CN1830963A - Method for synthesizing 2,3-difluoro-5-chloropyridine - Google Patents
Method for synthesizing 2,3-difluoro-5-chloropyridine Download PDFInfo
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- CN1830963A CN1830963A CN 200510053348 CN200510053348A CN1830963A CN 1830963 A CN1830963 A CN 1830963A CN 200510053348 CN200510053348 CN 200510053348 CN 200510053348 A CN200510053348 A CN 200510053348A CN 1830963 A CN1830963 A CN 1830963A
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Abstract
A 2,3-bifluoro-5-chlorophridine is prepared from 2,3,5-trichloropyridine and potassium (or cesium) fluoride through catalytic reaction in ionized solution.
Description
Technical field
The present invention relates to a kind of Synthetic 2, the novel method of 3-difluoro-5-chloropyridine.Present method is applicable to that with 2,3 the 5-trichloropyridine is a main raw material with containing villiaumite, Synthetic 2, the occasion of 3-difluoro-5-chloropyridine.
Background technology
2, the 3-difluoro-5-chloropyridine is chirality, efficient, low toxicity, broad-spectrum herbicide (R)-2-[4-(5-chloro-3-fluorine pyridine-2-base oxygen) phenoxy group] the indispensable intermediate of chemical pesticide such as propionic acid propargyl ester.This weedicide can be prevented and treated cotton effectively, rape, and soybean, beet, the weeds in the wheat paddock have broad application prospects.
Reference of the present invention all is a Synthetic 2, the relevant patent of 3-difluoro-5-chloropyridine.They are with 2,3, and the 5-trichloropyridine is main starting raw material Synthetic 2 with containing villiaumite, the 3-difluoro-5-chloropyridine.European patent (EP95810654) content relates to Potassium monofluoride as fluorizating agent, 2,3,5-trichloropyridine or 2,3,5-pyridinium tribromide are raw material, preparation 2,3-difluoro-5-chloropyridine or 2, the method for 3-two fluoro-5-bromopyridines, the solvent of employing is the N of tetramethylene sulfone and 5%～30% weight percent, N '-dimethyl propylene two ureas (N.N '-dimethylpropyleneurea), under the effect of phase-transfer catalyst in 150-240 ℃ of reaction.The solvent that is adopted among 24 embodiment of this patent is respectively: mixture, tetraethylene glycol dimethyl ether and the DMPU of mixture, tetraethylene glycol dimethyl ether and the tetramethylene sulfone of the mixture of dimethyl two ureas (DMPU), tetramethylene sulfone, tetramethylene sulfone and DMPU, 18 hat 6 ethers, Tetraglycol 99 dimethyl ether and DMPU and the mixture of tetramethylene sulfone.It is that fluorizating agent prepares α, β and β, γ-dichloropyridine compound that European patent (EP84115856) content relates to Potassium monofluoride and cesium fluoride, comprise 2,3,5-trichloropyridine or 2,3, the 5-pyridinium tribromide changes into 2 respectively, 3 difluoro-5-chloropyridines and 2,3-two fluoro-5-bromopyridines, used solvent is a polar aprotic solvent, used solvent is tetramethylene sulfone, 18 hat 6 ethers, N-Methyl pyrrolidone (NMP) and methyl-sulphoxides (DMDO) in this patent working example.All there is under the long-time high temperature reaction loss easily in the various polar aprotic solvents that use in the above-mentioned reaction process, in vacuum distillation process also easily with shortcomings such as product steam, also contaminate environment easily, the temperature of reaction and reaction times are also long.
Summary of the invention
The objective of the invention is to overcome the shortcoming of existing synthetic method, provide a kind of raw material be easy to get, easy and simple to handle and environment amenable 2,3-difluoro-5-chloropyridine synthetic novel method.
Of the present invention 2, the synthetic method of 3-difluoro-5-chloropyridine is characterized in that with room-temperature ion solution be solvent, in the presence of catalyzer, 2,3,5-trichloropyridine and contain villiaumite under 160～240 ℃ of temperature, reacted 8～20 hours, be cooled to 50～100 ℃, underpressure distillation obtains 2,3-difluoro-5-chloropyridine and 2-fluoro-3, the 5-dichloropyridine.
Synthetic 2-fluoro-3, the 5-dichloropyridine can be with the further Synthetic 2 of aforesaid method, 3-difluoro-5-chloropyridine.
The reaction formula of above-mentioned synthetic method is as follows:
Described solvent is the room-temperature ion solution of alkyl pyridine positively charged ion or alkyl imidazole positively charged ion and fluo anion composition, and the chemical structural formula of ionic liquid at room temperature is:
Wherein, R, R ' or R " to represent carbonatoms respectively be 1～16 alkyl, comprises straight-chain alkyl or branched hydrocarbyl; Y
-=BF
4 -, PF
6 -, AsF
6 -, SbF
6 -, CF
3COO
-, C
3F
7COO
-, CF
3SO
2 -, CF
3SO
3 -, (CF
3SO
2)
2N
-Or (C
2F
5SO
2)
2N-.
Described catalyzer is a kind of basic cpd, and this basic cpd is salt of wormwood or yellow soda ash or potassium hydroxide or sodium hydroxide or sodium methylate or sodium ethylate.
The described villiaumite that contains is that a kind of independent use in lithium fluoride, Sodium Fluoride, Potassium monofluoride, rubidium fluoride and the cesium fluoride or two kinds mix and use.
Of the present invention 2, the synthetic method of 3-difluoro-5-chloropyridine, its key problem in technology is with 2,3, the 5-trichloropyridine is a raw material, and having selected suitable room-temperature ion liquid for use is solvent, having selected the suitable villiaumite that contains for use is fluoro reagent, selected appropriate catalyst for use, the direct Synthetic 2 of one kettle way, 3-difluoro-5-chloropyridine.Present method has reduced the temperature of reaction of former method, has shortened the reaction times, and yield is higher, and solvent is reusable, and is environmentally friendly, easy and simple to handle, is suitable for suitability for industrialized production.
Embodiment
Embodiment 1
In the 100mL reaction flask, put into 2,3, and the 5-trichloropyridine (10.95g, 0.06mmol), KF (6.97g, 0.12mol), CsF (3.04g, 0.02mol), 0.5g K
2CO
3And 50mL room-temperature ion liquid 1-methyl-3-butyl imidazole a tetrafluoro borate ([Bmim] BF
4).。Reaction mixture was 200 ℃ of reactions 10 hours, reaction mixture cooling back underpressure distillation, collection liquid (86-127 ℃/150mmHg), column chromatography, with 5: 1 sherwood oils (60-90 ℃) and ethyl acetate is that leacheate gets 2-fluoro-3,5-dichloropyridine (3.60g, productive rate 36.1%) and 2-fluoro-3,5-dichloropyridine (1.89g, productive rate 21.0%).
Since 2-fluoro-3,5-dichloropyridine and 2, the boiling point of 3-difluoro-5-chloropyridine differs bigger, and also the method for available rectifying is separated, and below is the physical data and the detection data of these two compounds.
2-fluoro-3,5-dichloropyridine: low melting point colorless solid, molten some 38-39 ℃.
Boiling point: 173-174 ℃/760mmHg; 122-123 ℃/150mmHg,
IR(v
max，film)：3045，1568，1235，1130，1035Cm
-1.
1H?NMR：δ＝8.01(d，J＝2.0Hz，1H)，7.44(d，J＝2.0Hz，1H)。
2,3-difluoro-5-chloropyridine: colourless liquid.
Boiling point: 135-136 ℃/760mmHg; 83-84 ℃/150mmHg, 65-66 ℃/1mmHg,
IR(v
max，film)：3035，1558，1225，1125，1025Cm
-1.
1H?NMR：δ＝7.94(d，J＝2.1Hz，1H)，7.51(d，J＝2.1Hz，1H)。
Embodiment 2
50mL room-temperature ion liquid 1-methyl-3-butyl imidazole a tetrafluoro borate ([Bmim] BF packs in 100 milliliters of three mouthfuls of reaction flasks
4)., add 18.4g (0.122mol) CsF (using preceding), 0.5gK 200 ℃ of following vacuum-dryings 16 hours
2CO
3, 13.3g (0.08mol) 2-fluoro-3,5-dichloropyridine, decompression (about 200mmHg) down adds thermal distillation, and 6 hours, steaming temperature was 97-106 ℃/200mmHg, oil bath temperature is 139 ℃ to 144 ℃, and product slowly steams in reaction process, collects product 6.8g, reaction stops, and once more by last method reaction 3 hours, collects the 2.1g product again after spending the night, gas chromatographic analysis contains 7.4g 2,3-difluoro-5-chloropyridine (productive rate 62%), 1.0g 2-fluoro-3,5-dichloropyridine (reclaiming 7.5%).
Claims (5)
1. one kind 2, the synthetic method of 3-difluoro-5-chloropyridine is characterized in that with room-temperature ion solution be solvent, in the presence of catalyzer, 2,3,5-trichloropyridine and contain villiaumite under 160～240 ℃ of temperature, reacted 8～20 hours, be cooled to 50～100 ℃, underpressure distillation obtains 2,3-difluoro-5-chloropyridine and 2-fluoro-3, the 5-dichloropyridine.
2. synthetic method according to claim 1, it is characterized in that with room-temperature ion solution be solvent, in the presence of catalyzer, 2-fluoro-3,5-dichloropyridine and contain villiaumite under 160～240 ℃ of temperature reacted 8～20 hours, be cooled to 50～100 ℃, underpressure distillation obtains 2, the 3-difluoro-5-chloropyridine.
3. synthetic method according to claim 1, used solvent is the room-temperature ion solution of alkyl pyridine positively charged ion or alkyl imidazole positively charged ion and fluo anion composition in it is characterized in that reacting, the chemical structural formula of ionic liquid at room temperature is:
Wherein, R, R ' or R " to represent carbonatoms respectively be 1～16 alkyl, comprises straight-chain alkyl or branched hydrocarbyl; Y
-=BF
4 -, PF
6 -, AsF
6 -, SbF
6 -, CF
3COO
-, C
3F
7COO
-, CF
3SO
2 -, CF
3SO
3 -, (CF
3SO
2)
2N
-Or (C
2F
5SO
2)
2N
-
4. synthetic method according to claim 1, used catalyzer is a kind of basic cpd in it is characterized in that reacting, this basic cpd is salt of wormwood or yellow soda ash or potassium hydroxide or sodium hydroxide or sodium methylate or sodium ethylate.
5. synthetic method according to claim 1, the used villiaumite that contains is that a kind of independent use in lithium fluoride, Sodium Fluoride, Potassium monofluoride, rubidium fluoride and the cesium fluoride or two kinds mix and use in it is characterized in that reacting.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200510053348 CN1830963A (en) | 2005-03-09 | 2005-03-09 | Method for synthesizing 2,3-difluoro-5-chloropyridine |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648904B (en) * | 2009-09-14 | 2011-08-03 | 南京第一农药集团有限公司 | Synthesis method of 2,3-difluoro-5-chloropyridine |
| CN103044388A (en) * | 2011-10-17 | 2013-04-17 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of 3,4-difluoro sulfolane |
| CN106008329A (en) * | 2016-03-17 | 2016-10-12 | 维讯化工（南京）有限公司 | Preparation method of 5-chloro-2,3-difluoropyridine |
-
2005
- 2005-03-09 CN CN 200510053348 patent/CN1830963A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648904B (en) * | 2009-09-14 | 2011-08-03 | 南京第一农药集团有限公司 | Synthesis method of 2,3-difluoro-5-chloropyridine |
| CN103044388A (en) * | 2011-10-17 | 2013-04-17 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of 3,4-difluoro sulfolane |
| CN103044388B (en) * | 2011-10-17 | 2015-04-15 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of 3,4-difluoro sulfolane |
| CN106008329A (en) * | 2016-03-17 | 2016-10-12 | 维讯化工（南京）有限公司 | Preparation method of 5-chloro-2,3-difluoropyridine |
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