CN105669534A - Method for synthesizing 2-chloropyridine - Google Patents
Method for synthesizing 2-chloropyridine Download PDFInfo
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- CN105669534A CN105669534A CN201610125350.XA CN201610125350A CN105669534A CN 105669534 A CN105669534 A CN 105669534A CN 201610125350 A CN201610125350 A CN 201610125350A CN 105669534 A CN105669534 A CN 105669534A
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- chloropyridine
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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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Abstract
The invention discloses a method for synthesizing 2-chloropyridine. The method comprises the following steps: adding pyridine and a solvent into a 500mL container, controlling the pressure at normal pressure, stirring for 10-20 minutes, and dropwisely adding fluorine acetate, wherein the temperature is controlled to not exceed 30 DEG C; transferring the reaction mixture into a 500mL container, heating to 50-70 DEG C, and carrying out reduced pressure distillation under the vacuum degree of 0.07-0.09 MPa until no liquid is distilled out, thereby obtaining the residual material which is the 2-chloropyridine. The chlorination in the method does not need chlorine gas, phosphorus trichloride, phosphorous pentachloride, phosphorus oxychloride, phosgene or any other extremely toxic substance as a chlorination reagent, but uses dichloromethane as the chlorination reagent, and thus, the technique is safe and reliable for production. The reaction is carried out at normal temperature under normal pressure, and the yield of the 2-chloropyridine reaches 80%.
Description
Technical field
The invention belongs to chemosynthesis technical field, particularly to the synthetic method of a kind of 2-chloropyridine.
Background technology
2-chloropyridine is an important chemical intermediate, is mainly used in the synthesis of medicine and pesticide, and some of which product is widely used in daily-use chemical industry and crop protection, and market prospect is very good. In medicine, 2-chloropyridine can produce hydryllin pheniramine (1) and antiarrhythmics disopyramide (2); On daily chemical products, 2-chloropyridine can produce a kind of antifungal PTO zinc salt (3); CPPU (4) can be produced in pesticide, it is the plant growth regulator of a kind of brand-new high activity, low toxicity, wide spectrum, its cell division activity having is 10-100 times of kinetins and zeatin, use before the florescence and can become seedless fruit by induced parthenocarpy, improve the percentage of fertile fruit of crop, florescence or when using after spending, it is possible to increase fruit, thus significantly improve yield and the fruit quality of crops.
Start people from 1891 and begin to explore the synthetic route of 2-chloropyridine, elapse through 100 years, the gradual perfection constantly improved with chemical theory along with experiment condition, having developed some new synthetic methods, these methods are divided into three kinds according to the difference of raw material: the chlorination of (1) pyridine derivate; (2) direct chlorination of pyridine; (3) other cyclisation method.
Route 1: produce for raw material with PA:
The synthesis of the raw material PA of route 1 is relatively difficult, and total recovery is not high.
Route 2: produce for raw material with 2 hydroxy pyrimidine:
The raw material sources of route 2 are relatively difficult equally and need to pass into phosgene, are unfavorable for the protection of personal safety and environment.
Route 3: with pyridine for raw material through peroxidating, chlorination, also originally produced:
The raw material of route 3 is pyridine, and raw material is easy to get comparatively speaking, but the step of reaction is relatively more, and the yield causing entirety is relatively low.
Route 4: synthesize for raw material direct chlorination with pyridine:
The technological requirement of route 4 is higher, and by-product is relatively more and once through yield is low.
Summary of the invention
In order to overcome the problems referred to above, it is an object of the invention to provide a kind of method synthesizing 2-chloropyridine, it is to avoid use toxic raw materials, improve product yield, be beneficial to environmental conservation.
The method of 2-chloropyridine of the present invention synthesis, pyridine is made directly chlorination by the composition principle of this reaction exactly, and reaction mechanism is as follows:
Technical scheme is implemented as described below: a kind of method synthesizing 2-chloropyridine, concrete steps: 1) chlorination: pyridine and solvent are joined in 500mL container, Stress control is in condition of normal pressure, stirring 10-20min, then dropping acetic acid fluorine, rate of addition is 3-4g/min, time for adding 30min, controls temperature less than 30 DEG C;
2) distillation: moved to by reactant mixture in 500mL container, be warming up to 50 DEG C-70 DEG C, carries out decompression distillation when vacuum 0.07-0.09MPa, after waiting until not have liquid to steam, remaining material is 2-chloropyridine.
Optimize further, step 1) described in solvent be one or more mixture in dichloromethane, chloroform, carbon tetrachloride, dichloroethanes, wherein use dichloromethane the highest as the productivity of solvent.
Optimize further, step 1) in the mole of acetic acid fluorine be 1.2-1.5:1 with the ratio of the mole of pyridine.
Optimize further, step 1) in the temperature of reaction be 15-30 DEG C, react the dichloromethane volatilization more than more than 30 DEG C and accelerate, productivity is then substantially reduced.
Optimize further, step 1) in time of reaction be 4-6 hour, the response time below 4 hours, the As time goes on productivity of 2-chloropyridine raising gradually, between when reacted more than 6 hours after, the productivity of 2-chloropyridine is not changed in.
Compared with prior art, providing the benefit that: 1) chlorination of the inventive method is not required to the extremely toxic substances such as chlorine, Phosphorous chloride., phosphorus pentachloride, phosphorus oxychloride and phosgene as chlorinating agent, but used dichloromethane as chlorinating agent, explained hereafter is safe and reliable; 2) reaction carries out at normal temperatures and pressures, and after reaction terminates, decompression is distilled off the raw material such as dichloromethane, pyridine and some by-products, and remaining high boiling material is then 2-chloropyridine, and the productivity of 2-chloropyridine reaches 80%.
Detailed description of the invention
Illustrated embodiment is to better present disclosure be illustrated, but is not that present disclosure is only limitted to illustrated embodiment.
Embodiment 1
Joining in 500mL container by 79g pyridine and 170g dichloromethane, stir 15min, then dropping acetic acid fluorine 95g, rate of addition is 3g/min, time for adding 30min, reacts 4 hours at 20 DEG C; Being moved to by reactant mixture in 500mL container, at temperature 70 C, carry out decompression distillation when vacuum 0.07Mpa, after waiting until not have liquid to steam, remaining material is 2-chloropyridine. The content of 2-chloropyridine is 94.5% after testing, and productivity is 80.2%.
Embodiment 2
Joining in 500mL container by 79g pyridine and 170g dichloromethane, stir 15min, then dropping acetic acid fluorine 100g, rate of addition is 4g/min, time for adding 30min, reacts 4 hours at 20 DEG C; Being moved to by reactant mixture in 500mL container, at temperature 60 C, carry out decompression distillation when vacuum 0.07Mpa, after waiting until not have liquid to steam, remaining material is 2-chloropyridine. The content of 2-chloropyridine is 94.8% after testing, and productivity is 80.8%.
Embodiment 3
Joining in 500mL container by 79g pyridine and 170g dichloromethane, stir 15min, then dropping acetic acid fluorine 105g, rate of addition is 4g/min, time for adding 30min, reacts 4 hours at 20 DEG C;Being moved to by reactant mixture in 500mL container, at temperature 50 C, carry out decompression distillation when vacuum 0.07Mpa, after waiting until not have liquid to steam, remaining material is 2-chloropyridine. The content of 2-chloropyridine is 94.7% after testing, and productivity is 81.3%.
Embodiment 4
Joining in 500mL container by 79g pyridine and 170g dichloromethane, stir 15min, then dropping acetic acid fluorine 110g, rate of addition is 3g/min, time for adding 30min, reacts 4 hours at 20 DEG C; Being moved to by reactant mixture in 500mL container, at temperature 60 C, carry out decompression distillation when vacuum 0.07Mpa, after waiting until not have liquid to steam, remaining material is 2-chloropyridine. The content of 2-chloropyridine is 94.6% after testing, and productivity is 81.1%.
Embodiment 5
Joining in 500mL container by 79g pyridine and 170g dichloromethane, stir 15min, then dropping acetic acid fluorine 115g, rate of addition is 4g/min, time for adding 30min, reacts 4 hours at 20 DEG C; Being moved to by reactant mixture in 500mL container, at temperature 60 C, carry out decompression distillation when vacuum 0.07Mpa, after waiting until not have liquid to steam, remaining material is 2-chloropyridine. The content of 2-chloropyridine is 95.1% after testing, and productivity is 81.8%.
Embodiment 6
Joining in 500mL container by 79g pyridine and 170g dichloromethane, stir 15min, then dropping acetic acid fluorine 95g, rate of addition is 3g/min, time for adding 30min, reacts 6 hours at 15 DEG C; Being moved to by reactant mixture in 500mL container, at temperature 70 C, carry out decompression distillation when vacuum 0.08Mpa, after waiting until not have liquid to steam, remaining material is 2-chloropyridine. The content of 2-chloropyridine is 96.2% after testing, and productivity is 80.1%.
Embodiment 7
Joining in 500mL container by 79g pyridine and 170g dichloromethane, stir 15min, then dropping acetic acid fluorine 95g, rate of addition is 3g/min, time for adding 30min, reacts 6 hours at 25 DEG C; Being moved to by reactant mixture in 500mL container, at temperature 60 C, carry out decompression distillation when vacuum 0.08Mpa, after waiting until not have liquid to steam, remaining material is 2-chloropyridine. The content of 2-chloropyridine is 96.2% after testing, and productivity is 81.5%.
Embodiment 8
79g pyridine and 170g dichloromethane are joined in 500mL container, stirring 15min, then dropping acetic acid fluorine 95g, rate of addition is 4g/min, time for adding 30min, reacts 5 hours: moved to by reactant mixture in 500mL container at 25 DEG C, at temperature 60 C, carrying out decompression distillation when vacuum 0.09Mpa, after waiting until not have liquid to steam, remaining material is 2-chloropyridine. The content of 2-chloropyridine is 96.5% after testing, and productivity is 82.1%.
Embodiment 9
79g pyridine and 170g chloroform are joined in 500mL container, stirring 15min, then dropping acetic acid fluorine 95g, rate of addition is 4g/min, time for adding 30min, reacts 5 hours: moved to by reactant mixture in 500mL container at 25 DEG C, at temperature 60 C, carrying out decompression distillation when vacuum 0.09Mpa, after waiting until not have liquid to steam, remaining material is 2-chloropyridine. The content of 2-chloropyridine is 96.5% after testing, and productivity is 78.9%.
Embodiment 10
Joining in 500mL container by 79g pyridine and 170g dichloroethanes, stir 15min, then dropping acetic acid fluorine 95g, rate of addition is 4g/min, time for adding 30min, reacts 5 hours at 25 DEG C;Being moved to by reactant mixture in 500mL container, at temperature 60 C, carry out decompression distillation when vacuum 0.09Mpa, after waiting until not have liquid to steam, remaining material is 2-chloropyridine. The content of 2-chloropyridine is 95.4% after testing, and productivity is 79.6%.
Claims (5)
1. the method synthesizing 2-chloropyridine, it is characterized in that, concrete steps: 1) chlorination: pyridine and solvent are joined in 500mL container, Stress control is in condition of normal pressure, stirring 10-20min, then dropping acetic acid fluorine, rate of addition is 3-4g/min, time for adding 30min, controls temperature less than 30 DEG C;
2) distillation: moved to by reactant mixture in 500mL container, be warming up to 50 DEG C-70 DEG C, carries out decompression distillation when vacuum 0.07-0.09MPa, after waiting until not have liquid to steam, remaining material is 2-chloropyridine.
2. according to claim 1 synthesis 2-chloropyridine method, it is characterised in that described step 1) in solvent be one or more mixture in dichloromethane, chloroform, carbon tetrachloride, dichloroethanes.
3. according to claim 1 and 2 synthesis 2-chloropyridine method, it is characterised in that described step 1) in the mole of acetic acid fluorine be 1.2-1.5:1 with the ratio of the mole of pyridine.
4. according to claim 1 and 2 synthesis 2-chloropyridine method, it is characterised in that described step 1) in reaction temperature be 15-30 DEG C.
5. according to claim 1 and 2 synthesis 2-chloropyridine method, it is characterised in that described step 1) in reaction time be 4-6 hour.
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| CN201610125350.XA CN105669534A (en) | 2016-03-04 | 2016-03-04 | Method for synthesizing 2-chloropyridine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717096A (en) * | 2021-11-02 | 2021-11-30 | 潍坊新绿化工有限公司 | Preparation method of 2-chloropyridine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554013A (en) * | 2013-11-21 | 2014-02-05 | 山东谦诚工贸科技有限公司 | Method for producing 2-chloropyridine and 2,6-chloropyridine through organic solvent method |
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- 2016-03-04 CN CN201610125350.XA patent/CN105669534A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554013A (en) * | 2013-11-21 | 2014-02-05 | 山东谦诚工贸科技有限公司 | Method for producing 2-chloropyridine and 2,6-chloropyridine through organic solvent method |
Non-Patent Citations (3)
| Title |
|---|
| DAVID HEBEL ET AL.: "Chlorination, Bromination, and Oxygenation of the Pyridine Ring Using AcOF Made from F2", 《J.ORG.CHEM.》 * |
| 刘善和等: "二氯甲烷氯化合成2-氯吡啶", 《安徽化工》 * |
| 王顺明等: "2-氯吡啶的合成研究", 《应用化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717096A (en) * | 2021-11-02 | 2021-11-30 | 潍坊新绿化工有限公司 | Preparation method of 2-chloropyridine |
| CN113717096B (en) * | 2021-11-02 | 2022-01-25 | 潍坊新绿化工有限公司 | Preparation method of 2-chloropyridine |
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Application publication date: 20160615 |