CN1445213A - Method for synthesizing arylamine compound - Google Patents
Method for synthesizing arylamine compound Download PDFInfo
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- CN1445213A CN1445213A CN 02107742 CN02107742A CN1445213A CN 1445213 A CN1445213 A CN 1445213A CN 02107742 CN02107742 CN 02107742 CN 02107742 A CN02107742 A CN 02107742A CN 1445213 A CN1445213 A CN 1445213A
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Abstract
A process for synthesizing arylamine compounds features the reaction between CO, water, arylnitro compound, Se as catalyst and triethylamine or inorganic alkali as cocatalyst in solvent in sealed high-pressure reactor at 90-200 deg.C for 0.5-10 hr. Its advantages are simple operation, high selectivity, and less pollution.
Description
Technical field
The present invention relates to aromatic amine compounds, relate in particular to a kind of method of utilizing carbon monoxide and water to pass through selenium catalytic reduction 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 (document 1, Tafesh A M, Weiguny J.AReview of the Selecivity Catalytic Reduction of Aromatic Nitro Compoundsinto Aromatic Amines Isocyanates, Carbamates and Ureas Using CO.J ChemRev, 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 been found that, under the condition of gentleness, cheap nonmetal selenium can some reactions that utilize carbon monoxide to carry out of catalysis, and with synthesizing of this success some the compound such as the (documents 2: Yang Ying such as asymmetrical substitute urea compound and benzoglyoxaline ketone compounds of economic worth are arranged very much, Lu Shiwei, Chinese patent application numbers 99113353; Document 3: Yang Ying, Lu Shiwei, Chinese patent application numbers 992113354, document 4: Xue Yan, Lu Shiwei, Chinese patent application number 01103688.5; Document 5: Xue Yan, Lu Shiwei, Chinese patent application number 01113966.8).Have under than low reaction temperatures (80 ℃), selenium/carbon monoxide/aqueous systems is used to go back report (the document 6:T Miyata of original aromatic nitro compound system arylamine, K Kondo, S Murai, T Hirashima and N Sonoda.Selenium-CatalyzedReduction of Aromatic Nitro Compounds to Amines by CO/H2O in thePresence of Triethylamine.Angew Chem Int Ed Engl, 1980,19 (12): 1008), good by the time in the productive rate, but must use triethylamine to make promotor.
Summary of the invention
The object of the present invention is to provide the method for a kind of reaction conditions gentleness, catalytic reduction synthesizing arylamine compound that cost is low.
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, triethylamine or mineral alkali are promotor, or do not add any promotor, and in organic solvent, in the autoclave of sealing, react, be that amino prepares corresponding aromatic amine compound with nitroreduction; 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: 30; The mole dosage of selenium is the 0.5-20% of reactant aromatic nitro compound; The mole dosage of triethylamine or mineral alkali is the 0-200% of reactant aromatic nitro compound; Reaction times is 0.5-10 hour; Temperature of reaction is 90-200 ℃; The reaction of carbon monoxide original pressure is gauge pressure 1-5MPa;
Wherein, be alkyl, alkoxyl group etc. to electron substituent group in the described reactant aromatic nitro compound, electron-withdrawing substituent is the chlorine that directly links to each other with aromatic ring, fluorine, bromine, trifluoromethyl, alkyloyl etc., and the above alkyl, alkoxyl group and alkyloyl are carbon number smaller or equal to 5 alkyl, alkoxyl group and alkyloyl; Described mineral alkali is sodium hydroxide and/or potassium hydroxide and/or yellow soda ash; Describedly do not add any promotor and be meant and only make catalyzer and need not add other material can react as promotor with selenium; Described carbon monoxide can use the industrial carbon monoxide tail gas that contains air, nitrogen, carbonic acid gas and/or water vapour, and wherein the content sum of nitrogen, carbonic acid gas and/or water vapour is smaller or equal to 10% of cumulative volume, and air content is smaller or equal to 1% of cumulative volume; Wherein said organic solvent is one or more polarity and/or nonpolar inert solvent; Described polar solvent is toluene, tetrahydrofuran (THF) or acetone, and non-polar solvent is normal hexane or benzene.
The present invention has following advantage:
1, 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, and investment goods is few, easily operation.
2, 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.
3, 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.
4, good economy performance.Reaction preference height of the present invention, to adopt nonmetal selenium be catalyzer can reach more than 99% the reduction selectivity of nitro, and sensitive group such as halogen, alkyloyl 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.
5, 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 the homogeneous catalyzed reaction in reaction process, after reaction ends, catalyzer is separated out with the solid phase selenium powder again, very easily separates with product.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 stainless steel autoclave of 100ml, add oil of mirbane (10mmol), Se (0.2mmol), H
2O (35mmol), triethylamine (20mmol) and solvents tetrahydrofurane (15ml), with after the carbon monoxide displacement for several times carbon monoxide pressure being risen to 3MPa, put it into the interior stirring reaction of the oil bath pan that rises to 90 ℃ 3 hours, be cooled to room temperature, open still, aerating oxygen stirs 0.5-1 hour (also can open still stirs) in air after, filter out selenium powder, to filter after gained filtrate concentrates, carry out assay with gas-chromatography, aniline chromatogram yield be 99% (in oil of mirbane).Assay adopts the HP-4890D gas chromatography system, comprises fid detector, and (30m * 0.32mm * 1.5um), temperature of vaporization chamber is 280 ℃, column temperature: 150 ℃, external standard method is quantitative for the SE-54 capillary column.
Embodiment 2
Aromatic nitro compound is an o-chloronitrobenzene, and other experimental technique and condition are with embodiment 1, and it is 68% (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 98% (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 55% (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, 120 ℃ of oil bath temperatures, and other experimental technique and condition are with embodiment 1, and it is 30% (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 35% (in p-fluoronitrobenzene) that gas Chromatographic Determination gets the para-fluoroaniline yield.
Embodiment 9
The triethylamine consumption is 1mmol, and oil bath temperature is 150 ℃, and other experimental technique and condition are with embodiment 1, and it is 70% (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 triethylamine, oil bath temperature is 180 ℃, and other experimental technique and condition are with embodiment 1, and it is 43% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 12
The water yield is 0.3mol, and other experimental technique and condition are with embodiment 11, and it is 76% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 13
Oil bath temperature is 200 ℃, and other experimental technique and condition are with embodiment 11, and it is 29% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 14
The initial gauge pressure of reaction of carbon monoxide is 5MPa, and other experimental technique and condition are with embodiment 11, and it is 47% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 15
Reaction times is 10 hours, and other experimental technique and condition are with embodiment 11, and it is 90% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 16
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 17
Solvent is a normal hexane, and other experimental technique and condition are with embodiment 11, and it is 19% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 18
Solvent is a toluene, and other experimental technique and condition are with embodiment 11, and it is 26% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 19
Yellow soda ash 10mmol, other experimental technique and condition are with embodiment 11, and it is 75% (in oil of mirbane) that gas Chromatographic Determination gets aniline yield rate.
Embodiment 20
Aromatic nitro compound is a para-methylnitrobenzene, sodium hydroxide 10mmol, and other experimental technique and condition are with embodiment 11, and gas Chromatographic Determination must be 93% (in para-methylnitrobenzene) to the monomethylaniline yield.
Embodiment 21
Aromatic nitro compound is a m-trifluoromethyl oil of mirbane, potassium hydroxide 20mmol, and the reaction times is 3 hours, and other experimental technique and condition are with embodiment 11, and it is 98% (in m-trifluoromethyl oil of mirbane) that gas Chromatographic Determination gets the m-trifluoromethyl aniline yield rate.
Claims (9)
1, a kind of method of synthesizing arylamine compound, it is characterized in that: in the presence of carbon monoxide and water, with the aromatic nitro compound is raw material, selenium is catalyzer, in organic solvent, in the autoclave of sealing, react, with nitroreduction is that amino prepares corresponding aromatic amine compound, and reaction ends, and catalyzer separates with product; 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: 30
The mole dosage of selenium is the 0.5-20% of aromatic nitro compound;
Reaction times is 0.5-10 hour;
Temperature of reaction is 90-200 ℃;
The reaction of carbon monoxide original pressure is gauge pressure 1-5MPa.
2, according to the method for the described synthesizing arylamine compound of claim 1, it is characterized in that: with triethylamine or mineral alkali is promotor.
3, according to the method for the described synthesizing arylamine compound of claim 2, it is characterized in that: the mole dosage of described promotor is the 0-200% of aromatic nitro compound.
4, according to the method for the described synthesizing arylamine compound of claim 1; it is characterized in that: be alkyl, alkoxyl group to electron substituent group in the described reactant aromatic nitro compound, electron-withdrawing substituent is fluorine, chlorine, bromine, trifluoromethyl, the alkyloyl that directly links to each other with aromatic ring.
5, according to the method for claim 1 or 4 described synthesizing arylamine compounds, it is characterized in that: described alkyl, alkoxyl group and alkyloyl are carbon number smaller or equal to 5 alkyl, alkoxyl group and alkyloyl.
6, according to the method for the described synthesizing arylamine compound of claim 2, it is characterized in that: described mineral alkali is one or more in sodium hydroxide, potassium hydroxide or the yellow soda ash.
7, according to the method for the described synthesizing arylamine compound of claim 1, it is characterized in that: wherein said carbon monoxide uses the industrial carbon monoxide tail gas that contains air, 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 10% of cumulative volume, and air content is less than 1%.
8, according to the method for the described synthesizing arylamine compound of claim 1, it is characterized in that: wherein said organic solvent is one or more polarity and/or nonpolar inert solvent.
9, according to the method for the described synthesizing arylamine compound of claim 6, it is characterized in that: described polar solvent is toluene, tetrahydrofuran (THF) or acetone, and non-polar solvent is normal hexane or benzene.
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| CN 02107742 CN1445213A (en) | 2002-03-20 | 2002-03-20 | Method for synthesizing arylamine compound |
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| CN 02107742 CN1445213A (en) | 2002-03-20 | 2002-03-20 | Method for synthesizing arylamine compound |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312119C (en) * | 2004-04-29 | 2007-04-25 | 中国科学院大连化学物理研究所 | Process for synthesizing aryl substituted N-aryl amide compounds |
| CN102173999A (en) * | 2011-02-28 | 2011-09-07 | 盐城工学院 | Method for synthesizing 2-amino-N,N-dimethylbenzamide |
| CN102173993A (en) * | 2011-03-09 | 2011-09-07 | 南通市天时化工有限公司 | Method for synthesizing 4,6-diamino resorcinol dihydrochloride (DAR) |
| 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 |
-
2002
- 2002-03-20 CN CN 02107742 patent/CN1445213A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312119C (en) * | 2004-04-29 | 2007-04-25 | 中国科学院大连化学物理研究所 | Process for synthesizing aryl substituted N-aryl amide compounds |
| CN102173999A (en) * | 2011-02-28 | 2011-09-07 | 盐城工学院 | Method for synthesizing 2-amino-N,N-dimethylbenzamide |
| CN102173993A (en) * | 2011-03-09 | 2011-09-07 | 南通市天时化工有限公司 | Method for synthesizing 4,6-diamino resorcinol dihydrochloride (DAR) |
| CN102173993B (en) * | 2011-03-09 | 2013-10-09 | 江苏九九久科技股份有限公司 | Method for synthesizing 4,6-diamino resorcinol dihydrochloride (DAR) |
| 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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