CN108191673A - The method of the Synthesis liquid processing of right/o-trifluoromethyl aniline - Google Patents
The method of the Synthesis liquid processing of right/o-trifluoromethyl aniline Download PDFInfo
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- CN108191673A CN108191673A CN201810165932.XA CN201810165932A CN108191673A CN 108191673 A CN108191673 A CN 108191673A CN 201810165932 A CN201810165932 A CN 201810165932A CN 108191673 A CN108191673 A CN 108191673A
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- trifluoromethyl aniline
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
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Abstract
The invention discloses the method that a kind of Synthesis liquid of right/o-trifluoromethyl aniline is handled, the synthesis treatment fluid is：Under stannous chloride/potassium fluoride effect, the Synthesis liquid of Study on Catalytic Amination of Alcohols synthesis pair/o-trifluoromethyl aniline includes the following steps right/chlorobenzotrifluoride:After the Synthesis liquid decompression heating removing solvent after amination, most of free ammonia is also stripped of simultaneously, through first step separation of solid and liquid, after the most of stannous chloride of removing, potassium fluoride and by-product ammonium chloride, calcium hydroxide is added in filtrate, stirring heating under negative pressure, after heat preservation, is cooled to room temperature, add in flocculant, stirring, press filtration, the direct rectification under vacuum of filtrate.Good product quality of the present invention, simple process, product yield are high.
Description
Technical field
At a kind of Synthesis liquid of right/chlorobenzotrifluoride Study on Catalytic Amination of Alcohols synthesis pair/o-trifluoromethyl aniline
The process of reason.
Background technology
Right/o-trifluoromethyl aniline is a kind of important medicine, pesticide intermediate, and p-trifluoromethylaniline is in terms of medicine
It can be used for synthesizing the synthesis of the drugs such as diabetes, skin disease, rheumatism inflammation, domestic existing product is treatment rheumatism at present
Specific drug leflunomide for the synthesis of the Multiple Pesticides such as insecticide, fungicide, herbicide in terms of pesticide, is such as used for fluorine amine
The synthesis of the pesticides such as Cyano chrysanthemate, ethiprole, penfluron, fluazinam, benfluralin.O-trifluoromethyl aniline can be used for synthetic hydrochloric acid
The drugs such as Mefloquine, Mabuterol Hydrochloride, pesticide such as fungicide flutolanil, new material aspect can synthesize fluorine-containing anline resin.
As green chemical technology and newtype drug, new material research deepen continuously, the new purposes of right/o-trifluoromethyl aniline is not by
Disconnection issues, and is very promising chemical products.
The synthetic method of right/o-trifluoromethyl aniline has pair/chlorobenzotrifluoride direct aminatin method, right/adjacent nitro trifluoro
The methods of toluene reduction method, trifluoromethyl phenylisocyanate fluoride process.Right/adjacent nitro benzotrifluoride method needs first to obtain pair/and it is adjacent
Nitro-trifluoromethyl toluene, preparation process need that, by nitrification, a large amount of spent acid can be generated, isomers is more；Trifluoromethylbenzene isocyanic acid
The raw material of ester fluoride process can be raw material with open-chain crown ether, thang-kng gas is generated to three chloromethanes to trichloromethyl phenylisocyanate
Base chloromethane anilide, further generation is to trichloromethyl phenylisocyanate, complex process, in the market to trifluoromethylbenzene isocyanic acid
Ester number lattice are higher than p-trifluoromethylaniline.It is current produce in enormous quantities pair/o-trifluoromethyl aniline mostly using pair/adjacent chlorine fluoroform
Benzene is catalyst in stannous chloride/potassium fluoride, at 150~240 DEG C, under the conditions of 5.0~15.0MPa, using ammonia or ammonium hydroxide as amination
Agent carries out Study on Catalytic Amination of Alcohols, after the Synthesis liquid after amination filters off catalyst and ammonium chloride, also containing a large amount of copper ions, fluorine in filtrate
Ion, if do not removed, in rear workshop section's rectifying, right/o-trifluoromethyl aniline can react, and influence rectification and purification, need
With ammonia scrubbing, so as to generate a large amount of waste water.Therefore copper ion, fluorine ion are isolated using other processing methods, prevents or subtract
The generation of few waste water is the requirement of environmentally protective production.
Invention content
The present invention provides a kind of such as right/chlorobenzotrifluoride, under stannous chloride/potassium fluoride effect, Study on Catalytic Amination of Alcohols synthesis
The process of the Synthesis liquid processing of right/o-trifluoromethyl aniline, also may be used as stannous chloride/potassium fluoride etc. as catalyst
Other organic syntheses as reference.
The technical scheme is that：It (while will also be removed after Synthesis liquid decompression heating removing solvent after amination
Most of free ammonia), through first step separation of solid and liquid (such as press filtration, centrifugation), remove most of stannous chloride, potassium fluoride and by-product
After object ammonium chloride, calcium hydroxide is added in filtrate, under negative pressure stirring heating, after keeping the temperature one hour, be cooled to room temperature, added in
Flocculant, stir one hour, press filtration, filtrate can direct rectifying, without again use ammonia scrubbing, effect is suitable with ammonia scrubbing,
It is generated in the process without waste water, meanwhile, free ammonia content reduces in Synthesis liquid that treated, and the exhaust gas generated in distillation process is greatly
It reduces.Correlated response equation is as follows：
2KF+Ca(OH)2=2KOH+CaF2
2Cu(NH3)2Cl+Ca(OH)2=Cu2O+CaCl2+4NH3+H2O
2Cu(NH3)4Cl+Ca(OH)2=2CuO+CaCl2+NH3+H2O
In the present solution, added calcium hydroxide is solid powder, addition is Synthesis liquid pH value to 12~13.
In the present solution, added flocculant is cationic polyacrylamide (CPAM), 0.1%~0.3% solution is configured to, is added
Enter amount and add in 1~10 kilogram of 0.1%~0.3%CPAM solution for Synthesis liquid per ton.
In the present solution, holding temperature is 50~80 DEG C, cooling press filtration temperature is room temperature.
Good product quality of the present invention, simple process, product yield are high.
With reference to embodiment, the invention will be further described.
Specific embodiment
Example one
1000ml autoclaves add in chlorobenzotrifluoride 250g, ethyl alcohol 200g, water 30g, potassium fluoride 40g, stannous chloride
30g, fastening high kettle cover open stirring, are passed through liquefied ammonia 120g, are warming up to 180 DEG C, keep the temperature 12 hours, are cooled to 50 DEG C, venting
Excess ammonia (is absorbed) with water, Synthesis liquid air-distillation, and control liquidus temperature is less than 100 DEG C, until after gas phase is without steaming, raffinate cooling
It to 40~50 DEG C, filters, filtrate adds 6.5% ammonium hydroxide 250ml to wash, and stands split-phase, and upper strata is navy blue water phase, and lower floor is brown
Organic phase.After split-phase, organic phase 162g is obtained (containing chlorobenzotrifluoride 49.2%, o-trifluoromethyl aniline 44.8%, ethyl alcohol
0.9% (GC)；Ammonia 3.2% (titration)；Water 1.2% (Karl_Fischer method), similarly hereinafter), add KOH5g, rectification under vacuum obtains adjacent trifluoro
Methylaniline 62.1g, GC detection level 99.15%, rectifying yield 87.8%.Distillation process is steady, and it is residual that kettle is generated after rectifying
10.2g。
Example two
1000ml autoclaves add in p-chloro benzo trifluoride-99 250g, ethyl alcohol 200g, water 30g, potassium fluoride 40g, stannous chloride
30g, fastening high kettle cover open stirring, are passed through liquefied ammonia 120g, are warming up to 180 DEG C, keep the temperature 12 hours, are cooled to 50 DEG C, venting
Excess ammonia (is absorbed) with water, Synthesis liquid air-distillation, and control liquidus temperature is less than 100 DEG C, until after gas phase is without steaming, raffinate cooling
It to 40~50 DEG C, filters, obtains filtrate 168g (containing p-chloro benzo trifluoride-99 47.6%, p-trifluoromethylaniline 46.4%, ethyl alcohol
1.2%；Ammonia 0.8%；Water 0.9%), add KOH5g, rectification under vacuum obtains p-trifluoromethylaniline 41.2g, GC detection level
98.45%, rectifying yield 52.29%, rectifying product has acid mist generation.Rectifying latter temperature drastically increases, and material decomposes, and generates
Yellow flue gas, the residual 36.8g of rectifying still.
Example three
1000ml autoclaves add in p-chloro benzo trifluoride-99 250g, ethyl alcohol 200g, water 30g, potassium fluoride 40g, stannous chloride
30g, fastening high kettle cover open stirring, are passed through liquefied ammonia 120g, are warming up to 180 DEG C, keep the temperature 12 hours, are cooled to 50 DEG C, venting
Excess ammonia (is absorbed) with water, Synthesis liquid air-distillation, and control liquidus temperature is less than 100 DEG C, until after gas phase is without steaming, raffinate cooling
It to 40~50 DEG C, filters, filtrate adds 6.5% ammonium hydroxide 250ml to wash, and stands split-phase, and upper strata is navy blue water phase, and lower floor is brown
Organic phase.After split-phase, organic phase 163g is obtained (containing p-chloro benzo trifluoride-99 47.6%, p-trifluoromethylaniline 45.2%, ethyl alcohol
0.8%；Ammonia 3.5%；Water 1.1%), add KOH5g, rectification under vacuum obtains o-trifluoromethyl aniline 62.8g, GC detection level
99.17%, rectifying yield 88.61%.Distillation process is steady, and the residual 11.2g of kettle is generated after rectifying.
Example four
1000ml autoclaves add in p-chloro benzo trifluoride-99 250g, ethyl alcohol 200g, water 30g, potassium fluoride 40g, stannous chloride
30g, fastening high kettle cover open stirring, are passed through liquefied ammonia 120g, are warming up to 180 DEG C, keep the temperature 12 hours, are cooled to 50 DEG C, venting
Excess ammonia (is absorbed) with water, Synthesis liquid air-distillation, and control liquidus temperature is less than 100 DEG C, until after gas phase is without steaming, raffinate cooling
It to 40~50 DEG C, filters, obtains filtrate 170g (containing p-chloro benzo trifluoride-99 48.4%, p-trifluoromethylaniline 45.8%, ethyl alcohol
1.1%；Ammonia 0.9%；Water 1.1%), filtrate is added to 500ml four-hole bottles, and four-hole bottle dress pH meter (thunder magnetic PHSJ-3F) adds hydrogen-oxygen
Change calcium powder 4g, vacuumize, be warming up to 70 DEG C, pH value 11.52 adds calcium hydroxide 1g, pH value 12.38.After heat preservation one hour,
30 DEG C are cooled to, adds in 0.3%CPAM solution 2ml, insulated and stirred one hour filters, and obtains light brown filtrate 165g and (contains to chlorine three
Toluene fluoride 48.2%, p-trifluoromethylaniline 46.1%, ethyl alcohol 0.8%；Ammonia 0.6%；Water 0.9%), 10ml filtrates is taken to add
6.5% ammonium hydroxide shakes 5 minutes, and stratification, upper strata aqueous phase achromaticity and clarification is transparent, and organic phase is incorporated in filtrate after split-phase.It is above-mentioned
Filtrate adds KOH5g, rectification under vacuum, obtains p-trifluoromethylaniline 61.5g, GC detection level 99.21%, rectifying yield 88.73%,
Distillation process is steady, and product is distributed without acid mist, the residual 10.5g of rectifying still.
Example five
1000ml autoclaves add in chlorobenzotrifluoride 250g, ethyl alcohol 200g, water 30g, potassium fluoride 40g, stannous chloride
30g, fastening high kettle cover open stirring, are passed through liquefied ammonia 120g, are warming up to 180 DEG C, keep the temperature 12 hours, are cooled to 50 DEG C, venting
Excess ammonia (is absorbed) with water, Synthesis liquid air-distillation, and control liquidus temperature is less than 100 DEG C, until after gas phase is without steaming, raffinate cooling
It to 40~50 DEG C, filters, filtrate is added to 500ml four-hole bottles, and four-hole bottle dress pH meter (thunder magnetic PHSJ-3F) adds calcium hydroxide powder
Last 5g, vacuumizes, and is warming up to 70 DEG C, pH value 12.62.After heat preservation one hour, 30 DEG C are cooled to, adds in 0.3%CPAM solution
2ml, insulated and stirred one hour filter, and obtain light brown filtrate 138g (containing chlorobenzotrifluoride 43.8%, o-trifluoromethyl aniline
51.2%, ethyl alcohol 0.6%；Ammonia 1.2%；Water 1.3), take 10ml filtrates that 6.5% ammonium hydroxide is added to shake 5 minutes, stratification, upper strata
Water phase achromaticity and clarification is transparent, and organic phase is incorporated in filtrate after split-phase.Above-mentioned filtrate adds KOH5g, and rectification under vacuum obtains o-trifluoromethyl
Aniline 62.1g, GC detection level 99.08%, rectifying yield 87.3%, distillation process is steady, and product is distributed without acid mist, rectifying still
Residual 9.8g.
Claims (4)
1. a kind of method of the Synthesis liquid processing of right/o-trifluoromethyl aniline, the synthesis treatment fluid are：Right/adjacent chlorine fluoroform
Benzene is under stannous chloride/potassium fluoride effect, the Synthesis liquid of Study on Catalytic Amination of Alcohols synthesis pair/o-trifluoromethyl aniline, it is characterized in that：Including
Following steps:
After the Synthesis liquid decompression heating removing solvent after amination, while most of free ammonia is also stripped of, through the first step
Separation of solid and liquid after removing most of stannous chloride, potassium fluoride and by-product ammonium chloride, adds in calcium hydroxide, negative in filtrate
Pressure stirring heating, after heat preservation, is cooled to room temperature, adds in flocculant, stirring, press filtration, the direct rectification under vacuum of filtrate.
2. the method for the Synthesis liquid processing of right/o-trifluoromethyl aniline according to claim 1, it is characterized in that：Added hydrogen
Calcium oxide is solid powder, and addition is makes Synthesis liquid pH value to 12 ~ 13.
3. the method for the Synthesis liquid processing of right/o-trifluoromethyl aniline according to claim 1, it is characterized in that：Added wadding
Solidifying agent is cationic polyacrylamide, is configured to 0.1% ~ 0.3% solution, and addition adds in 0.1% ~ 0.3% sun for Synthesis liquid per ton
1 ~ 10 kilogram of cationic polyacrylamide solution.
4. the method for the Synthesis liquid processing of right/o-trifluoromethyl aniline according to claim 1, it is characterized in that：Heat preservation temperature
It is 50 ~ 80 DEG C to spend, and cooling press filtration temperature is room temperature.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110416263A (en) * | 2019-07-22 | 2019-11-05 | 深圳市华星光电半导体显示技术有限公司 | A kind of display panel and preparation method thereof |
| CN112676307A (en) * | 2020-12-11 | 2021-04-20 | 江苏优普生物化学科技股份有限公司 | Method for reducing and recycling catalyst residues |
| US11985859B2 (en) | 2019-07-22 | 2024-05-14 | Shenzhen China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Display panel and method for fabricating same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847215A (en) * | 2006-05-15 | 2006-10-18 | 南通市东昌化工有限公司 | Production process of o-trifluoromethyl aniline |
| CN102643202A (en) * | 2012-04-09 | 2012-08-22 | 南通市东昌化工有限公司 | Production method of p-trifluoromethylaniline |
-
2018
- 2018-02-28 CN CN201810165932.XA patent/CN108191673A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847215A (en) * | 2006-05-15 | 2006-10-18 | 南通市东昌化工有限公司 | Production process of o-trifluoromethyl aniline |
| CN102643202A (en) * | 2012-04-09 | 2012-08-22 | 南通市东昌化工有限公司 | Production method of p-trifluoromethylaniline |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110416263A (en) * | 2019-07-22 | 2019-11-05 | 深圳市华星光电半导体显示技术有限公司 | A kind of display panel and preparation method thereof |
| US11985859B2 (en) | 2019-07-22 | 2024-05-14 | Shenzhen China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Display panel and method for fabricating same |
| CN112676307A (en) * | 2020-12-11 | 2021-04-20 | 江苏优普生物化学科技股份有限公司 | Method for reducing and recycling catalyst residues |
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Application publication date: 20180622 |