CN104892497A - Synthetic method of 2,4,6-trichloropyridine - Google Patents
Synthetic method of 2,4,6-trichloropyridine Download PDFInfo
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- CN104892497A CN104892497A CN201510241620.9A CN201510241620A CN104892497A CN 104892497 A CN104892497 A CN 104892497A CN 201510241620 A CN201510241620 A CN 201510241620A CN 104892497 A CN104892497 A CN 104892497A
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- dichloropyridine
- trichloropyridine
- oxynitride
- trifluoroacetic acid
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Abstract
The invention discloses a synthetic method of 2,4,6-trichloropyridine. The synthetic method comprises a step of N-O synthesis and a step of chlorination. According to the synthetic method, 2,6-dichloropyridine and hydrogen peroxide are taken as raw materials, trifluoroacetic acid is taken as a solvent, in the presence of a specific catalyst, reaction is carried out for 3 to 5h at 85 DEG C, and a 2,6-dichloropyridine nitrogen oxide is obtained via separation; the 2,6-dichloropyridine nitrogen oxide is reacted with phosphorus oxychloride for 4 to 6h under reflux conditions, and 2,4,6-trichloropyridine is obtained via separation. Target product selectivity of the synthetic method is high; the synthetic method is simple and high in efficiency; product purity can be higher than 98%, and total yield can be higher than 75%; and the synthetic method is suitable for industrialized production.
Description
Technical field
The present invention relates to chemical field, be specifically related to a kind of synthesis technique of 2,4,6-trichloropyridine.
Background technology
2,4,6-trichloropyridine, molecular formula C
5h
2cl
3n, molecular weight 182.44, sterling is white to faint yellow solid, is the important intermediate of organic synthesis, is mainly used in medicine intermediate, organic synthesis, organic solvent, also can be applicable to the aspects such as DYE PRODUCTION, pesticide producing and spices.
The synthetic method of 2,4,6-trichloropyridine, divides according to adopted starting raw material, mainly contains pyridine chlorination method and the large route of 2,6-dichloropyridine oxidation-chlorination process two.The selectivity of 2,4,6-trichloropyridines of pyridine chlorination method is low, and 2,4,6-trichloropyridine yield is low, is not suitable for industrialized production.2,6-traditional dichloropyridine oxidation-chlorination processs due to the oxidation of 2,6-dichloropyridine incomplete, target product low conversion rate, thus make 2,4, the 6-trichloropyridine yields obtained only have about 60%.
Technical problem to be solved by this invention there is provided a kind of 2, the synthesis technique of 4,6-trichloropyridine, this scheme not only makes target product transformation efficiency be improved, and product purity and total recovery have brought up to 98% and 75% respectively, are suitable for the features such as suitability for industrialized production.
Summary of the invention
The object of this invention is to provide a kind of synthesis technique of 2,4,6-trichloropyridine, this scheme not only makes target product transformation efficiency be improved, and product purity and total recovery have brought up to more than 98% and 75% respectively, are suitable for the features such as suitability for industrialized production.
The object of the invention is to be achieved through the following technical solutions:
A kind of synthesis technique of 2,4,6-trichloropyridine, refer to 2,6-dichloropyridines and hydrogen peroxide under normal pressure, under the effect of molybdic oxide or aluminum oxide, after 85 DEG C of reaction 3-5h, cool, leach catalyzer, mother liquor precipitation, extraction, separatory, precipitation obtains 2,6-dichloropyridine oxynitride, and 2, after 6-dichloropyridine oxynitride and phosphorus oxychloride under reflux conditions react 4-6h
Decompression steams chlorizating agent, and mother liquor extraction, separatory, precipitation obtain 2,4,6-trichloropyridine, specifically comprise following step:
(1) oxidizing reaction: 2,6-dichloropyridine, solvent trifluoroacetic acid, specific catalyzer are mixed in certain proportion, stirs after 20-40 minute, oxygenant is dripped at 85 DEG C of temperature, reaction 3-5h, is cooled to-5 DEG C to obtain 2,6-dichloropyridine oxynitride dilute solution;
(2) oxide compound is separated: 2,6-dichloropyridine oxynitride dilute solution is filtered out catalyzer, and filtrate is again by underpressure distillation, and reclaim moisture and trifluoroacetic acid, mother liquor appropriate extraction agent extraction, separatory, precipitation obtain 2,6-dichloropyridine oxynitride;
(3) chlorination reaction is separated with target product: 2,6-dichloropyridine oxynitride is added excessive chlorizating agent, under reflux conditions reacts 4-6h, excessive chlorizating agent is sloughed after reaction terminates, mother liquor appropriate extraction agent extraction, separatory, precipitation obtain 2,4,6-trichloropyridine.
The synthesis technique of described one 2,4,6-trichloropyridine, is characterized in that: the specific catalyzer described in step (1) is molybdic oxide or aluminum oxide, and catalyst levels is 0.5% ~ 1.5% of 2,6-dichloropyridine quality, and described oxygenant is 30%H
2o
2solution, 2,6-dichloropyridine and 30%H
2o
2the mass ratio of solution is 1:1.0 ~ 2.5, and the mass ratio of 2,6-dichloropyridine and solvent trifluoroacetic acid is 1:3.0 ~ 3.5.
The synthesis technique of described one 2,4,6-trichloropyridine, is characterized in that: extraction agent used in step (2) can be any one or combination in methylene dichloride, ethylene dichloride, trichloromethane, toluene, Benzene Chloride.
Technical characteristics of the present invention: oxidizing reaction introduces molybdic oxide or aluminium oxide catalyst, greatly improve 2, the transformation efficiency of 6-dichloropyridine oxynitride, product purity and total recovery have brought up to more than 98% and 75% respectively, are suitable for the features such as suitability for industrialized production.
Embodiment
embodiment 1:
In the enamel glass reactor of 3000L, add 396Kg 2,6 dichloropyridines, 1188kg trifluoroacetic acid, 3.96kg molybdic oxide, stir after 20-40 minute, at 85 DEG C of temperature, drip 454.9Kg30% H
2o
2, reaction 3-5h, is cooled to-5 DEG C to obtain 2,6-dichloropyridine oxynitride dilute solution.2,6-dichloropyridine oxynitride dilute solution is filtered out catalyzer, and filtrate is again by underpressure distillation, and reclaim moisture and trifluoroacetic acid, mother liquor 800L dichloromethane extraction, separatory, precipitation obtain 2,6-dichloropyridine oxynitride.2,6-dichloropyridine oxynitride is added 818.7Kg POCl
3, under reflux conditions react 4-6h,
Excessive POCl is sloughed after reaction terminates
3, mother liquor 800L dichloromethane extraction, separatory, precipitation obtain 2,4,6-trichloropyridine, and yield is 75.4%.
embodiment 2:
In the enamel glass reactor of 3000L, add 396Kg2,6 dichloropyridines, 1300kg trifluoroacetic acid, 5.4kg aluminum oxide, stir after 20-40 minute, at 85 DEG C of temperature, drip 454.9Kg30% H
2o
2, reaction 3-5h, is cooled to-5 DEG C to obtain 2,6-dichloropyridine oxynitride dilute solution.2,6-dichloropyridine oxynitride dilute solution is filtered out catalyzer, and filtrate is again by underpressure distillation, and reclaim moisture and trifluoroacetic acid, mother liquor 800L dichloromethane extraction, separatory, precipitation obtain 2,6-dichloropyridine oxynitride.2,6-dichloropyridine oxynitride is added 818.7Kg POCl
3, under reflux conditions react 4-6h, after reaction terminates, slough excessive POCl
3, mother liquor 800L dichloromethane extraction, separatory, precipitation obtain 2,4,6-trichloropyridine, and yield is 75.8%.
embodiment 3:
In the enamel glass reactor of 3000L, add 396Kg2,6 dichloropyridines, 1188kg trifluoroacetic acid, 5.14kg molybdic oxide, stir after 20-40 minute, at 85 DEG C of temperature, drip 990Kg30% H
2o
2, reaction 3-5h, is cooled to-5 DEG C to obtain 2,6-dichloropyridine oxynitride dilute solution.2,6-dichloropyridine oxynitride dilute solution is filtered out catalyzer, and filtrate is again by underpressure distillation, and reclaim moisture and trifluoroacetic acid, mother liquor 800L dichloromethane extraction, separatory, precipitation obtain 2,6-dichloropyridine oxynitride.2,6-dichloropyridine oxynitride is added 818.7Kg POCl
3, under reflux conditions react 4-6h, after reaction terminates, slough excessive POCl
3, mother liquor 800L dichloromethane extraction, separatory, precipitation obtain 2,4,6-trichloropyridine, and yield is 76.1%.
embodiment 4:
In the enamel glass reactor of 3000L, add 396Kg2,6 dichloropyridines, 1188kg trifluoroacetic acid, 3.96kg aluminum oxide, stir after 20-40 minute, at 85 DEG C of temperature, drip 606.5Kg30% H
2o
2, reaction 3-5h, is cooled to-5 DEG C to obtain 2,6-dichloropyridine oxynitride dilute solution.2,6-dichloropyridine oxynitride dilute solution is filtered out catalyzer, and filtrate is again by underpressure distillation, and reclaim moisture and trifluoroacetic acid, mother liquor 800L dichloromethane extraction, separatory, precipitation obtain 2,6-dichloropyridine oxynitride.2,6-dichloropyridine oxynitride is added 818.7Kg POCl
3, under reflux conditions react 4-6h, after reaction terminates, slough excessive POCl
3, mother liquor 800L dichloromethane extraction, separatory, precipitation obtain 2,4,6-trichloropyridine, and yield is 75.7%.
embodiment 5:
In the enamel glass reactor of 3000L, add 396Kg2,6 dichloropyridines, 1188kg trifluoroacetic acid, 3.96kg molybdic oxide, stir after 20-40 minute, at 85 DEG C of temperature, drip 606.5Kg30% H
2o
2, reaction 3-5h, is cooled to-5 DEG C
Obtain 2,6-dichloropyridine oxynitride dilute solution.2,6-dichloropyridine oxynitride dilute solution is filtered out catalyzer, and filtrate is again by underpressure distillation, and reclaim moisture and trifluoroacetic acid, mother liquor 800L dichloromethane extraction, separatory, precipitation obtain 2,6-dichloropyridine oxynitride.2,6-dichloropyridine oxynitride is added 614.0Kg POCl
3, under reflux conditions react 4-6h, after reaction terminates, slough excessive POCl
3, mother liquor 800L dichloromethane extraction, separatory, precipitation obtain 2,4,6-trichloropyridine, and yield is 75.3%.
embodiment 6:
In the enamel glass reactor of 3000L, add 396Kg2,6 dichloropyridines, 1188kg trifluoroacetic acid, 2.8kg aluminum oxide, stir after 20-40 minute, at 85 DEG C of temperature, drip 860.5Kg30% H
2o
2, reaction 3-5h, is cooled to-5 DEG C to obtain 2,6-dichloropyridine oxynitride dilute solution.2,6-dichloropyridine oxynitride dilute solution is filtered out catalyzer, and filtrate is again by underpressure distillation, and reclaim moisture and trifluoroacetic acid, mother liquor 800L dichloromethane extraction, separatory, precipitation obtain 2,6-dichloropyridine oxynitride.2,6-dichloropyridine oxynitride is added 614.0Kg POCl
3, under reflux conditions react 4-6h, after reaction terminates, slough excessive POCl
3, mother liquor 800L dichloromethane extraction, separatory, precipitation obtain 2,4,6-trichloropyridine, and yield is 75.2%.
Claims (3)
1. the synthesis technique of a trichloropyridine, is characterized in that, comprises following step:
(1) oxidizing reaction: 2,6-dichloropyridine, solvent trifluoroacetic acid, specific catalyzer are mixed in certain proportion, stirs after 20-40 minute, oxygenant is dripped at 85 DEG C of temperature, reaction 3-5h, is cooled to-5 DEG C to obtain 2,6-dichloropyridine oxynitride dilute solution;
(2) oxide compound is separated: 2,6-dichloropyridine oxynitride dilute solution is filtered out catalyzer, and filtrate is again by underpressure distillation, and reclaim moisture and trifluoroacetic acid, mother liquor appropriate extraction agent extraction, separatory, precipitation obtain 2,6-dichloropyridine oxynitride;
(3) chlorination reaction is separated with target product: 2,6-dichloropyridine oxynitride is added excessive chlorizating agent, under reflux conditions reacts 4-6h, excessive chlorizating agent is sloughed after reaction terminates, mother liquor appropriate extraction agent extraction, separatory, precipitation obtain 2,4,6-trichloropyridine.
2. the synthesis technique of a kind of 2,4,6-trichloropyridine as claimed in claim 1, it is characterized in that: the specific catalyzer described in step (1) is molybdic oxide or aluminum oxide, catalyst levels is 0.5% ~ 1.5% of 2,6-dichloropyridine quality, and described oxygenant is 30%H
2o
2solution, 2,6-dichloropyridine and 30%H
2o
2the mass ratio of solution is 1:1.0 ~ 2.5, and the mass ratio of 2,6-dichloropyridine and solvent trifluoroacetic acid is 1:3.0 ~ 3.5.
3. the synthesis technique of 2,4,6-trichloropyridine as claimed in claim 1 a kind of, is characterized in that: extraction agent used in step (2) can be any one or combination in methylene dichloride, ethylene dichloride, trichloromethane, toluene, Benzene Chloride.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423368A (en) * | 2020-04-07 | 2020-07-17 | 中触媒新材料股份有限公司 | 2-chloropyridine oxidation device and method |
Citations (3)
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| WO2012097479A1 (en) * | 2011-01-21 | 2012-07-26 | Abbott Laboratories | Bicyclic inhibitors of anaphastic lymphoma kinase |
| CN103384669A (en) * | 2011-01-21 | 2013-11-06 | Abbvie公司 | Bicyclic inhibitors of ALK |
| CN103415516A (en) * | 2011-01-21 | 2013-11-27 | Abbvie公司 | Bicyclic inhibitors of ALK |
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- 2015-05-13 CN CN201510241620.9A patent/CN104892497A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012097479A1 (en) * | 2011-01-21 | 2012-07-26 | Abbott Laboratories | Bicyclic inhibitors of anaphastic lymphoma kinase |
| CN103384669A (en) * | 2011-01-21 | 2013-11-06 | Abbvie公司 | Bicyclic inhibitors of ALK |
| CN103415516A (en) * | 2011-01-21 | 2013-11-27 | Abbvie公司 | Bicyclic inhibitors of ALK |
Non-Patent Citations (1)
| Title |
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| WENMIN CHEN，等: "Discovery of 2-pyridone derivatives as potent HIV-1 NNRTIs using molecular hybridization based on crystallographic overlays", 《BIOORGANIC & MEDICINAL CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423368A (en) * | 2020-04-07 | 2020-07-17 | 中触媒新材料股份有限公司 | 2-chloropyridine oxidation device and method |
| CN111423368B (en) * | 2020-04-07 | 2021-09-24 | 中触媒新材料股份有限公司 | 2-chloropyridine oxidation device and method |
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Application publication date: 20150909 |