CN107778221A - A kind of preparation technology of 2,3 dichloropyridine - Google Patents
A kind of preparation technology of 2,3 dichloropyridine Download PDFInfo
- Publication number
- CN107778221A CN107778221A CN201610739907.9A CN201610739907A CN107778221A CN 107778221 A CN107778221 A CN 107778221A CN 201610739907 A CN201610739907 A CN 201610739907A CN 107778221 A CN107778221 A CN 107778221A
- Authority
- CN
- China
- Prior art keywords
- preparation technology
- organic
- dichloropyridines
- solvent
- technology according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GPAKJVMKNDXBHH-UHFFFAOYSA-N Clc(c(Cl)n1)ccc1Cl Chemical compound Clc(c(Cl)n1)ccc1Cl GPAKJVMKNDXBHH-UHFFFAOYSA-N 0.000 description 1
- MAKFMOSBBNKPMS-UHFFFAOYSA-N Clc1cccnc1Cl Chemical compound Clc1cccnc1Cl MAKFMOSBBNKPMS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a kind of preparation technology of 2,3 dichloropyridine.The technical process is：With 2,3,6 trichloropyridines for initiation material, in the mixed solvent system of organic solvent and water, using organic base or inorganic base as acid binding agent, under the catalysis of palladium carbon, 2,3 dichloropyridines are obtained by hydrogenation.The high conversion rate of the technique, good reaction selectivity, product are easily isolated, and are adapted to industrialized production.
Description
Technical field
The present invention relates to a kind of preparation technology of 2,3- dichloropyridines.
Background technology
A kind of 2, the 3- dichloropyridines chloropyridine derivative that to be purposes larger compared with wide, dosage, be widely used in medicine and
Pesticide field, it is one of important intermediate of new Rynaxypyr insecticides.
The document synthetic method of 2,3- dichloropyridines is at home and abroad reported a lot.The main method of commercial Application has following two
Kind：
(1) using niacinamide as initiation material, reset by Curtius, chloro forms 2- chlorine-3-aminopyridines, then passed through
Diazo-reaction, it is refining to obtain 2,3- dichloropyridines.
(2) using pyridine as initiation material, 2,3,6- trichloropyridines are obtained by Light chlorimation, then by hydrogenation selectivity dechlorination,
Form 2,3- dichloropyridines.
2,3,6- trichloropyridine catalytic dehydrogenations, the Japan patent JP1193246 of 1989 is seen earliest, in recent years domestic difference
There are the CN102153507 of connectionization science and technology, the CN102432528 of auspicious Deco skill and the permanent CN103145609 for containing chemical industry to enter it
Process Exploration is gone.
The content of the invention
The invention discloses a kind of preparation technology of 2,3- dichloropyridines.
The technical scheme of preparation technology of the present invention is as follows：With 2,3,6- trichloropyridines for initiation material, organic molten
In the mixed solvent system of agent and water, using organic amine, organic base or inorganic base as acid binding agent, under the catalysis of palladium carbon, pass through hydrogen
Change obtains 2,3- dichloropyridines.
In above-mentioned technique, described hydrogenation occurs in the mixed solvent system of organic solvent and water, wherein organic
Solvent includes aromatic hydrocarbons, esters, alcohols, the one or more in ethers, amide solvent, preferred aromatic hydrocarbons class.
In above-mentioned technique, aromatic hydrocarbons described in organic solvent are toluene, and the esters are ethyl acetate, and the alcohols is first
Alcohol or ethanol, the ethers are tetrahydrofuran, and the amide solvent is DMF, preferably toluene.
In above-mentioned technique, the organic amine includes triethylamine, pyridine, and described organic base includes sodium acetate, described nothing
Machine alkali includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
In above-mentioned technique, described acid binding agent and 2, the amount ratio of the material of 3,6- trichloropyridines is 0.6~2.5, preferably
0.6~1.
In above-mentioned technique：0~50 DEG C, 0~15atm of pressure limit of the temperature range of described hydrogenation, reaction time 3~8
Hour；10~15 DEG C, 4~5atm of pressure limit of preferred range, 8 hours reaction time.
The beneficial effects of the invention are as follows：The invention provides a kind of brand-new 2,3- dichloropyridine preparation technologies, the technique
High conversion rate, good reaction selectivity, product is easily isolated, and unit is simple to operate, and equipment requirement is low, is adapted to industrialization big raw
Production.The present invention mainly passes through the addition of reaction system reclaimed water in addition so that the salt that hydrogen chloride caused by hydrogenation is formed with acid binding agent
It is dissolved in water, eliminates inactivation of the salt to catalyst of precipitation；Simultaneously because dissolubility of the salt in water, expands acid binding agent
Etc. the range of choice of process conditions.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Embodiment
It is the specific embodiment of the present invention below, technical scheme is further described, but the present invention is simultaneously
Not limited to this embodiment.
Embodiment 1：The synthesis (one) of 2,3- dichloropyridines
In 1000mL autoclaves, 2,3,6- trichloropyridine 50g, toluene 150g are added；Water 150g, triethylamine 30g, is added
5% palladium carbon 2g, 8~10atm of Hydrogen Vapor Pressure is controlled, 10~15 DEG C of temperature, is reacted 8 hours, HPLC monitoring and controllings raw material (2,3,6-
Trichloropyridine)<10%, stop reaction.
Reacting liquid filtering, reclaim palladium carbon；Filtrate liquid separation, aqueous phase recovery triethylamine；Organic phase is concentrated under reduced pressure, and reclaims toluene；
Residue rectification under vacuum, obtain product 2,3- dichloropyridines~32.5g, yield~80% (theory：40.56g).
LC-MS：M/e=147
1H NMR (400MHz, dmso) δ 8.37 (d, J=4.7Hz, 1H), 8.12 (d, J=8.0Hz, 1H), 7.45 (dd, J
=8.0,4.7Hz, 1H)
13C NMR(101MHz,dmso)δ148.51(s),147.98(s),140.13(s),129.74(s),125.05
(s).
Embodiment 2：The synthesis (two) of 2,3- dichloropyridines
In 1000mL autoclaves, 2,3,6- trichloropyridine 50g, toluene 150g are added；Water 150g, sodium carbonate 40g, is added
5% palladium carbon 0.8g, 4~5atm of Hydrogen Vapor Pressure is controlled, 10~15 DEG C of temperature, is reacted 8 hours, HPLC monitoring and controllings raw material (2,3,
6- trichloropyridines)<10%, stop reaction.
Reacting liquid filtering, reclaim palladium carbon；Filtrate liquid separation, divide and go aqueous phase；Organic phase is concentrated under reduced pressure, and reclaims toluene；Residue
Rectification under vacuum, obtain product 2,3- dichloropyridines~30g, yield~74% (theory：40.56g).
Embodiment 3：The synthesis (three) of 2,3- dichloropyridines
In 1000mL autoclaves, 2,3,6- trichloropyridine 50g, ethyl acetate 150g are added；Water 150g, triethylamine 40g, then
5% palladium carbon 1g is added, 4~5atm of Hydrogen Vapor Pressure is controlled, 25~30 DEG C of temperature, reacts 3 hours, HPLC monitoring and controllings raw material (2,
3,6- trichloropyridines)<10%, stop reaction.
Reacting liquid filtering, reclaim palladium carbon；Filtrate liquid separation, divide and go aqueous phase；Organic phase is concentrated under reduced pressure, recovery of acetic acid ethyl ester；It is residual
Excess rectification under vacuum, obtain product 2,3- dichloropyridines~28g, yield~69% (theory：40.56g).
Claims (7)
1. one kind 2, the preparation technology of 3- dichloropyridines, it is characterised in that：With 2,3,6- trichloropyridines for initiation material, organic
In the mixed solvent system of solvent and water, using organic amine, organic base or inorganic base as acid binding agent, under the catalysis of palladium carbon, pass through
Hydrogenation obtains 2,3- dichloropyridines.
2. preparation technology according to claim 1, it is characterised in that：Described hydrogenation occurs in organic solvent and water
Mixed solvent system in, wherein organic solvent includes aromatic hydrocarbons, esters, alcohols, one kind or several in ethers, amide solvent
Kind, preferred aromatic hydrocarbons class.
3. preparation technology according to claim 2, it is characterised in that：Aromatic hydrocarbons described in organic solvent are toluene, described
Esters are ethyl acetate, and the alcohols is methanol or ethanol, and the ethers is tetrahydrofuran, and the amide solvent is DMF, preferably
Toluene.
4. preparation technology according to claim 1, it is characterised in that：The organic amine includes triethylamine, pyridine, described
Organic base includes sodium acetate, and described inorganic base includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
5. preparation technology according to claim 1, it is characterised in that：Described acid binding agent and the thing of 2,3,6- trichloropyridines
The amount ratio of matter is 0.6~2.5, preferably 0.6~1.0.
6. preparation technology according to claim 1, it is characterised in that：0~50 DEG C of the temperature range of described hydrogenation, pressure
0~15atm of scope, 3 ~ 8 hours reaction time.
7. according to the preparation technology described in claim 6, it is characterised in that：10 ~ 15 DEG C of the temperature range of described hydrogenation, pressure model
Enclose 4 ~ 5atm, 8 hours reaction time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610739907.9A CN107778221A (en) | 2016-08-26 | 2016-08-26 | A kind of preparation technology of 2,3 dichloropyridine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610739907.9A CN107778221A (en) | 2016-08-26 | 2016-08-26 | A kind of preparation technology of 2,3 dichloropyridine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107778221A true CN107778221A (en) | 2018-03-09 |
Family
ID=61440150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610739907.9A Pending CN107778221A (en) | 2016-08-26 | 2016-08-26 | A kind of preparation technology of 2,3 dichloropyridine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107778221A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574415A (en) * | 2020-05-27 | 2020-08-25 | 山东阳谷华泰化工股份有限公司 | Synthetic method of perchloromethylmercaptan |
Citations (3)
| 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 |
| CN102432528A (en) * | 2011-12-01 | 2012-05-02 | 武汉市祥德科技发展有限公司 | Process for synthesizing 2,3-dichloropyridine |
| CN103145609A (en) * | 2013-03-05 | 2013-06-12 | 衢州恒顺化工有限公司 | Preparation method of 2,3-dichloropyridine |
-
2016
- 2016-08-26 CN CN201610739907.9A patent/CN107778221A/en active Pending
Patent Citations (3)
| 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 |
| CN102432528A (en) * | 2011-12-01 | 2012-05-02 | 武汉市祥德科技发展有限公司 | Process for synthesizing 2,3-dichloropyridine |
| CN103145609A (en) * | 2013-03-05 | 2013-06-12 | 衢州恒顺化工有限公司 | Preparation method of 2,3-dichloropyridine |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574415A (en) * | 2020-05-27 | 2020-08-25 | 山东阳谷华泰化工股份有限公司 | Synthetic method of perchloromethylmercaptan |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2687510B1 (en) | Method for preparing 2,3-dichloropyridine | |
| CN106588758B (en) | Synthesis process of 2-hydrazinopyridine derivative | |
| CN109280026A (en) | A kind of preparation method of 2,3- dichloropyridine | |
| CN108129288B (en) | Synthesis method of trans-3-hydroxycyclobutylformic acid | |
| CN105330616A (en) | Preparation method of cariprazine | |
| CN108947891A (en) | The method for safely preparing a Mo Fanselin and its tartrate using triphosgene | |
| CN109369545B (en) | Synthesis process of 2-methyl-5-pyrazine formate | |
| CN108794351A (en) | A kind of preparation method of Mo Fanselin key intermediate | |
| CN110903248A (en) | Synthesis method of 5-chloro-4-aminopyridazine | |
| CN107445819A (en) | A kind of preparation method of n-capric acid | |
| CN106674084B (en) | A kind of preparation method of 2- isopropyl oxygroup -5- methyl -4- (piperidin-4-yl) aniline dihydrochloride | |
| CN103025715A (en) | Intermediates and process for preparing a thrombin specific inhibitor | |
| CN107778221A (en) | A kind of preparation technology of 2,3 dichloropyridine | |
| CN103113290B (en) | Preparation method of Balofloxacin intermediate | |
| CN107001250B (en) | A method of Ao Dangka is prepared for intermediate | |
| CN105884746B (en) | The synthetic method of fluorine imatinib | |
| CN101671296A (en) | New method for obtaining 2-chloro-3-methylpyridine from mixture of 2-chloro-5-methylpyridine and 2-chloro-3-methylpyridine | |
| CN105294556A (en) | Method for preparing montelukast acid | |
| CN103992241B (en) | The preparation method of N-substituted-phenyl glycine | |
| CN105906563B (en) | The synthetic method of 7,8- difluoro-quinoline -3- formic acid | |
| CN108003102A (en) | A kind of synthetic method of Ivabradine | |
| CN103664755B (en) | A kind of preparation method of dichloromethyl substituted pyridines | |
| CN104447509A (en) | Tirofiban hydrochloride preparation process | |
| CN106946724A (en) | The synthetic method of the benzyl malonic acid mono ethyl ester of 2 acetylamino of monoamine base inhibitor class intermediate 2 | |
| CN105152953A (en) | New method for synthesizing metolachlor through raney nickel catalytic hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180309 |
|
| RJ01 | Rejection of invention patent application after publication |