CN112159349B - Synthetic method of 2,3, 5-trichloropyridine - Google Patents
Synthetic method of 2,3, 5-trichloropyridine Download PDFInfo
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- CN112159349B CN112159349B CN202010967116.8A CN202010967116A CN112159349B CN 112159349 B CN112159349 B CN 112159349B CN 202010967116 A CN202010967116 A CN 202010967116A CN 112159349 B CN112159349 B CN 112159349B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a synthetic method of 2,3, 5-trichloropyridine, which comprises the following steps: (1) under the condition of existence of a phase transfer catalyst and a polymerization inhibitor, performing chemical reaction on chloral, acrylonitrile and the catalyst at the temperature of 60-90 ℃ to prepare an intermediate product 2, 4, 4-trichloro-4-formylbutyronitrile; (2) and (2) heating the reaction liquid obtained in the step (1) to 60-100 ℃, and slowly introducing hydrogen chloride gas into the reaction liquid to perform cyclization reaction to prepare the target compound 2,3, 5-trichloropyridine. The synthesis method has mild reaction conditions, does not need harsh reaction conditions such as high temperature, high pressure and reaction solvent, can recycle the catalyst, has little heavy metal pollution, high yield of target products up to 80 percent, high purity up to 99 percent, simple post-treatment of the products, reduces the cost and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of pesticide chemical industry, and particularly relates to a synthetic method of 2,3, 5-trichloropyridine.
Background
2,3, 5-trichloropyridine is an important fine chemical intermediate, is widely applied to the research field of medicines and pesticides, and can be used for preparing various herbicides and insecticides. The reaction of 2,3, 5-trichloropyridine and alkali metal hydroxide to prepare 3, 5-dichloro-2-pyridinol is an important raw material for synthesizing insecticidal acarid and herbicide oxazapyr and other series pesticides. The 2,3, 5-trichloropyridine can also be further subjected to fluorination reaction to synthesize 2, 3-difluoro-5-chloropyridine which is a basic raw material for synthesizing the herbicide clodinafop-propargyl.
Through consulting the literature, the chemical synthesis of the 2,3, 5-trichloropyridine has a plurality of feasible process routes. US4111938 describes the synthesis of 2,3, 5-trichloropyridine from pyridine as starting material by chlorination to give polychlorinated pyridine, followed by zinc powder dechlorination under alkaline conditions. The method has the disadvantages that the process has no cost advantage due to the large use of zinc powder, heavy metal pollution is serious, the reaction time is long, and the yield is not high.
U.S. Pat. No. 4, 4245098 discloses a catalytic ring closure process for synthesizing 2,3, 5-trichloropyridine, which mainly comprises using trichloroacetaldehyde and acrylonitrile as raw materials, using acetonitrile as solvent, and preparing 2,3, 5-trichloropyridine in a high-pressure autoclave under the action of catalyst. The method has the advantages of easily obtained raw materials, few synthesis steps, complex process operation, high-pressure reaction, harsh conditions, difficult control, application to a large amount of catalysts, such as cuprous chloride, incapability of recycling and reusing, environmental pollution and unsatisfactory product yield.
Disclosure of Invention
The invention aims to provide a method for synthesizing 2,3, 5-trichloropyridine based on the prior art.
The technical scheme of the invention is as follows:
a synthetic method of 2,3, 5-trichloropyridine comprises the following steps:
(1) in the presence of a phase transfer catalyst and a polymerization inhibitor, chloral, acrylonitrile and the catalyst are subjected to chemical reaction at 60-90 ℃ to prepare an intermediate product 2, 4, 4-trichloro-4-formylbutyronitrile.
(2) And (2) heating the reaction liquid obtained in the step (1) to 60-100 ℃, and slowly introducing hydrogen chloride gas into the reaction liquid to perform cyclization reaction to prepare the target compound 2,3, 5-trichloropyridine.
The synthetic route of the 2,3, 5-trichloropyridine provided by the invention is as follows:
the invention adds polymerization inhibitor and phase transfer catalyst in the reaction process, and prepares the target product 2,3, 5-trichloropyridine without adding organic solvent and high pressure under the coordination of other conditions. The synthesis method has the advantages of mild reaction conditions, recoverable catalyst, less heavy metal pollution, high yield of target products up to 80 percent, high purity up to 99 percent, simple post-treatment of the products, cost reduction and suitability for industrial production.
In step (1), the phase transfer catalyst may be, but is not limited to, polyethylene glycol 200, tetrabutylammonium bromide, tetrabutylammonium chloride or benzyltriethylammonium chloride. In order to better practice the present invention, the phase transfer catalyst is preferably polyethylene glycol 200.
For the purposes of the present invention, the amount of phase transfer catalyst used has a significant influence on the yield and purity of the intermediate products and also of the target products. In a preferred embodiment, in step (1), the weight of the phase transfer catalyst is 0.5% to 10% of the weight of chloral. For better carrying out the invention, the weight of the phase transfer catalyst is preferably between 1% and 5%, for example 1%, of the weight of chloral.
In step (1), the polymerization inhibitor may be, but is not limited to, hydroquinone, t-butylcatechol, or p-benzoquinone. The polymerization inhibitor is preferably hydroquinone without affecting the effect of the present invention.
When preparing 2, 4, 4-trichloro-4-formylbutyronitrile as an intermediate product and a target product from chloral and acrylonitrile in the presence of a catalyst without adding a phase transfer catalyst and a polymerization inhibitor, severe reaction conditions such as high temperature, high pressure and a reaction solvent are required, and yield and purity are not ideal. The amount of inhibitor used also has a non-negligible effect for the purposes of the present invention. In a preferable scheme, in the step (1), the weight of the polymerization inhibitor is 0.05-2% of the weight of the chloral. For better carrying out the invention, the weight of the inhibitor is preferably 0.1% to 1%, for example 0.1% by weight of chloral.
In a preferred embodiment, in step (1), the molar ratio of chloral to acrylonitrile is 1: 1-2, and may be, but is not limited to, 1:1, 1:1.2, 1:1.5, 1:1.8 or 1:2.
In the step (1), when chloral, acrylonitrile and a catalyst are subjected to a chemical reaction in the presence of a phase transfer catalyst and a polymerization inhibitor to prepare the intermediate product 2, 4, 4-trichloro-4-formylbutyronitrile, the reaction temperature can be, but is not limited to, 60 ℃, 70 ℃, 80 ℃, 85 ℃ or 90 ℃, for example, 85-90 ℃.
Further, the reaction time is 20 to 40 hours, preferably 30 hours.
In step (1), the catalyst may be, but is not limited to, copper powder, cuprous chloride or cupric chloride, for example, cuprous chloride. In order to save cost, the weight of the catalyst is 1 to 10 percent of the weight of the chloral; preferably 5 to 10 percent; more preferably 5%.
And (2) after the chemical reaction in the step (1) is finished, separating and recovering the catalyst from the reaction liquid in a filtering and separating mode without any treatment, wherein the loss is small in the separating and recovering process, and the catalyst is directly used in the next reaction.
For the step (2), the intermediate product prepared in the step (1) does not need a complex post-treatment process, hydrogen chloride gas is slowly introduced into the intermediate product for cyclization reaction, so that the target compound 2,3, 5-trichloropyridine can be prepared, an organic solvent does not need to be added, the yield and the purity of the target product are high, and the reaction process is simple and easy to operate.
In a preferred embodiment, in the step (2), the reaction temperature is 75-85 ℃, and can be, but is not limited to, 75 ℃, 80 ℃ or 85 ℃.
Further, the reaction time is 2 to 5 hours, preferably 3 hours.
In the step (2), when hydrogen chloride gas is slowly introduced into the intermediate 2, 4, 4-trichloro-4-formylbutyronitrile for cyclization reaction, the molar ratio of the 2, 4, 4-trichloro-4-formylbutyronitrile to the hydrogen chloride is 1: 2-5, preferably 1: 2-3, and may be, but is not limited to, 1:2, 1:2.1, 1:2.2, 1:2.5, 1:2.8, 1:3, 1:3.5, 1:3.8, 1:4, 1:4.5 or 1: 5.
The invention provides a method for synthesizing 2,3, 5-trichloropyridine, which comprises the following more detailed steps:
(1) reacting chloral, acrylonitrile and cuprous chloride at 85 ℃ for 30 hours in the presence of polyethylene glycol 200 and hydroquinone, filtering, separating out the catalyst, distilling under reduced pressure, obtaining an intermediate product 2, 4, 4-trichloro-4-formylbutyronitrile when no liquid flows out, and directly using the intermediate product in the next reaction without separation.
(2) And (2) heating the reaction liquid obtained in the step (1) to 80 ℃, slowly introducing hydrogen chloride gas into the reaction liquid to carry out cyclization reaction, and after the reaction is finished, carrying out reduced pressure distillation to obtain the target compound 2,3, 5-trichloropyridine.
By adopting the technical scheme of the invention, the advantages are as follows:
the invention takes the chloral and the acrylonitrile as raw materials, prepares the 2,3, 5-trichloropyridine in the presence of a phase transfer catalyst, a polymerization inhibitor and a catalyst, has mild reaction conditions, does not need harsh reaction conditions such as high temperature, high pressure and reaction solvent, can recycle and reuse the catalyst, has less heavy metal pollution, high yield of target products reaching 80 percent, high purity reaching 99 percent, simple post-treatment of the products, reduces the cost and is suitable for industrial production.
Detailed Description
The synthesis of 2,3, 5-trichloropyridine of the present invention is further illustrated by the following examples, which are not intended to limit the invention in any way.
Example 1
After chloral (240 g, 1.62 mol) and acrylonitrile (95 g, 1.79 mol) were added to the flask and mixed uniformly, 12 g of cuprous chloride, 0.24 g of hydroquinone and 2.4 g of polyethylene glycol 200 were added and reacted at 85 ℃ for 30 hours, then filtering, separating out the catalyst, then carrying out reduced pressure distillation, obtaining 2, 4, 4-trichloro-4-formylbutyronitrile reaction liquid when no liquid flows out, (wherein, the mass of the 2, 4, 4-trichloro-4-formylbutyronitrile is 310 g, 1.54 mol, the purity is 95.5 percent, the yield is 94.9 percent), without separation, then the temperature is raised to 80 ℃, 120 g (3.28 mol) of hydrogen chloride gas is slowly pumped into the mixture to react for 3 hours, after the reaction is completed, reduced pressure distillation is carried out to obtain 240 g (3.28 mol) of 2,3, 5-trichloropyridine with the purity of 99.2 percent and the yield of 80.8 percent.
Example 2
Adding chloral (240 g, 1.62 mol) and acrylonitrile (95 g, 1.79 mol) into a flask, uniformly mixing, then adding 12 g of cuprous chloride recovered by filtering separation, 0.24 g of hydroquinone and 2.4 g of polyethylene glycol 200, reacting for 30 hours at 85 ℃, then filtering, separating out a catalyst, distilling under reduced pressure, obtaining a 2, 4, 4-trichloro-4-formylbutyronitrile reaction solution when no liquid flows out, (wherein, the mass of the 2, 4, 4-trichloro-4-formylbutyronitrile is 309 g, 1.54 mol, the purity is 95.9 percent, the yield is 94.6 percent), heating to 80 ℃, slowly introducing 120 g (3.28 mol) of hydrogen chloride gas, reacting for 3 hours, distilling under reduced pressure after the reaction is completed, obtaining 238 g of 2,3, 5-trichloropyridine, the purity is 99.0 percent, the yield thereof was found to be 80.1%.
Example 3
Adding chloral (240 g, 1.62 mol) and acrylonitrile (172 g, 3.24 mol) into a flask, uniformly mixing, then adding 12 g of cuprous chloride, 0.24 g of hydroquinone and 2.4 g of polyethylene glycol 200, reacting for 30 hours at 85 ℃, filtering, separating out a catalyst, distilling under reduced pressure, obtaining a 2, 4, 4-trichloro-4-formylbutyronitrile reaction solution when no liquid flows out, (wherein the mass of the 2, 4, 4-trichloro-4-formylbutyronitrile is 311 g, 1.54 mol, the purity is 96.5%, and the yield is 95.3%), not separating, heating to 80 ℃, slowly introducing 120 g (3.28 mol) of hydrogen chloride gas, reacting for 3 hours, and distilling under reduced pressure after the reaction is completed to obtain 241.7 g of 2,3, 5-trichloropyridine, the purity is 99.5%, and the yield is 81.4%.
Example 4
Adding chloral (240 g, 1.62 mol) and acrylonitrile (95 g, 1.79 mol) into a flask, uniformly mixing, then adding 24 g of cuprous chloride, 0.24 g of hydroquinone and 2.4 g of polyethylene glycol 200, reacting for 30 hours at 85 ℃, filtering, separating out a catalyst, distilling under reduced pressure, obtaining a 2, 4, 4-trichloro-4-formylbutyronitrile reaction solution when no liquid flows out, (wherein the mass of the 2, 4, 4-trichloro-4-formylbutyronitrile is 310 g, 1.54 mol, the purity is 95.7%, the yield is 94.9%), not separating, heating to 80 ℃, slowly introducing 120 g (3.28 mol) of hydrogen chloride gas, reacting for 3 hours, and distilling under reduced pressure after the reaction is completed to obtain 240 g of 2,3, 5-trichloropyridine, the purity is 99.3%, and the yield is 80.8%.
Example 5
Adding chloral (240 g, 1.62 mol) and acrylonitrile (95 g, 1.79 mol) into a flask, uniformly mixing, then adding 12 g of cuprous chloride, 2.4 g of hydroquinone and 2.4 g of polyethylene glycol 200, reacting for 30 hours at 85 ℃, filtering, separating out a catalyst, distilling under reduced pressure, obtaining a 2, 4, 4-trichloro-4-formylbutyronitrile reaction solution when no liquid flows out, (wherein the mass of the 2, 4, 4-trichloro-4-formylbutyronitrile is 307 g, 1.53 mol, the purity is 95.9%, the yield is 94.9%), not separating, heating to 80 ℃, slowly introducing 120 g (3.28 mol) of hydrogen chloride gas, reacting for 3 hours, and distilling under reduced pressure after the reaction is completed to obtain 243.8 g of 2,3, 5-trichloropyridine, the purity is 99.5%, and the yield is 82.1%.
Example 6
Adding chloral (240 g, 1.62 mol) and acrylonitrile (95 g, 1.79 mol) into a flask, uniformly mixing, then adding 12 g of cuprous chloride, 0.24 g of hydroquinone and 2.4 g of polyethylene glycol 200, reacting for 30 hours at 90 ℃, filtering, separating out a catalyst, distilling under reduced pressure, obtaining a 2, 4, 4-trichloro-4-formylbutyronitrile reaction solution when no liquid flows out, (wherein the mass of the 2, 4, 4-trichloro-4-formylbutyronitrile is 312 g, 1.55 mol, the purity is 96.2%, the yield is 95.5%), not separating, heating to 80 ℃, slowly introducing 120 g (3.28 mol) of hydrogen chloride gas, reacting for 3 hours, and distilling under reduced pressure after the reaction is completed to obtain 240.8 g of 2,3, 5-trichloropyridine, the purity is 99.3%, and the yield is 81.1%.
Comparative example 1
Adding chloral (240 g, 1.62 mol) and acrylonitrile (95 g, 1.79 mol) into a flask, uniformly mixing, then adding cuprous chloride (12 g) and hydroquinone (0.24 g), reacting at 85 ℃ for 30 hours, then filtering, separating out a catalyst, carrying out reduced pressure distillation, obtaining a 2, 4, 4-trichloro-4-formylbutyronitrile reaction solution when no liquid flows out, (wherein the mass of the 2, 4, 4-trichloro-4-formylbutyronitrile is 244.8 g, 1.22 mol, the purity is 95.5%, the yield is 75%), not needing separation, then heating to 80 ℃, slowly introducing hydrogen chloride gas (93.5 g, 2.56 mol), reacting for 3 hours, and carrying out reduced pressure distillation after the reaction is completed, thus obtaining 189 g of 2,3, 5-trichloropyridine, the purity is 99.2%, and the yield is 63.6%.
Comparative example 2
Adding chloral (240 g, 1.62 mol) and acrylonitrile (95 g, 1.79 mol) into a flask, uniformly mixing, then adding cuprous chloride (12 g) and polyethylene glycol (2.4 g) to react for 30 hours at 85 ℃, then filtering, separating out a catalyst, carrying out reduced pressure distillation, obtaining a 2, 4, 4-trichloro-4-formylbutyronitrile reaction solution when no liquid flows out, (wherein the mass of the 2, 4, 4-trichloro-4-formylbutyronitrile is 305 g, 1.52 mol, the purity is 85.5%, the yield is 93.4%), not needing separation, then heating to 80 ℃, slowly introducing hydrogen chloride gas (3.2 mol) into the reaction solution, reacting for 3 hours, and carrying out reduced pressure distillation after the reaction is completed to obtain 199 g of 2,3, 5-trichloropyridine, the purity is 90.5%, and the yield is 67%.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: modifications of the technical solutions described in the foregoing embodiments are still possible, or some technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (18)
1. A synthetic method of 2,3, 5-trichloropyridine is characterized by comprising the following steps:
(1) under the condition of existence of a phase transfer catalyst and a polymerization inhibitor, performing chemical reaction on chloral, acrylonitrile and the catalyst at the temperature of 60-90 ℃ for 20-40 hours to prepare an intermediate product 2, 4, 4-trichloro-4-formylbutyronitrile; the phase transfer catalyst is polyethylene glycol 200; the polymerization inhibitor is hydroquinone; the catalyst is cuprous chloride;
(2) and (2) heating the reaction liquid obtained in the step (1) to 60-100 ℃, slowly introducing hydrogen chloride gas into the reaction liquid to carry out cyclization reaction for 2-5 hours, and preparing the target compound 2,3, 5-trichloropyridine.
2. The method for synthesizing 2,3, 5-trichloropyridine according to claim 1, wherein in step (1), the weight of the phase transfer catalyst is 0.5-10% of the weight of the chloral.
3. The method for synthesizing 2,3, 5-trichloropyridine according to claim 2, wherein in the step (1), the weight of the phase transfer catalyst is 1-5% of the weight of the chloral.
4. The process according to claim 2,3, 5-trichloropyridine, wherein in step (1), the weight of the phase transfer catalyst is 1% of the weight of the chloral.
5. The method for synthesizing 2,3, 5-trichloropyridine according to claim 1, wherein in the step (1), the weight of the polymerization inhibitor is 0.05-2% of the weight of the chloral.
6. The method for synthesizing 2,3, 5-trichloropyridine according to claim 5, wherein in the step (1), the weight of the polymerization inhibitor is 0.1-1% of the weight of the chloral.
7. The method for synthesizing 2,3, 5-trichloropyridine according to claim 5, wherein in step (1), the weight of the polymerization inhibitor is 0.1% of the weight of the chloral.
8. The method for synthesizing 2,3, 5-trichloropyridine according to claim 1, wherein in the step (1), the molar ratio of the chloral to the acrylonitrile is 1: 1-2; the reaction temperature is 85-90 ℃; the reaction time was 30 hours.
9. The method for synthesizing 2,3, 5-trichloropyridine according to claim 8, wherein in the step (1), the molar ratio of the chloral to the acrylonitrile is 1: 1.1.
10. The method for synthesizing 2,3, 5-trichloropyridine according to claim 8, wherein in the step (1), the reaction temperature is 85 ℃.
11. The method for synthesizing 2,3, 5-trichloropyridine according to claim 1, wherein in the step (1), the weight of the catalyst is 1-10% of the weight of the chloral.
12. The method for synthesizing 2,3, 5-trichloropyridine according to claim 11, wherein in the step (1), the weight of the catalyst is 5-10% of the weight of the chloral.
13. The process according to claim 11, wherein in step (1) the weight of the catalyst is 5% of the weight of the chloral.
14. The method for synthesizing 2,3, 5-trichloropyridine according to claim 1, wherein in the step (2), the reaction temperature is 75-85 ℃; the reaction time was 3 hours.
15. The method for synthesizing 2,3, 5-trichloropyridine according to claim 14, wherein in the step (2), the reaction temperature is 80 ℃.
16. The method for synthesizing 2,3, 5-trichloropyridine according to claim 1, wherein in the step (2), the molar ratio of 2, 4, 4-trichloro-4-formylbutyronitrile to hydrogen chloride is 1: 2-5.
17. The method for synthesizing 2,3, 5-trichloropyridine according to claim 16, wherein in the step (2), the molar ratio of 2, 4, 4-trichloro-4-formylbutyronitrile to hydrogen chloride is 1: 2-3.
18. The process according to claim 16, wherein in step (2), the molar ratio of 2, 4, 4-trichloro-4-formylbutyronitrile to hydrogen chloride is 1: 2.1.
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| CN104710350A (en) * | 2015-03-17 | 2015-06-17 | 湖北犇星农化有限责任公司 | Synthesis method of sodium trichloro pyridinol |
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