CN109280026A - A kind of preparation method of 2,3- dichloropyridine - Google Patents
A kind of preparation method of 2,3- dichloropyridine Download PDFInfo
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- CN109280026A CN109280026A CN201811227295.0A CN201811227295A CN109280026A CN 109280026 A CN109280026 A CN 109280026A CN 201811227295 A CN201811227295 A CN 201811227295A CN 109280026 A CN109280026 A CN 109280026A
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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 present invention discloses a kind of preparation method of 2,3- dichloropyridine.The method of the present invention realizes that steps are as follows: with 2,3,6- trichloropyridines are raw material, in pure organic solvent system, using alkali compounds as acid binding agent, using palladium carbon as catalyst, hydrogen is as hydrogen source, at 20~100 DEG C of temperature, 1.0~8.0Mpa of pressure, speed of agitator control carries out hydrogenation-dechlorination reaction at 100~1000rmp/min, and reaction solution obtains 2,3- dichloropyridine product after post treatment after reacting 2~10h.Preparation method feed stock conversion of the present invention is 95% or more, selectivity of product is up to 88%, catalyst amount is few simultaneously, easy to operate, low for equipment requirements, solvent is easy to recycle, product is easily isolated, product quality is high, and the three wastes of generation are few, is the friendly process preparation method for being suitable for industrialized production.
Description
Technical field
The invention belongs to organic synthesis fields, are related to the important chemical intermediate 2 of a kind of medicine and pesticide field, 3- dichloro
The preparation method of pyridine, the specifically preparation method of one kind 2,3- dichloropyridine.
Background technique
2,3- dichloropyridines are the important intermediates for synthesizing Rynaxypyr insecticide, which has efficient, low
The characteristic of poison, the preparation synthetic method of 2,3- dichloropyridines directly affect the exploitation and application of product downstream.At present about 2,
3- dichloropyridine synthetic route mainly includes following several:
(1) using niacinamide as raw material, DuPont Corporation reports that niacinamide is former for starting in patent CN1910152A
Material, obtains target product through Hofmann degradation, chlorination, diazotising and chloro.The synthesis route operating procedure is more numerous
The unfavorable factors such as trivial, the three wastes are more, high production cost, and product quality is poor cause the process route commercial application value not high.
(2) it using 3- aminopyridine as raw material, is mentioned in patent CN101302190A by 3- aminopyridine in concentrated hydrochloric acid and mistake
It aoxidizes in hydrogen mixture or chlorine, generates 3- Amino-2-Chloropyridine under the effect of the catalyst, obtained by diazotising, chloro
To target product.The process route and route (one) have similarity, the value without industrial applications.
(3) using pyridine as raw material, 2 are obtained by the liquid phase chlorination of pyridine or pyridine hydrochloride in patent JP61249965,
3- dichloropyridine, since yield is low, without industrial application value.
(4) using 2- chloropyridine as raw material, 2- chloropyridine is mentioned in patent US5380862 by butoxylated, with chlorine chlorine
Change, again to obtain 2,3- dichloropyridine after phosphorus oxychloride chlorination.The process route step is more, the three wastes are more and yield is low, thus
The process route is not suitable for carrying out industrialized production.
(5) using 3- chloropyridine as raw material, author obtains 2,3- dichloropyridine by chlorination in patent US45156953,
But yield is low, without industrial application value.
It (six) with 2,6- dichloropyridine is raw material through chlorination in patent CN102153507A with 2,6- dichloropyridine for raw material
2,3,6- trichloropyridines, using catalytic hydrogenation and dechlorination prepare 2,3- dichloropyridine.
(7) with 2,3,6- trichloropyridines for raw material, which mainly under the effect of the catalyst, passes through hydrogenation-dechlorination
Prepare 2,3- dichloropyridine.But catalyst used in the route is costly, catalyst easy in inactivation, turns so as to cause raw material
Rate and product yield be not high, and production cost increases.
In conclusion the problem of technology of existing preparation 2,3- dichloropyridine is primarily present following several respects at present:
Preparation step is relatively complicated, and product yield is not high, and raw material is not easy to obtain, and costly, the three wastes generated in technical process are more, ring for price
Border is unfriendly, and used Hydrodechlorinating catalyst is expensive and recycling is ineffective etc..
Summary of the invention
The present invention proposes a kind of preparation method of 2,3- dichloropyridine.
A kind of preparation method of 2,3- dichloropyridine of the present invention realizes that steps are as follows: being with 2,3,6- trichloropyridines
Raw material, in pure organic solvent system, using alkali compounds as acid binding agent, using palladium carbon as catalyst, hydrogen as hydrogen source,
At 20~100 DEG C of temperature, 1.0~8.0Mpa of pressure, it is anti-that speed of agitator control carries out catalytic hydrogenation at 100~1000r/min
It answers, obtains 2,3- dichloropyridine product after post treatment after reacting 2~10h.
The reaction system be pure organic solvent system, wherein organic solvent include methanol, ethyl alcohol, isopropanol, toluene,
One or more of tetrahydrofuran and ethyl acetate.
The acid binding agent of the alkali compounds includes triethylamine, pyridine, sodium carbonate, sodium bicarbonate, potassium carbonate, acetic acid
Sodium, potassium acetate, one or more of sodium hydroxide and potassium hydroxide.
Described 2,3,6- trichloropyridines and solvent quality ratio are 1:10, preferably 1:3~6.
The acid binding agent and 2, the mass ratio of the material example of 3,6- trichloropyridines are 1.0~5.0, preferably 1.2~2.
The reaction pressure range is 1.0~8.0Mpa, preferably 2.0~4.0Mpa.
The temperature range is 20~100 DEG C, preferably 40~60 DEG C.
The reaction speed of agitator is 100~1000r/min, preferably 300~500r/min.
The reaction time is 2~10h, preferably 3~5h.
The present invention invents a kind of preparation method of 2,3- dichloropyridine, the beneficial effect is that: the present invention with 2,3,
6- trichloropyridine is that raw material is converted to 2,3- dichloropyridine under palladium carbon catalytic action, the technique high conversion rate, selecting response
Property it is good, catalyst amount is few, easy to operate, low for equipment requirements, while solvent is easy to recycle, and product is easily isolated, and is produced
Product quality is high, and the three wastes of generation are few, is the friendly process preparation method for being suitable for industrialized production.
Specific embodiment
Embodiment 1
In 1000ml stainless steel autoclave, addition 2,3,6- trichloropyridine 50g, methanol 300g, triethylamine 35g, then plus
Enter 10% palladium carbon 0.05g, three times with air in nitrogen displacement kettle first, then with after hydrogen displacement three times, is pressurized to 4.0Mpa, it will be warm
At 45~50 DEG C, reaction revolving speed is set as 300rmp/min, and hydrogen is constantly filled into reaction process for degree control, maintains reaction pressure
In 3.0~4.0Mpa, stop reaction after reacting 4h.Cooling, sampling carry out liquid phase quantitative detecting analysis, raw material 2,3,6- trichlorine
Pyridine conversion ratio 96.5%, 2,3- dichloropyridines are selectively 86.7%.After reaction solution is filtered, rectifying is carried out except dereaction is molten
After agent, after adding water stratification, takes organic phase to carry out rectifying and obtain white 2,3- dichloropyridine product 33.1g, product purity 99.5%.
Embodiment 2
In 1000ml stainless steel autoclave, addition 2,3,6- trichloropyridine 50g, methanol 300g, pyridine 27.4g, then plus
Enter 10% palladium carbon 0.2g, three times with air in nitrogen displacement kettle first, then with after hydrogen displacement three times, is pressurized to 2.5Mpa, it will be warm
At 50~60 DEG C, reaction revolving speed is set as 400rmp/min, and hydrogen is constantly filled into reaction process for degree control, maintains reaction pressure
In 2.0~2.5Mpa, stop reaction after reacting 5h.Cooling, sampling carry out liquid phase quantitative detecting analysis, raw material 2,3,6- trichlorine
Pyridine conversion ratio 95.8%, 2,3- dichloropyridines are selectively 88.5%.After reaction solution is filtered, rectifying is carried out except dereaction is molten
After agent, after adding water stratification, takes organic phase to carry out rectifying and obtain white 2,3- dichloropyridine product 33.4g, product purity 99.6%.
Embodiment 3
In 1000ml stainless steel autoclave, 2,3,6- trichloropyridine 50g, isopropanol 200g, triethylamine 35g is added, then
10% palladium carbon 0.05g is added, three times with air in nitrogen displacement kettle first, then with after hydrogen displacement three times, is pressurized to 3.0Mpa, it will
Temperature is controlled at 45~50 DEG C, and reaction revolving speed is set as 300rmp/min, and hydrogen is constantly filled into reaction process, maintains reaction pressure
Power in 1.5~2.0Mpa, stop reaction after reacting 5h.Cooling, sampling carry out liquid phase quantitative detecting analysis, raw material 2,3,6- tri-
Chloropyridine conversion ratio 94.3%, 2,3- dichloropyridines are selectively 85.8%.After reaction solution is filtered, carries out rectifying and remove dereaction
After solvent, after adding water stratification, takes organic phase to carry out rectifying and obtain white 2,3- dichloropyridine product 31.8g, product purity 99.8%.
Embodiment 4
In 1000ml stainless steel autoclave, 2,3,6- trichloropyridine 50g, methanol 150g, ethyl acetate 150g, three is added
Ethamine 35g adds 10% palladium carbon 0.05g, three times with air in nitrogen displacement kettle first, then with hydrogen displacement three times after, pressurising
To 2.5Mpa, temperature is controlled at 45~50 DEG C, reaction revolving speed is set as 300rmp/min, constantly fills into hydrogen in reaction process
Gas maintains reaction pressure in 2.0~2.5Mpa, stop reaction after reacting 5h.Cooling, sampling carry out liquid phase quantitative detecting analysis,
Raw material 2,3,6- trichloropyridine conversion ratio 95.6%, 2,3- dichloropyridines are selectively 85.6%.After reaction solution is filtered, carry out
After rectifying removes reaction dissolvent, after adding water stratification, takes organic phase to carry out rectifying and obtain white 2,3- dichloropyridine product 31.3g, produce
Product purity 99.6%.
Claims (9)
1. one kind 2, the preparation method of 3- dichloropyridine, speciality are: with 2,3,6- trichloropyridines for raw material, pure organic molten
In agent system, using alkali compounds as acid binding agent, described 2,3,6- trichloropyridines and solvent quality ratio are 1:10, described to tie up acid
The mass ratio of the material example of agent and 2,3,6- trichloropyridine is 1.0~5.0；Using palladium carbon as catalyst, hydrogen is as hydrogen source, in temperature
20~100 DEG C, 1.0~8.0Mpa of pressure of degree, speed of agitator control carry out hydrogenation-dechlorination reaction at 100~1000rmp/min,
Reaction solution obtains 2,3- dichloropyridine product after post treatment after 2~10h of reaction.
2. the preparation method of one kind 2,3- dichloropyridine, speciality are according to claim 1: the organic solvent includes
One or more of methanol, ethyl alcohol, isopropanol, toluene, tetrahydrofuran and ethyl acetate.
3. the preparation method of one kind 2,3- dichloropyridine, speciality are according to claim 1: the alkali compounds
Acid binding agent includes triethylamine, pyridine, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium acetate, potassium acetate, sodium hydroxide and potassium hydroxide
One or more of.
4. the preparation method of one kind 2,3- dichloropyridine, speciality are according to claim 1: described 2,3,6- trichlorine pyrroles
Pyridine and solvent quality ratio are 1:3~6.
5. the preparation method of one kind 2,3- dichloropyridine, speciality are according to claim 1: the acid binding agent and 2,3,
The mass ratio of the material example of 6- trichloropyridine is 1.2~2.0.
6. the preparation method of one kind 2,3- dichloropyridine, speciality are according to claim 1: the reaction pressure range
For 2.0~4.0Mpa.
7. the preparation method of one kind 2,3- dichloropyridine, speciality are according to claim 1: the temperature range is 40
~60 DEG C.
8. the preparation method of one kind 2,3- dichloropyridine, speciality are according to claim 1: the reaction speed of agitator
For 300~500r/min.
9. the preparation method of one kind 2,3- dichloropyridine, speciality are according to claim 1: the reaction time is 3
~5h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003099A (en) * | 2019-03-29 | 2019-07-12 | 李焕成 | A kind of preparation method of 2,3- dichloropyridine and obtained 2,3- dichloropyridine |
| CN110551062A (en) * | 2019-09-16 | 2019-12-10 | 西安凯立新材料股份有限公司 | Method for preparing 2,3, 5-trichloropyridine by adopting 2,3,5, 6-tetrachloropyridine |
| CN112159350A (en) * | 2020-10-15 | 2021-01-01 | 山东省农药科学研究院 | Preparation method of 2-chloro-3-trifluoromethylpyridine |
| CN112194617A (en) * | 2020-10-13 | 2021-01-08 | 安徽国星生物化学有限公司 | Method and device for synthesizing 2, 3-dichloropyridine |
| CN112479990A (en) * | 2020-12-17 | 2021-03-12 | 重庆华歌生物化学有限公司 | High-efficiency synthesis method of 2, 3-dichloropyridine |
| WO2022053994A1 (en) | 2020-09-11 | 2022-03-17 | Pi Industries Limited | A process for the preparation of substituted pyridine compounds and intermediates thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102153507A (en) * | 2011-03-13 | 2011-08-17 | 联化科技股份有限公司 | Preparation method of 2,3-dichloropyridine |
| CN107721913A (en) * | 2017-11-28 | 2018-02-23 | 利尔化学股份有限公司 | A kind of preparation method of 2,3 dichloropyridine |
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2018
- 2018-10-22 CN CN201811227295.0A patent/CN109280026A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153507A (en) * | 2011-03-13 | 2011-08-17 | 联化科技股份有限公司 | Preparation method of 2,3-dichloropyridine |
| CN107721913A (en) * | 2017-11-28 | 2018-02-23 | 利尔化学股份有限公司 | A kind of preparation method of 2,3 dichloropyridine |
Non-Patent Citations (1)
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|---|
| 龚亚军 等: "2,3,6-三氯吡啶催化加氢制备2,3-二氯吡啶", 《农药》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003099A (en) * | 2019-03-29 | 2019-07-12 | 李焕成 | A kind of preparation method of 2,3- dichloropyridine and obtained 2,3- dichloropyridine |
| CN110551062A (en) * | 2019-09-16 | 2019-12-10 | 西安凯立新材料股份有限公司 | Method for preparing 2,3, 5-trichloropyridine by adopting 2,3,5, 6-tetrachloropyridine |
| WO2022053994A1 (en) | 2020-09-11 | 2022-03-17 | Pi Industries Limited | A process for the preparation of substituted pyridine compounds and intermediates thereof |
| CN112194617A (en) * | 2020-10-13 | 2021-01-08 | 安徽国星生物化学有限公司 | Method and device for synthesizing 2, 3-dichloropyridine |
| CN112159350A (en) * | 2020-10-15 | 2021-01-01 | 山东省农药科学研究院 | Preparation method of 2-chloro-3-trifluoromethylpyridine |
| CN112479990A (en) * | 2020-12-17 | 2021-03-12 | 重庆华歌生物化学有限公司 | High-efficiency synthesis method of 2, 3-dichloropyridine |
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