CN103408436B - 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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- CN103408436B CN103408436B CN201310385926.2A CN201310385926A CN103408436B CN 103408436 B CN103408436 B CN 103408436B CN 201310385926 A CN201310385926 A CN 201310385926A CN 103408436 B CN103408436 B CN 103408436B
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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 technical field of chemical material preparation.It take p-chloro benzo trifluoride-99 as raw material that present method is applicable to, under the effect of catalyzer, liquefied ammonia and acid binding agent, carry out the occasion that high pressure ammonia solution prepares p-trifluoromethylaniline in solvent.
Background technology
P-trifluoromethylaniline (p-trifluromethylaniline, is abbreviated as PTFMA, and CAS accession number is 455-14-1) is a kind of important industrial chemicals, particularly agricultural chemicals and medical in application very extensive.P-trifluoromethylaniline can obtain 2 through superchlorination, 6-dichloro is to 5 amido benzotrifluoride, it is a kind of important intermediate, for the synthesis of high-efficient low toxicity insecticide ethiprole (Frontline), taufluvalinate, penfluron on pesticide industry, weedicide benfluralin, ethalfluralin etc., for the synthesis of neotype immunosuppressant medicine leflunomide etc. on medicine industry.That studies along with green chemical technology and newtype drug deepens continuously, and new purposes is developed continuously, and oneself is through becoming important promising Chemicals.
The synthetic method of p-trifluoromethylaniline is a lot, method main so far has, p-chloro benzo trifluoride-99 ammonia solution prepares the method for p-trifluoromethylaniline, the method that p-nitrobenzyl chloride and sulfide react post chlorization, fluorine replaces, reduces, methyl isocyanate chlorination, fluorine are replaced, are hydrolyzed the method generating p-trifluoromethylaniline, take aniline as starting raw material, by reacting with bromotrifluoromethane the method generating p-trifluoromethylaniline.
(1) nitro-trifluoromethyl toluene is reduced.Adopt SnCl
2-HCl and H
2it is the method used the earliest that/Raney-Ni catalytic reduction prepares PTFMA to nitro-trifluoromethyl toluene.But, to nitro-trifluoromethyl toluene be do not allow facile, be subject to nitro-trifluoromethyl toluene or to nitrotrichloromethane benzene raw materials source restriction, be difficult to carry out large-scale production.
(2) the direct ammonia solution of aromatic compound just obtains the extensive concern of people in the 30's of 20th century, all achieves gratifying achievements in theoretical investigation and production application.The ammonia solution agent that ammonia solution adopts can be liquefied ammonia, ammoniacal liquor, dissolving ammonia in organic solvent, gaseous ammonia or the ammonia of being released in the reaction by urea or ammonium salt.
React with ammonia or liquefied ammonia and trifluoromethyl muriate and produce PTFMA and muriate is also a kind of method meeting the requirement of Modern Green Chemistry Atom economy.But in actual production, there is hydrolysis reaction, so the ammonia solution technique of p-chloro benzo trifluoride-99 exists many problems due to the C-F key easy fracture on trifluoromethyl.Such as make catalyzer p-chloro benzo trifluoride-99 with CaO-CuCl and ammoniacal liquor reacts, while obtaining PTFMA, there is hydrolysis reaction and obtain some by products (Hasek W R, Smith W C, Engelthardt V A. The Chemistry of Sulfur Tetrafluoride-The Fluorination of OrganicCarbonyl Compounds. Journal of the American ChemicalSociety, 1960,82:543-548.).Therefore, in the production process of this technique, generally select organic solvent, to avoid the generation of hydrolytic side reactions, improve reactive behavior by the selection of solvent and catalyzer.US Patent No. 4096185 to propose with cuprous chloride and Potassium monofluoride, for catalyzer, to generate p-trifluoromethylaniline by high-temperature high-voltage reaction.CuCl-KF drastically increases the transformation efficiency of reaction as catalyzer.But also have the generation of p-aminophenyl formonitrile HCN by product in the reaction, and catalyzer is difficult to apply mechanically, shared production cost is too high.
(3) hydrazinolysis reduction method.US Patent No. 6479703 discloses from p-chloro benzo trifluoride-99, and react to hydrazine hydrate and generate corresponding to trifluoromethyl phenyl hydrazine, then use Pd/C, the catalyzer hydrogenolysis reducings such as RaneyNi obtain corresponding PTFMA.But hydrazinolysis reaction is carried out in autoclave, have corrosion, and hydrazine hydrate is under the existence of metal ion, easily decomposes, causes the loss of raw material to autoclave.
(4) aniline trifiuoroniethylation.The method utilizes arylamine and trifluoromethyl free radical to react to prepare object product.Report that maximum is CF3I, under the condition of illumination or heating, there is dissociation generate trifluoromethyl free radical, 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) method that p-nitrobenzyl chloride and sulfide react post chlorization, fluorine replaces, reduce also is a method, US Patent No. 4783562 pairs of systematic introductions of the method, but first the method does not preponderate on cost, simultaneous reactions generates the muriate of the sulphur of severe toxicity, aftertreatment difficulty.
Summary of the invention
Technical barrier to be solved by this invention is, the deficiencies in the prior art, and provide a kind of high pressure ammonia solution to prepare the novel method of p-trifluoromethylaniline, 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, take p-chloro benzo trifluoride-99 as raw material, under the effect of catalyzer, liquefied ammonia and acid binding agent, in solvent, carries out 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 the above mixture in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus; Organic bases is the mixture of any one or two kinds of 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:
P-chloro benzo trifluoride-99 100 parts;
30 ~ 80 parts, liquefied ammonia, is wherein preferably 50 ~ 70 parts;
Solvent 200 ~ 500 parts, is wherein preferably 300 ~ 400 parts;
Catalyzer 1 ~ 12 part;
Acid binding agent 10 ~ 45 parts, is wherein preferably 20 ~ 30 parts.
The processing parameter of ammonolysis reaction of the present invention is, temperature is 180 ~ 220 DEG C, 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:
Prepare the method for p-trifluoromethylaniline according to a kind of high pressure ammonia solution provided by the invention, its key problem in technology is under the effect of catalyzer, liquefied ammonia and acid binding agent, carries out high pressure ammonia solution p-chloro benzo trifluoride-99 is converted into p-trifluoromethylaniline in solvent.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, the effect of concerted catalysis can be played again, overcome per pass conversion in current p-trifluoromethylaniline ammonia solution preocess low, the defect of the deficiency of catalyst utilization, improves production efficiency; (2) used catalyst can, organic solvent composition catalyst system of to environmental hazard less cheap with ethanol etc., and can avoid the generation of hydrolytic side reactions, and not have the generation of p-aminophenyl formonitrile HCN by product, product purity is high, quality good; (3) unreacted raw materials recovery recycle is convenient, reduces production cost, the requirement of compound cycle economy, has good industrial applications prospect.
Embodiment
By the following examples in detail the present invention is described in detail, these embodiments are only clear open the present invention, but not as limitation of the present invention.
Embodiment 1
300g p-chloro benzo trifluoride-99 is added, 25g cuprous chloride, 10g copper powder in 3L autoclave, 90g sodium carbonate, 900g Liquid Macrogol, sealing autoclave, after logical nitrogen replacement three times, in autoclave, pass into 150g liquefied ammonia, be then warming up to 200 DEG C, pressure is 10MPa, react 10h at such a temperature, cross after being then cooled to room temperature and filter insoluble solids, the rectifying of gained liquid pressure-reducing, 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
300g p-chloro benzo trifluoride-99 is added, 25g cuprous chloride, 10g copper powder in 3L autoclave, 90g sodium bicarbonate, 900g ethanol, sealing autoclave, after logical nitrogen replacement three times, in autoclave, pass into 150g liquefied ammonia, be then warming up to 200 DEG C, pressure is 10MPa, react 12h at such a temperature, then cross after being cooled to room temperature and filter insoluble solids, the rectifying of gained liquid pressure-reducing obtains 158g p-chloro benzo trifluoride-99,92g p-trifluoromethylaniline.
Embodiment 3
300g p-chloro benzo trifluoride-99 is added, 2.5g cuprous chloride, 0.5g copper powder in 3L autoclave, 60g sodium hydroxide, 600g methyl alcohol, sealing autoclave, after logical nitrogen replacement three times, in autoclave, pass into 240g liquefied ammonia, be then warming up to 210 DEG C, pressure is 11MPa, react 12h at such a temperature, then cross after being cooled to room temperature and filter insoluble solids, the rectifying of gained liquid pressure-reducing obtains 155g p-chloro benzo trifluoride-99,95g p-trifluoromethylaniline.
Embodiment 4
300g p-chloro benzo trifluoride-99 is added, 2.5g cuprous chloride, 1.0g copper powder in 3L autoclave, 30g potassium hydroxide, 600g ethanol, sealing autoclave, after logical nitrogen replacement three times, in autoclave, pass into 190g liquefied ammonia, be then warming up to 220 DEG C, pressure is 10MPa, react 8h at such a temperature, then cross after being cooled to room temperature and filter insoluble solids, the rectifying of gained liquid pressure-reducing obtains 156g p-chloro benzo trifluoride-99,95g p-trifluoromethylaniline.
Embodiment 5
300g p-chloro benzo trifluoride-99 is added, 25g cuprous chloride, 1.5g copper powder in 3L autoclave, 135g salt of wormwood, 1500g ethanol, sealing autoclave, after logical nitrogen replacement three times, in autoclave, pass into 90g liquefied ammonia, be then warming up to 200 DEG C, pressure is 10MPa, react 8h at such a temperature, then cross after being cooled to room temperature and filter insoluble solids, the rectifying of gained liquid pressure-reducing obtains 150g p-chloro benzo trifluoride-99,102g p-trifluoromethylaniline.
Embodiment 6
300g p-chloro benzo trifluoride-99 is added, 20g cuprous chloride, 12g copper powder in 3L autoclave, 100g saleratus, 1200gN, dinethylformamide, sealing autoclave, after logical nitrogen replacement three times, passes into 200g liquefied ammonia in autoclave, then 180 DEG C are warming up to, pressure is 8MPa, reacts 14h at such a temperature, crosses and filter insoluble solids after being then cooled to room temperature, the rectifying of gained liquid pressure-reducing obtains 152g p-chloro benzo trifluoride-99,100g p-trifluoromethylaniline.
Embodiment 7
300g p-chloro benzo trifluoride-99 is added, 15g cuprous chloride, 3g copper powder in 3L autoclave, 80g pyridine, 900g Macrogol 3000, sealing autoclave, after logical nitrogen replacement three times, in autoclave, pass into 180g liquefied ammonia, be then warming up to 200 DEG C, pressure is 10MPa, react 9h at such a temperature, then cross after being cooled to room temperature and filter insoluble solids, the rectifying of gained liquid pressure-reducing obtains 154g p-chloro benzo trifluoride-99,97g p-trifluoromethylaniline.
Embodiment 8
300g p-chloro benzo trifluoride-99 is added, 10g cuprous chloride, 4g copper powder in 3L autoclave, 80g triethylamine, 900g cetomacrogol 1000, sealing autoclave, after logical nitrogen replacement three times, in autoclave, pass into 160g liquefied ammonia, be then warming up to 200 DEG C, pressure is 10MPa, react 13h at such a temperature, then cross after being cooled to room temperature and filter insoluble solids, the rectifying of gained liquid pressure-reducing obtains 153g p-chloro benzo trifluoride-99,98g p-trifluoromethylaniline.
Embodiment 9
300g p-chloro benzo trifluoride-99 is added, 25g cuprous chloride, 11g copper powder in 3L autoclave, 50g sodium carbonate, 40g sodium bicarbonate, 900g Polyethylene Glycol-600, sealing autoclave, after logical nitrogen replacement three times, passes into 140g liquefied ammonia in autoclave, then 200 DEG C are warming up to, pressure is 10MPa, reacts 11h at such a temperature, crosses and filter insoluble solids after being then cooled to room temperature, the rectifying of gained liquid pressure-reducing obtains 152g p-chloro benzo trifluoride-99,99g p-trifluoromethylaniline.
Embodiment 10
300g p-chloro benzo trifluoride-99 is added in 3L autoclave, 22g cuprous chloride, 8g copper powder, 50g salt of wormwood, 30g saleratus, 10g sodium carbonate, 200g Liquid Macrogol, 200g Polyethylene Glycol-600,500g ethanol, sealing autoclave, after logical nitrogen replacement three times, in autoclave, pass into 130g liquefied ammonia, be then warming up to 200 DEG C, pressure is 10MPa, react 10h at such a temperature, then cross after being cooled to room temperature and filter insoluble solids, the rectifying of gained liquid pressure-reducing obtains 150g p-chloro benzo trifluoride-99,100g p-trifluoromethylaniline.
Embodiment 11
300g p-chloro benzo trifluoride-99 is added in 3L autoclave, 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 operations are with embodiment 1, obtain 150g p-chloro benzo trifluoride-99,102g p-trifluoromethylaniline.
Embodiment 12
In 3L autoclave, add 300g p-chloro benzo trifluoride-99, be that the unreacted raw material of accumulation gained is reclaimed in embodiment 1 rectification under vacuum, all the other operations, with embodiment 1, obtain 150g p-chloro benzo trifluoride-99,102g p-trifluoromethylaniline.
Claims (2)
1. high pressure ammonia solution prepares a method for p-trifluoromethylaniline, it is characterized in that: take p-chloro benzo trifluoride-99 as raw material, under the effect of catalyzer, liquefied ammonia and acid binding agent, in solvent, carries out High Temperature High Pressure ammonolysis reaction, generates p-trifluoromethylaniline; Wherein, catalyzer is the mixture of cuprous chloride and copper powder, and the mass ratio of cuprous chloride and copper powder is 1:0.06 ~ 0.6; Acid binding agent is sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus any one or two kinds of and above inorganic alkali compound, or pyridine, any one or two kinds of organic bases mixtures of triethylamine, the solvent used is methyl alcohol, ethanol, Liquid Macrogol ~ 3000, any one or two kinds of and above mixed solvent in DMF; The mass fraction of each material is: p-chloro benzo trifluoride-99 100 parts; 30 ~ 80 parts, liquefied ammonia; Solvent 200 ~ 500 parts; Catalyzer 1 ~ 12 part; Acid binding agent 10 ~ 45 parts.
2. a kind of high pressure ammonia solution according to claim 1 prepares the method for p-trifluoromethylaniline, and it is characterized in that the temperature of ammonolysis reaction is 180 ~ 220 DEG C, pressure is 8 ~ 11MPa, and the reaction times is 8 ~ 14h.
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| DE4140536A1 (en) * | 1991-12-09 | 1993-06-17 | Bayer Ag | METHOD FOR PRODUCING FLUORINE-CONTAINING ANILINES AND NEW FLUORINE-CONTAINING ANILINES |
| CN101298421B (en) * | 2008-05-30 | 2010-10-13 | 中化国际（苏州）新材料研发有限公司 | Synthetic method of p-trifluoromethylaniline |
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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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