CN103554013A - Method for producing 2-chloropyridine and 2,6-chloropyridine through organic solvent method - Google Patents
Method for producing 2-chloropyridine and 2,6-chloropyridine through organic solvent method Download PDFInfo
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- CN103554013A CN103554013A CN201310587615.4A CN201310587615A CN103554013A CN 103554013 A CN103554013 A CN 103554013A CN 201310587615 A CN201310587615 A CN 201310587615A CN 103554013 A CN103554013 A CN 103554013A
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- chloropyridine
- pyridine
- dichloropyridine
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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
Abstract
The invention discloses a method for producing 2-chloropyridine and 2,6-chloropyridine through an organic solvent method. The method comprises the following steps: mixing pyridine and carbon tetrachloride to form a pyridine solution according to a mass ratio of (0.2-2): 1, and vaporizing the pyridine solution to obtain a vaporized product; mixing the vaporized product and chlorine according to a mass ratio of (1-3): 1 and introducing the mixture into a reactor, so that the mixture reacts under the condition of 150-250 DEG C, and cooling to prepare a reaction solution after the reaction is ended; distilling the reaction solution to remove the carbon tetrachloride, performing rectification under reduced pressure under the condition of -0.08 to -0.085MPa, collecting fractions of which the temperature ranges from 110 DEG C to 113 DEG C to obtain the 2-chloropyridine, and collecting fractions of which the temperature ranges from 142 DEG C to 146 DEG C, thus obtaining the 2,6-chloropyridine. According to the method, protective gases such as nitrogen and carbon dioxide are not needed, a precious metal catalyst is not added, the pyridine is not needed to be directly chlorinated under high-pressure conditions, the yield is 90-98 percent, and the main byproduct 2,6-chloropyridine is an important chemical material, is easy to separate and has a relatively high economic value.
Description
Technical field
The present invention relates to a kind of organic solvent method and produce the method for 2-chloropyridine and 2,6-dichloropyridine.
Background technology
Pyridine is a kind of important Organic Chemicals, and pyridine and its derivatives is efficient owing to having, the characteristic of spectrum, low residue, is widely used in the aspects such as medicine, agricultural chemicals.Pyridinium chloride is important pharmaceutical intermediate, and 2-chloropyridine is for the production of shampoo, larger in household chemicals field application; Aspect medical, for the raw material of his woods of medicine Toldrin, central nervous excitation agent, the uneven medicine of pulse.2,6-dichloropyridine development potentiality is very large, synthetic drugs intermediate, and as sterilant, synthetic Pirozadil is for reducing blood-fat, platelet aggregation inhibitor; Synthetic musk pyridine etc.
The synthetic of 2-chloropyridine starts from 1891, along with the continuous improvement of experiment condition and the gradual perfection of chemical theory, developed many new synthetic methods, by raw material difference used, can be divided into three kinds:
(1) take PA as waste.
On surface, react simple, but the synthetic of PA will be take oxalic acid as raw material reacts, wherein have some factors of instability to exist, total recovery is not high, and employing is few at present.
(2) take 2 hydroxy pyrimidine as waste.
2 hydroxy pyrimidine source is difficult, and need to pass into phosgene, and operability is little, is unfavorable for environment protection.
(3) direct chlorination of pyridine
Raw material is easy to get, but has protection gas and the catalyzer such as the nitrogen of needs, carbonic acid gas, and processing requirement is high, has by product, the low deficiency that waits of once through yield, and economic benefit is low.
Summary of the invention
The object of this invention is to provide a kind of organic solvent method and produce the method for 2-chloropyridine and 2,6-dichloropyridine.
In order to realize foregoing invention object, the method that organic solvent method provided by the present invention is produced 2-chloropyridine and 2,6-dichloropyridine comprises the following steps:
(1) by pyridine and tetracol phenixin in mass ratio for the ratio of 0.2-2:1 is mixed to form pyridine solution, pyridine solution is vaporized and is made vaporizer;
(2) by vaporizer in (1) and chlorine in mass ratio for the ratio of 1-3:1 is mixed and pass into reactor, make it to react under temperature 150-250 ℃ condition, reacted by the cooling reaction solution that makes;
(3) reaction solution in (2) is removed after tetracol phenixin through distillation, again-0.08 to rectification under vacuum under-0.085MPa condition, the cut of collecting 110-113 ℃ of scope of temperature obtains 2-chloropyridine, and the cut of collecting 142-146 ℃ of scope obtains 2,6-dichloropyridine.
In described step (1), the vaporization temperature of pyridine solution is 100-180 ℃.
In described step (1), the vaporization temperature of pyridine solution is 125-130 ℃.
Before in described step (2), vaporizer and chlorine mix, the temperature of chlorine is 30-60 ℃.
The reaction of described vaporizer and chlorine is carried out under blue-ray light or fluorescent lamp.
The reaction of described vaporizer and chlorine is carried out to-2KPa pressure condition at-0.3KPa.
Described pyridine solution by pyridine and tetracol phenixin in mass ratio for the ratio of 0.9-1.1:1 is mixed to form.
Temperature of reaction in described step (2) is 200-240 ℃.
The present invention uses the direct gas phase chlorination technique of pyridine; can realize and not need the protection gas such as nitrogen, carbonic acid gas, do not add noble metal catalyst, do not needing under the condition of high pressure; carry out the direct chlorination of pyridine; yield is up to 90%-98%; the Main By product 2 of this operational path, 6-dichloropyridine are also important industrial chemicals; and be easy to separation, there is higher economic worth.
Embodiment
Further illustrate by the following examples inorganic solvent method and produce 2-chloropyridine and 2; the method of 6-dichloropyridine; these embodiment are only for illustrating the exploitativeness of method provided by the present invention; to not restriction of protection scope of the present invention, any the technology of the present invention of utilizing is conceived formed similar scheme still within protection scope of the present invention.
Embodiment 1
Pyridine and tetracol phenixin are mixed for the ratio of 1.5:1 in mass ratio, be mixed with pyridine solution 20Kg, pyridine solution is vaporized and made vaporizer; Vaporizer and chlorine are sent into autoclave quartz reactor with the inlet amount of 4Kg/h after the ratio mixing for 1:1 in mass ratio, make it to react under the irradiation of ultraviolet lamp, reaction pressure is controlled at-0.5 to-1.0KPa, temperature of reaction is controlled at 190-200 ℃, has reacted by the cooling reaction solution that makes; Distillation reaction liquid is removed tetracol phenixin, again-0.08 to rectification under vacuum under-0.085MPa condition, collect the cut of 110-113 ℃ of scope of temperature, obtain colourless 2-chloropyridine 3.1Kg(purity 99.2%), collect the cut of 142-146 ℃ of scope, white 2,6-dichloropyridine 16.8Kg(purity 99.0%), total recovery 92.7%.
Embodiment 2
Pyridine and tetracol phenixin are mixed for the ratio of 0.5:1 in mass ratio, be mixed with pyridine solution 20Kg, pyridine solution is vaporized and made vaporizer; Vaporizer and chlorine are sent into autoclave quartz reactor with the inlet amount of 7Kg/h after the ratio mixing for 3:1 in mass ratio, make it to react under the irradiation of ultraviolet lamp, reaction pressure is controlled at-0.5 to-1.0KPa, temperature of reaction is controlled at 180-210 ℃, has reacted by the cooling reaction solution that makes; Distillation reaction liquid is removed tetracol phenixin, again-0.08 to rectification under vacuum under-0.085MPa condition, collect the cut of 110-113 ℃ of scope of temperature, obtain colourless 2-chloropyridine 8.0 Kg(purity 99.6%), collect the cut of 142-146 ℃ of scope, obtain white 2,6-dichloropyridine 0.7Kg(purity 99.8%), total recovery 90.0%.
Embodiment 3
Pyridine and tetracol phenixin are mixed for the ratio of 0.5:1 in mass ratio, be mixed with pyridine solution 20Kg, pyridine solution is vaporized and made vaporizer; Vaporizer and chlorine are sent into autoclave quartz reactor with the inlet amount of 7Kg/h after the ratio mixing for 2.5:1 in mass ratio, make it to react under the irradiation of ultraviolet lamp, reaction pressure is controlled at-0.5 to-1.0KPa, temperature of reaction is controlled at 180-210 ℃, has reacted by the cooling reaction solution that makes; Distillation reaction liquid is removed tetracol phenixin, again-0.08 to rectification under vacuum under-0.085MPa condition, collect the cut of 110-113 ℃ of scope of temperature, obtain colourless 2-chloropyridine 7.1Kg(purity 99.6%), collect the cut of 142-146 ℃ of scope, obtain white 2,6-dichloropyridine 2.7Kg(purity 99.8%), total recovery 97.3%.
Embodiment 4
Pyridine and tetracol phenixin are mixed for the ratio of 1:1 in mass ratio, be mixed with pyridine solution 20Kg, pyridine solution is vaporized and made vaporizer; Vaporizer and chlorine are sent into autoclave quartz reactor with the inlet amount of 5Kg/h after the ratio mixing for 2.5:1 in mass ratio, make it to react under the irradiation of ultraviolet lamp, reaction pressure is controlled at-0.5 to-1.0KPa, temperature of reaction is controlled at 200-230 ℃, has reacted by the cooling reaction solution that makes; Distillation reaction liquid is removed tetracol phenixin, again-0.08 to rectification under vacuum under-0.085MPa condition, collect the cut of 110-113 ℃ of scope of temperature, obtain colourless 2-chloropyridine 13.5Kg(purity 99.7%), collect the cut of 142-146 ℃ of scope, obtain white 2,6-dichloropyridine 0.6Kg(purity 99.7%), total recovery 97.2%.
Embodiment 5
Pyridine and tetracol phenixin are mixed for the ratio of 1:1 in mass ratio, be mixed with pyridine solution 20Kg, pyridine solution is vaporized and made vaporizer; Vaporizer and chlorine are sent into autoclave quartz reactor with the inlet amount of 5Kg/h after the ratio mixing for 1.5:1 in mass ratio, make it to react under the irradiation of ultraviolet lamp, reaction pressure is controlled at-0.5 to-1.0KPa, temperature of reaction is controlled at 230-250 ℃, has reacted by the cooling reaction solution that makes; Distillation reaction liquid is removed tetracol phenixin, again-0.08 to rectification under vacuum under-0.085MPa condition, collect the cut of 110-113 ℃ of scope of temperature, obtain colourless 2-chloropyridine 7.8Kg(purity 99.2%), collect the cut of 142-146 ℃ of scope, obtain white 2,6-dichloropyridine 8.0Kg(purity 99.0%), total recovery 97.0%.
Embodiment 6
Pyridine and tetracol phenixin are mixed for the ratio of 1.5:1 in mass ratio, be mixed with pyridine solution 20Kg, pyridine solution is vaporized and made vaporizer; Vaporizer and chlorine are sent into autoclave quartz reactor with the inlet amount of 4Kg/h after the ratio mixing for 1.7:1 in mass ratio, make it to react under the irradiation of ultraviolet lamp, reaction pressure is controlled at-0.5 to-1.0KPa, temperature of reaction is controlled at 200-230 ℃, has reacted by the cooling reaction solution that makes; Distillation reaction liquid is removed tetracol phenixin, again-0.08 to rectification under vacuum under-0.085MPa condition, collect the cut of 110-113 ℃ of scope of temperature, obtain colourless 2-chloropyridine 15.9Kg(purity 99.5%), collect the cut of 142-146 ℃ of scope, obtain white 2,6-dichloropyridine 0.7Kg(purity 99.6%), total recovery 95.3%.
Claims (8)
1. an organic solvent method is produced the method for 2-chloropyridine and 2,6-dichloropyridine, it is characterized in that comprising the following steps:
(1) by pyridine and tetracol phenixin in mass ratio for the ratio of 0.2-2:1 is mixed to form pyridine solution, pyridine solution is vaporized and is made vaporizer;
(2) by vaporizer in (1) and chlorine in mass ratio for the ratio of 1-3:1 is mixed and pass into reactor, make it to react under temperature 150-250 ℃ condition, reacted by the cooling reaction solution that makes;
(3) reaction solution in (2) is removed after tetracol phenixin through distillation, again-0.08 to rectification under vacuum under-0.085MPa condition, the cut of collecting 110-113 ℃ of scope of temperature obtains 2-chloropyridine, and the cut of collecting 142-146 ℃ of scope obtains 2,6-dichloropyridine.
2. organic solvent method as claimed in claim 1 is produced the method for 2-chloropyridine and 2,6-dichloropyridine, it is characterized in that the vaporization temperature of pyridine solution in described step (1) is 100-180 ℃.
3. organic solvent method as claimed in claim 2 is produced the method for 2-chloropyridine and 2,6-dichloropyridine, it is characterized in that the vaporization temperature of pyridine solution in described step (1) is 125-130 ℃.
4. organic solvent method as claimed in claim 2 is produced the method for 2-chloropyridine and 2,6-dichloropyridine, and before it is characterized in that the middle vaporizer of described step (2) and chlorine mix, the temperature of chlorine is 30-60 ℃.
5. organic solvent method as claimed in claim 1 is produced the method for 2-chloropyridine and 2,6-dichloropyridine, it is characterized in that the reaction of described vaporizer and chlorine is carried out under blue-ray light or fluorescent lamp.
6. organic solvent method as claimed in claim 1 is produced the method for 2-chloropyridine and 2,6-dichloropyridine, and the reaction that it is characterized in that described vaporizer and chlorine is carried out to-2KPa pressure condition at-0.3KPa.
7. organic solvent method as claimed in claim 1 is produced the method for 2-chloropyridine and 2,6-dichloropyridine, it is characterized in that described pyridine solution by pyridine and tetracol phenixin in mass ratio for the ratio of 0.9-1.1:1 is mixed to form.
8. organic solvent method as claimed in claim 1 is produced the method for 2-chloropyridine and 2,6-dichloropyridine, it is characterized in that the temperature of reaction in described step (2) is 200-240 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310587615.4A CN103554013A (en) | 2013-11-21 | 2013-11-21 | Method for producing 2-chloropyridine and 2,6-chloropyridine through organic solvent method |
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| CN201310587615.4A CN103554013A (en) | 2013-11-21 | 2013-11-21 | Method for producing 2-chloropyridine and 2,6-chloropyridine through organic solvent method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669534A (en) * | 2016-03-04 | 2016-06-15 | 安徽国星生物化学有限公司 | Method for synthesizing 2-chloropyridine |
| CN109134355A (en) * | 2018-10-30 | 2019-01-04 | 浙江埃森化学有限公司 | A kind of method that pyridine liquid phase Light chlorimation prepares 2,6- dichloropyridine |
| CN109516948A (en) * | 2018-10-30 | 2019-03-26 | 浙江埃森化学有限公司 | A kind of pyridine gas phase Light chlorimation prepares the method and production line of 2,6- dichloropyridine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5141608A (en) * | 1987-10-09 | 1992-08-25 | Daicel Chemical Industries, Ltd. | Process of preparing 2-chloropyridine and/or 2,6-dichloropyridine |
| US5536376A (en) * | 1992-12-28 | 1996-07-16 | Sumitomo Seika Chemicals Co., Ltd. | Method for production of 2-chloropyridine and 2,6-dichloropyridine |
| CN1245167A (en) * | 1998-08-17 | 2000-02-23 | 天津师范大学 | Process for separating chloropyridine product |
| CN1245801A (en) * | 1998-08-21 | 2000-03-01 | 天津师范大学 | Synthesis process of pyridine chloro-product |
-
2013
- 2013-11-21 CN CN201310587615.4A patent/CN103554013A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5141608A (en) * | 1987-10-09 | 1992-08-25 | Daicel Chemical Industries, Ltd. | Process of preparing 2-chloropyridine and/or 2,6-dichloropyridine |
| US5536376A (en) * | 1992-12-28 | 1996-07-16 | Sumitomo Seika Chemicals Co., Ltd. | Method for production of 2-chloropyridine and 2,6-dichloropyridine |
| CN1245167A (en) * | 1998-08-17 | 2000-02-23 | 天津师范大学 | Process for separating chloropyridine product |
| CN1245801A (en) * | 1998-08-21 | 2000-03-01 | 天津师范大学 | Synthesis process of pyridine chloro-product |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669534A (en) * | 2016-03-04 | 2016-06-15 | 安徽国星生物化学有限公司 | Method for synthesizing 2-chloropyridine |
| CN109134355A (en) * | 2018-10-30 | 2019-01-04 | 浙江埃森化学有限公司 | A kind of method that pyridine liquid phase Light chlorimation prepares 2,6- dichloropyridine |
| CN109516948A (en) * | 2018-10-30 | 2019-03-26 | 浙江埃森化学有限公司 | A kind of pyridine gas phase Light chlorimation prepares the method and production line of 2,6- dichloropyridine |
| CN109516948B (en) * | 2018-10-30 | 2022-01-11 | 浙江埃森化学有限公司 | Method and production line for preparing 2, 6-dichloropyridine by gas-phase photochlorination of pyridine |
| CN109134355B (en) * | 2018-10-30 | 2022-04-12 | 浙江埃森化学有限公司 | Method for preparing 2, 6-dichloropyridine by liquid-phase photochlorination of pyridine |
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Application publication date: 20140205 |