CN109721529A - A kind of simple and convenient process for preparing of 2,5- dichloropyridine - Google Patents
A kind of simple and convenient process for preparing of 2,5- dichloropyridine Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of green safe, easy 2,5- dichloropyridine.The present invention is condensed with nitromethane using maleic acid ester as initial feed plus hydrogen cyclisation, chloro prepares 2,5- dichloropyridine.Preparation method of the present invention is simple, easily operated, and reaction selectivity is high, product yield, purity is high；The method of the present invention waste water yield is few, environmentally protective, and reaction safety is high；And it is raw materials used cheap and easy to get, it is at low cost.
Description
Technical field
The present invention relates to the simple and convenient process for preparing of one kind 2,5- dichloropyridine, belong to technical field of medical chemistry.
Background technique
2,5- dichloropyridines are a kind of important pesticide, medicine intermediate, can synthesizing anti-AIDS, antiulcer drug
Equal pharmaceutical intermediates, are alternatively arranged as the intermediate of pyridine insecticides, and in dyestuff, the fields such as medicine and pesticide, which have, is widely answered
With.
2,5- dichloropyridines mainly have following three kinds of synthetic methods, are with 2- chloropyridine, 2-aminopyridine and 23 respectively,
6- trichloropyridine is prepared for starting material.
1, using 2- chloropyridine as raw material, 2- butoxy pyridine is obtained by reacting with n-butanol, then leads to chlorine and obtains
Then the 2- butoxy -5- chloropyridine of 85wt% and the 2- butoxy -3- chloropyridine mixture of 15wt% use phosphorus oxychloride chlorine
In generation, prepare 2,5- dichloropyridine and 2,3- dichloropyridine mixture, then with isolated 2, the 5- dichloropyridine of isopropanol water solution,
Total recovery is 36.29%, is described as following synthetic route 1 (referring to patent document US 5380862):
Above 1 method and step of synthetic route is more, the period is long, processing is complicated, and raw materials used chlorine, toxicity is big, is unfavorable for pacifying
Loopful is protected, simultaneous reactions poor selectivity, needs to carry out 2,5- dichloropyridine and 2, the separation of 3- dichloropyridine mixture, separation hardly possible
Degree is big, and total recovery is low, is difficult to realize industrialization.
2, using 2-aminopyridine as raw material, 2-aminopyridine is dissolved in concentrated hydrochloric acid and hydrogen peroxide, chlorination generates intermediate
Then product 2- amino -5- chloropyridine reacts to obtain target product 2 using diazotising and sandmeyer, 5- dichloropyridine, always
Yield is 58%, be described as following synthetic route 2 (referring to document: Harbin University of Science and Technology's Master's thesis, 2012, dichloropyridine
Synthesis, Wang Huijuan):
In the above synthetic route 2 diazonium salt caused by diazo-reaction under the action of temperature is slightly higher or light i.e. easily point
Solution, diazonium salt is unstable, it is active it is high, heated or friction, hit, energy decomposition explosion is unfavorable for safety and environmental protection, and target product 2,
5- dichloropyridine yield is relatively low, therefore, is not suitable for industrialized developing.
3,2,3,6- trichloropyridines are dissolved in benzene or toluene, hydrogen-oxygen is then added for raw material with 2,3,6- trichloropyridines
To change sodium solution, be heated to flowing back, zinc powder is added in three batches and carries out reduction reaction, cold filtration obtains 2,5- dichloropyridine crude product,
Then 2,5- dichloropyridine is made with ethyl alcohol recrystallization, total recovery 78.3% is described as following synthetic route 3 (referring to patent
Document CN101709050A):
Above 3 method of synthetic route raw materials used 2,3,6- trichloropyridines are expensive, and big using benzene and toluene toxicity
Solvent, zinc powder is added portionwise, inconvenient for operation, crude product needs recrystallizing and refining, needs a large amount of alcohol solvents, and generate a large amount of
Solid waste is unfavorable for safety and environmental protection.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation side of green safe, easy 2,5- dichloropyridine
Method.Preparation method of the present invention is simple, easily operated, and reaction selectivity is high, product yield, purity is high；The method of the present invention waste water produces
Raw amount is few, environmentally protective, and reaction safety is high；And it is raw materials used cheap and easy to get, it is at low cost.
Term explanation:
Maleic acid ester: also known as maleic acid diester；
II compound of formula: cis- 5- nitro -4- oxo -2- n-pentene acid esters；
III compound of formula: 2,5- dihydroxy-pyridines also known as 5- pyridone -2 (1H) -one.
Technical scheme is as follows:
The preparation method of one kind 2,5- dichloropyridine, comprising steps of
(1) maleic acid ester and nitromethane carry out condensation reaction under organic base catalytic, and II chemical combination containing formula is made
The reaction solution of object；Without isolation, solvent and catalyst is added in reaction solution, the hydrogenated cyclisation preparation of II compound of formula in reaction solution
Obtain III compound of formula；
Wherein, one of the alkyl that R is C1-4 in II compound of formula；Preferably, R is methyl, ethyl, isopropyl or uncle
One of butyl；
(2) 2,5- dichloropyridine is made through chloro in III compound of formula and chlorinating agent.
Preferred according to the present invention, the molar ratio of maleic acid ester described in step (1) and nitromethane is 1:
(0.90~1.1).
Preferred according to the present invention, maleic acid ester described in step (1) is dimethyl maleate, maleic
One of diethyl adipate, maleic acid diisopropyl ester or maleic acid di tert butyl carbonate.
Preferred according to the present invention, organic base described in step (1) is 1,8- diazabicyclo [5.4.0] -7-, 11 carbon
The combination of one or both of alkene (DBU) or 1,5- diazabicyclo [4.3.0] -5- nonene (DBN).
It is preferred according to the present invention, the quality of organic base described in step (1) be maleic acid ester quality 1.2~
5%；Preferably, the quality of organic base described in step (1) is the 1.5-4% of maleic acid ester quality.
Preferred according to the present invention, setting-up point described in step (1) is 30~90 DEG C；Preferably, in step (1)
The setting-up point is 60-70 DEG C.Reaction time is 2~8 hours.
It is preferred according to the present invention, the quality of catalyst described in step (1) be maleic acid ester quality 0.5~
15%.
Preferred according to the present invention, catalyst described in step (1) is palladium charcoal or Raney Ni.
Preferably, the quality of the palladium charcoal is the 0.5%~5% of maleic acid ester quality；It is further preferred that institute
The quality for stating palladium charcoal is the 1%~3% of maleic acid ester quality.
Preferably, the quality of the Raney Ni is the 1%~15% of maleic acid ester quality, it is further preferred that
The quality of the Raney Ni is the 5%~10% of maleic acid ester quality.Catalyst type and dosage are for improving 2,5-
The yield of dihydroxy-pyridine is particularly significant.
Preferred according to the present invention, solvent described in step (1) is methanol, ethyl alcohol, isopropanol, tetrahydrofuran, dichloromethane
The mixing of one or more of alkane, 1,2- dichloroethanes or toluene.
It is preferred according to the present invention, the mass ratio of maleic acid ester described in step (1) and solvent be 1:(3~
15)。
It is preferred according to the present invention, in step (1) plus hydrogen cyclization, Hydrogen Vapor Pressure 0.1-0.3MPa；In step (1)
Described plus hydrogen cyclization temperature is 20~80 DEG C；Preferably, it is 50~70 that hydrogen cyclization temperature is added described in step (1)
℃.Reaction time is 3~8 hours.
Preferred according to the present invention, chlorinating agent described in step (2) is in thionyl chloride, phosphorus oxychloride or phosphorus pentachloride
A combination of one or more.
It is preferred according to the present invention, the molar ratio of III compound of formula and chlorinating agent described in step (2) be 1:(5~
15)。
Preferred according to the present invention, chlorination temperature described in step (2) is 40~160 DEG C；Preferably, step (2)
Described in chlorination temperature be 60~150 DEG C.Reaction time is 2-18 hours.
Method of the invention is described as following synthetic route 4:
Technical characterstic of the invention and the utility model has the advantages that
1, the present invention carries out condensation reaction using maleic acid ester and nitromethane under organic base catalytic and is made cis-
5- nitro -4- oxo -2- n-pentene acid esters (II), then hydrogenated cyclisation preparation 2,5- dihydroxy-pyridine (III), then and chloro
2,5- dichloropyridine (I) is made through chloro in reagent.
2, unit process designed by the present invention is highly-safe, is not related to the big low temperature chlorination of security risk or diazotising
Reaction, while also without using toxic gases such as the big chlorine of toxicity, reaction selectivity used is high, and it is easily operated, product yield high,
Purity is high, total recovery are up to 88.6%, are suitable for industrialized production.
3, the raw materials used in the present invention is cheap and easy to get, and route is easy, and post-processing is simple, at low cost, does not need using solvent pair
Final product is recrystallized, so that waste water yield is few, it is environmentally protective.
Specific embodiment
The present invention is described in detail with reference to embodiments, but the present invention is not only limited to this.
Embodiment is raw materials used and reagent is commercial product." % " described in embodiment is weight percentage, especially
Except illustrating.Yield in embodiment is molar yield.
The preparation of embodiment 1:2,5- dihydroxy-pyridine
To be connected to stirring, thermometer, reflux condensing tube 500 milliliters of four-hole boiling flasks in, be added 30.5 grams of (0.5 mole) nitre
Methylmethane, 72.0 grams of (0.5 mole) dimethyl maleates, 1.8 grams of DBU, 60-65 DEG C is stirred to react 5 hours, is cooled to
20-25℃.During gained reaction liquid is transferred in 1 liter of autoclave pressure, 400 grams of methanol are added, 1.0 grams of palladium mass contents are 5%
Palladium carbon (aqueous 50wt%) catalyst be passed through hydrogen after nitrogen displacement three times, holdings Hydrogen Vapor Pressure is 0.1-0.2MPa, 50-
55 DEG C are reacted 4 hours.After nitrogen displacement three times, Filtration of catalyst, filtrate concentration is evaporated, and 100 grams of methyl tertiary butyl ethers are added
Recrystallization, obtains 51.7 grams of light yellow solids 2,5- dihydroxy-pyridine (III), liquid phase purity 99.7%, product yield 93.1%.
The preparation of embodiment 2:2,5- dihydroxy-pyridine
To be connected to stirring, thermometer, reflux condensing tube 500 milliliters of four-hole boiling flasks in, be added 30.5 grams of (0.5 mole) nitre
Methylmethane, 86.1 grams of (0.5 mole) diethyl maleates, 1.8 grams of DBN, 65-70 DEG C is stirred to react 5 hours, is cooled to
20-25℃.During gained reaction liquid is transferred in 1 liter of autoclave pressure, 400 grams of ethyl alcohol are added, 1.2 grams of palladium mass contents are 5%
Palladium carbon (aqueous 50wt%) catalyst be passed through hydrogen after nitrogen displacement three times, holdings Hydrogen Vapor Pressure is 0.1-0.2MPa, 50-
55 DEG C are reacted 4 hours.After nitrogen displacement three times, Filtration of catalyst, filtrate concentration is evaporated, and 100 grams of methyl tertiary butyl ethers are added
Recrystallization, obtains 52.2 grams of light yellow solids 2,5- dihydroxy-pyridine (III), liquid phase purity 99.8%, product yield 94.0%.
The preparation of embodiment 3:2,5- dihydroxy-pyridine
To be connected to stirring, thermometer, reflux condensing tube 500 milliliters of four-hole boiling flasks in, be added 30.5 grams of (0.5 mole) nitre
Methylmethane, 100.1 grams of (0.5 mole) maleic acid diisopropyl esters, 1.8 grams of DBU, 65-70 DEG C is stirred to react 5 hours, cooling
To 20-25 DEG C.During gained reaction liquid is transferred in 1 liter of autoclave pressure, 400 grams of isopropanols are added, 8.0 grams of nickel mass contents are
50% Raney Ni (aqueous 50wt%) catalyst after nitrogen displacement three times, is passed through hydrogen, and holding Hydrogen Vapor Pressure is 0.1-
0.2MPa, 60-65 DEG C are reacted 4 hours.After nitrogen displacement three times, Filtration of catalyst, filtrate concentration is evaporated, and is added 100 grams
Methyl tertiary butyl ether recrystallization, obtains 52.0 grams of light yellow solids 2,5- dihydroxy-pyridine (III), liquid phase purity 99.6%, product yield
93.6%.
The preparation of embodiment 4:2,5- dihydroxy-pyridine
To be connected to stirring, thermometer, reflux condensing tube 500 milliliters of four-hole boiling flasks in, be added 30.5 grams of (0.5 mole) nitre
Methylmethane, 114.1 grams of (0.5 mole) maleic acid di tert butyl carbonates, 1.8 grams of DBU, 65-70 DEG C is stirred to react 5 hours, cooling
To 20-25 DEG C.During gained reaction liquid is transferred in 1 liter of autoclave pressure, 400 grams of tetrahydrofurans, 9.0 grams of nickel mass contents are added
For 50% Raney Ni (aqueous 50wt%) catalyst, after nitrogen displacement three times, it is passed through hydrogen, holding Hydrogen Vapor Pressure is 0.1-
0.2MPa, 60-65 DEG C are reacted 5 hours.After nitrogen displacement three times, Filtration of catalyst, filtrate concentration is evaporated, and is added 100 grams
Methyl tertiary butyl ether recrystallization, obtains 50.8 grams of light yellow solids 2,5- dihydroxy-pyridine (III), liquid phase purity 99.7%, product yield
91.5%.
The preparation of embodiment 5:2,5- dichloropyridine
150 grams of phosphorus oxychloride are added into 500 milliliters of four-hole boiling flasks that thermometer, mechanical stirring, reflux condensing tube are housed,
2, the 5- dihydroxy-pyridine of 22.0 grams of (0.2 mole) embodiments 2 preparation, 105.0 grams of (0.5 mole) phosphorus pentachlorides, 70-75 DEG C is stirred
Reaction 12 hours is mixed, then extra phosphorus oxychloride is recycled in vacuum distillation, slowly pours into residue in 300 grams of ice water, sufficiently
Then stirring is 7-9 with pH value in 40% sodium hydrate aqueous solution, is extracted with dichloromethane three times, 50 grams every time, merges organic
Phase, it is then dry with 5 grams of anhydrous sodium sulfates with 30 grams of saturated common salt water washings, revolving remove solvent obtain 27.5 grams it is faint yellow
Powder 2,5- dichloropyridine (I), yield 92.9%, liquid phase purity 99.7%.The nuclear magnetic data of product is as follows:
1H NMR(CDCl3, δ, ppm):
7.38 (d, 1H), 7.64 (d, 1H), 8.35 (s, 1H).
The preparation of embodiment 6:2,5- dichloropyridine
200 grams of thionyl chlorides are added into 500 milliliters of four-hole boiling flasks that thermometer, mechanical stirring, reflux condensing tube are housed,
2, the 5- dihydroxy-pyridine of 22.0 grams of (0.2 mole) embodiments 2 preparation, 105.0 grams of (0.5 mole) phosphorus pentachlorides, 60-65 DEG C is stirred
Reaction 15 hours is mixed, then extra thionyl chloride is recycled in vacuum distillation, slowly pours into residue in 300 grams of ice water, sufficiently
Then stirring is 7-9 with pH value in 40% sodium hydrate aqueous solution, is extracted with dichloromethane three times, 50 grams every time, merges organic
Phase, it is then dry with 5 grams of anhydrous sodium sulfates with 30 grams of saturated common salt water washings, revolving remove solvent obtain 26.8 grams it is faint yellow
Powder 2,5- dichloropyridine (I), yield 90.5%, liquid phase purity 99.8%.
The preparation of embodiment 7:2,5- dichloropyridine
200 grams of phosphorus oxychloride are added into 500 milliliters of four-hole boiling flasks that thermometer, mechanical stirring, reflux condensing tube are housed,
2, the 5- dihydroxy-pyridine of 22.0 grams of (0.2 mole) embodiments 2 preparation, 140-145 DEG C is stirred to react 4 hours, and then decompression is steamed
It evaporates and recycles extra phosphorus oxychloride, slowly residue is poured into 300 grams of ice water, is sufficiently stirred, then 40% sodium hydroxide water
In solution and pH value is 7-9, is extracted with dichloromethane three times, 50 grams every time, merges organic phase, is washed with 30 grams of saturated common salts
It washs, then dry with 5 grams of anhydrous sodium sulfates, revolving removes solvent and obtains 27.9 grams of pale yellow powders 2, and 5- dichloropyridine (I) is received
Rate 94.3%, liquid phase purity 99.5%.
The preparation of comparative example 1:2,5- dihydroxy-pyridine
To be connected to stirring, thermometer, reflux condensing tube 500 milliliters of four-hole boiling flasks in, be added 30.5 grams of (0.5 mole) nitre
Methylmethane, 72.0 grams of (0.5 mole) dimethyl maleates, 0.8 gram of DBU, 60-65 DEG C is stirred to react 5 hours, is cooled to
20-25℃.During gained reaction liquid is transferred in 1 liter of autoclave pressure, 400 grams of methanol are added, 1.0 grams of palladium mass contents are 5%
Palladium carbon (aqueous 50wt%) catalyst be passed through hydrogen after nitrogen displacement three times, holdings Hydrogen Vapor Pressure is 0.1-0.2MPa, 50-
55 DEG C are reacted 4 hours.After nitrogen displacement three times, Filtration of catalyst, filtrate concentration is evaporated, and 100 grams of methyl tertiary butyl ethers are added
Recrystallization, obtains 31.2 grams of light yellow solids 2,5- dihydroxy-pyridine (III), liquid phase purity 99.1%, product yield 56.2%.
Thus it is found that organic alkali catalyst dosage is too low, reaction is not thorough comparative example, causes 2,5- dihydroxy-pyridine yield
It is lower.
The preparation of comparative example 2:2,5- dihydroxy-pyridine
To be connected to stirring, thermometer, reflux condensing tube 500 milliliters of four-hole boiling flasks in, be added 30.5 grams of (0.5 mole) nitre
Methylmethane, 72.0 grams of (0.5 mole) dimethyl maleates, 1.8 grams of DBU, 98-100 DEG C is stirred to react 3 hours, is cooled to
20-25℃.During gained reaction liquid is transferred in 1 liter of autoclave pressure, 400 grams of methanol are added, 1.0 grams of palladium mass contents are 5%
Palladium carbon (aqueous 50wt%) catalyst be passed through hydrogen after nitrogen displacement three times, holdings Hydrogen Vapor Pressure is 0.1-0.2MPa, 50-
55 DEG C are reacted 4 hours.After nitrogen displacement three times, Filtration of catalyst, filtrate concentration is evaporated, and 100 grams of methyl tertiary butyl ethers are added
Recrystallization, obtains 28.5 grams of light yellow solids 2,5- dihydroxy-pyridine (III), liquid phase purity 98.6%, product yield 51.4%.
Thus for comparative example it is found that setting-up point is excessively high, other by-products are more, and yield reduces.
The preparation of comparative example 3:2,5- dihydroxy-pyridine
To be connected to stirring, thermometer, reflux condensing tube 500 milliliters of four-hole boiling flasks in, be added 42.0 grams of (0.7 mole) nitre
Methylmethane, 72.0 grams of (0.5 mole) dimethyl maleates, 1.8 grams of DBU, 60-65 DEG C is stirred to react 5 hours, is cooled to
20-25℃.During gained oily liquids is transferred in 1 liter of autoclave pressure, 400 grams of methanol are added, 1.0 grams of palladium mass contents are 5%
Palladium carbon (aqueous 50wt%) catalyst be passed through hydrogen after nitrogen displacement three times, holdings Hydrogen Vapor Pressure is 0.1-0.2MPa, 50-
55 DEG C are reacted 4 hours.After nitrogen displacement three times, Filtration of catalyst, filtrate concentration is evaporated, and 100 grams of methyl tertiary butyl ethers are added
Recrystallization, obtains 34.1 grams of light yellow solids 2,5- dihydroxy-pyridine (III), liquid phase purity 99.3%, product yield 61.5%.
Thus comparative example will lead to two molecule nitro first it is found that nitromethane and maleic acid ester ratio are improper
Alkane and the condensation of 1 molecule maleic acid ester, sticky by-product is more, and reduces yield.
Claims (10)
1. one kind 2, the preparation method of 5- dichloropyridine, comprising steps of
(1) maleic acid ester and nitromethane carry out condensation reaction under organic base catalytic, and II compound containing formula is made
Reaction solution；Without isolation, solvent and catalyst is added in reaction solution, and the hydrogenated cyclisation of II compound of formula in reaction solution is prepared into formula
III compound；
Wherein, R is C in II compound of formula1-4One of alkyl；Preferably, R is methyl, ethyl, isopropyl or tert-butyl
One of；
(2) 2,5- dichloropyridine is made through chloro in III compound of formula and chlorinating agent.
2. the preparation method of 2,5- dichloropyridine according to claim 1, which is characterized in that along fourth described in step (1)
The molar ratio of enedioic acid diester and nitromethane is 1:(0.90~1.1)；
Preferably, maleic acid ester described in step (1) be dimethyl maleate, it is diethyl maleate, suitable
One of butene dioic acid diisopropyl ester or maleic acid di tert butyl carbonate.
3. the preparation method of 2,5- dichloropyridine according to claim 1, which is characterized in that organic described in step (1)
Alkali is 1,8- diazabicyclo [5.4.0] -7- endecatylene (DBU) or 1,5- diazabicyclo [4.3.0] -5- nonene (DBN)
One or both of combination；
Preferably, the quality of organic base described in step (1) is the 1.2~5% of maleic acid ester quality；Further preferably
, the quality of organic base described in step (1) is the 1.5-4% of maleic acid ester quality.
4. the preparation method of 2,5- dichloropyridine according to claim 1, which is characterized in that be condensed described in step (1)
Reaction temperature is 30~90 DEG C；Preferably, setting-up point described in step (1) is 60-70 DEG C.
5. the preparation method of 2,5- dichloropyridine according to claim 1, which is characterized in that be catalyzed described in step (1)
The quality of agent is the 0.5~15% of maleic acid ester quality.
6. the preparation method of 2,5- dichloropyridine according to claim 1, which is characterized in that be catalyzed described in step (1)
Agent is palladium charcoal or Raney Ni；
Preferably, the quality of the palladium charcoal is the 0.5%~5% of maleic acid ester quality；It is further preferred that the palladium
The quality of charcoal is the 1%~3% of maleic acid ester quality；
Preferably, the quality of the Raney Ni is the 1%~15% of maleic acid ester quality；It is further preferred that described
The quality of Raney Ni is the 5%~10% of maleic acid ester quality.
7. the preparation method of 2,5- dichloropyridine according to claim 1, which is characterized in that solvent described in step (1)
It is the mixed of one or more of methanol, ethyl alcohol, isopropanol, tetrahydrofuran, methylene chloride, 1,2- dichloroethanes or toluene
It closes；
Preferably, the mass ratio of maleic acid ester described in step (1) and solvent is 1:(3~15).
8. the preparation method of 2,5- dichloropyridine according to claim 1, which is characterized in that step (1) plus hydrogen cyclisation are anti-
Ying Zhong, Hydrogen Vapor Pressure 0.1-0.3MPa；Described in step (1) plus hydrogen cyclization temperature is 20~80 DEG C；Preferably, step
(1) described in plus hydrogen cyclization temperature is 50~70 DEG C.
9. the preparation method of 2,5- dichloropyridine according to claim 1, which is characterized in that chloro described in step (2)
Reagent is the combination of one or more of thionyl chloride, phosphorus oxychloride or phosphorus pentachloride；
Preferably, the molar ratio of III compound of formula and chlorinating agent described in step (2) is 1:(5~15).
10. the preparation method of 2,5- dichloropyridine according to claim 1, which is characterized in that chloro described in step (2)
Reaction temperature is 40~160 DEG C；Preferably, chlorination temperature described in step (2) is 60~150 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5380862A (en) * | 1992-10-07 | 1995-01-10 | Rutgerswerke Aktiengesellschaft | Preparation of isomer-free 2,5-dichloro-pyridine |
| CN101709050A (en) * | 2009-11-24 | 2010-05-19 | 南京第一农药集团有限公司 | New method for synthesizing 2, 5-dichloropyridine |
| KR20160050361A (en) * | 2014-10-29 | 2016-05-11 | 삼성에스디아이 주식회사 | Compound, organic optoelectric device and display device |
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2017
- 2017-10-27 CN CN201711020260.5A patent/CN109721529B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5380862A (en) * | 1992-10-07 | 1995-01-10 | Rutgerswerke Aktiengesellschaft | Preparation of isomer-free 2,5-dichloro-pyridine |
| CN101709050A (en) * | 2009-11-24 | 2010-05-19 | 南京第一农药集团有限公司 | New method for synthesizing 2, 5-dichloropyridine |
| KR20160050361A (en) * | 2014-10-29 | 2016-05-11 | 삼성에스디아이 주식회사 | Compound, organic optoelectric device and display device |
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| Title |
|---|
| ANDRIY V.TYMTSUNIK ET AL.: "Synthesis of Boc-protected 4,5-methano-β-proline", 《TETRAHEDRON LETTERS》 * |
| KIMBERLY YEARICK SPANGLER ET AL.: "Asymmetric Copper(I)-Catalyzed Henry Reaction with an Aminoindanol-Derived Bisoxazolidine Ligand", 《ORGANIC LETTERS》 * |
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| 杨祥宇 等: "2, 3, 5-三氯吡啶合成的研究", 《化学工业与工程》 * |
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Denomination of invention: A simple preparation method of 2,5-dichloropyridine Effective date of registration: 20211130 Granted publication date: 20200901 Pledgee: Zhejiang Commercial Bank Co.,Ltd. Dongying Branch Pledgor: Xinfa pharmaceutical Co.,Ltd. Registration number: Y2021980013546 |
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