CN108003092A - A kind of synthetic method of 2,3- dichloropyridines - Google Patents
A kind of synthetic method of 2,3- dichloropyridines Download PDFInfo
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- CN108003092A CN108003092A CN201711388683.2A CN201711388683A CN108003092A CN 108003092 A CN108003092 A CN 108003092A CN 201711388683 A CN201711388683 A CN 201711388683A CN 108003092 A CN108003092 A CN 108003092A
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- dichloropyridines
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- phosphine
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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 one kind 2, the synthetic method of 3 dichloropyridines, in the presence of solvent and acid binding agent, be raw material with 2,3,6 trichloropyridines, hydrogen be hydrogen source, three (triphenylphosphine) radium chlorides (I) or three (triphenylphosphine) bromination rhodiums (I) are catalyst, organic auxiliary agent containing phosphine is added, catalytic hydrogenation reaction is carried out under the conditions of 0.1~8MPa of pressure, 20~200 DEG C of temperature and obtains 2,3 dichloropyridines.The present invention is by adding cheap organic auxiliary agent containing phosphine, under the conditions of catalyst three (triphenylphosphine) radium chloride (I) or three (triphenylphosphine) bromination rhodium (I) dosages is greatly reduced, good raw material 2 is still obtained, 3,6 trichloropyridine conversion ratios and product 2,3 dichloropyridines selectivity, 2,3,6 trichloropyridine conversion ratios may be up to 97%, 2,3 dichloropyridines are selective close to 90%, the manufacture cost of 2,3 dichloropyridines is significantly reduced, there is higher industrial value.
Description
Technical field
The invention belongs to organic synthesis field, and in particular to the synthetic method of one kind 2,3- dichloropyridines.
Background technology
2,3- dichloropyridines are important fine-chemical intermediates, are the keys of synthesizing new insecticide Rynaxypyr
Intermediate.
JP1193246, CN103145609A etc. with 2,3,6- trichloropyridines for raw material, using palladium, platinum, ruthenium, raney nickel or
One kind in raney copper etc. is catalyst, and with the reducing agent reductase 12 such as hydrogen, 3,6- trichloropyridines obtain 2,3- dichloropyridines, institute
There are the problem of be that 2,3,6- trichloropyridine conversion per pass and 2,3- dichloropyridine selectivity be not high, separation is difficult.
For WO2017085476 with 2,3,6- trichloropyridines for raw material, three (triphenylphosphine) radium chlorides (I) are catalyst, are being tied up
Homogeneous catalytic hydrogenation is carried out in the presence of sour agent, solvent to react to obtain 2,3- dichloropyridines.This method 2,3- dichloropyridines selectivity
Height, overcomes the deficiency using heterogeneous catalysts such as traditional palladium carbons.But catalyst amount is big in the system, catalyst with
2,3,6- trichloropyridine mass ratioes are up to 1:11, three (triphenylphosphine) radium chlorides (I) are a kind of expensive catalyst, with
Catalytic amount preparation 2,3- dichloropyridines are of high cost described in WO2017085476 embodiments, without industrial production value.There is mirror
In this, it is necessary to the prior art is improved, on the premise of guarantee product 2,3- dichloropyridine selectivity, reduces catalyst
Dosage, so that preparation 2 is reduced, the cost of 3- dichloropyridines.
The content of the invention
It is an object of the invention in view of the shortcomings of the prior art, providing the synthetic method of one kind 2,3- dichloropyridines.This hair
Bright purpose is achieved by the following technical solution：
The synthetic method of one kind 2,3- dichloropyridines, is original with 2,3,6- trichloropyridines in the presence of solvent and acid binding agent
Material, hydrogen be hydrogen source, three (triphenylphosphine) radium chlorides (I) or three (triphenylphosphine) bromination rhodiums (I) are catalyst, by added with
Machine auxiliary agent containing phosphine, progress catalytic hydrogenation reaction obtains 2,3- bis- under 20~200 DEG C of 0.1~8MPa of pressure, temperature reaction conditions
Chloropyridine.
Described catalyst three (triphenylphosphine) radium chloride (I) or three (triphenylphosphine) bromination rhodiums (I) and 2,3,6- trichlorines
The molar ratio of pyridine is at least 1:10000, the dosage for increasing catalyst helps to improve conversion ratio and 2, the selection of 3- dichloropyridines
Property, but excessive use causes cost to be significantly increased；Catalyst amount is reduced, when molar ratio is less than 1:When 10000, reaction rate
Very slow, reaction can hardly carry out.In order to obtain satisfied reaction while the production cost of 2,3- dichloropyridines is reduced
Effect, catalyst and 2, the molar ratio of 3,6- trichloropyridines is preferably 1:100~3000, more preferably 1:200~2000.
Organic auxiliary agent containing phosphine is triphenylphosphine, diphenyl (o- tolyls) phosphine, diphenyl (m- tolyls) phosphine, two
Phenyl (p- tolyls) phosphine (diphenyl-p base phosphine), it is double (o- tolyls) Phenylphosphines, double (m- tolyls) Phenylphosphines, double
(p- tolyls) Phenylphosphine, three (o-tolyl) phosphines, three (tolyl) phosphines, three (p-methylphenyl) phosphines, diphenylcyclohexyl phosphine,
Double (diphenylphosphine) ethane of dicyclohexlphenylphosphine, tricyclohexyl phosphine, double diphenylphosphine methane, 1,2-, the double (diphenyl of 1,3-
Phosphine) propane, one kind in double (diphenylphosphine) butane of 1,4-；Preferably triphenylphosphine.Adding organic auxiliary agent containing phosphine can be aobvious
Write under conditions of reducing catalyst amount, keep good feed stock conversion and 2,3- dichloropyridine selectivity.Described is organic
The molar ratio of auxiliary agent containing phosphine and catalyst is at least 1:1, when molar ratio is more than 20:When 1, the influence and 3~20 to reaction:1 institute
The effect reached is suitable, and in order to avoid the wasting of resources, the molar ratio of organic auxiliary agent containing phosphine and catalyst is more preferably 5~
15:1。
The solvent a kind of in aromatic hydrocarbons, alkanes, alcohols, ethers, esters or water or at least two
Mixing；The aromatic hydrocarbon solvent is selected from toluene, benzene, dimethylbenzene, pyridine；The alkane solvents are selected from n-hexane, hexamethylene
Alkane；The alcohols solvent is selected from methanol, ethanol, isopropanol；The ether solvent is selected from tetrahydrofuran, ether；The ester
Class solvent is selected from ethyl acetate, methyl acetate, butyl acetate.
Preferably, the solvent be toluene, methanol, ethanol, a kind of in isopropanol or at least two mixing or
The mixing of any one alcohols solvent and water in methanol, ethanol, isopropanol.
The molar ratio of the acid binding agent and 2,3,6- trichloropyridines is at least 1:1, it is preferably 1.2~2:1.Described ties up
Sour agent is selected from organic base or inorganic alkali compound.The organo-alkali compound is selected from triethylamine, tetramethylethylenediamine, tetramethyl third
One kind in diamines, pyridine；The inorganic base is selected from ammonia, the hydroxide of alkali metal or carbonate, bicarbonate, acetic acid
One kind in salt；The alkali metal is sodium or potassium.Specifically, the inorganic base is selected from sodium hydroxide, potassium hydroxide, carbonic acid
One kind in sodium, potassium carbonate, sodium acid carbonate or saleratus, sodium acetate or potassium acetate.
Preferably, the organic base is triethylamine or pyridine, and the inorganic base is sodium acetate or sodium hydroxide.
Preferably, the reaction pressure is 0.4~3MPa, and temperature is 40~120 DEG C.
It is further preferred that the reaction pressure is 0.5~2.5MPa, temperature is 75~110 DEG C.
Compared with prior art, the beneficial effects are mainly as follows：
Compared with the technical solution of patent WO2017085476, organic containing phosphine auxiliary agent of the present invention by addition inexpensively,
It is greatly reduced under the conditions of catalyst three (triphenylphosphine) radium chloride (I) or three (triphenylphosphine) bromination rhodium (I) dosages, still obtains
Good 2,3,6- trichloropyridine conversion ratio of raw material and product 2,3- dichloropyridines selectivity, 2,3,6- trichloropyridine conversion ratios can
Up to 97%, 2,3- dichloropyridines selectivity is close to 90%, so as to significantly reduce 2, the manufacture cost of 3- dichloropyridines, has
Higher industrial value.The product 2 being prepared using the method for the present invention, 3- dichloropyridines can be stripped by vapor and separated,
Organic auxiliary agent containing phosphine does not interfere with purification treating method.
Embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
Embodiment 1
In 250ml autoclaves, 30g2,3,6- trichloropyridines, 90g ethanol, 30g triethylamines, 0.5g tri- (three are put into
Phenylphosphine) radium chloride (I), 1g triphenylphosphines, are passed through air in nitrogen displacement reaction kettle, replacement completion, leads to hydrogen and be simultaneously warming up to
80 DEG C are reacted, and reaction pressure is gradually reduced in reaction process, fill into hydrogen maintain reaction pressure 0.8~1.0MPa it
Between, successive reaction 20h, reaction terminates.Sampling analysis 2,3,6- trichloropyridines conversion ratio 97%, 2,3- dichloropyridines selectivity
89%, 2,3- dichloropyridine yields 86.3%.
Embodiment 2
In 250ml autoclaves, 30g2,3,6- trichloropyridines, 90g ethanol, 30g triethylamines, 0.08g tri- are put into
(triphenylphosphine) radium chloride (I), 0.2g triphenylphosphines are passed through air in nitrogen displacement reaction kettle, replacement completion, and logical hydrogen simultaneously rises
Warm to 83 DEG C are reacted, and reaction pressure is gradually reduced in reaction process, are filled into hydrogen and are maintained reaction pressure in 0.8~1.0MPa
Between, successive reaction 26h, reaction terminates.Sampling analysis 2,3,6- trichloropyridines conversion ratio 93%, 2,3- dichloropyridines selectivity
89%, 2,3- dichloropyridine yields 82.8%.
Embodiment 3
In 250ml autoclaves, 30g2,3,6- trichloropyridines, 90g ethanol, 30g triethylamines, 0.08g tri- are put into
(triphenylphosphine) radium chloride (I), 0.3g triphenylphosphines are passed through air in nitrogen displacement reaction kettle, replacement completion, and logical hydrogen simultaneously rises
Warm to 83 DEG C are reacted, and reaction pressure is gradually reduced in reaction process, are filled into hydrogen and are maintained reaction pressure in 0.8~1.0MPa
Between, successive reaction 24h, reaction terminates.Sampling analysis 2,3,6- trichloropyridines conversion ratio 95%, 2,3- dichloropyridines selectivity
90%, 2,3- dichloropyridine yields 85.5%.
Embodiment 4
In 250ml autoclaves, 20g2,3,6- trichloropyridines, 90g isopropanols, 20g triethylamines, 0.15g tri- are put into
(triphenylphosphine) radium chloride (I), 0.4g triphenylphosphines are passed through air in nitrogen displacement reaction kettle, replacement completion, and logical hydrogen simultaneously rises
Warm to 88 DEG C are reacted, and reaction pressure is gradually reduced in reaction process, are filled into hydrogen and are maintained reaction pressure in 1.0~1.2MPa
Between, successive reaction 22h, reaction terminates.Sampling analysis 2,3,6- trichloropyridines conversion ratio 95%, 2,3- dichloropyridines selectivity
88%, 2,3- dichloropyridine yields 83.6%.
Embodiment 5
In 250ml autoclaves, 30g2,3,6- trichloropyridines, 90g methanol, 30g triethylamines, 0.2g tri- (three are put into
Phenylphosphine) radium chloride (I), 0.4g triphenylphosphines, are passed through air in nitrogen displacement reaction kettle, replacement completion, leads to hydrogen and simultaneously heat up
Reacted to 75 DEG C, reaction pressure is gradually reduced in reaction process, fill into hydrogen maintain reaction pressure 2.0~2.2MPa it
Between, successive reaction 18h, reaction terminates.Sampling analysis 2,3,6- trichloropyridines conversion ratio 95%, 2,3- dichloropyridines selectivity
87.8%, 2,3- dichloropyridine yields 83.4%.
Embodiment 6
In 250ml autoclaves, input 30g2,3,6- trichloropyridines, 80g ethanol, 10g water, 30g triethylamines,
0.2g tri- (triphenylphosphine) radium chloride (I), 0.4g triphenylphosphines, are passed through air in nitrogen displacement reaction kettle, replacement completion, leads to hydrogen
Gas is simultaneously warming up to 110 DEG C and is reacted, and reaction pressure is gradually reduced in reaction process, fills into hydrogen and maintains reaction pressure 0.5
Between~0.6MPa, successive reaction 18h, reaction terminates.Sampling analysis 2,3,6- trichloropyridines conversion ratio 95%, 2,3- dichloro pyrroles
Pyridine selectivity 85.6%, 2,3- dichloropyridine yields 81.3%.
Embodiment 7
In 250ml autoclaves, input 30g2,3,6- trichloropyridines, 90g methanol, 20g water, 10g sodium hydroxides,
0.15g tri- (triphenylphosphine) radium chloride (I), 0.4g triphenylphosphines, are passed through air in nitrogen displacement reaction kettle, replacement completion, leads to
Hydrogen is simultaneously warming up to 83 DEG C and is reacted, and reaction pressure is gradually reduced in reaction process, fills into hydrogen and maintains reaction pressure 0.8
Between~1.0MPa, successive reaction 16h, reaction terminates.Sampling analysis 2,3,6- trichloropyridines conversion ratio 94%, 2,3- dichloro pyrroles
Pyridine selectivity 85.1%, 2,3- dichloropyridine yields 80.0%.
Embodiment 8
In 250ml autoclaves, 30g2,3,6- trichloropyridines, 90g ethanol, 30g triethylamines, 0.5g tri- (three are put into
Phenylphosphine) bromination rhodium (I), 1g triphenylphosphines, are passed through air in nitrogen displacement reaction kettle, replacement completion, leads to hydrogen and be simultaneously warming up to
75 DEG C are reacted, and reaction pressure is gradually reduced in reaction process, fill into hydrogen maintain reaction pressure 0.8~1.0MPa it
Between, successive reaction 18h, reaction terminates.Sampling analysis 2,3,6- trichloropyridines conversion ratio 96%, 2,3- dichloropyridines selectivity
89.3%, 2,3- dichloropyridine yields 85.7%.
Comparative example 1
In 250ml autoclaves, 30g2,3,6- trichloropyridines, 90g ethanol, 30g triethylamines, 2.58g tri- are put into
(triphenylphosphine) radium chloride (I), is passed through air in nitrogen displacement reaction kettle, replacement completion, and logical hydrogen is simultaneously warming up to 80 DEG C of progress
React, reaction pressure is gradually reduced in reaction process, is filled into hydrogen and is maintained reaction pressure between 0.8~1.0MPa, continuous anti-
20h is answered, reaction terminates.Sampling analysis 2,3,6- trichloropyridines conversion ratio 99%, 2,3- dichloropyridines selectivity 90%, 2,3- bis-
Chloropyridine yield 89.1%.
Comparative example 2
In 250ml autoclaves, 30g2,3,6- trichloropyridines, 90g ethanol, 30g triethylamines, 0.5g tri- (three are put into
Phenylphosphine) radium chloride (I), air in nitrogen displacement reaction kettle, replacement completion are passed through, logical hydrogen is simultaneously warming up to 80 DEG C of progress instead
Should, reaction pressure is gradually reduced in reaction process, is filled into hydrogen and is maintained reaction pressure between 0.8~1.0MPa, successive reaction
20h, reaction terminate.Sampling analysis 2,3,6- trichloropyridines conversion ratio 72%, 2,3- dichloropyridines selectivity 82%, 2,3- dichloros
Pyridine yield 59.0%.
Comparative example 3
In 250ml autoclaves, 30g2,3,6- trichloropyridines, 90g ethanol, 30g triethylamines, 0.08g tri- are put into
(triphenylphosphine) radium chloride (I), is passed through air in nitrogen displacement reaction kettle, replacement completion, and logical hydrogen is simultaneously warming up to 83 DEG C of progress
React, reaction pressure is gradually reduced in reaction process, is filled into hydrogen and is maintained reaction pressure between 0.8~1.0MPa, continuous anti-
24h is answered, reaction terminates.Sampling analysis：2,3,6- trichloropyridine conversion ratios 62%, 2,3- dichloropyridines selectivity 78%, 2,3-
Dichloropyridine yield 48.3%.
Comparative example 4
In 250ml autoclaves, 30g2,3,6- trichloropyridines, 90g ethanol, 30g triethylamines, 0.5g tri- (three are put into
Phenylphosphine) bromination rhodium (I), air in nitrogen displacement reaction kettle, replacement completion are passed through, logical hydrogen is simultaneously warming up to 75 DEG C of progress instead
Should, reaction pressure is gradually reduced in reaction process, is filled into hydrogen and is maintained reaction pressure between 0.8~1.0MPa, successive reaction
18h, reaction terminate.Sampling analysis 2,3,6- trichloropyridines conversion ratio 74%, 2,3- dichloropyridines selectivity 80%, 2,3- dichloros
Pyridine yield 59.2%.
By comparative example 1 compared with embodiment 1, the present invention is by adding organic triphenylphosphine of auxiliary agent containing phosphine, big
Width reduce catalyst amount under conditions of, can still significantly improve feed stock conversion and purpose product selectivity, be substantially achieved with it is right
The suitable effect of ratio 1；And expensive three (triphenylphosphine) radium chloride (I) catalyst usage amounts can be greatly reduced, greatly
Width reduces the production cost of 2,3- dichloropyridines.By comparative example 2 compared with embodiment 1, comparative example 3 and embodiment 2,3 compare
Understood compared with, comparative example 4 compared with embodiment 8, by adding organic triphenylphosphine of auxiliary agent containing phosphine, raw material 2,3,6- can be significantly improved
The selectivity and yield of trichloropyridine conversion ratio and purpose product 2,3- dichloropyridines；In amount ranges of the present invention, with having
The increase of machine auxiliary dosage containing phosphine, raw material 2,3,6- trichloropyridines conversion ratio and purpose product 2, the yield of 3- dichloropyridines also increase
Add.
Claims (10)
1. one kind 2, the synthetic method of 3- dichloropyridines, it is characterised in that in the presence of solvent and acid binding agent, with 2,3,6- trichlorines
Pyridine is raw material, hydrogen is hydrogen source, and three (triphenylphosphine) radium chlorides (I) or three (triphenylphosphine) bromination rhodiums (I) are catalyst, is led to
Cross and add organic auxiliary agent containing phosphine, catalytic hydrogenation reaction is carried out under 20~200 DEG C of 0.1~8MPa of pressure, temperature reaction conditions and is obtained
To 2,3- dichloropyridines.
2. the synthetic method of 2,3- dichloropyridines according to claim 1, it is characterised in that the catalyst and 2,3,
The molar ratio of 6- trichloropyridines is at least 1:10000；The molar ratio of organic auxiliary agent containing phosphine and catalyst is at least 1：1；Acid binding agent
It is at least 1 with the molar ratio of 2,3,6- trichloropyridines:1.
3. the synthetic method of 2,3- dichloropyridines according to claim 2, it is characterised in that the catalyst and 2,3,
The molar ratio of 6- trichloropyridines is 1:100~3000；The molar ratio of organic auxiliary agent containing phosphine and catalyst is 3~20:1；Acid binding agent
Molar ratio with 2,3,6- trichloropyridines is 1.2~2:1.
4. the synthetic method of 2,3- dichloropyridines according to claim 3, it is characterised in that the catalyst and 2,3,
The molar ratio of 6- trichloropyridines is 1:200~2000；The molar ratio of organic auxiliary agent containing phosphine and catalyst is 5~15:1.
5. the synthetic method of 2,3- dichloropyridines according to claim 1, it is characterised in that organic auxiliary agent containing phosphine
For triphenylphosphine, diphenyl (o- tolyls) phosphine, diphenyl (m- tolyls) phosphine, diphenyl (p- tolyls) phosphine, double (o- toluene
Base) Phenylphosphine, double (m- tolyls) Phenylphosphines, double (p- tolyls) Phenylphosphines, three (o-tolyl) phosphines, three (tolyl)
Phosphine, three (p-methylphenyl) phosphines, diphenylcyclohexyl phosphine, dicyclohexlphenylphosphine, tricyclohexyl phosphine, double diphenylphosphine methane, 1,
One kind in double (diphenylphosphine) ethane of 2-, double (diphenylphosphine) propane of 1,3-, double (diphenylphosphine) butane of 1,4-；Preferably three
Phenylphosphine.
6. the synthetic method of 2,3- dichloropyridines according to claim 1, it is characterised in that the solvent is selected from aromatic hydrocarbons
A kind of in class, alkanes, alcohols, ethers, esters or water or at least two mixing；
The aromatic hydrocarbon solvent is selected from toluene, benzene, dimethylbenzene, pyridine；
The alkane solvents are selected from n-hexane, hexamethylene；The alcohols solvent is selected from methanol, ethanol, isopropanol；Described
Ether solvent is selected from tetrahydrofuran, ether；
The esters solvent is selected from ethyl acetate, methyl acetate, butyl acetate.
7. the synthetic method of 2,3- dichloropyridines according to claim 6, it is characterised in that the solvent is toluene, first
Any one alcohols in a kind of or at least two mixing or methanol, ethanol, isopropanol in alcohol, ethanol, isopropanol is molten
Agent and the mixing of water.
8. the synthetic method of 2,3- dichloropyridines according to claim 1, it is characterised in that the acid binding agent, which is selected from, to be had
Machine alkali or inorganic alkali compound；
The one kind of the organo-alkali compound in triethylamine, tetramethylethylenediamine, 4-methyl-diaminopropane, pyridine；
The one kind of the inorganic base in ammonia, the hydroxide of alkali metal or carbonate, bicarbonate, acetate；Institute
The alkali metal stated is sodium or potassium.
9. the synthetic method of 2,3- dichloropyridines according to claim 8, it is characterised in that the acid binding agent is selected from three
Ethamine or pyridine, sodium acetate or sodium hydroxide.
10. the synthetic method of 2,3- dichloropyridines according to claim 1, it is characterised in that the reaction pressure is
0.4~3MPa, temperature are 40~120 DEG C.
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| 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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