CN107935920A - Preparation method of 2-fluoro-3-chloro-5-trifluoromethylpyridine - Google Patents
Preparation method of 2-fluoro-3-chloro-5-trifluoromethylpyridine Download PDFInfo
- Publication number
- CN107935920A CN107935920A CN201711234027.7A CN201711234027A CN107935920A CN 107935920 A CN107935920 A CN 107935920A CN 201711234027 A CN201711234027 A CN 201711234027A CN 107935920 A CN107935920 A CN 107935920A
- Authority
- CN
- China
- Prior art keywords
- chloro
- fluoro
- trifluoromethylpyridines
- preparation
- reaction
- 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
- GDSROTVTTLUHCO-UHFFFAOYSA-N 3-chloro-2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=NC=C(C(F)(F)F)C=C1Cl GDSROTVTTLUHCO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- XVBWGQSXLITICX-UHFFFAOYSA-N 2,3-dichloro-5-(trichloromethyl)pyridine Chemical compound ClC1=CC(C(Cl)(Cl)Cl)=CN=C1Cl XVBWGQSXLITICX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 19
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 17
- VLJIVLGVKMTBOD-UHFFFAOYSA-N 2-chloro-5-(trichloromethyl)pyridine Chemical compound ClC1=CC=C(C(Cl)(Cl)Cl)C=N1 VLJIVLGVKMTBOD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 claims abstract description 8
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000460 chlorine Substances 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- ABNQGNFVSFKJGI-UHFFFAOYSA-N 2,3-dichloro-5-(trifluoromethyl)pyridine Chemical class FC(F)(F)C1=CN=C(Cl)C(Cl)=C1 ABNQGNFVSFKJGI-UHFFFAOYSA-N 0.000 claims description 7
- JFZJMSDDOOAOIV-UHFFFAOYSA-N 2-chloro-5-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=C(Cl)N=C1 JFZJMSDDOOAOIV-UHFFFAOYSA-N 0.000 claims description 7
- 210000003298 dental enamel Anatomy 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 22
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 description 10
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000004009 herbicide Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 230000002363 herbicidal effect Effects 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- 239000005780 Fluazinam Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- UISUNVFOGSJSKD-UHFFFAOYSA-N chlorfluazuron Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC(C=C1Cl)=CC(Cl)=C1OC1=NC=C(C(F)(F)F)C=C1Cl UISUNVFOGSJSKD-UHFFFAOYSA-N 0.000 description 2
- UZCGKGPEKUCDTF-UHFFFAOYSA-N fluazinam Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=C(Cl)C([N+]([O-])=O)=C1NC1=NC=C(C(F)(F)F)C=C1Cl UZCGKGPEKUCDTF-UHFFFAOYSA-N 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- QMDKBCLEIGIEBO-UHFFFAOYSA-N 3-(trichloromethyl)pyridine Chemical compound ClC(Cl)(Cl)C1=CC=CN=C1 QMDKBCLEIGIEBO-UHFFFAOYSA-N 0.000 description 1
- JTZSFNHHVULOGJ-UHFFFAOYSA-N 3-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CN=C1 JTZSFNHHVULOGJ-UHFFFAOYSA-N 0.000 description 1
- CMBSSVKZOPZBKW-UHFFFAOYSA-N 5-methylpyridin-2-amine Chemical class CC1=CC=C(N)N=C1 CMBSSVKZOPZBKW-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910015400 FeC13 Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- WHDHEVMINMZADQ-UHFFFAOYSA-N [F].N1C=CC=C1 Chemical compound [F].N1C=CC=C1 WHDHEVMINMZADQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001399 anti-metabolic effect Effects 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical group Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- YOWNVPAUWYHLQX-UHFFFAOYSA-N fluazuron Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC1=CC=C(Cl)C(OC=2C(=CC(=CN=2)C(F)(F)F)Cl)=C1 YOWNVPAUWYHLQX-UHFFFAOYSA-N 0.000 description 1
- 229950006719 fluazuron Drugs 0.000 description 1
- -1 halo aldehyde Chemical class 0.000 description 1
- MFSWTRQUCLNFOM-SECBINFHSA-N haloxyfop-P-methyl Chemical group C1=CC(O[C@H](C)C(=O)OC)=CC=C1OC1=NC=C(C(F)(F)F)C=C1Cl MFSWTRQUCLNFOM-SECBINFHSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000006273 synthetic pesticide Substances 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 relates to the technical field of chemical synthesis, and particularly discloses a preparation method of 2-fluoro-3-chloro-5-trifluoromethylpyridine. The preparation method of the 2-fluoro-3-chloro-5-trifluoromethylpyridine is characterized by comprising the following steps: taking 2-chloro-5-trichloromethylpyridine as a raw material, taking tungsten hexachloride as a catalyst, heating and introducing chlorine gas for chlorination reaction to obtain 2, 3-dichloro-5-trichloromethylpyridine; putting 2, 3-dichloro-5-trichloromethylpyridine into a fluorination kettle, adding antimony pentafluoride and anhydrous hydrogen fluoride, stirring, heating for reaction, cooling, washing with water, layering, sending to a rectification kettle, and carrying out rectification under reduced pressure to obtain the 2-fluoro-3-chloro-5-trifluoromethylpyridine. The method has the advantages of reliable process, sufficient and easily-obtained raw materials in the market, low production cost, simple operation, high yield and contribution to large-scale production.
Description
（One）Technical field
The present invention relates to chemosynthesis technical field, the preparation side of more particularly to a kind of fluoro- 3- chloro-5-trifluoromethylpyridines of 2-
Method.
（Two）Background technology
Fluorochemical has higher membrane permeability, antimetabolic stability and affinity, heat endurance and chemistry with adipose membrane
The features such as stability, be widely used in pesticide, and fluoro-containing pesticide is highly important fluoride-containing PMMA, has high selection
Property, high suitable wide spectrum, high added value, low dosage, cost be low, less toxic, low-residual, it is environmentally friendly the features such as, meet modern
Development trend, in the past 10 years domestic and international fluoro-containing pesticide developed rapidly.At present in more than 1300 pesticide species in the world
Fluoro-containing pesticide accounts for 12%, and the herbicide in fluoro-containing pesticide accounts for 45%, and insecticide accounts for 33%, and fungicide accounts for 15%, other to account for 7%.
Fluoric Herbicides are that exploitation is most in recent years, and the herbicide fluorochemical developed in nearly 10 years accounts for 50%, and herbicide is not
Come the direction of Agrochemicals, fluoro-containing pesticide has become the emphasis of world pesticide development.
The fluoro- 3- chloro-5-trifluoromethylpyridines of 2-, are a kind of of great value chemicals of fluorine-containing pyridine heterocycle class, main to use
In in synthetic pesticide chlorfluazuron（Pyridine worm is grand）, fungicide fluazinam（Good fortune agriculture is handsome）, herbicide haloxyfop-r-methyl（Efficient fluorine pyrrole first
Standing grain spirit）, insecticidal/acaricidal agent fluazuron（Pyrrole worm is grand）, it is also used for the intermediate that some medicine synthesize.Chlorfluazuron, fluazinam, efficiently
Cover grass energy etc. is all the principal item of fluoro-containing pesticide at this stage, occupies the larger share of pesticide market.
At present, the synthetic method of the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- mainly has several：First, by the chloro- 5- fluoroforms of 2-
Yl pyridines synthesis 2,3-, bis- chloro-5-trifluoromethylpyridines (2.3.5DCTF) are fluorinated again；Second, 2 are first prepared, bis- chloro- 5- of 3-
Trichloromethyl pyridine (2.3.5DCTC), then the fluoro- 3- chloro-5-trifluoromethylpyridines of perfluorinated preparation 2-.In above two method,
Fluorization agent is generally with potassium fluoride, sodium fluoride, hydrogen fluoride etc..
（1）The method of synthesis bis- chloro-5-trifluoromethylpyridines of 2,3- has：
1. use activated-carbon catalyst
This method is mainly the chlorination on 3 of 2- chloro-5-trifluoromethylpyridines, and catalyst is activated carbon, and highest yield is
74.1%, shortcoming is that isomers is more, it is difficult to is separated.
2. pyridone method
Document report, 2- chloro-5-trifluoromethylpyridines are in FeC13Under catalysis, chlorination is carried out, 2,3,5-DCTF can be obtained.But
The yield and selectivity of this method are all not ideal enough.Improved method is 2- chloro-5-trifluoromethylpyridines in alkali and trimethyl first
Under the action of alcohol, the chlorine of 2 is taken off, becomes 5- trifluoromethyl pyridine -2- ketone, its purpose is to activate 3, enables next step
The chlorination on 3, then further in 2 chlorinations, total recovery 43.2%.
The advantages of this method is that reaction condition is gentleer, and shortcoming is that step is more, still needs to be investigated each step, is received with improving reaction
Rate.
2,3-, bis- chloro-5-trifluoromethylpyridines after above-mentioned synthesis, then perfluorinated reaction prepare the chloro- 5- fluoroforms of the fluoro- 3- of 2-
There are relevant report in yl pyridines, the country, and fluorization agent selects potassium fluoride.But the raw material 2- chloro-5-trifluoromethylpyridines of this technique and 2,
Bis- chloro-5-trifluoromethylpyridine higher prices of 3-, the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- of this method production are of high cost, no market
Competitiveness.
Another method is exactly first to synthesize 2,3-, bis- chloro-5-trichloromethylpyridines, then is fluorinated the chloro- 5- trifluoros of the fluoro- 3- of obtained 2-
Picoline, synthesizing 2,3-, bis- chloro-5-trichloromethylpyridines in this process route has multi-method：
1. it is cyclized method
Cyclisation method is using perhalogeno aldehyde and unsaturated nitrile as raw material, synthesizes 2,3-, bis- chloro-5-trichloromethylpyridines, this process recovery ratio
76%, due to synthesis and the separating-purifying relative difficult of starting halo aldehyde, still studied up for further deep people；
。
2. by 2- amino -5- picolines elder generation bromo, chlorination is produced again, and this route technique is simple, but separate isomers compared with
It is difficult；
。
The above method is all more there is accessory substance, hardly possible separation, the shortcomings such as yield is low, it is difficult to industrialized production.
（Three）The content of the invention
In order to compensate for the shortcomings of the prior art, the present invention provides one kind is easy to operate, product yield is high, suitable for industrialized production
The fluoro- 3- chloro-5-trifluoromethylpyridines of 2- preparation method.
The present invention is achieved through the following technical solutions：
A kind of preparation method of the fluoro- 3- chloro-5-trifluoromethylpyridines of 2-, includes the following steps：
（1）Using 2- chloro-5-trichloromethylpyridines as raw material, tungsten hexachloride is used as catalyst, and it is anti-to heat logical chlorine progress chlorination
Should, obtain 2,3-, bis- chloro-5-trichloromethylpyridines；
（2）2,3-, bis- chloro-5-trichloromethylpyridines are put into fluorination kettle, and add antimony pentafluoride and anhydrous hydrogen fluoride, stirring rises
Temperature reaction, cools down, washes, layering, sending to rectifying still, the chloro- 5- trifluoromethyls of the fluoro- 3- of 2- are made through rectification under vacuum after reaction
Pyridine.
The present invention uses 2- chloro-5-trifluoromethylpyridines as raw material, positioning catalyst is selected, under certain reaction condition
Chlorination reaction is carried out, 2,3-, bis- chloro-5-trichloromethylpyridines is prepared, then under the conditions of existing for catalyst, is fluorinated with sewage
Hydrogen makees hatch machine, prepares the fluoro- 3- chloro-5-trifluoromethylpyridines of 2-.
The reaction equation of the present invention is as follows：
；
。
The present invention more excellent technical solution be：
Step（1）In, 2- chloro-5-trichloromethylpyridines are placed in enamel chlorination tank, add heat-conducting oil heating after catalyst, are risen
Chlorine is passed through when temperature is to 130 DEG C, controlling reaction temperature is 180-190 DEG C, when the reaction time is 70-100 small, after reaction,
50 DEG C are cooled to, filters out catalyst.
Step（1）In, the mass ratio of 2- chloro-5-trichloromethylpyridines and catalyst is 200:15；The chloro- 5- trichloromethyls of 2-
Pyridine prepares 2,3 two chloro-5-trichloromethylpyridines it is important that the selection of catalyst, the country is it has been reported that here no longer
Repeat.The present invention uses tungsten hexachloride as catalyst, synthesizes the yield of 2,3-, bis- chloro-5-trichloromethylpyridines up to 95%.
Step（2）In, the molar ratio of 2,3- bis- chloro-5-trichloromethylpyridines and hydrogen fluoride is 1:10-12, hydrogen fluoride are in
Excessive state, is conducive to reaction and carries out；The mass ratio of bis- chloro-5-trichloromethylpyridines of 2,3- and antimony pentafluoride is 23:2.
Step（2）In, fluorination kettle heats up and is kept for 180-210 DEG C, reacts 24h under pressure 6-7MPa, after being cooled to 60 DEG C,
Transfer the material into advance plus in the washing kettle of water, it is 7 that material, which is washed twice to be neutralized to pH value again, then by material layering extremely
Rectifying still.
Step（2）In, 2,3-, the bis- chloro-5-trifluoromethylpyridines return fluorination kettle that rectifying still is isolated is fluorinated again,
Can be directly as production marketing.
Step（1）With（2）In byproduct hydrogen chloride gas absorb to obtain hydrochloric acid through water, the complete chlorine of unreacted is through lye
Absorption obtains sodium hypochlorite.
Present invention process is reliable, and raw material market abundance is easy to get, and production cost is low, easy to operate, high income, beneficial to scale
Metaplasia is produced.
（Four）Brief description of the drawings
The present invention is further illustrated below in conjunction with the accompanying drawings.
Fig. 1 is the process flow diagram of the present invention.
（Five）Embodiment
The specific embodiment of the technical program is described in detail below in conjunction with the accompanying drawings, but the embodiment of the technical program is not limited to
This.
Use raw material：2- chloro-5-trichloromethylpyridines（≥99%）；Chlorination catalyst is tungsten hexachloride 99%；Fluorination catalyst
Agent is Antimony pentachloride；Fluorization agent is anhydrous hydrogen fluoride.
Embodiment 1：
By in the 2- chloro-5-trichloromethylpyridines input enamel chlorination tank of 2000kg, catalyst is then added into reaction kettle
150kg reaction kettle heat-conducting oil heatings, when temperature is raised to 130 DEG C, chlorine is passed through to reaction kettle, logical chlorine dose is controlled, makes reaction temperature
Degree control is at 180 DEG C.Reaction time be generally 100 it is small when, after reaction, be cooled to 50 DEG C, filter out catalyst, 2,3- bis-
Enter fluorination kettle fluorination after chloro-5-trichloromethylpyridine metering.
By good 2,3-, the bis- chloro-5-trichloromethylpyridines input fluorination kettle of chlorination（About 2300kg）, put into reaction fluorine
Catalyst antimony pentafluoride 200kg, adds anhydrous hydrogen fluoride 1700kg, by 2,3-, bis- chloro-5-trichloromethylpyridines and hydrogen fluoride
Molar ratio is 1：10, excessive hydrogen fluoride, which is conducive to reaction, to carry out.
Reaction kettle stirring is opened, heating, is kept for 180 DEG C, when pressure 6MPa reactions 24 are small, be cooled to 60 DEG C, material is turned
To in advance plus in the washing kettle of good 3000L water, material is washed twice and neutralizes pH value 7 again, then by material layering to rectifying
The fluoro- 3- chloro-5-trifluoromethylpyridines of 2- of content >=99% are made in kettle, rectification under vacuum.
It is not 2,3 two chloro-5-trifluoromethylpyridines by the product of fluoro that fluorination reaction, which has the chlorine of part 2, passes through rectifying point
From, production marketing can be used as, also can return to reaction kettle be fluorinated again prepare the fluoro- 3- chloro-5-trifluoromethylpyridines of 2-.
Chlorination, the hydrogen chloride gas of fluorination by-product absorb by-product hydrochloric acid through water, and the complete chlorine of unreacted is through absorbing by liquid caustic soda pair
Parity sodium chlorate.
Embodiment 2：
By in the 2- chloro-5-trichloromethylpyridines input enamel chlorination tank of 2000kg, catalyst is then added into reaction kettle
150kg reaction kettle heat-conducting oil heatings, when temperature is raised to 130 DEG C, chlorine is passed through to reaction kettle, logical chlorine dose is controlled, makes reaction temperature
Degree control is at 190 DEG C or so.Reaction time be generally 70 it is small when, after reaction, be cooled to 50 DEG C, filter out catalyst, 2,
Enter fluorination kettle fluorination after the metering of bis- chloro-5-trichloromethylpyridines of 3-.
By good 2,3-, the bis- chloro-5-trichloromethylpyridines input fluorination kettle of chlorination（About 2300kg）, put into reaction fluorine
Catalyst antimony pentafluoride 200kg, adds anhydrous hydrogen fluoride 1700kg, by 2,3-, bis- chloro-5-trichloromethylpyridines and hydrogen fluoride
Molar ratio is 1：12, excessive hydrogen fluoride, which is conducive to reaction, to carry out.
Reaction kettle stirring is opened, heating, is kept for 210 DEG C, when pressure 7MPa reactions 24 are small, be cooled to 60 DEG C, material is turned
To in advance plus in the washing kettle of good 3000L water, material is washed twice and neutralizes pH value 7 again, then by material layering to rectifying
The fluoro- 3- chloro-5-trifluoromethylpyridines of 2- of content >=99% are made in kettle, rectification under vacuum.
Embodiment 3：
By in the 2- chloro-5-trichloromethylpyridines input enamel chlorination tank of 2000kg, catalyst is then added into reaction kettle
150kg reaction kettle heat-conducting oil heatings, when temperature is raised to 130 DEG C, chlorine is passed through to reaction kettle, logical chlorine dose is controlled, makes reaction temperature
Degree control is at 185 DEG C or so.Reaction time be generally 85 it is small when, after reaction, be cooled to 50 DEG C, filter out catalyst, 2,
Enter fluorination kettle fluorination after the metering of bis- chloro-5-trichloromethylpyridines of 3-.
By good 2,3-, the bis- chloro-5-trichloromethylpyridines input fluorination kettle of chlorination（About 2300kg）, put into reaction fluorine
Catalyst antimony pentafluoride 200kg, adds anhydrous hydrogen fluoride 1700kg, by 2,3-, bis- chloro-5-trichloromethylpyridines and hydrogen fluoride
Molar ratio is 1：11, excessive hydrogen fluoride, which is conducive to reaction, to carry out.
Reaction kettle stirring is opened, heating, is kept for 195 DEG C, when pressure 6.5MPa reactions 24 are small, 60 DEG C are cooled to, by material
Go in advance plus in the washing kettle of good 3000L water, material is washed twice and neutralizes pH value 7 again, then by material layering to essence
Kettle is evaporated, the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- of content >=99% are made in rectification under vacuum.
Claims (8)
1. a kind of preparation method of the fluoro- 3- chloro-5-trifluoromethylpyridines of 2-, it is characterized in that, include the following steps：（1）It is chloro- with 2-
5- trichloromethyl pyridines are raw material, use tungsten hexachloride as catalyst, heat logical chlorine and carry out chlorination reaction, obtain 2,3- bis-
Chloro-5-trichloromethylpyridine；（2）2,3-, bis- chloro-5-trichloromethylpyridines are put into fluorination kettle, and add antimony pentafluoride and anhydrous
Hydrogen fluoride, stirs temperature reaction, cools down after reaction, washes, layering, sending to rectifying still, the fluoro- 3- of 2- are made through rectification under vacuum
Chloro-5-trifluoromethylpyridine.
2. the preparation method of the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- according to claim 1, it is characterised in that：Step
（1）In, 2- chloro-5-trichloromethylpyridines are placed in enamel chlorination tank, are added heat-conducting oil heating after catalyst, are warming up to 130
DEG C when be passed through chlorine, controlling reaction temperature is 180-190 DEG C, the reaction time for 70-100 it is small when, after reaction, be cooled to 50
DEG C, filter out catalyst.
3. the preparation method of the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- according to claim 1, it is characterised in that：Step
（1）In, the mass ratio of 2- chloro-5-trichloromethylpyridines and catalyst is 200:15.
4. the preparation method of the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- according to claim 1, it is characterised in that：Step
（2）In, the molar ratio of 2,3- bis- chloro-5-trichloromethylpyridines and hydrogen fluoride is 1:10-12.
5. the preparation method of the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- according to claim 1, it is characterised in that：Step
（2）In, the mass ratio of 2,3- bis- chloro-5-trichloromethylpyridines and antimony pentafluoride is 23:2.
6. the preparation method of the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- according to claim 1, it is characterised in that：Step
（2）In, fluorination kettle heats up and is kept for 180-210 DEG C, reacts 24h under pressure 6-7MPa, after being cooled to 60 DEG C, transfers the material into
In advance plus in the washing kettle of water, it is 7 that material, which is washed twice to be neutralized to pH value again, then by material layering to rectifying still.
7. the preparation method of the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- according to claim 1, it is characterised in that：Step
（2）In, 2,3-, the bis- chloro-5-trifluoromethylpyridines return fluorination kettle that rectifying still is isolated is fluorinated again.
8. the preparation method of the fluoro- 3- chloro-5-trifluoromethylpyridines of 2- according to claim 1, it is characterised in that：Step
（1）With（2）In byproduct hydrogen chloride gas absorb to obtain hydrochloric acid through water, the complete chlorine of unreacted absorbs to obtain time chlorine through lye
Sour sodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711234027.7A CN107935920A (en) | 2017-11-30 | 2017-11-30 | Preparation method of 2-fluoro-3-chloro-5-trifluoromethylpyridine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711234027.7A CN107935920A (en) | 2017-11-30 | 2017-11-30 | Preparation method of 2-fluoro-3-chloro-5-trifluoromethylpyridine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107935920A true CN107935920A (en) | 2018-04-20 |
Family
ID=61947836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711234027.7A Pending CN107935920A (en) | 2017-11-30 | 2017-11-30 | Preparation method of 2-fluoro-3-chloro-5-trifluoromethylpyridine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107935920A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110038587A (en) * | 2019-05-14 | 2019-07-23 | 中触媒新材料股份有限公司 | It is a kind of for synthesizing the catalyst and preparation method thereof of bis- chloro-5-trifluoromethylpyridine of 2,3- |
| CN113527192A (en) * | 2021-03-15 | 2021-10-22 | 武威广达科技有限公司 | Preparation method of 2, 3-dichloro-5-trifluoromethylpyridine |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0004414A1 (en) * | 1978-03-01 | 1979-10-03 | Imperial Chemical Industries Plc | Mixtures of herbicidal pyridyloxyphenoxypropanoic acid derivatives with other herbicides, and processes of killing unwanted plants therewith |
| US4331811A (en) * | 1981-03-12 | 1982-05-25 | The Dow Chemical Company | Preparation of 2,3-dichloro-5-trichloromethylpyridine |
| US4547577A (en) * | 1984-06-08 | 1985-10-15 | The Dow Chemical Company | Preparation of (trifluoromethyl)pyridines |
| US4567274A (en) * | 1984-11-26 | 1986-01-28 | The Dow Chemical Company | Chlorine exchange for fluorine in 2-fluoropyridine compounds |
| CN86105880A (en) * | 1982-04-16 | 1988-03-23 | 陶氏化学公司 | The recirculation of catalyzer in liquid phase halogen exchange reaction |
| JPH07304738A (en) * | 1994-05-09 | 1995-11-21 | Ihara Chem Ind Co Ltd | Production of trifluoromethylpyridines |
-
2017
- 2017-11-30 CN CN201711234027.7A patent/CN107935920A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0004414A1 (en) * | 1978-03-01 | 1979-10-03 | Imperial Chemical Industries Plc | Mixtures of herbicidal pyridyloxyphenoxypropanoic acid derivatives with other herbicides, and processes of killing unwanted plants therewith |
| US4331811A (en) * | 1981-03-12 | 1982-05-25 | The Dow Chemical Company | Preparation of 2,3-dichloro-5-trichloromethylpyridine |
| CN86105880A (en) * | 1982-04-16 | 1988-03-23 | 陶氏化学公司 | The recirculation of catalyzer in liquid phase halogen exchange reaction |
| US4547577A (en) * | 1984-06-08 | 1985-10-15 | The Dow Chemical Company | Preparation of (trifluoromethyl)pyridines |
| US4567274A (en) * | 1984-11-26 | 1986-01-28 | The Dow Chemical Company | Chlorine exchange for fluorine in 2-fluoropyridine compounds |
| JPH07304738A (en) * | 1994-05-09 | 1995-11-21 | Ihara Chem Ind Co Ltd | Production of trifluoromethylpyridines |
Non-Patent Citations (2)
| Title |
|---|
| 卞克建，等: "《工业化学反应及应用》", 28 February 1999, 中国科学技术大学出版社 * |
| 魏优昌: "含氟芳香族化合物的合成", 《化工生产与技术》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110038587A (en) * | 2019-05-14 | 2019-07-23 | 中触媒新材料股份有限公司 | It is a kind of for synthesizing the catalyst and preparation method thereof of bis- chloro-5-trifluoromethylpyridine of 2,3- |
| CN113527192A (en) * | 2021-03-15 | 2021-10-22 | 武威广达科技有限公司 | Preparation method of 2, 3-dichloro-5-trifluoromethylpyridine |
| CN113527192B (en) * | 2021-03-15 | 2024-02-13 | 武威广达科技有限公司 | Preparation method of 2, 3-dichloro-5-trifluoromethyl pyridine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101351426B (en) | Method for producing fluorinated organic compounds | |
| CN103274895B (en) | The preparation method of fluorinated organic compounds | |
| CN102892739B (en) | Process for cis-1,1,1,4,4,4,-hexafluoro-2-butene | |
| JP2013519631A (en) | Process for producing 2-chloro-3,3,3-trifluoropropene | |
| CN102992943A (en) | Trifluoroiodomethane preparation method | |
| CN109503315A (en) | The preparation method of tetrafluoropropene | |
| CN107935920A (en) | Preparation method of 2-fluoro-3-chloro-5-trifluoromethylpyridine | |
| CN105439867A (en) | A preparing method of 2-nitrobenzaldehyde | |
| CN111995502B (en) | Method for synthesizing perfluorobutyl methyl ether | |
| CN110283042A (en) | A method of the synthesis chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- | |
| CN105418493A (en) | 2-chloropyridine synthetic method | |
| CN108383679A (en) | A kind of co-production of anti-form-1-chloro- 3,3,3- trifluoro propenes and 2,3,3,3- tetrafluoropropenes | |
| CN106866352A (en) | A kind of preparation method of the fluoro- 2- vinyl chloride of 1,1- bis- | |
| JP2015120668A (en) | Method for manufacturing fluoromethanes | |
| CN108069994B (en) | A kind of boron-containing compound and its application in catalytic fluorination reaction | |
| CN107162871A (en) | A kind of fluoroform resource utilization process | |
| CN116060010B (en) | Initiator, fluorination catalyst and process for the preparation of E-1, 4-hexafluoro-2-butene | |
| CN107652160A (en) | A kind of method for preparing the trans trifluoro propene of 1 chlorine 3,3,3 | |
| CN108017574B (en) | A kind of method of the chloro- 2,4,6- trifluoromethyl pyridine continuous production of fluroxypramide intermediate 3,5- bis- | |
| CN109721465A (en) | It is a kind of to prepare anti-form-1, the method for 1,1,4,4,4- hexafluoro -2- butylene | |
| CN115246808B (en) | Preparation method of chloroethylene carbonate | |
| CN105418439A (en) | Method and device for producing 3-chlorine-4-fluoroaniline | |
| CN107805262A (en) | A kind of production method of chlopyrifos | |
| CN105315126B (en) | A kind of 2,3,3,3 tetrafluoropropene preparation methods | |
| CN102993108B (en) | Selective chlorination for 1-phenyl-4-difluoromethyl-3-methyl-4,5-dihydro-1H-1,2,4-triazole-5-ketone |
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: 20180420 |
|
| RJ01 | Rejection of invention patent application after publication |