CN101798272A - Method for synthesizing para aminophenylmethylether by catalytic hydrogenation of paranitroanisole - Google Patents
Method for synthesizing para aminophenylmethylether by catalytic hydrogenation of paranitroanisole Download PDFInfo
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- CN101798272A CN101798272A CN200910217949A CN200910217949A CN101798272A CN 101798272 A CN101798272 A CN 101798272A CN 200910217949 A CN200910217949 A CN 200910217949A CN 200910217949 A CN200910217949 A CN 200910217949A CN 101798272 A CN101798272 A CN 101798272A
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Abstract
The invention provides a method for synthesizing para aminophenylmethylether by catalytic hydrogenation paranitroanisole. In the method, the paranitroanisole is subjected to catalytic reduction reaction with hydrogen to generate the para aminophenylmethylether in the presence of a load type palladium catalyst in a supercritical carbon dioxide reaction medium under mild conditions. Compared with the traditional processes, such as a nitrobenzene method, a sodium sulfide or ferrum reduction method, a method for synthesizing the para aminophenylmethylether by reducing the paranitroanisole by activated carbon load type palladium catalyst hydrazine hydrate, and the like, the invention has the advantages of mild reaction condition, fast reaction, clean reaction process and easy product separation, achieving the product yield more than 99 percent, and the like; in addition, in the invention, reaction temperature is reduced from 75-125 DEG C in the nitrobenzene method to 50-80 DEG C, and reaction time is reduced from 130 minutes in the method for synthesizing the para aminophenylmethylether by reducing the paranitroanisole by the activated carbon load type palladium catalyst hydrazine hydrate to 10-30 minutes without adding any organic solvent and additive or generating any side products in the reaction process.
Description
Technical field
The invention relates to the novel method of the synthetic Para-Anisidine of p-Nitromethoxybenzene hydrogenation, be specifically related in the supercritical co reaction medium, the method for the synthetic Para-Anisidine of load type palladium catalyst Catalysis p-nitroanisole hydrogenation.
Background technology
The Para-Anisidine of p-Nitromethoxybenzene shortening preparation (also claim P-nethoxyaniline or to the benzene methyl oxyaniline) is clear crystal, is a kind of fine chemicals, is widely used in fields such as medicine, photographic material, agricultural chemicals, polymkeric substance, dyestuff.The Para-Anisidine of the high yield of research preparation has important use and is worth and wide application prospect.As dyestuff intermediate, it can be used for ice dyeing coupling component 11,13,35, C.I. DISPERSE ORANGE 30 200 15, blue 64, C.I. Vat Red 29, C.I. reactive violet 8,46, and synthesizing of dyestuffs such as C.I. basic yellow 13,20,28 also can be used for vat dyes and reactive dyestuffs etc., can synthesize nearly 20 kinds of dyestuffs, and the dyestuff that Para-Anisidine is produced on the market is sold better.Pharmaceutically be used to produce Quinacrime, uncle's quinoline etc.The traditional industrial process of Para-Anisidine is to adopt sulfuration alkaline process or iron powder reducing method.The synthetic method of Para-Anisidine mainly contains at present: (1) oil of mirbane method: at 75-125 ℃, 0.6-1.5MPa under the hydrogen pressure, with the precious metal is catalyzer, and sulfuric acid-methyl alcohol and 10-20% (weight percentage. with oil of mirbane weight is benchmark) methyl-sulphoxide is solvent, can make Para-Anisidine.This method with an organic solvent, difficult separation and recycling causes environmental pollution.(Para-Anisidine Study on Process, Henan chemical industry, 1992 (2)) (2) phenol hydrogenation method is not still avoided the use of organic solvent.(Para-Anisidine Study on Process, Henan chemical industry, 1992 (2)) (3) parachloronitrobenzene method: with the parachloronitrobenzene is raw material, carries out methoxylation earlier, then obtains Para-Anisidine in difference reduction mode.The reduction mode has: (a) sodium sulphite reduction method: contain sodium hydroxide and Sulfothiorine in this reduction method product, not easily separated, the sodium sulphite utilization ratio is low; (Para-Anisidine Study on Process, Henan chemical industry, 1992 (2)) are the iron reduction method (b): this method raw material low price that is easy to get, low for equipment requirements, but the offal treatment difficulty that this reduction method is discharged is big for environment pollution, does not meet the development course of " Green Chemistry "; (with the p-Nitrophenyl chloride is the synthetic Para-Anisidine of raw material, Liaoning chemical industry, 2002,31 (6)) (c) shortening method: A: adopt ammonia synthesis gas to prepare Para-Anisidine for the hydrogen source shortening, this method adopts ammonia synthesis gas to replace pure hydrogen catalytic hydrogenation, technical process is short, investment is little, cost is low, quality product and yield and pure hydrogen technology are basic identical, have remarkable economic efficiency and technological competitiveness, but temperature of reaction are higher, time is longer, and efficient is not high; (synthesizing of Para-Anisidine, meticulous and specialty chemicals, 2001 (13)) B: backbone ruthenium nickel charcoal selectivity catalysis ammonification prepares Para-Anisidine, tetrahydrofuran (THF) (THF) is a solvent, though this method temperature is suitable, pressure requires lower, and the purpose selectivity of product is very high, but THF belongs to organic solvent, and environment is had certain harm; (prepare Para-Anisidine with backbone ruthenium nickel charcoal selective catalytic hydrogenation, fine chemistry industry, 2006,23 (5)) C: the liquid-phase catalyst hydrogenation method synthesizes Para-Anisidine, although overcome the with serious pollution deadly defect of sodium sulfide reducing technology, and product yield height, quality are good, but temperature requirement is higher; (the liquid-phase catalyst hydrogenation method synthesizes Para-Anisidine, China's chlor-alkali, 2003 (5)) D:Fe-Al/C Compounds with Hydrazine Hydrate Catalyzed reduction p-Nitromethoxybenzene prepares Para-Anisidine, have little, the reductive yield height of investment, do not produce advantage such as waste residue, mainly be fit to the production of short run, short-term road aromatic amine compound; (Para-Anisidine, dyestuff and dyeing, 2008,45 (3) are synthesized in Fe-Al/C catalysis) E:Pd/C Compounds with Hydrazine Hydrate Catalyzed is synthesized Para-Anisidine, and reaction medium is a Virahol, and the reaction times is longer, does not meet the green chemistry process requirement; (Para-Anisidine, Sino-South African Forestry University of Science and Technology's journal, 2008 (3) are synthesized in Pd/C catalysis) F: three phase catalytics prepare Para-Anisidine, though this method purification of products convenient separation, and be beneficial to the catalyst recovery utilization, operation sequence is complicated.(three phase catalytics prepare Para-Anisidine, Jiangsu chemical industry, 1992 (3)).
Summary of the invention
The present invention is directed to the problem that exists in the existing p-Nitromethoxybenzene hydrogenation reaction technology, utilizing is the loaded catalyst catalysis of active ingredient efficiently with the palladium, under low temperature, low pressure, in the carbon dioxide reaction medium, do not have under the condition of any organic solvent and promotor, the p-Nitromethoxybenzene method of hydrotreating synthesizes Para-Anisidine, and by dissolving, filters to separate to obtain yield and reach Para-Anisidine more than 99%.
The condition and the step of the method for the synthetic Para-Anisidine of p-Nitromethoxybenzene hydrogenation provided by the invention are as follows:
(1), according to mass ratio is: 500: 1 to 200: 1, the massfraction of analytically pure p-Nitromethoxybenzene and palladium (Pd) be 5% be that the Pd/C loaded catalyst of active ingredient adds in the autoclave with Pd, at room temperature purge the air in the emptying reaction system with carbonic acid gas;
(2), reactor is heated to 40-80 ℃, optimal temperature is 50-80 ℃; Charge into hydrogen in reactor, pressure is the 1-6 MPa in the reactor, charges into carbonic acid gas then, and pressure is the 10-18 MPa in the reactor, stirs, and the reaction times is 10-30 minute; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, obtains Para-Anisidine.
The reaction product that method of the present invention obtained takes gas-chromatography to analyze with qualitative through dissolve with ethanol after the dilution.Analytical results is shown in Fig. 1-4.
Beneficial effect: compare with methods such as existing reaction process such as the synthetic Para-Anisidines of oil of mirbane method, sodium sulphite iron reduction method or Pd/C catalyst hydrazine hydrate reduction p-Nitromethoxybenzene, the present invention has the reaction conditions gentleness, speed of response is fast, the reaction process cleaning, product is easily separated, and yield can reach 99% with first-class advantage.Temperature of reaction of the present invention has dropped to 50-80 ℃ from 75-125 ℃ of oil of mirbane method; reaction times, the 130min from the synthetic Para-Anisidine of Pd/C catalyst hydrazine hydrate reduction p-Nitromethoxybenzene dropped to 10-30min; and do not add any organic solvent and additive; reaction process does not generate any by product, helps environment protection.Referring to Comparative Examples 1-2.Comparative Examples 1-2 is solvent-free, the reaction result in the organic solvent ethanol, and the technical scheme result in supercritical co of the present invention is good by the contrast proof.
Description of drawings
Fig. 1 is the gas chromatographic analysis spectrogram (retention time: Para-Anisidine is 6.615min, and p-Nitromethoxybenzene is 7.682min) of the Para-Anisidine that obtains of embodiment 3
Fig. 2 is the gas chromatographic analysis spectrogram (retention time: Para-Anisidine is 6.115min, and p-Nitromethoxybenzene is 7.715min) of the Para-Anisidine that obtains of embodiment 4
Fig. 3 is the gas chromatographic analysis spectrogram (retention time: Para-Anisidine is 6.148min, and p-Nitromethoxybenzene is 7.632min) of the Para-Anisidine that obtains of embodiment 5
Fig. 4 is the gas chromatographic analysis spectrogram (retention time: Para-Anisidine is 6.148min, and p-Nitromethoxybenzene is 7.665min) of the Para-Anisidine that obtains of embodiment 10
Embodiment
(1), in 50 milliliters of autoclaves, adds 0.306 gram p-Nitromethoxybenzene (analytical pure) and 0.0015 gram Pd/C catalyzer (massfraction of Pd is 5%), at room temperature with carbonic acid gas purging, the air in the emptying reaction system;
(2), reactor is heated to 40 ℃; Charge into hydrogen in reactor, pressure is 2 MPas in the reactor; Charge into carbonic acid gas then, pressure is 14 MPas in the reactor; Stir, the reaction times is 10 minutes; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, obtains Para-Anisidine.Its yield is 25.51%.
(1) with embodiment 1;
(2), reactor is heated to 60 ℃; Charge into hydrogen in reactor, pressure is 4 MPas in the reactor; Charge into carbonic acid gas then, pressure is 16 MPas in the reactor; Stir, the reaction times is 10 minutes; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, obtains Para-Anisidine.Its yield is 98.87%.
(1) with embodiment 1;
(2), reactor is heated to 60 ℃; Charge into hydrogen in reactor, pressure is 1 MPa in the reactor; Charge into carbonic acid gas then, pressure is 13 MPas in the reactor; Stir, the reaction times is 20 minutes; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, and obtaining the Para-Anisidine yield is 99.95%.
(1) with embodiment 1;
(2), reactor is heated to 50 ℃; Charge into hydrogen in reactor, pressure is 2 MPas in the reactor; Charge into carbonic acid gas then, pressure is 14 MPas in the reactor; Stir, the reaction times is 20 minutes; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, obtains Para-Anisidine.Its yield is 84.67%.
(1) with embodiment 1;
(2), reactor is heated to 80 ℃; Charge into hydrogen in reactor, pressure is 2 MPas in the reactor; Charge into carbonic acid gas then, pressure is 14 MPas in the reactor; Stir, the reaction times is 20 minutes; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, obtains Para-Anisidine.Its yield is 99.46%.
(1) with embodiment 1;
(2), reactor is heated to 60 ℃; Charge into hydrogen in reactor, pressure is 2 MPas in the reactor; Charge into carbonic acid gas then, pressure is 14 MPas in the reactor; Stir, the reaction times is 30 minutes; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, obtains Para-Anisidine.Its yield is 97.81%.
(1) with embodiment 1;
(2), reactor is heated to 60 ℃; Charge into hydrogen in reactor, pressure is 2 MPas in the reactor; Charge into carbonic acid gas then, pressure is 16 MPas in the reactor; Stir, the reaction times is 20 minutes; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, obtains Para-Anisidine.Its yield is 55.98%.
(1) with embodiment 1;
(2), reactor is heated to 60 ℃; Charge into hydrogen in reactor, pressure is 2 MPas in the reactor; Charge into carbonic acid gas then, pressure is 18 MPas in the reactor; Stir, the reaction times is 20 minutes; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, obtains Para-Anisidine.Its yield is 25.28%.
(1) with embodiment 1;
(2), reactor is heated to 60 ℃; Charge into hydrogen in reactor, pressure is 2 MPas in the reactor; Charge into carbonic acid gas then, pressure is 10 MPas in the reactor; Stir, the reaction times is 20 minutes; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, obtains Para-Anisidine.Its yield is 96.93%.
(1) with embodiment 1;
(2), reactor is heated to 60 ℃; Charge into hydrogen in reactor, pressure is 6 MPas in the reactor; Charge into carbonic acid gas then, pressure is 18 MPas in the reactor; Stir, the reaction times is 10 minutes; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, obtains Para-Anisidine.Its yield is 99.35%.
(1), in 50 milliliters of autoclaves, adds 0.300 gram p-Nitromethoxybenzene (analytical pure) and 0.0015 gram Pd/C catalyzer (massfraction of Pd is 5%), at room temperature with carbonic acid gas purging, the air in the emptying reaction system;
(2), reactor is heated to 70 ℃; Charge into hydrogen in reactor, pressure is 2 MPas in the reactor; Carbonic acid gas then, charged pressure is 14 MPas in the reactor; Stir, the reaction times is 10 minutes; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, obtains Para-Anisidine.Its yield is 99.25%.
(1) in 50 milliliters of autoclaves, adds 0.300 gram p-Nitromethoxybenzene (analytical pure) and 0.001 gram Pd/C catalyzer (massfraction of Pd is 5%), at room temperature purge the air in the emptying reaction system with carbonic acid gas;
(2), reactor is heated to 60 ℃; Charge into hydrogen in reactor, pressure is 2 MPas in the reactor; Charge into carbonic acid gas then, pressure is 14 MPas in the reactor; Stir, the reaction times is 20 minutes; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, obtains Para-Anisidine.Its yield is 95.47%.
(1), in 50 milliliters of autoclaves, adds 0.500 gram p-Nitromethoxybenzene (analytical pure) and 0.001 gram Pd/C catalyzer (massfraction of Pd is 5%), at room temperature with carbonic acid gas purging, the air in the emptying reaction system;
(2), reactor is heated to 60 ℃; Charge into hydrogen in reactor, pressure is 2 MPas in the reactor; Charge into carbonic acid gas then, pressure is 14 MPas in the reactor; Stir, the reaction times is 20 minutes; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, obtains Para-Anisidine.Its yield is 89.56%.
Comparative Examples 1
(1), in 50 milliliters of autoclaves, adds 0.306 gram p-Nitromethoxybenzene (analytical pure) and 0.0015 gram Pd/C catalyzer (massfraction of Pd is 5%), at room temperature with carbonic acid gas purging, the air in the emptying reaction system;
(2), reactor is heated to 60 ℃; Charge into hydrogen in reactor, pressure is 2 MPas in the reactor; Stir, the reaction times is 20 minutes; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, obtains Para-Anisidine.Its yield is 56.49%.
Comparative Examples 2
(1), in 50 milliliters of autoclaves, adds 0.306 gram p-Nitromethoxybenzene (analytical pure) and 0.0015 gram Pd/C catalyzer (massfraction of Pd is 5%), add 10 milliliters of ethanol (analytical pure then, wt＞99.7%), at room temperature purge the air in the emptying reaction system with carbonic acid gas;
(2), reactor is heated to 60 ℃; Charge into hydrogen in reactor, pressure is 2 MPas in the reactor; Stir, the reaction times is 20 minutes; Reaction naturally cools to room temperature after finishing, and isolates product, the Para-Anisidine that obtains.Its yield is 31.51%.
Claims (1)
1. the p-Nitromethoxybenzene shortening synthesizes the method for Para-Anisidine, and its step and condition are as follows:
(1), according to mass ratio is: 500: 1 to 200: 1, the massfraction of analytically pure p-Nitromethoxybenzene and palladium (Pd) be 5% be that the Pd/C loaded catalyst of active ingredient adds in the autoclave with Pd, at room temperature purge the air in the emptying reaction system with carbonic acid gas;
(2), reactor is heated to 40-80 ℃, optimal temperature is 50-80 ℃; Charge into hydrogen in reactor, pressure is the 1-6 MPa in the reactor, charges into carbonic acid gas then, and pressure is the 10-18 MPa in the reactor, stirs, and the reaction times is 10-30 minute; Reaction naturally cools to room temperature after finishing, and filters, and isolates product, obtains Para-Anisidine.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329279A (en) * | 2011-10-31 | 2012-01-25 | 济南德爱医药技术有限公司 | Preparation method for Linezolid |
| CN106496046A (en) * | 2016-09-28 | 2017-03-15 | 连云港泰盛化工有限公司 | The method that solvent-free catalytic hydrogenation produces aminoanisole |
| CN113582859A (en) * | 2021-06-28 | 2021-11-02 | 佳尔科生物科技南通有限公司 | Preparation method of 4-phenoxy-3-aminoanisole |
-
2010
- 2010-03-13 CN CN200910217949A patent/CN101798272A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| FENGYU ZHAO ET AL.: "Hydrogenation of nitro compounds with supported platinum catalyst in supercritical carbon dioxide", 《CATALYSIS TODAY》 * |
| 袁忠义等: "骨架钌镍炭选择性催化加氢制备对氨基苯甲醚", 《精细化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329279A (en) * | 2011-10-31 | 2012-01-25 | 济南德爱医药技术有限公司 | Preparation method for Linezolid |
| CN102329279B (en) * | 2011-10-31 | 2013-11-06 | 济南德爱医药技术有限公司 | Preparation method for Linezolid |
| CN106496046A (en) * | 2016-09-28 | 2017-03-15 | 连云港泰盛化工有限公司 | The method that solvent-free catalytic hydrogenation produces aminoanisole |
| CN113582859A (en) * | 2021-06-28 | 2021-11-02 | 佳尔科生物科技南通有限公司 | Preparation method of 4-phenoxy-3-aminoanisole |
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Application publication date: 20100811 |