CN103408436A - Method for preparing p-trifluoromethylaniline by performing high pressure ammonolysis - Google Patents
Method for preparing p-trifluoromethylaniline by performing high pressure ammonolysis Download PDFInfo
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- CN103408436A CN103408436A CN2013103859262A CN201310385926A CN103408436A CN 103408436 A CN103408436 A CN 103408436A CN 2013103859262 A CN2013103859262 A CN 2013103859262A CN 201310385926 A CN201310385926 A CN 201310385926A CN 103408436 A CN103408436 A CN 103408436A
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Abstract
The invention relates to a new method for preparing p-trifluoromethylaniline by performing high pressure ammonolysis. P-trifluoromethyl chlorobenzene serving as a raw material is subjected to high-temperature high pressure ammonolysis reaction in a solvent under the action of a catalyst, liquid ammonia and an acid-binding agent to generate p-trifluoromethyl phenylamine; the catalyst is a mixture of cuprous chloride and copper powder; the acid-binding agent is one or two of inorganic base mixtures of sodium hydroxide and the like, or one or two of organic base mixtures of pyridine and triethylamine; and the solvent is one or two of mixing solvents of methanol, ethanol, polyethylene glycol 300-3,000 and N,N-dimethylformamide. The method has the advantages that the inorganic base, serving as the acid-binding agent, with low cost and easy availability is adopted, the loss of liquid ammonia in the reaction process is greatly reduced, and the production efficiency is improved; and the catalyst can be prepared from organic solvents with the cost as low as that of ethanol and less harm, so that the generation of hydrolysis side reaction is avoided, the purity of the product is high and the quality is high; and raw materials without being totally reacted can be recycled.
Description
Technical field
The present invention relates to a kind of method that high pressure ammonia solution prepares p-trifluoromethylaniline, belong to the chemical material preparing technical field.Present method is applicable to take p-chloro benzo trifluoride-99 as raw material, under the effect of catalyzer, liquefied ammonia and acid binding agent, in solvent, carries out the occasion that the high pressure ammonia solution prepares p-trifluoromethylaniline.
Background technology
P-trifluoromethylaniline (p-trifluromethylaniline, be abbreviated as PTFMA, and the CAS accession number is 455-14-1) is a kind of important industrial chemicals, particularly agricultural chemicals and medical aspect application very extensive.P-trifluoromethylaniline can obtain 2 through superchlorination, the 6-dichloro is to 5 amido benzotrifluoride, it is a kind of important intermediate, on pesticide industry for the synthesis of high-efficient low toxicity insecticide ethiprole (Frontline), taufluvalinate, penfluron, weedicide benfluralin, ethalfluralin etc., on medicine industry for the synthesis of neotype immunosuppressant medicine leflunomide etc.Along with deepening continuously of green chemical industry technology and newtype drug research, new purposes is developed continuously, and oneself is through becoming important promising Chemicals.
The synthetic method of p-trifluoromethylaniline is a lot, main method has so far, p-chloro benzo trifluoride-99 ammonia solution prepares the method for p-trifluoromethylaniline, the nitro benzyl chloride is reacted to the method for post chlorization, fluorine replacement, reduction with sulfide, to the method that methyl isocyanate chlorination, fluorine replace, hydrolysis generates p-trifluoromethylaniline, the aniline of take is starting raw material, by with bromotrifluoromethane, reacting the method that generates p-trifluoromethylaniline.
(1) nitro-trifluoromethyl toluene is reduced.Adopt SnCl
2-HCl and H
2It is the method for using the earliest that/Raney-Ni catalytic reduction prepares PTFMA to nitro-trifluoromethyl toluene.But, to nitro-trifluoromethyl toluene, be not allow facilely, be subject to, to nitro-trifluoromethyl toluene or to the restriction in nitrotrichloromethane benzene raw materials source, being difficult to carry out large-scale production.
(2) the direct ammonia solution of aromatic compound has just obtained people's extensive concern in the 30's of 20th century, has all obtained gratifying achievements in theory research and production application.The ammonia solution agent that the ammonia solution adopts can be liquefied ammonia, ammoniacal liquor, be dissolved in ammonia, the gaseous ammonia in organic solvent or the ammonia of being emitted in reaction by urea or ammonium salt.
With ammonia or liquefied ammonia, with the trifluoromethyl muriate, react and produce PTFMA and muriate is also a kind of method that meets the requirement of Modern Green Chemistry Atom economy.But in actual production, because hydrolysis reaction occurs the C on trifluoromethyl-F key easy fracture, so there are many problems in the ammonia solution technique of p-chloro benzo trifluoride-99.For example with CaO-CuCl, making the catalyzer p-chloro benzo trifluoride-99 reacts with ammoniacal liquor, when obtaining PTFMA, hydrolysis reaction occurs and obtain some by products (Hasek W R, Smith W C, Engelthardt V A. The Chemistry of Sulfur Tetrafluoride-The Fluorination of Organic Carbonyl Compounds. Journal of the American Chemical Society, 1960,82:543-548.).Therefore, in the production process of this technique, generally select organic solvent, to avoid the generation of hydrolytic side reactions, the selection by solvent and catalyzer improves reactive behavior.U.S. Pat 4096185 proposes take cuprous chloride and Potassium monofluoride is catalyzer, generates p-trifluoromethylaniline by high-temperature high-voltage reaction.CuCl-KF makes the transformation efficiency that catalyzer has greatly improved reaction.But in this reaction, also have the generation of p-aminophenyl formonitrile HCN by product, and catalyzer is difficult to apply mechanically, shared production cost is too high.
(3) hydrazinolysis reduction method.U.S. Pat 6479703 discloses from p-chloro benzo trifluoride-99, with hydrazine hydrate, reacts and generates accordingly to trifluoromethyl phenyl hydrazine, then uses Pd/C, and the catalyzer hydrogenolysis reducings such as RaneyNi obtain corresponding PTFMA.But the hydrazinolysis reaction is carried out in autoclave, autoclave is had to corrosion, and hydrazine hydrate easy the decomposition, causes the loss of raw material under the existence of metal ion.
(4) aniline trifiuoroniethylation.The method is to utilize arylamine and trifluoromethyl free radical to react to prepare the purpose product.Report that maximum is CF3I, under the condition of illumination or heating, occur to generate the trifluoromethyl free radical from separating, then trifluoromethyl free radical and the substitution reaction of aromatic ring generation free radical generate object (Martin A M C, Deborh A M C. Trifluoromethylation Related Reactions In Organic Chemistr. Tetrahedron, 1992,48 (32): 6585-6594.).The PTFMA generated in reaction and the mixture of o-trifluoromethyl aniline, the transformation efficiency of reaction is lower, and the cost of trifluoromethyl reagent is too high.
(5) the nitro benzyl chloride is reacted with sulfide to post chlorization, fluorine replace, the method for reduction is also a method, 4783562 pairs of systematic introductions of the method for U.S. Pat, but at first the method does not preponderate on cost, simultaneous reactions generates the muriate of hypertoxic sulphur, aftertreatment difficulty.
Summary of the invention
Technical barrier to be solved by this invention is, the deficiencies in the prior art, provide a kind of high pressure ammonia solution to prepare the novel method of p-trifluoromethylaniline, and the method production cost is low, yield is high, and product purity is high, unreacted raw material recoverable.
Technical solution of the present invention is yes, and the p-chloro benzo trifluoride-99 of take is raw material, under the effect of catalyzer, liquefied ammonia and acid binding agent, in solvent, carries out the High Temperature High Pressure ammonolysis reaction, generates p-trifluoromethylaniline.
Described catalyzer is the mixture of cuprous chloride and copper powder.Wherein the mass ratio of cuprous chloride and copper powder is 1:0.06 ~ 0.6, wherein preferred 1:0.1 ~ 0.4.
Described acid binding agent is mineral alkali or organic bases.Wherein, mineral alkali is any one or two kinds of and above mixture in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus; Organic bases is any one or two kinds of mixture in pyridine, triethylamine.
Described solvent is any one or two kinds of and above mixed solvent in methyl alcohol, ethanol, Liquid Macrogol ~ 3000, DMF.
The mass fraction of the present invention's material used is:
100 parts of p-chloro benzo trifluoride-99s;
30 ~ 80 parts, liquefied ammonia, wherein be preferably 50 ~ 70 parts;
200 ~ 500 parts of solvents, wherein be preferably 300 ~ 400 parts;
1 ~ 12 part of catalyzer;
10 ~ 45 parts of acid binding agents, wherein be preferably 20 ~ 30 parts.
The processing parameter of ammonolysis reaction of the present invention is, temperature is 180 ~ 220 ℃, and pressure is 8 ~ 11MPa, and the reaction times is 8 ~ 14h.
The chemical reaction flow process of institute of the present invention foundation is as follows:
According to a kind of high pressure ammonia solution provided by the invention, prepare the method for p-trifluoromethylaniline, its key problem in technology is under the effect of catalyzer, liquefied ammonia and acid binding agent, in solvent, carries out the high pressure ammonia solution p-chloro benzo trifluoride-99 is converted into to p-trifluoromethylaniline.The present invention compared with prior art advantage is: (1) adopts mineral alkali cheap and easy to get to make acid binding agent, greatly reduce the loss of liquefied ammonia in reaction process, can play the effect of concerted catalysis again, overcome in current p-trifluoromethylaniline ammonia solution process per pass conversion low, the defect of the deficiency of catalyst utilization, improved production efficiency; (2) used catalyst can with ethanol etc. cheap, the less organic solvent of environmental hazard is formed to catalyst system, can avoid the generation of hydrolytic side reactions, and there is no the generation of p-aminophenyl formonitrile HCN by product, product purity is high, quality good; (3) unreacted raw materials recovery recycle is convenient, has reduced production cost, and the requirement of compound cycle economy, have good industrial applications prospect.
Embodiment
The present invention is described in detail in detail by the following examples, and these embodiment only are clear open the present invention, but not as limitation of the present invention.
Embodiment 1
In the 3L autoclave, add the 300g p-chloro benzo trifluoride-99,25g cuprous chloride, 10g copper powder, 90g sodium carbonate, 900g Liquid Macrogol, sealing autoclave, after logical nitrogen replacement three times, pass into 150g liquefied ammonia in autoclave, then be warming up to 200 ℃, pressure is 10MPa, at this temperature, react 10h, remove by filter insoluble solids, the rectifying of gained liquid pressure-reducing after then being cooled to room temperature, obtain the unreacted raw material p-chloro benzo trifluoride-99 of 150g, and 102g product p-trifluoromethylaniline.Unreacted raw material can reclaim, and recycles.
Embodiment 2
In the 3L autoclave, add the 300g p-chloro benzo trifluoride-99,25g cuprous chloride, 10g copper powder, the 90g sodium bicarbonate, 900g ethanol, sealing autoclave, after logical nitrogen replacement three times, in autoclave, pass into 150g liquefied ammonia, then be warming up to 200 ℃, pressure is 10MPa, at this temperature, react 12h, then after being cooled to room temperature, remove by filter insoluble solids, the rectifying of gained liquid pressure-reducing obtains the 158g p-chloro benzo trifluoride-99, the 92g p-trifluoromethylaniline.
Embodiment 3
In the 3L autoclave, add the 300g p-chloro benzo trifluoride-99,2.5g cuprous chloride, 0.5g copper powder, 60g sodium hydroxide, 600g methyl alcohol, sealing autoclave, after logical nitrogen replacement three times, in autoclave, pass into 240g liquefied ammonia, then be warming up to 210 ℃, pressure is 11MPa, at this temperature, react 12h, then after being cooled to room temperature, remove by filter insoluble solids, the rectifying of gained liquid pressure-reducing obtains the 155g p-chloro benzo trifluoride-99, the 95g p-trifluoromethylaniline.
Embodiment 4
In the 3L autoclave, add the 300g p-chloro benzo trifluoride-99,2.5g cuprous chloride, 1.0g copper powder, 30g potassium hydroxide, 600g ethanol, sealing autoclave, after logical nitrogen replacement three times, in autoclave, pass into 190g liquefied ammonia, then be warming up to 220 ℃, pressure is 10MPa, at this temperature, react 8h, then after being cooled to room temperature, remove by filter insoluble solids, the rectifying of gained liquid pressure-reducing obtains the 156g p-chloro benzo trifluoride-99, the 95g p-trifluoromethylaniline.
Embodiment 5
In the 3L autoclave, add the 300g p-chloro benzo trifluoride-99,25g cuprous chloride, 1.5g copper powder, 135g salt of wormwood, 1500g ethanol, sealing autoclave, after logical nitrogen replacement three times, in autoclave, pass into 90g liquefied ammonia, then be warming up to 200 ℃, pressure is 10MPa, at this temperature, react 8h, then after being cooled to room temperature, remove by filter insoluble solids, the rectifying of gained liquid pressure-reducing obtains the 150g p-chloro benzo trifluoride-99, the 102g p-trifluoromethylaniline.
Embodiment 6
In the 3L autoclave, add the 300g p-chloro benzo trifluoride-99,20g cuprous chloride, 12g copper powder, the 100g saleratus, 1200gN, dinethylformamide, after sealing autoclave, logical nitrogen replacement three times, pass into 200g liquefied ammonia in autoclave, then be warming up to 180 ℃, pressure is 8MPa, reacts 14h at this temperature, removes by filter insoluble solids after then being cooled to room temperature, the rectifying of gained liquid pressure-reducing obtains the 152g p-chloro benzo trifluoride-99, the 100g p-trifluoromethylaniline.
Embodiment 7
In the 3L autoclave, add the 300g p-chloro benzo trifluoride-99,15g cuprous chloride, 3g copper powder, the 80g pyridine, 900g Macrogol 3000, sealing autoclave, after logical nitrogen replacement three times, in autoclave, pass into 180g liquefied ammonia, then be warming up to 200 ℃, pressure is 10MPa, at this temperature, react 9h, then after being cooled to room temperature, remove by filter insoluble solids, the rectifying of gained liquid pressure-reducing obtains the 154g p-chloro benzo trifluoride-99, the 97g p-trifluoromethylaniline.
Embodiment 8
In the 3L autoclave, add the 300g p-chloro benzo trifluoride-99,10g cuprous chloride, 4g copper powder, the 80g triethylamine, 900g cetomacrogol 1000, sealing autoclave, after logical nitrogen replacement three times, in autoclave, pass into 160g liquefied ammonia, then be warming up to 200 ℃, pressure is 10MPa, at this temperature, react 13h, then after being cooled to room temperature, remove by filter insoluble solids, the rectifying of gained liquid pressure-reducing obtains the 153g p-chloro benzo trifluoride-99, the 98g p-trifluoromethylaniline.
Embodiment 9
In the 3L autoclave, add the 300g p-chloro benzo trifluoride-99,25g cuprous chloride, 11g copper powder, 50g sodium carbonate, 40g sodium bicarbonate, 900g Polyethylene Glycol-600, after sealing autoclave, logical nitrogen replacement three times, pass into 140g liquefied ammonia in autoclave, then be warming up to 200 ℃, pressure is 10MPa, reacts 11h at this temperature, removes by filter insoluble solids after then being cooled to room temperature, the rectifying of gained liquid pressure-reducing obtains the 152g p-chloro benzo trifluoride-99, the 99g p-trifluoromethylaniline.
Embodiment 10
In the 3L autoclave, add the 300g p-chloro benzo trifluoride-99, the 22g cuprous chloride, the 8g copper powder, 50g salt of wormwood, 30g saleratus, 10g sodium carbonate, the 200g Liquid Macrogol, the 200g Polyethylene Glycol-600,500g ethanol, sealing autoclave, after logical nitrogen replacement three times, in autoclave, pass into 130g liquefied ammonia, then be warming up to 200 ℃, pressure is 10MPa, at this temperature, react 10h, then after being cooled to room temperature, remove by filter insoluble solids, the rectifying of gained liquid pressure-reducing obtains the 150g p-chloro benzo trifluoride-99, the 100g p-trifluoromethylaniline.
Embodiment 11
In the 3L autoclave, add the 300g p-chloro benzo trifluoride-99, wherein 150g is that unreacted raw material is reclaimed in embodiment 1 rectification under vacuum, and 150g is original fresh feed in addition, and all the other operate with embodiment 1, obtain the 150g p-chloro benzo trifluoride-99, the 102g p-trifluoromethylaniline.
Embodiment 12
In the 3L autoclave, adding the 300g p-chloro benzo trifluoride-99, is that the unreacted raw material of accumulation gained is reclaimed in embodiment 1 rectification under vacuum, and all the other operate with embodiment 1, obtain the 150g p-chloro benzo trifluoride-99, the 102g p-trifluoromethylaniline.
Claims (5)
1. a high pressure ammonia solution prepares the method for p-trifluoromethylaniline, and it is characterized in that: the p-chloro benzo trifluoride-99 of take is raw material, under the effect of catalyzer, liquefied ammonia and acid binding agent, in solvent, carries out the High Temperature High Pressure ammonolysis reaction, generates p-trifluoromethylaniline; Wherein, catalyzer is the mixture of cuprous chloride and copper powder; Acid binding agent is any one or two kinds of and above mineral alkali mixture of sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, or pyridine, any one or two kinds of organic bases mixtures of triethylamine; Solvent is any one or two kinds of and above mixed solvent in methyl alcohol, ethanol, Liquid Macrogol ~ 3000, DMF.
2. a kind of high pressure ammonia solution according to claim 1 prepares the method for p-trifluoromethylaniline, it is characterized in that: the mass fraction of material: 100 parts of p-chloro benzo trifluoride-99s; 30 ~ 80 parts, liquefied ammonia, wherein be preferably 50 ~ 70 parts; 200 ~ 500 parts of solvents, wherein be preferably 300 ~ 400 parts; 1 ~ 12 part of catalyzer; 10 ~ 45 parts of acid binding agents, wherein be preferably 20 ~ 30 parts.
3. a kind of high pressure ammonia solution according to claim 1 prepares the method for p-trifluoromethylaniline, it is characterized in that: the mass ratio of cuprous chloride and copper powder is 1:0.06 ~ 0.6, wherein preferred 1:0.1 ~ 0.4.
4. a kind of high pressure ammonia solution according to claim 1 prepares the method for p-trifluoromethylaniline, it is characterized in that: the temperature of ammonolysis reaction is 180 ~ 220 ℃, and pressure is 8 ~ 11MPa, and the reaction times is 8 ~ 14h.
5. a kind of high pressure ammonia solution according to claim 1 prepares the method for p-trifluoromethylaniline, and it is characterized in that: chemical equation is as follows:
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880686A (en) * | 2014-02-21 | 2014-06-25 | 江苏丰华化学工业有限公司 | Method for recycling wastes of trifluoromethyl phenylamine kettle residue |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4096185A (en) * | 1976-01-08 | 1978-06-20 | E. I. Du Pont De Nemours And Company | Preparation of p-aminobenzotrifluoride |
| US6077973A (en) * | 1991-12-09 | 2000-06-20 | Bayer Aktiengesellschaft | Process for the preparation of anilines which contain fluorine and new anilines which contain fluorine |
| CN101298421A (en) * | 2008-05-30 | 2008-11-05 | 中化国际（苏州）新材料研发有限公司 | Synthetic method of p-trifluoromethylaniline |
-
2013
- 2013-08-30 CN CN201310385926.2A patent/CN103408436B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4096185A (en) * | 1976-01-08 | 1978-06-20 | E. I. Du Pont De Nemours And Company | Preparation of p-aminobenzotrifluoride |
| US6077973A (en) * | 1991-12-09 | 2000-06-20 | Bayer Aktiengesellschaft | Process for the preparation of anilines which contain fluorine and new anilines which contain fluorine |
| CN101298421A (en) * | 2008-05-30 | 2008-11-05 | 中化国际（苏州）新材料研发有限公司 | Synthetic method of p-trifluoromethylaniline |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880686A (en) * | 2014-02-21 | 2014-06-25 | 江苏丰华化学工业有限公司 | Method for recycling wastes of trifluoromethyl phenylamine kettle residue |
| CN103880686B (en) * | 2014-02-21 | 2015-03-25 | 江苏丰华化学工业有限公司 | Method for recycling wastes of trifluoromethyl phenylamine kettle residue |
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Inventor after: Zhang Liang Inventor after: Li Qi Inventor after: Zheng Longsheng Inventor after: Zheng Longzhou Inventor after: Fang Dong Inventor after: Li Fuxiang Inventor before: Zheng Longsheng Inventor before: Li Fuxiang Inventor before: Chu Jicheng |
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