72g of dodecyl trimethyl ammonium bromide into a 1L high-pressure reaction kettle, introducing nitrogen to replace air for 6 times, introducing hydrogen to the partial pressure of the hydrogen of 3kgf, stirring and heating to 85 ℃ to react for 3.5 hours, cooling, filtering, recovering 3.15g of catalyst wet base, and analyzing the hydrogenation filtrate by liquid chromatography to obtain 8.9 percent of p-aminophenol, 80.5 percent of p-anisidine and 8.8 percent of byproduct aniline.
Adjusting the pH value of the filtrate to 7-7.5 by using 20% ammonia water, distilling at normal pressure to recover unreacted methanol and byproduct aniline, and analyzing the aniline content in the kettle liquid to stop at 0.08%; slowly cooling the distillation kettle liquid to be less than or equal to 0 ℃, precipitating crystals, filtering to obtain a mixed product of p-aminophenol and p-anisidine, and carrying out reduced pressure rectification on the mixed product to obtain 72.5g of a p-anisidine product, wherein the yield of the p-anisidine is 80.1%; the rectification residue is recrystallized in 50% methanol water solution to obtain 6.3g of p-aminophenol product, and the PAP yield is 7.8%.
Example 5
Adding 90g of nitrobenzene, 394.4g of 20 percent sulfuric acid, 48.8g of methanol, 0.5g of 3 percent Pt/C catalyst and 0.9g of PEG4000.9g into a 1L high-pressure reaction kettle, introducing nitrogen to replace air for 6 times, introducing hydrogen to the partial pressure of the hydrogen of 3kgf, stirring and heating to 75 ℃ to react for 6 hours, cooling, filtering, recovering 0.55g of catalyst wet base, and analyzing hydrogenation filtrate by liquid chromatography to obtain 8.5 percent of p-aminophenol, 78.5 percent of p-anisidine and 10.8 percent of byproduct aniline.
Adjusting the pH value of the filtrate to 7-7.5 by using 25% ammonia water, distilling at normal pressure to recover unreacted methanol and byproduct aniline, and analyzing the aniline content in the kettle liquid to stop at 0.08%; slowly cooling the distillation kettle liquid to be less than or equal to 0 ℃, precipitating crystals, filtering to obtain a mixed product of p-aminophenol and p-anisidine, and carrying out reduced pressure rectification on the mixed product to obtain 70.6g of a p-anisidine product, wherein the yield of the p-anisidine is 78.1%; the rectification residue is recrystallized in 20 percent methanol water solution to obtain 6.3g of p-aminophenol product, and the PAP yield is 7.8 percent.
Example 6
75g of nitrobenzene, 657.3g of 10 percent sulfuric acid, 10g of methanol, 1.5g of 1 percent Pt/C catalyst and 1.5g of PEG6000.75g of nitrogen are added into a 1L high-pressure reaction kettle, the nitrogen is introduced for 6 times to replace air, hydrogen is introduced until the hydrogen partial pressure is 2kgf, then the mixture is stirred and heated to 85 ℃ for reaction for 4.5 hours, the temperature is reduced, the filtration is carried out, 1.6g of catalyst wet base is recovered, and the yield of p-aminophenol, the yield of p-anisidine and the yield of byproduct aniline are respectively found to be 78.5 percent, 8.5 percent and 10.8 percent by utilizing liquid chromatography analysis on hydrogenation filtrate.
Adjusting the pH value of the filtrate to 7-7.5 by using 30% ammonia water, distilling at normal pressure to recover unreacted methanol and byproduct aniline, and analyzing the aniline content in the kettle liquid to stop at 0.05%; slowly cooling the distillation kettle liquid to be less than or equal to 0 ℃, precipitating crystals, filtering to obtain a mixed product of p-aminophenol and p-anisidine, and carrying out reduced pressure rectification on the mixed product to obtain 6.1g of a p-anisidine product, wherein the yield of the p-anisidine is 8.1%; the rectification residue is recrystallized in 20 percent methanol water solution to obtain 52g of p-aminophenol product, and the PAP yield is 77.9 percent.
Example 7
75g of nitrobenzene, 657.3g of 10 percent sulfuric acid and 10g of methanol are added into a 1L high-pressure reaction kettle, the catalyst is recovered by using the embodiment 6, 0.5 percent by weight of new catalyst and 0.75g of hexadecyl trimethyl ammonium chloride are added, air is replaced by nitrogen for 6 times, hydrogen is introduced until the hydrogen partial pressure is 2kgf, then stirring is started and the temperature is raised to 85 ℃, the reaction is finished for 4.7 hours, the temperature is reduced, the filtration is carried out, 1.63g of catalyst wet base is recovered, and the yield of p-aminophenol, the yield of p-anisidine and the yield of byproduct aniline are respectively found to be 78.3 percent, 8.2 percent and 11.0 percent by utilizing the liquid chromatography analysis of hydrogenation filtrate.
Adjusting the pH value of the filtrate to 7-7.5 by using 30% ammonia water, distilling at normal pressure to recover unreacted methanol and byproduct aniline, and analyzing the aniline content in the kettle liquid to stop at 0.05%; slowly cooling the distillation kettle liquid to be less than or equal to 0 ℃, precipitating crystals, filtering to obtain a mixed product of p-aminophenol and p-anisidine, and carrying out reduced pressure rectification on the mixed product to obtain 5.9g of a p-anisidine product, wherein the yield of the p-anisidine is 7.83%; the rectification residue is recrystallized in 20 percent methanol water solution to obtain 51.8g of p-aminophenol product, and the PAP yield is 77.5 percent.
Examples 8 to 13
The process conditions and procedures were the same as in examples 1 to 6, except that all the methanol was replaced with ethanol. The results obtained are shown in the following table:
the invention is not limited to the embodiments of the invention described.
The present invention has been described in terms of the preferred embodiment, and it is understood that the invention is not limited to the particular embodiment, but is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (2)
1. A method for synthesizing p-aminophenol and co-producing p-aminophenyl ether by catalytic hydrogenation is characterized by comprising the following steps:
putting a Pt/C catalyst, nitrobenzene, alcohol, a phase transfer catalyst and dilute sulfuric acid into a high-pressure reaction kettle, introducing nitrogen to replace air for more than 5 times, introducing hydrogen to the hydrogen partial pressure of 0.5-4 kgf, stirring, heating to 65-95 ℃, and reacting for 2-6 hours; the alcohol is methanol or ethanol; the dosage of the phase transfer catalyst accounts for 0.5-1 wt% of the nitrobenzene; the molar ratio of nitrobenzene to alcohol is 1: 0.5 to 2.5; the Pt/C catalyst contains 1-3 wt% of metal Pt, the dosage of the Pt/C catalyst is 0.5-5 wt% of the weight of nitrobenzene, and the concentration of dilute sulfuric acid is 10-20 wt%; the phase transfer catalyst is cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, PEG400 and PEG600, and the molar ratio of the nitrobenzene to the sulfuric acid is 1: 0.9 to 1.2;
after the reaction in the step (2) is finished, cooling to room temperature for suction filtration, washing the recovered catalyst filter cake with deionized water for recycling, adjusting the pH of the filtrate to be 7-7.5 by using liquid caustic soda or ammonia water, and distilling at normal pressure to recover unreacted alcohol and byproduct aniline until the content of aniline in the kettle liquid is less than or equal to 0.1%;
and (3) slowly cooling the distillation kettle liquid to be less than or equal to 0 ℃, precipitating crystals, filtering to obtain a mixed product of p-aminophenol and p-aminophenyl ether, rectifying the mixed product under reduced pressure to obtain a p-aminophenyl ether product, and recrystallizing the rectifying kettle material in an organic or inorganic medium to obtain the p-aminophenol product.
2. The method for the co-production of p-aminophenol and p-aminophenyl ether through the catalytic hydrogenation according to claim 1, wherein the recrystallization medium in the step (3) is one or more of water, methanol and ethanol.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2765342A (en) * | 1952-10-22 | 1956-10-02 | Du Pont | Manufacture of aromatic parahydroxyamines |
| US3383416A (en) * | 1965-07-08 | 1968-05-14 | Roland G. Benner | Process for preparing aminophenol |
| US3535382A (en) * | 1967-11-02 | 1970-10-20 | Cpc International Inc | Amino phenol production |
| US5304680A (en) * | 1990-07-20 | 1994-04-19 | Bayer Aktiengesellschaft | Process for the preparation of aromatic amines which are substituted by C1 -C4 -alkoxy in the p-position |
| CN107417541A (en) * | 2017-05-17 | 2017-12-01 | 周龙根 | The preparation technology of para aminophenyl ethyl ether and aniline |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2765342A (en) * | 1952-10-22 | 1956-10-02 | Du Pont | Manufacture of aromatic parahydroxyamines |
| US3383416A (en) * | 1965-07-08 | 1968-05-14 | Roland G. Benner | Process for preparing aminophenol |
| US3535382A (en) * | 1967-11-02 | 1970-10-20 | Cpc International Inc | Amino phenol production |
| US5304680A (en) * | 1990-07-20 | 1994-04-19 | Bayer Aktiengesellschaft | Process for the preparation of aromatic amines which are substituted by C1 -C4 -alkoxy in the p-position |
| CN107417541A (en) * | 2017-05-17 | 2017-12-01 | 周龙根 | The preparation technology of para aminophenyl ethyl ether and aniline |
Non-Patent Citations (1)
| Title |
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| Hydrogenation of Nitrobenzene to 4-Aminophenol over Supported Platinum Catalysts;Setrak K. Tanielyan等;《Organic Process Research & Development》;20070613;第11卷(第4期);第681-688页 * |
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