CN102911115A - Method for preparing fluazinam intermediate 2-amino-3-chloro-5-trifluoromethyl pyridine - Google Patents
Method for preparing fluazinam intermediate 2-amino-3-chloro-5-trifluoromethyl pyridine Download PDFInfo
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Abstract
The invention provides a method for preparing 2-amino-3-chloro-5-trifluoromethyl pyridine. The method includes that (1) 2, 3-dichloro-5-trifluoromethyl pyridine and water-soluble auxiliary which can achieve transference function between an ammonia water phase and a pyridine oil phase are added in ammonia water with concentration of 20% to 50%, the temperature is increased to 60 DEG C to 120 DEG C, an ammonolysis reaction is performed for 8 to 20 hours under the pressure of 0.5Mpa to 1.5Mpa, and the water-soluble auxiliary is an organic solvent or one of phase transfer catalysts or mixture of two of the phase transfer catalysts; and (2) ammonia gas and the auxiliary are recycled from a reaction liquid obtained in the step (1), and centrifugation is performed to obtain the 2-amino-3-chloro-5-trifluoromethyl pyridine. According to the method, the water-soluble auxiliary which can achieve transference function between the ammonia water phase and the pyridine oil phase is added in the ammonia water, so that the required product can be obtained in high yield under the mild reaction conditions, the product purity is larger than or equal to 99%, the yield is larger than or equal to 97%, the pollution is basically absent in the process, and the environmental protection pressure is low.
Description
Technical field
The present invention relates to a kind of preparation method of compound, be specifically related to the preparation method of compound 2-amido-3-5-trifluoro picoline.
Background technology
Fluazinam is by the successful N-methyl-p-nitroaniline series bactericidal agent of the former industry of Japanese stone company research, has heterocycle structure, has again fluorine atom to come enhanced activity, and fungicidal spectrum is wide.Because its drug effect is rapid, consumption is few, holding effect is moderate, the economic benefit high, is widely used all over the world.In recent years, it is found that owing to introducing the lipotropy that trifluoromethyl can improve compound on the heterocycle, thereby improve the perviousness of organism film and tissue and the electron attractivity when reacting with organism, strengthen the physiologically active of compound, compound 2-amido-3-5-trifluoro picoline is exactly the novel cpd of having introduced trifluoromethyl on the pyridine ring, is the key intermediate of preparation sterilant fluazinam.
The primitive technology United States Patent (USP) is take the 3-chloro-5-trifluoromethylpyridine as raw material, the nitrated 2-amido-3-5-trifluoro picoline that obtains under sulfuric acid, nitric acid condition, and the spent acid, the waste water that produce are too many, and environmental issue is difficult to solve.
US Patent No. 4349681 has proposed directly to react with 2,3-, two chloro-5-trifluoromethylpyridines and ammoniacal liquor, obtained needed product 2-amido-3-5-trifluoro picoline, but yield is lower, and only about 50%, there is not industrial application value at all; Domestic have the people on this basis by adding copper containing catalyst, can suitably improve reaction yield, but exist the reluctant problem of cuprammonium waste water.
Chinese patent CN200610044598 is with 2,3-two chloro-5-trifluoromethylpyridines are raw material, pass into the liquefied ammonia of 10-18mol under the neat solvent condition, under 125-135 ℃ and 2.0-3.0MPa, react 15hr, obtained needed product 2-amido-3-5-trifluoro picoline, the quality product of the method is better, and yield brings up to 90% simultaneously, but reaction conditions is relatively harsher, require the neat solvent condition, carry out under a large amount of liquefied ammonia exist, the recycling possibility of excessive ammonia is little, and environmental protection pressure is larger, the simultaneously existence of more liquefied ammonia, corrosion to equipment under the high-temperature and high-pressure conditions is also more serious, needs to select special material, and the industrialization safety requirements is higher.
Therefore based on the pesticide activity of sterilant fluazinam excellence, its application is more and more wider, wishes to prepare fluazinam or its intermediate 2-amido-3-5-trifluoro picoline with environmental friendliness mode and low cost, the simple suitable operating method of high yield.
Summary of the invention
Technical problem to be solved by this invention provide a kind of easy, safe, prepare the method for 2-amido-3-5-trifluoro picoline efficiently.
In order to be more conducive to production operation, improve safe reliability and quality product, yield, the contriver is by the further investigation to reaction conditions and reaction process, discovery is by adding a kind of auxiliary agent that can change system two-phase character, make 2,3-two chloro-5-trifluoromethylpyridines can carry out ammonification in ammoniacal liquor, and obtain needed product 2-amido-3-5-trifluoro picoline with high yield, reaction pressure and temperature of reaction are gentleer, production security improves greatly, be more conducive to simultaneously the lock out operation in later stage, can realize the recycling of ammoniacal liquor and auxiliary agent.Concrete technical scheme of the present invention is as follows:
A kind of method of the 2-of preparation amido-3-5-trifluoro picoline is provided, comprises the steps:
(1) in concentration is 20 ~ 50% ammoniacal liquor, adds 2,3-, two chloro-5-trifluoromethylpyridines and can at ammoniacal liquor mutually and play the water-soluble additive of transfer function between the pyridine oil phase, be warmed up to 60 ~ 120 ℃, aminating reaction 8 ~ 20hr under pressure 0.5 ~ 1.5MPa; Described water-soluble additive is the mixture of any one or two kinds in organic solvent or the phase-transfer catalyst;
(2) after the reaction solution that step (1) is obtained reclaims ammonia and auxiliary agent, the centrifugal product 2-amido-3-5-trifluoro picoline that obtains.
The mixture of any one in the small molecules amides of the small molecule alcohol of the preferred C1-C8 of the described organic solvent of step (1), the small molecules ethers of C1-C8, C1-C8 or the small molecules nitrile of C1-C8 or two kinds.
The small molecule alcohol of described C1-C8 is preferably the mixture of any one or two kinds in methyl alcohol, ethanol, propyl alcohol, Virahol, the trimethyl carbinol, ethylene glycol or the glycerol; The small molecules ethers of described C1-C8 is preferably the mixture of any one or two kinds in ether, methyl tertiary butyl ether or the tetrahydrofuran (THF); The small molecules amides of described C1-C8 is preferably the mixture of any one or two kinds in dimethyl formamide or the N,N-DIMETHYLACETAMIDE; The small molecules nitrile of described C1-C8 is preferably one or more mixtures in acetonitrile, propionitrile or the butyronitrile.
Most preferred organic solvent auxiliary agent comprises in the step (1): methyl alcohol, ethanol, Virahol or the trimethyl carbinol.
The described phase-transfer catalyst of step (1) is preferably one or more mixtures of polyethers, quaternary ammonium salt or quaternary phosphine salt phase-transfer catalyst.
Described polyethers phase-transfer catalyst is preferably Macrogol 200, poly(oxyethylene glycol) 400, Polyethylene Glycol-600 or polyoxyethylene glycol 800; Described quaternary ammonium salt-type phase transfer catalyst is preferably triethyl benzyl ammonia chloride, trimethyl benzyl ammonia chloride, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutyl ammonium sulfate, etamon chloride, tetraethylammonium bromide, tri-n-octyl methyl ammonium chloride or Dodecyl trimethyl ammonium chloride; Described quaternary phosphonium salt phase-transfer catalyst is preferably trityl group phosphonium bromide, tri-phenyl-ethyl phosphonium bromide, triphenyl ethyl iodination phosphonium, triphenyl propyl group phosphonium bromide, triphenyl butyl phosphonium bromide, benzyl base triphenyl phosphonium chloride, benzyl three phenyl phosphonium bromides, methoxyl methyl triphenyl phosphonium chloride or 4-phenyl phosphonium bromide.
Most preferred phase-transfer catalysis agent aid comprises in the step (1): Polyethylene Glycol-600, polyoxyethylene glycol 800, triethyl benzyl ammonia chloride, Tetrabutyl amonium bromide, trityl group phosphonium bromide or benzyl base triphenyl phosphonium chloride.
Another preferred auxiliary agent is the mixture of above-mentioned preferred organic solvent and phase-transfer catalyst in the step (1), for example, the mixture of methyl alcohol and triethyl benzyl ammonia chloride, the perhaps mixture of Virahol and Tetrabutyl amonium bromide, perhaps Virahol and Polyethylene Glycol-600 and mixture.
In the step (1) 2, the mol ratio of 3-two chloro-5-trifluoromethylpyridines and ammonia is preferably 1:2 ~ 10; More preferably 1:2.5 ~ 10.
In the step (1), with respect to 100 gram 2,3-two chloro-5-trifluoromethylpyridines, the amount that institute adds auxiliary agent is preferably 0.5 ~ 100 and restrains, and more preferably 1 ~ 100 restrains.
Preferred 80 ~ 120 ℃ of temperature of reaction in the step (1).
Step (2) but described recovery ammonia and auxiliary agent direct reuse to the reaction process of step (1).
According to the inventive method, in the preparation process of fluazinam intermediate 2-amino-3-chloro-5-trifluoromethylpyridine, by in ammoniacal liquor, adding one or more the water-soluble additive that can between ammoniacal liquor phase and pyridine oil phase, play transfer function, can be under relatively mild reaction conditions, high yield obtains needed product, product purity 〉=99%, yield 〉=97%, process is substantially pollution-free, environmental protection pressure is lower, excess of ammonia gas and the auxiliary agent that has neither part nor lot in reaction have carried out efficient recovery, and cover is used for reaction process, greatly reduce production cost.
Embodiment
The below is described with the form of embodiment, need to prove, these embodiment are only for the preferred embodiments of the invention of explaining, and does not mean that restriction or limit the scope of the invention.
Embodiment 1
In the 1L autoclave, drop into successively 2 of 200g, 3-two chloro-5-trifluoromethylpyridines, 25% ammoniacal liquor 314g, methyl alcohol 100g, airtightly be warming up to 100 ℃, pressure 0.6MPa insulation reaction 12hr is in the reaction process, reaction pressure progressively descends, react the complete 85 ℃ of pressure releases that are cooled to, excessive ammonia and auxiliary agent methyl alcohol water absorb, until the reactor normal pressure, with vacuum reaction mass is sucked four-hole bottle, be cooled to 0 ℃ of centrifugal product 2-amido-3-5-trifluoro picoline, content 99.2%, yield 97.05% of getting.
Embodiment 2
In the 1L autoclave, drop into successively 2 of 200g, 3-two chloro-5-trifluoromethylpyridines, 25% ammoniacal liquor 314g, methyl alcohol 100g, and adding 1g triethyl benzyl ammonia chloride, airtightly be warming up to 100 ℃, pressure 0.6MPa insulation reaction 12hr, in the reaction process, reaction pressure progressively descends, and reacts to finish to be cooled to 85 ℃ of pressure releases, excessive ammonia and auxiliary agent methyl alcohol water absorb, until the reactor normal pressure sucks four-hole bottle with vacuum with reaction mass, be cooled to 0 ℃ of centrifugal product 2-amido-3-5-trifluoro picoline that gets, content 99.0%, yield 98.15%.
Embodiment 3
With embodiment 1 operating process, changing auxiliary agent is the 100g Virahol, throws 30% ammoniacal liquor 261g, and temperature of reaction is 90-95 ℃, pressure 0.6MPa insulation reaction 12hr, the finished product 2-amido-3-5-trifluoro picoline, content 99.0%, yield 97.25%.
Embodiment 4
With embodiment 2 operating process, auxiliary agent is the 100g Virahol, and adds the 1.5g Tetrabutyl amonium bromide, throw 30% ammoniacal liquor 261g, temperature of reaction is 90-95 ℃, pressure 0.6MPa insulation reaction 12hr, the finished product 2-amido-3-5-trifluoro picoline, content 99.0%, yield 98.25%.
Embodiment 5
With embodiment 1 operating process, changing auxiliary agent is the 100g Virahol, throws 30% ammoniacal liquor 261g, and passing into liquefied ammonia 48g, temperature of reaction is 80-85 ℃, pressure 0.8MPa insulation reaction 10hr, the finished product 2-amido-3-5-trifluoro picoline, content 99.5%, yield 97.65%.
Embodiment 6
With embodiment 1 operating process, changing auxiliary agent is the 80g tetrahydrofuran (THF), throws 30% ammoniacal liquor 261g, and temperature of reaction is 60-65 ℃, pressure 0.6MPa insulation reaction 10hr, the finished product 2-amido-3-5-trifluoro picoline, content 98.5%, yield 96.3%.
Embodiment 7
With embodiment 1 operating process, changing auxiliary agent is the 90g dimethyl formamide, throws 30% ammoniacal liquor 261g, and temperature of reaction is 115-120 ℃, pressure 0.6MPa insulation reaction 8hr, the finished product 2-amido-3-5-trifluoro picoline, content 98%, yield 95.8%.
Embodiment 8
With embodiment 1 operating process, changing auxiliary agent is the 110g acetonitrile, throws 30% ammoniacal liquor 261g, and temperature of reaction is 80-83 ℃, pressure 0.6MPa insulation reaction 14hr, the finished product 2-amido-3-5-trifluoro picoline, content 98.5%, yield 96.7%.
Embodiment 9
With embodiment 2 operating process, changing auxiliary agent is the 100g trimethyl carbinol, and adding 2g Polyethylene Glycol-600,30% ammoniacal liquor 261g, and pass into liquefied ammonia 48g, temperature of reaction is 80-85 ℃, pressure 0.8MPa insulation reaction 10hr, the finished product 2-amido-3-5-trifluoro picoline, content 99.3%, yield 98.55%.
Embodiment 10
With embodiment 2 operating process, add separately 2g auxiliary agent trityl group phosphonium bromide, 30% ammoniacal liquor 300g, and passing into liquefied ammonia 48g, temperature of reaction is 95-100 ℃, pressure 0.8MPa insulation reaction 10hr, the finished product 2-amido-3-5-trifluoro picoline, content 99.3%, yield 96.55%.
The comparative example 1
In the 1L autoclave, drop into successively 2 of 200g, 3-two chloro-5-trifluoromethylpyridines, 25% ammoniacal liquor 314g airtightly are warming up to 100 ℃, pressure 0.6MPa insulation reaction 22hr, reaction Bi Jiangwen pressure release, until the reactor normal pressure sucks four-hole bottle with vacuum with reaction mass, be cooled to 0 ℃ of centrifugal product 2-amido-3-5-trifluoro picoline that gets, content 94.2%, yield 82.5%.
The comparative example 2
In the 1L autoclave, drop into successively 2 of 200g, 3-two chloro-5-trifluoromethylpyridines, methyl alcohol 300g, liquefied ammonia 187g, airtightly be warming up to 135 ℃, pressure 3.5MPa insulation reaction 8hr, reaction Bi Jiangwen pressure release, until reactor normal pressure, with vacuum reaction mass is sucked four-hole bottle, behind the desolvation methyl alcohol, add 300g water for cooling to the 0 ℃ centrifugal product 2-amido-3-5-trifluoro picoline that gets, content 99%, yield 85%.
Claims (10)
1. a method for preparing the 2-amido-3-5-trifluoro picoline comprises the steps:
(1) in concentration is 20 ~ 50% ammoniacal liquor, adds 2,3-, two chloro-5-trifluoromethylpyridines and can at ammoniacal liquor mutually and play the water-soluble additive of transfer function between the pyridine oil phase, be warmed up to 60 ~ 120 ℃, aminating reaction 8 ~ 20hr under pressure 0.5 ~ 1.5MPa; Described water-soluble additive is the mixture of any one or two kinds in organic solvent or the phase-transfer catalyst;
(2) after the reaction solution that step (1) is obtained reclaims ammonia and auxiliary agent, the centrifugal product 2-amido-3-5-trifluoro picoline that obtains.
2. method claimed in claim 1 is characterized in that: described organic solvent is selected from the mixture of any one or two kinds in the small molecules nitrile of the small molecules amides of small molecules ethers, C1-C8 of small molecule alcohol, the C1-C8 of C1-C8 or C1-C8.
3. method claimed in claim 2 is characterized in that: in the described organic solvent, the small molecule alcohol of C1-C8 is the mixture of any one or two kinds in methyl alcohol, ethanol, propyl alcohol, Virahol, the trimethyl carbinol, ethylene glycol or the glycerol; The small molecules ethers of C1-C8 is the mixture of any one or two kinds in ether, methyl tertiary butyl ether or the tetrahydrofuran (THF); The small molecules amides of C1-C8 is the mixture of any one or two kinds in dimethyl formamide or the N,N-DIMETHYLACETAMIDE; The small molecules nitrile of C1-C8 is one or more mixtures in acetonitrile, propionitrile or the butyronitrile.
4. method claimed in claim 1, it is characterized in that: described organic solvent is selected from methyl alcohol, ethanol, Virahol or the trimethyl carbinol.
5. method claimed in claim 1, it is characterized in that: described phase-transfer catalyst is one or more mixtures of polyethers, quaternary ammonium salt or quaternary phosphonium salt phase-transfer catalyst.
6. method claimed in claim 5, it is characterized in that: in the described phase-transfer catalyst, the polyethers phase-transfer catalyst is Macrogol 200, poly(oxyethylene glycol) 400, Polyethylene Glycol-600 or polyoxyethylene glycol 800; Quaternary ammonium salt-type phase transfer catalyst is triethyl benzyl ammonia chloride, trimethyl benzyl ammonia chloride, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutyl ammonium sulfate, etamon chloride, tetraethylammonium bromide, tri-n-octyl methyl ammonium chloride or Dodecyl trimethyl ammonium chloride; Quaternary phosphine salt phase-transfer catalyst is trityl group phosphonium bromide, tri-phenyl-ethyl phosphonium bromide, triphenyl ethyl iodination phosphonium, triphenyl propyl group phosphonium bromide, triphenyl butyl phosphonium bromide, benzyl base triphenyl phosphonium chloride, benzyl three phenyl phosphonium bromides, methoxyl methyl triphenyl phosphonium chloride or 4-phenyl phosphonium bromide.
7. method claimed in claim 1 is characterized in that: described phase-transfer catalyst is selected from Polyethylene Glycol-600, polyoxyethylene glycol 800, triethyl benzyl ammonia chloride, Tetrabutyl amonium bromide, trityl group phosphonium bromide or Bian base triphenyl phosphonium chloride.
8. method claimed in claim 1 is characterized in that: described auxiliary agent is selected from any one or the two or more mixtures in methyl alcohol, ethanol, Virahol, the trimethyl carbinol, Polyethylene Glycol-600, polyoxyethylene glycol 800, triethyl benzyl ammonia chloride, Tetrabutyl amonium bromide, trityl group phosphonium bromide or the Bian base triphenyl phosphonium chloride.
9. method claimed in claim 1 is characterized in that: in the step (1) 2, the mol ratio of 3-two chloro-5-trifluoromethylpyridines and ammonia is 1:2 ~ 10.
10. method claimed in claim 1 is characterized in that: in the step (1), with respect to 100 grams, 2,3-, two chloro-5-trifluoromethylpyridines, the amount that institute adds auxiliary agent is 0.5 ~ 100 to restrain.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574439A (en) * | 2020-05-13 | 2020-08-25 | 山东汇盟生物科技有限公司 | Method for preparing 2-amino-3 chloro-5-trifluoromethylpyridine |
| CN115181060A (en) * | 2022-08-19 | 2022-10-14 | 江苏禾裕泰化学有限公司 | Clean production process for producing 2-amino-3-chloro-5-trifluoromethylpyridine |
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| US4349681A (en) * | 1979-12-24 | 1982-09-14 | Ishihara Sangyo Kaisha, Ltd. | 2-Amino-3-chloro-5-trifluoromethylpyridine |
| CN1869003A (en) * | 2006-07-03 | 2006-11-29 | 沈阳化工研究院 | Preparation method of 4-aminobenzoyl-N-(4-aminobenzoyl) amine |
| CN101081833A (en) * | 2006-05-29 | 2007-12-05 | 山东广恒化工有限公司 | Preparation method of 2-amido-3-5-trifluoro picoline |
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2012
- 2012-11-19 CN CN201210469382.3A patent/CN102911115B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4349681A (en) * | 1979-12-24 | 1982-09-14 | Ishihara Sangyo Kaisha, Ltd. | 2-Amino-3-chloro-5-trifluoromethylpyridine |
| CN101081833A (en) * | 2006-05-29 | 2007-12-05 | 山东广恒化工有限公司 | Preparation method of 2-amido-3-5-trifluoro picoline |
| CN1869003A (en) * | 2006-07-03 | 2006-11-29 | 沈阳化工研究院 | Preparation method of 4-aminobenzoyl-N-(4-aminobenzoyl) amine |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574439A (en) * | 2020-05-13 | 2020-08-25 | 山东汇盟生物科技有限公司 | Method for preparing 2-amino-3 chloro-5-trifluoromethylpyridine |
| CN115181060A (en) * | 2022-08-19 | 2022-10-14 | 江苏禾裕泰化学有限公司 | Clean production process for producing 2-amino-3-chloro-5-trifluoromethylpyridine |
| CN115181060B (en) * | 2022-08-19 | 2024-03-19 | 江苏禾裕泰化学有限公司 | Clean production process for producing 2-amino-3-chloro-5-trifluoromethyl pyridine |
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