CN1403436A - Synthesis of arylamine compound - Google Patents
Synthesis of arylamine compound Download PDFInfo
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- CN1403436A CN1403436A CN 02147591 CN02147591A CN1403436A CN 1403436 A CN1403436 A CN 1403436A CN 02147591 CN02147591 CN 02147591 CN 02147591 A CN02147591 A CN 02147591A CN 1403436 A CN1403436 A CN 1403436A
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Abstract
Arylamine compound is prepared with aromatic nitro compound and through reaction in organic solvent at normal pressure in the presence of CO and water by using Se as catalyst and alkali as cocatalyst. The said aromatic nitro compound may have substituent radical in the phenyl radical and the substituent radical may be one or several electron donating and/or accepting group. The reaction conditions include the molar ratio between aromatic nitro compound and water of 1 to 1-1000; molar amount of Se is 0.1-100% of the aromatic nitro compound; molar amount of alkali is 0-400 % of the aromatic nitro compound; the weight ratio between aromatic nitro compound and solvent of 1 to 2-1000; reaction time of 1-36 hr; and reaction temperature of 20-120 deg.c.
Description
Technical field
The present invention relates to a kind of synthetic method of aromatic amine compounds, relate in particular to a kind of method of under normal pressure, utilizing carbon monoxide and water to pass through selenium catalytic reduction aromatic nitro compound synthesizing arylamine compound.
Background technology
Arylamine is widely used in fields such as medicine, agricultural chemicals, dyestuff as important organic synthesis intermediate and the raw material of a big class.At present, most arylamine all are to make via the aromatic nitro compound reduction, and relevant quantity of document is huge, integrate to be used for industrialized nitro-compound method of reducing and to mainly contain following several: iron reduction, sodium sulfide reducing, electrolytic reduction and catalytic hydrogenating reduction.Though it is wide that iron filings method and sulfuration alkaline process adapt to, technology is simple, and Technological Economy is more reasonable, and environmental pollution is serious, has begun to be eliminated gradually; Electrolytic process productive rate height, easy and simple to handle, environmental friendliness, but energy consumption is big, existing synthetic and half suitability for industrialized production in laboratory that is used for more; Shortening method output is big, the quality product height, to solving problem of environmental pollution significant superiority is arranged, therefore, the industrial main flow that become of this method, but this method need be used good catalyzer, the cost height, and poor selectivity is difficult to from this method preparation for many arylamine that contain sensitive group such as functional groups such as halogen, carbonyl.In addition, also have under catalyst action with reduction methods such as the reduction method of hydrazine and metal hydrides, but they only are applicable to special aromatic nitro compound reduction, and cost is higher, does not have ubiquity.In recent years, a kind of is the also reaction of original aromatic nitro compound of reductive agent with the carbon monoxide, with it to the highly selective of nitro and cause people's interest (Tafesh A M, Weiguny J.A Review of the Selecivity CatalyticReduction of Aromatic Nitro Compounds into Aromatic Amines Isocyanates, Carbamates and Ureas Using CO.J Chem Rev, 1996,96:2035-2052) but that related reaction precious metal catalyst system has is comparatively complicated, the cost height that has also is not best industrial method.Have under than low reaction temperatures (80 ℃), selenium/carbon monoxide/aqueous systems is used to go back report (the T Miyata of original aromatic nitro compound system arylamine, K Kondo, S Murai, THirashima and N Sonoda.Selenium-Catalyzed Reduction of Aromatic NitroCompounds to Amines by CO/H2O in the Presence of Triethylamine.AngewChem Int Ed Engl, 1980,19 (12): 1008), good by the time in the productive rate, but must use triethylamine to make promotor.We have reported at mineral alkali and have not added selenium/carbon monoxide under the alkali condition/aqueous systems and have been used to go back original aromatic nitro compound and efficiently make the reaction of arylamine (Peng Aidong, Lu Shiwei, CN02107742.8，2002)。Above-mentioned carbon monoxide/water reduction system mostly need under high pressure be finished.
Summary of the invention
The object of the present invention is to provide a kind of method of synthesizing arylamine compound.This method reaction conditions gentleness, carry out easy to operate and safely under normal pressure, raw material is easy to get, pollute few, the selectivity height, sensitive group such as halogen, acyl group is unaffected on the aromatic ring, productive rate is therefrom waited until good, reaction easily separated recovery of end of a period catalyzer and recycle.
For achieving the above object, the technical solution used in the present invention is as follows: in the presence of carbon monoxide and water, with the aromatic nitro compound is raw material, selenium is catalyzer, with alkali is promotor, or do not add any promotor, and in organic solvent, react under the normal pressure, be that amino prepares corresponding aromatic amine compound with the nitro partial reduction; Reaction formula is as follows:
Wherein:
Can not have substituting group on the aromatic nitro compound phenyl, also substituting group can be arranged, substituent X can be one or more electron-donating groups and/or electron-withdrawing group; The molar ratio of material of aromatic nitro compound and water is 1: 1 to 1: 1000; The mole dosage of selenium is 0.1～100% of a reactant aromatic nitro compound; The mole dosage of alkali is 0～400% of a reactant aromatic nitro compound; Reaction times is 1～36 hour; Temperature of reaction is 20～120 ℃; The weight ratio of aromatic nitro compound and solvent is 1: 2 to 1: 1000.
Among the present invention:
Be alkyl, alkoxyl group, amido etc. to electron substituent group in the described reactant aromatic nitro compound, electron-withdrawing substituent is fluorine, chlorine, bromine, iodine, cyano group, aldehyde radical, ketone group, trifluoromethyl or the carboxyl etc. that directly link to each other with aromatic ring;
Described alkali is mineral alkali or organic bases; Described mineral alkali is one or more in sodium hydroxide, potassium hydroxide, salt of wormwood, yellow soda ash and the sodium acetate; Described organic bases is pyridine, triethylamine, aniline, triphenylphosphine, 1,5-diaza-bicyclo [5.4.0]-5-undecylene (DBU), 1,5-diaza-bicyclo [5.3.0]-5-nonene (DBN), N-crassitude and 1, one or more of 4-diaza-bicyclo [2.2.2] octane (DABCO).
Describedly do not add any promotor and be meant and only make catalyzer and need not add promotor and can react with selenium;
Described carbon monoxide can use the industrial carbon monoxide tail gas that contains air, hydrogen, nitrogen, carbonic acid gas and/or water vapour, wherein the content sum of nitrogen, carbonic acid gas and/or water vapour is smaller or equal to 95% of cumulative volume, and air content is smaller or equal to 30% of cumulative volume;
Described organic solvent is that one or more polarity and/or the described polar solvent of nonpolar inert solvent are tetrahydrofuran (THF) (THF), N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), glycol ether, N-formyl piperidine (FP), ethylene glycol diethyl ether, dioxane, crown ether or acetone; Non-polar solvent is toluene, normal hexane, dimethylbenzene or benzene.
The present invention has following advantage:
1, the present invention is a synthesis under normal pressure.Facility investment is few, and is easy to operate and safe.
2, cost is low.Raw material of the present invention is simple, be easy to get, and only uses the lower nonmetal selenium of price to be catalyzer.
3, environmentally friendly.It is little that the present invention reacts corrosion, and the three wastes are handled burden and obviously reduced, and have reached the requirement of cleaner production, help large-scale industrial production.
4, the reaction process difficulty is low.The present invention is easy and simple to handle, and product separates easily with the postorder of catalyzer, just can separate with simply being separated.
5, good economy performance.Reaction preference height of the present invention, adopting nonmetal selenium is that catalyzer is good to the reduction selectivity of nitro, and sensitive group such as halogen, cyano group is unaffected on the aromatic ring, and productive rate is therefrom waited until height; The present invention has the efficient of atomic economy reaction in addition.
6, has phase transfer function.In catalyzed reaction of the present invention, solid selenium powder catalyzer is insoluble in the reaction system before the reaction beginning, the selenium of solid phase changes the active specy that is dissolved in reaction system into and carries out homogeneous catalytic reaction efficiently in reaction process, after reaction ends, catalyzer is separated out with the solid phase selenium powder again, very easy and product Separation and Recovery can be recycled.Therefore, the present invention combines the advantage of homogeneous catalysis and heterogeneous catalyst.
Embodiment
Below by embodiment in detail the present invention is described in detail, yet, the invention is not restricted to following embodiment.
Embodiment 1
In the there-necked flask that has prolong and stirring of 100ml, add oil of mirbane (10mmol), Se (0.2mmol), H
2O (0.5mol), sodium acetate (20mmol) and solvent DMF (40ml), continue to feed carbon monoxide, and be heated to 88 ℃ of stirring reactions 4 hours, be cooled to room temperature, carbon monoxide is switched to oxygen or after pneumatic blending 0.5-1 hour, filters out selenium powder, will filter after gained filtrate concentrates, carry out assay with gas-chromatography, getting aniline chromatogram yield is 100% (in oil of mirbane).Assay adopts the HP-4890D gas chromatography system, comprises fid detector, and SE-54 capillary column (30mm) * 0.32mm * 1.5, temperature of vaporization chamber are 280 ℃, column temperature: 150 ℃, external standard method is quantitative.
Embodiment 2
Aromatic nitro compound is an o-chloronitrobenzene, and other experimental technique and condition are with embodiment 1, and it is 89% (in o-chloronitrobenzene) that gas Chromatographic Determination gets the Ortho-Chloro aniline yield.
Embodiment 3
Aromatic nitro compound is to ethyl-nitrobenzene, and other experimental technique and condition are with embodiment 1, and gas Chromatographic Determination must be 99% (in to ethyl-nitrobenzene) to the ethylaniline yield.
Embodiment 4
Aromatic nitro compound is to ethanoyl oil of mirbane, and other experimental technique and condition are with embodiment 1, and gas Chromatographic Determination must be 99% (in to ethanoyl oil of mirbane) to ethanoyl aniline yield.
Embodiment 5
Aromatic nitro compound is to oxyethyl group oil of mirbane, and other experimental technique and condition are with embodiment 1, and it is 67% (in to oxyethyl group oil of mirbane) that gas Chromatographic Determination gets the p-ethoxyaniline yield.
Embodiment 6
Aromatic nitro compound is an ortho-methylnitrobenzene, and other experimental technique and condition are with embodiment 1, and it is 99% (in ortho-methylnitrobenzene) that gas Chromatographic Determination gets ortho-methylnitrobenzene amine yield.
Embodiment 7
Aromatic nitro compound is a p-Nitrobromobenzene, and 100 ℃ of temperature of reaction, other experimental technique and condition are with embodiment 1, and it is 56% (in p-Nitrobromobenzene) that gas Chromatographic Determination gets the para-bromoaniline yield.
Embodiment 8
Aromatic nitro compound is a p-fluoronitrobenzene, and other experimental technique and condition are with embodiment 7, and it is 45% (in p-fluoronitrobenzene) that gas Chromatographic Determination gets the para-fluoroaniline yield.
Embodiment 9
The triethylamine consumption is 10mmol, and in 9 hours reaction times, other experimental technique and condition are with embodiment 1, and it is 100% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 10
Oil of mirbane (20mmol), selenium (0.1mmol), water (20mmol), triethylamine (20mmol), 150 ℃ of oil bath temperatures, the initial gauge pressure of reaction of carbon monoxide is 1Mpa, reacted 2 hours, other experimental technique and condition are with embodiment 1, and it is 63% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 11
Do not add sodium acetate, temperature of reaction is 50 ℃, and other experimental technique of 20 hours reaction times and condition are with embodiment 1, and it is 98% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 12
The water yield is 1mol, and other experimental technique and condition are with embodiment 11, and it is 87% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 13
Solvent is an acetone, and other experimental technique and condition are with embodiment 11, and it is 21% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 14
Solvent is 10 hours for the formyl piperidine reaction times, and other experimental technique and condition are with embodiment 11, and it is 98% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 15
Solvent is a toluene, and in 20 hours reaction times, other experimental technique and condition are with embodiment 1, and it is 87% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 16
Yellow soda ash 10mmol, other experimental technique and condition are with embodiment 1, and it is 90% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 17
Aromatic nitro compound is a para-methylnitrobenzene, sodium hydroxide 10mmol, and other experimental technique and condition are with embodiment 1, and gas Chromatographic Determination must be 93% (in para-methylnitrobenzene) to the monomethylaniline yield.
Embodiment 18
Aromatic nitro compound is a m-trifluoromethyl oil of mirbane, potassium hydroxide 20mmol, and the reaction times is 5 hours, and other experimental technique and condition are with embodiment 1, and it is 98% (in m-trifluoromethyl oil of mirbane) that gas Chromatographic Determination gets the m-trifluoromethyl aniline yield rate.
Claims (8)
1, a kind of method of synthesizing arylamine compound in the presence of carbon monoxide and water, is a raw material with the aromatic nitro compound, and selenium is catalyzer, and alkali is promotor, reacts under normal pressure in organic solvent, and its reaction is shown below:
Wherein:
The molar ratio of material of aromatic nitro compound and water is 1: 1 to 1: 1000;
The mole dosage of selenium is 0.1～100% of an aromatic nitro compound;
The mole dosage of alkali is 0～400% of an aromatic nitro compound;
The weight ratio of aromatic nitro compound and solvent is 1: 2 to 1: 1000;
Reaction times is 1～36 hour;
Temperature of reaction is 20～120 ℃.
2, the method for claim 1 is characterized in that, the substituting group in the described aromatic nitro compound is one or more electron-donating groups and/or electron-withdrawing group.
3, method as claimed in claim 2 is characterized in that, the electron-donating group in the described aromatic nitro compound is alkyl, alkoxyl group or amido; Electron-withdrawing group is fluorine, chlorine, bromine, iodine, cyano group, aldehyde radical, ketone group, trifluoromethyl or the carboxyl that directly links to each other with aromatic ring.
4, the method for synthesizing arylamine compound as claimed in claim 1 is characterized in that, described alkali is mineral alkali or organic bases.
5, method as claimed in claim 4 is characterized in that, described mineral alkali is one or more in sodium hydroxide, potassium hydroxide, salt of wormwood, yellow soda ash and the sodium acetate; Described organic bases is pyridine, sodium alkoxide, triethylamine, aniline, triphenylphosphine, 1,5-diaza-bicyclo [5.4.0]-5-undecylene, 1,5-diaza-bicyclo [5.3.0]-5-nonene, N-crassitude and 1, one or more of 4-diaza-bicyclo [2.2.2] octane.
6. the method for claim 1, it is characterized in that, described carbon monoxide is the industrial carbon monoxide tail gas that contains air, hydrogen, nitrogen, carbonic acid gas and/or water vapour, wherein the content sum of nitrogen, carbonic acid gas and/or water vapour is smaller or equal to 95% of cumulative volume, and air content is less than 30%.
7, the method for claim 1 is characterized in that, described organic solvent is one or more polarity and/or nonpolar inert solvent.
8, method as claimed in claim 7, it is characterized in that, described polar solvent is ethanol, tetrahydrofuran (THF), N, dinethylformamide, dimethyl sulfoxide (DMSO), glycol ether, N-formyl piperidine, ethylene glycol diethyl ether, dioxane, crown ether or acetone; Non-polar solvent is normal hexane, toluene, dimethylbenzene or benzene.
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| CNB021475911A CN1187314C (en) | 2002-10-17 | 2002-10-17 | Synthesis of arylamine compound |
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| CNB021475911A CN1187314C (en) | 2002-10-17 | 2002-10-17 | Synthesis of arylamine compound |
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| CN1187314C CN1187314C (en) | 2005-02-02 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173999A (en) * | 2011-02-28 | 2011-09-07 | 盐城工学院 | Method for synthesizing 2-amino-N,N-dimethylbenzamide |
| CN102491863A (en) * | 2011-11-30 | 2012-06-13 | 浙江大学 | Selective hydrogenation reduction method for aromatic nitro compound |
| CN101665450B (en) * | 2009-09-28 | 2012-11-28 | 辽宁大学 | Method for synthesizing Schiff base |
| CN103113245A (en) * | 2013-02-18 | 2013-05-22 | 辽宁大学 | Method for synthesizing 1-aminoanthraquinone |
| CN105085286A (en) * | 2015-08-05 | 2015-11-25 | 盐城市瓯华化学工业有限公司 | Method for synthesizing 1-aminoanthraquinone |
| CN110437110A (en) * | 2019-08-26 | 2019-11-12 | 辽宁大学 | A method of synthesis M acid |
| CN110437111A (en) * | 2019-08-26 | 2019-11-12 | 辽宁大学 | A method of synthesis C acid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130821B (en) * | 2015-07-27 | 2017-05-31 | 江阴市华亚化工有限公司 | It is a kind of to reduce the green synthesis method that ortho-nitraniline prepares o-phenylenediamine |
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2002
- 2002-10-17 CN CNB021475911A patent/CN1187314C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665450B (en) * | 2009-09-28 | 2012-11-28 | 辽宁大学 | Method for synthesizing Schiff base |
| CN102173999A (en) * | 2011-02-28 | 2011-09-07 | 盐城工学院 | Method for synthesizing 2-amino-N,N-dimethylbenzamide |
| CN102491863A (en) * | 2011-11-30 | 2012-06-13 | 浙江大学 | Selective hydrogenation reduction method for aromatic nitro compound |
| CN102491863B (en) * | 2011-11-30 | 2013-11-27 | 浙江大学 | Selective hydrogenation reduction method for aromatic nitro compound |
| CN103113245A (en) * | 2013-02-18 | 2013-05-22 | 辽宁大学 | Method for synthesizing 1-aminoanthraquinone |
| CN103113245B (en) * | 2013-02-18 | 2015-08-19 | 辽宁大学 | A kind of method of synthesizing 1-aminoanthraquinone |
| CN105085286A (en) * | 2015-08-05 | 2015-11-25 | 盐城市瓯华化学工业有限公司 | Method for synthesizing 1-aminoanthraquinone |
| CN110437110A (en) * | 2019-08-26 | 2019-11-12 | 辽宁大学 | A method of synthesis M acid |
| CN110437111A (en) * | 2019-08-26 | 2019-11-12 | 辽宁大学 | A method of synthesis C acid |
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| CN1187314C (en) | 2005-02-02 |
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