CN113024414A - Method for efficiently synthesizing fluorine-containing compound - Google Patents
Method for efficiently synthesizing fluorine-containing compound Download PDFInfo
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- CN113024414A CN113024414A CN202110310090.4A CN202110310090A CN113024414A CN 113024414 A CN113024414 A CN 113024414A CN 202110310090 A CN202110310090 A CN 202110310090A CN 113024414 A CN113024414 A CN 113024414A
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 35
- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- 239000011737 fluorine Substances 0.000 title claims abstract description 34
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 27
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 27
- 230000009471 action Effects 0.000 claims abstract description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001555 benzenes Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000004693 imidazolium salts Chemical class 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- -1 aromatic chlorides Chemical class 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 2
- 150000002221 fluorine Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 238000010438 heat treatment Methods 0.000 description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- 238000001816 cooling Methods 0.000 description 17
- 238000004821 distillation Methods 0.000 description 17
- 238000004817 gas chromatography Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 239000012074 organic phase Substances 0.000 description 13
- 239000004576 sand Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
- 238000005485 electric heating Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SOWRUJSGHKNOKN-UHFFFAOYSA-N 2,6-difluorobenzaldehyde Chemical compound FC1=CC=CC(F)=C1C=O SOWRUJSGHKNOKN-UHFFFAOYSA-N 0.000 description 3
- MBTGBRYMJKYYOE-UHFFFAOYSA-N 2,6-difluoropyridine Chemical compound FC1=CC=CC(F)=N1 MBTGBRYMJKYYOE-UHFFFAOYSA-N 0.000 description 3
- GOYNRDSJTYLXBU-UHFFFAOYSA-N 5-chloro-2,4,6-trifluoropyrimidine Chemical compound FC1=NC(F)=C(Cl)C(F)=N1 GOYNRDSJTYLXBU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 2
- WDBAXYQUOZDFOJ-UHFFFAOYSA-N 2,3-difluorobenzaldehyde Chemical compound FC1=CC=CC(C=O)=C1F WDBAXYQUOZDFOJ-UHFFFAOYSA-N 0.000 description 2
- GJNGXPDXRVXSEH-UHFFFAOYSA-N 4-chlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1 GJNGXPDXRVXSEH-UHFFFAOYSA-N 0.000 description 2
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 2
- AEKVBBNGWBBYLL-UHFFFAOYSA-N 4-fluorobenzonitrile Chemical compound FC1=CC=C(C#N)C=C1 AEKVBBNGWBBYLL-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000004812 organic fluorine compounds Chemical class 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 238000006561 solvent free reaction Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 description 1
- GVBHCMNXRKOJRH-UHFFFAOYSA-N 2,4,5,6-tetrachloropyrimidine Chemical compound ClC1=NC(Cl)=C(Cl)C(Cl)=N1 GVBHCMNXRKOJRH-UHFFFAOYSA-N 0.000 description 1
- YSFBEAASFUWWHU-UHFFFAOYSA-N 2,4-dichlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C(Cl)=C1 YSFBEAASFUWWHU-UHFFFAOYSA-N 0.000 description 1
- WCGPCBACLBHDCI-UHFFFAOYSA-N 2,4-difluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C(F)=C1 WCGPCBACLBHDCI-UHFFFAOYSA-N 0.000 description 1
- DMIYKWPEFRFTPY-UHFFFAOYSA-N 2,6-dichlorobenzaldehyde Chemical compound ClC1=CC=CC(Cl)=C1C=O DMIYKWPEFRFTPY-UHFFFAOYSA-N 0.000 description 1
- FILKGCRCWDMBKA-UHFFFAOYSA-N 2,6-dichloropyridine Chemical compound ClC1=CC=CC(Cl)=N1 FILKGCRCWDMBKA-UHFFFAOYSA-N 0.000 description 1
- GDHXJNRAJRCGMX-UHFFFAOYSA-N 2-fluorobenzonitrile Chemical compound FC1=CC=CC=C1C#N GDHXJNRAJRCGMX-UHFFFAOYSA-N 0.000 description 1
- PUJSUOGJGIECFQ-UHFFFAOYSA-N 3,5-dichlorobenzonitrile Chemical compound ClC1=CC(Cl)=CC(C#N)=C1 PUJSUOGJGIECFQ-UHFFFAOYSA-N 0.000 description 1
- CQXZSEXZQVKCHW-UHFFFAOYSA-N 3,5-difluorobenzonitrile Chemical compound FC1=CC(F)=CC(C#N)=C1 CQXZSEXZQVKCHW-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000007045 Balz-Schiemann reaction Methods 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/30—Halogen atoms or nitro radicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for efficiently synthesizing fluorine-containing compounds, which relates to the field of synthesis of fluorine-containing compounds, and is a method for generating corresponding fluorine atom substituted fluorine-containing compounds by taking aromatic chlorides or activated chlorides as raw materials and reacting with potassium fluoride under the action of a novel catalyst.
Description
Technical Field
The invention relates to the field of synthesis of fluorine-containing compounds, in particular to a method for efficiently synthesizing a fluorine-containing compound.
Background
Fluorine is the element with the largest electronegativity in the periodic table of elements, and has a small radius, a short carbon-fluorine bond and a large bond energy. The organic fluorine compound has the advantages of low intermolecular cohesion, small molecular acting force between air and a polymer interface, low surface free energy, small surface friction coefficient and the like, and the organic fluorine compound has excellent water resistance, oil resistance and wear resistance. The fluorine-containing compound has the characteristics of three high (high surface activity, high heat resistance and high chemical stability) and two high (hydrophobic and oleophobic), so that the fluorine-containing compound has incomparable advantages in the aspects of hydrophobicity, oleophobicity, antifouling property, washing resistance, rubbing resistance, corrosion resistance and the like. The fluorine chemical products and the new fluorine-containing materials have increasingly important new application in the industrial fields of national defense, aviation, aerospace, navigation, automobiles, chemical engineering, petroleum, nuclear energy, environmental protection, communication, electric power, electrical appliance and the like, instrument and meter, electronic information, textile, machinery, medicine, coating, optical fiber, photovoltaic, nuclear materials, special rubber, refrigerant manufacturing, high-tech agriculture and the like. With the rapid development of our country and the continuous breakthrough of fluorine chemical and fluorine-containing materials, the application fields of fluorine-containing chemicals and new fluorine-containing materials will be continuously expanded.
The general synthesis method of the fluorine-containing aromatic compound mainly comprises the following steps: Balz-Schiemann method, direct fluorination method, halogen exchange method and the like. Wherein the halogen exchange method is to react with aromatic compounds containing other halogens (i.e. chlorine, bromine and iodine) on the aromatic ring by using alkali metal fluoride, and replace other halogen atoms by fluorine atoms. The reaction of halogen exchange between an organic halide and an inorganic halide is called a Finkelstein halogen exchange reaction, also called a Finkelstein process. The method is a wide synthetic method of aromatic fluorine-containing compounds in industrial application due to wide substrate application range and mild reaction conditions. Catalysis is usually carried out with a phase transfer catalyst using a high-boiling liquid as a solvent. This aspect, however, suffers from poor thermal stability of the catalyst, which is generally not recyclable; meanwhile, the high-temperature reaction decomposes the solvent, which causes the defects of large solvent loss, high recovery cost, large energy consumption and the like, so that the development of the high-efficiency catalyst, particularly the catalyst suitable for the solvent-free condition, is always a hot spot in the field.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for efficiently synthesizing a fluorine-containing compound.
The invention adopts the following technical scheme:
a method for efficiently synthesizing fluorine-containing compounds is shown as the following formula, chlorine-containing compounds with the general formula I react with potassium fluoride under the action of a catalyst III to generate fluorine-containing compounds with the general formula II,
in the formula (I), the compound is shown in the specification,
x is selected from C, N, S and O atoms;
cl is a chlorine atom which is a single chlorine atom or more than 2 chlorine atoms;
the aromatic compound refers to substituted or unsubstituted benzene ring, pyridine ring, naphthalene ring, furan ring, thiophene ring and derivatives thereof, and the substituent of the derivative includes but is not limited to nitrile group, aldehyde group, carboxyl group, nitro group and other functional groups.
Further, the catalyst III is imidazole salt and derivatives thereof, and the structure of the catalyst III can be represented by the following group:
in the formula (I), the compound is shown in the specification,
r1, R2, R3 are each independently selected from: hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C4-C12 aryl or heteroaryl;
wherein R1, R2 and R3 can be connected to form C3-C10 cycloalkyl, C4-C24 aryl or heteroaryl; r3 and R4 can be connected to form C3-C10 naphthenic base, C4-C24 aryl or heteroaryl.
Further, by substituted is meant that one or more hydrogen atoms in the group are substituted with a substituent selected from the group consisting of: halogen, C1-C4 alkyl, C1-C6 alkoxy and amino.
Further, Y is a complex anion, and may be chlorine, fluorine, bromine, iodine, hexachlorophosphate, tetrachloroborate, or the like.
Further, in the formula, the groups of R1 and R2 are n-butyl, and Y is chloride.
Further, the molar ratio of the chlorine-containing compound to the catalyst III is 100-1000: 1.
Further, the reaction time is 2-100 hours.
Further, the reaction is carried out at a temperature in the range of 100 ℃ to 240 ℃.
Further, the reaction is carried out under the condition of no solvent or under the condition of organic solvent.
Further, the organic solvent is DMF, dioxane, ethylene glycol dimethyl ether, benzene, toluene, xylene, or a combination thereof.
The invention has the following beneficial effects:
1. compared with the traditional preparation method of the fluorine-containing compound, the method of the invention realizes the solvent-free reaction, avoids the volatilization of organic matters, is an environment-friendly synthesis technology and has good application prospect.
2. The imidazole catalyst used in the method disclosed by the invention is high-temperature resistant, has a good phase transfer catalysis effect, is more efficient than the traditional tetraphenylphosphonium or crown ether catalyst, has less catalyst dosage, and can be recycled.
3. The method of the invention uses chlorine-containing compound and potassium fluoride to generate under the solvent-free reaction, has high atom economy, mild reaction condition, high catalyst efficiency and less three wastes, thereby having important application value, and being used independently and being matched with other phase transfer catalysts.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are percentages and parts by weight.
Firstly, taking o-chlorobenzonitrile as an example, carrying out system research and reaction condition optimization screening on a catalytic system.
Control experiment 1:
in a 100 ml round bottom flask equipped with a thermometer, condenser and stirrer were added 13.7 g (10mmol) of solid 2-chlorobenzonitrile, 5.8 g (10mmol) of potassium fluoride and 1.0 g (7.3%) of tetrabutylammonium bromide, and 45 ml (3 times by weight) of sulfolane as a solvent was added, and the temperature was raised by heating in a sand bath, stirring was started, circulating water was turned on, and the temperature was gradually raised to a set temperature of 180 ℃. The reaction was incubated for 4 hours. After cooling, a small amount of sample was diluted with acetonitrile and the reaction was checked by gas chromatography with a yield of 34%.
Control experiment 2:
in a 100 ml round bottom flask equipped with a thermometer, a condenser and a stirrer, 13.7 g (10mmol) of solid 2-chlorobenzonitrile, 5.8 g (10mmol) of potassium fluoride and 1.0 g (7.3%) of catalyst a (1-butyl-3-methylimidazolium tetrafluoroborate) were charged, 45 ml (3 times by weight) of sulfolane as a solvent was added, and the temperature was raised by heating with a sand bath. Starting stirring, opening circulating water, and gradually heating to the set temperature of 180 ℃. The reaction was incubated for 4 hours. After cooling, a small amount of sample was diluted with acetonitrile and the reaction was checked by gas chromatography with a yield of 75%.
Example 1.
In a 100 ml round bottom flask equipped with a thermometer, condenser and stirrer were added 13.7 g (10mmol) of solid 2-chlorobenzonitrile and 5.8 g (10mmol) of potassium fluoride and 1.0 g (7.3%) of the self-made catalyst a, and the temperature was raised by heating with a sand bath. After the system is melted, starting stirring, opening circulating water, and continuously heating to the set temperature of 180 ℃. The reaction was incubated for 4 hours. After cooling, a small amount of sample was diluted with acetonitrile and the reaction was checked by gas chromatography, yielding 86%.
Example 2.
In a 100 ml round bottom flask equipped with a thermometer, a condenser and a stirrer were added 13.7 g (10mmol) of solid 2-chlorobenzonitrile and 5.8 g (10mmol) of potassium fluoride and 1.0 g (7.3%) of the self-made catalyst b, and the temperature was raised by heating with a sand bath. After the system is melted, starting stirring, opening circulating water, and continuously heating to the set temperature of 180 ℃. The reaction was incubated for 4 hours. After cooling, a small amount of sample was diluted with acetonitrile and the reaction result was checked by gas chromatography, and the yield was 93%.
Example 3.
In a 100 ml round bottom flask equipped with a thermometer, condenser and stirrer were added 13.7 g (10mmol) of solid 2-chlorobenzonitrile and 5.8 g (10mmol) of potassium fluoride and 1.0 g (7.3%) of the self-made catalyst c, and the temperature was raised by heating with a sand bath. After the system is melted, starting stirring, opening circulating water, and continuously heating to the set temperature of 180 ℃. The reaction was incubated for 4 hours. After cooling, a small amount of sample was diluted with acetonitrile and the reaction was checked by gas chromatography with a yield of 81%.
As can be seen from examples 1-3, the self-made catalyst b (1-butyl-3-methylimidazole hydrochloride) has the best catalytic effect and is suitable for being applied in a solvent-free system. The reaction result is greatly improved compared with the results reported in the literature or the results of the known methods.
Examples 4 to 7:
in a 100 ml round bottom flask equipped with a thermometer, a condenser and a stirrer were added 13.7 g (10mmol) of solid 2-chlorobenzonitrile and 5.8 g (10mmol) of potassium fluoride and 1.0 g (7.3%) of the self-made catalyst b, and the temperature was raised by heating with a sand bath. After the system is melted, starting stirring, opening circulating water, and continuously heating to the set temperature. The reaction was incubated for 4 hours. After cooling, a small sample was diluted with acetonitrile and the reaction results were checked by gas chromatography, giving the yields shown in the following table. From the reaction results, the optimum reaction temperature was 180 ℃.
| Examples | Reaction temperature | Yield (%) |
| 4 | 140 | 0 |
| 5 | 160 | 43 |
| 2 | 180 | 93 |
| 6 | 200 | 92 |
Examples 7 to 9:
in a 100 ml round-bottom flask equipped with a thermometer, condenser and stirrer, 13.7 g (10mmol) of solid 2-chlorobenzonitrile and various amounts of potassium fluoride and 1.0 g (7.3%) of the self-made catalyst b were added and the temperature was raised by heating in a sand bath. After the system is melted, starting stirring, opening circulating water, and continuously heating to 180 ℃. The reaction was incubated for 4 hours. After cooling, a small sample was diluted with acetonitrile and the reaction results were checked by gas chromatography, giving the yields shown in the following table. From the reaction results, the optimum amount of potassium fluoride to be used is 1.05 molar equivalents.
| Examples | Mass (g) of potassium fluoride | Yield (%) |
| 2 | 5.8 g (10mmol) | 93 |
| 8 | 6.1 g (10.5mmol) | 95 |
| 9 | 6.9 g (12mmol) | 95 |
Examples 10 to 12:
in a 100 ml round bottom flask equipped with a thermometer, a condenser and a stirrer were added 13.7 g (10mmol) of solid 2-chlorobenzonitrile, 6.1 g (10.5mmol) of potassium fluoride and 1.0 g (7.3%) of the self-prepared catalyst b, and the temperature was raised by heating with a sand bath. After the system is melted, starting stirring, opening circulating water, and continuously heating to 180 ℃. The reaction was incubated for 4 hours. After cooling, a small sample was diluted with acetonitrile and the reaction results were checked by gas chromatography, giving the yields shown in the following table.
Example 11(500 ml scale-up experiment):
in a 500 ml round bottom flask equipped with a thermometer, a condenser and a stirrer were added 137 g (100mmol) of solid 2-chlorobenzonitrile, 61 g (105mmol) of potassium fluoride and 10 g (7.3%) of the self-prepared catalyst b, and the temperature was raised by heating with a sand bath. After the system is melted, starting stirring, opening circulating water, and continuously heating to 180 ℃. The reaction was incubated for 8 hours (doubling time over the lab). After cooling. Adding 200 ml of distilled water, and layering to obtain an organic phase; the subsequent 130-degree 135 fraction was collected by distillation under reduced pressure to give 115 g, isolated in 95% yield. The content of the 2-fluorobenzonitrile is 99.5 percent by gas chromatography detection.
Example 12 (para-fluorobenzonitrile):
in a 500 ml round bottom flask equipped with a thermometer, a condenser and a stirrer were added 137 g (100mmol) of solid 4-chlorobenzonitrile, 61 g (105mmol) of potassium fluoride and 10 g (7.3%) of the self-prepared catalyst b, and the temperature was raised by heating with a sand bath. After the system is melted, starting stirring, opening circulating water, and continuously heating to 180 ℃. The reaction was incubated for 8 hours (doubling time over the small runs to ensure complete reaction). After cooling. Adding 200 ml of distilled water, and layering to obtain an organic phase; the subsequent 130-degree 135 fraction was collected by distillation under reduced pressure to give 111.3 g, isolated in 92% yield. The content of 4-fluorobenzonitrile is 99.6 percent by gas chromatography detection.
Example 13 (p-fluorobenzaldehyde):
in a 500 ml round bottom flask equipped with a thermometer, a condenser and a stirrer were added 140 g (100mmol) of solid 4-chlorobenzonitrile, 61 g (105mmol) of potassium fluoride and 10 g (7.3%) of the self-prepared catalyst b, and the temperature was raised by heating with a sand bath. After the system is melted, starting stirring, opening circulating water, and continuously heating to 210 ℃. The reaction was incubated for 8 hours (doubling time over the small runs to ensure complete reaction). After cooling. Adding 200 ml of distilled water, and layering to obtain an organic phase; the 130-degree 135 fraction was collected by distillation under the reduced pressure to give 110.3 g, isolated in 89% yield. The content of p-fluorobenzaldehyde is 99.4 percent by gas chromatography detection.
Example 13 (difluorobenzaldehyde):
in a 500 ml round bottom flask equipped with a thermometer, condenser and stirrer were charged 175 g (100mmol) of solid 2, 4-dichlorobenzaldehyde, 122 g (210mmol) of potassium fluoride and 10 g (7.3%) of the self-prepared catalyst b, and the temperature was raised by heating with a sand bath. After the system is melted, starting stirring, opening circulating water, and continuously heating to 210 ℃. The reaction was incubated for 8 hours (doubling time over the small runs to ensure complete reaction). After cooling. Adding 300 ml of distilled water, and layering to obtain an organic phase; the subsequent 138-140 degree fraction was collected by distillation under reduced pressure to give 128.3 g, isolated in 90% yield. The content of 2,4 difluorobenzaldehyde is 99.0% by gas chromatography detection.
Example 13 (difluorobenzaldehyde):
in a 500 ml round bottom flask equipped with a thermometer, condenser and stirrer were added 172 g (100mmol) of solid 3, 5-dichlorobenzonitrile, 122 g (210mmol) of potassium fluoride and 10 g (7.3%) of the self-prepared catalyst b, and the temperature was raised by heating with a sand bath. After the system is melted, starting stirring, opening circulating water, and continuously heating to 160 ℃. The reaction was incubated for 8 hours (doubling time over the small runs to ensure complete reaction). Cooling, adding 300 ml of distilled water, and layering to obtain an organic phase; the 113-degree and 115-degree fractions were collected by distillation under the reduced pressure to give 128.3 g, isolated in 92% yield. The content of 3,5 difluorobenzonitrile was 99.3% by gas chromatography.
The following is a further scale-up experiment for a 20 liter reactor:
example 14 (p-nitrofluorobenzene):
A20L stainless steel reaction kettle heated by an electric jacket is provided with a mechanical stirrer, a temperature measuring rod and a condenser pipe. Adding 7.88 kg (50mol) of solid p-chloronitrobenzene (melting point 44-46 ℃ and boiling point 235-. Mechanical stirring was turned on and then 3.05 kg of potassium fluoride (52.5mol) and 394 g of the in-house catalyst (5% by weight) were added in one portion. And opening circulating water, continuously starting electric heating, gradually heating to 150 ℃, and initiating a reaction. The reaction was incubated for 8 hours. After cooling. Distilled water (5L) was added and the mixture was separated to obtain an aqueous phase and an organic phase. Distilling the water phase to remove water to obtain 4.0 kg of a potassium chloride salt byproduct (containing a small amount of potassium fluoride); the organic phase was transferred to a 20L distillation flask and the 130-135 degree fraction (boiling point 205 ℃ C. at atmospheric pressure) was collected by distillation under reduced pressure to give 6.63 kg with a separation yield of 92%. The gas chromatography detection shows that the content of parafluoronitrobenzene is 99.5 percent, and a small amount of distillation kettle residues mainly contain catalyst and a small amount of raw materials and are used for the next batch.
Example 15(2, 6-difluorobenzaldehyde)
A20L stainless steel reaction kettle heated by an electric jacket is provided with a mechanical stirrer, a temperature measuring rod and a condenser pipe. 8.75 kilograms (50mol) of solid 2, 6-dichlorobenzaldehyde (melting point is 68-71 ℃, boiling point is 239.2 ℃ at 760mmHg) is put into a reaction kettle, electric heating is started to raise the temperature to 80 ℃, so that the system is completely melted, and heat is preserved. Mechanical stirring is started, and then 6.1 kg of potassium fluoride (105mol) and 437 g of the self-made catalyst (5% by weight of the raw materials) are added in one portion. And opening circulating water, continuously starting electric heating, gradually heating to 170 ℃, and initiating a reaction. The reaction was incubated for 10 hours. After cooling. Distilled water (5L) was added and the mixture was separated to obtain an aqueous phase and an organic phase. Distilling the water phase to remove water to obtain a potassium chloride salt byproduct of 8.1 kg (containing a small amount of potassium fluoride); the organic phase was transferred to a 20L distillation flask and the 82-84 ℃ fraction was collected by distillation under reduced pressure (15mm Hg) to give 6.68 kg of 2, 6-difluorobenzaldehyde in an isolated yield of 94%. The content of 2, 6-difluorobenzaldehyde is 99.6% by gas chromatography detection, and a small amount of distillation kettle residues mainly contain a catalyst and a small amount of raw materials and are used for the next batch.
Example 16(2, 6-difluoropyridine):
A20L stainless steel reaction kettle heated by an electric jacket is provided with a mechanical stirrer, a temperature measuring rod and a condenser pipe. Adding 7.4 kg (50mol) of solid 2, 6-dichloropyridine (melting point 86 ℃, boiling point 212 ℃, at 760mmHg), starting electric heating, raising the temperature to 90 ℃, completely melting the system, and keeping the temperature. Mechanical stirring is started, and then 6.1 kg of potassium fluoride (105mol) and 370 g of the in-house catalyst (5% by weight of the raw materials) are added in one portion. And opening circulating water, continuously starting electric heating, gradually heating to 160 ℃, and initiating a reaction. The reaction was incubated for 10 hours. After cooling. Distilled water (5L) was added and the mixture was separated to obtain an aqueous phase and an organic phase. Distilling the water phase to remove water to obtain 7.9 kg of a potassium chloride salt byproduct (containing a small amount of potassium fluoride); the organic phase was transferred to a 20L distillation flask, and the 124-126 ℃ fraction was collected by distillation under slightly reduced pressure (743mm Hg) to give 5.4 kg of 2, 6-difluoropyridine in an isolated yield of 94%. The gas chromatography detection shows that the content of the 2, 6-difluoropyridine is 99.3 percent, and a small amount of distillation kettle residues mainly contain the catalyst and a small amount of raw materials and are used for the next batch.
Example 16 (tetra, 2,4, 6-trifluoro-5-chloropyrimidine):
A20L stainless steel reaction kettle heated by an electric jacket is provided with a mechanical stirrer, a temperature measuring rod and a condenser pipe. Adding 6.54 kg (30mol) of solid 2,4,5, 6-tetrachloropyrimidine (melting point is 68-70 ℃, 108 ℃ and 112 ℃ (12mmHg), starting electric heating and raising the temperature to 80 ℃ to completely melt the system, preserving the temperature, starting mechanical stirring, then adding 5.49 kg of potassium fluoride (94.5mol) and 327 g of self-made catalyst (the weight ratio of the raw materials is 5%), opening circulating water, continuing to start electric heating, gradually raising the temperature to 150 ℃ to initiate reaction, preserving the temperature for 10 hours, cooling, adding 5L of distilled water, layering to obtain an aqueous phase and an organic phase, distilling the aqueous phase to remove water to obtain 7.1 (containing a small amount of potassium fluoride) potassium chloride byproduct, transferring the organic phase into a 20L distillation bottle, carrying out reduced pressure distillation to collect 115 ℃ and 117 ℃ fraction (boiling point is 247.3 ℃ and 760mmHg) to obtain 4.65 kg of 2,4, 6-trifluoro-5-chloropyrimidine, the isolation yield was 92%. The gas chromatography detection shows that the content of the 2,4, 6-trifluoro-5-chloropyrimidine is 99.6 percent, and a small amount of distillation kettle residues mainly contain the catalyst and a small amount of raw materials and are used for the next batch.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions or modifications made based on the present invention to solve the same technical problems and achieve the same technical effects are within the scope of the present invention.
Claims (10)
1. A method for efficiently synthesizing fluorine-containing compounds is characterized by comprising the following steps: as shown in the following formula, reacting chlorine-containing compound with general formula I with potassium fluoride under the action of catalyst III to generate fluorine-containing compound with general formula II,
in the formula (I), the compound is shown in the specification,
x is selected from C, N, S and O atoms;
cl is a chlorine atom which is a single chlorine atom or more than 2 chlorine atoms;
the aromatic compound refers to substituted or unsubstituted benzene ring, pyridine ring, naphthalene ring, furan ring, thiophene ring and derivatives thereof, and the substituent of the derivatives comprises nitrile group, aldehyde group, carboxyl group and nitro functional group.
2. The method for efficiently synthesizing fluorine-containing compounds according to claim 1, wherein the catalyst III is an imidazolium salt or a derivative thereof, and the structure thereof can be represented by the following group:
in the formula (I), the compound is shown in the specification,
r1, R2, R3 are each independently selected from: hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C4-C12 aryl or heteroaryl;
wherein R1, R2 and R3 can be connected to form C3-C10 cycloalkyl, C4-C24 aryl or heteroaryl; r3 and R4 can be connected to form C3-C10 naphthenic base, C4-C24 aryl or heteroaryl.
3. The method for efficiently synthesizing fluorine-containing compounds according to claim 2, wherein: by substituted is meant that one or more hydrogen atoms in the group are replaced by a substituent selected from the group consisting of: halogen, C1-C4 alkyl, C1-C6 alkoxy and amino.
4. The method for efficiently synthesizing fluorine-containing compounds according to claim 2, wherein: and Y is a complex anion.
5. The method for efficiently synthesizing fluorine-containing compounds according to claim 2, wherein: wherein the groups of R1 and R2 are n-butyl and Y is chloride.
6. The method for efficiently synthesizing fluorine-containing compounds according to claim 1, wherein: the molar ratio of the chlorine-containing compound to the catalyst III is 100-1000: 1.
7. The method for efficiently synthesizing fluorine-containing compounds according to claim 1, wherein: the reaction time is 2-100 hours.
8. The method for efficiently synthesizing fluorine-containing compounds according to claim 1, wherein: the reaction is carried out at a temperature in the range of 100 ℃ and 240 ℃.
9. The method for efficiently synthesizing fluorine-containing compounds according to claim 1, wherein: the reaction is carried out under the condition of no solvent or under the condition of organic solvent.
10. The method for efficiently synthesizing a fluorine-containing compound according to claim 9, wherein: the organic solvent is DMF, dioxane, ethylene glycol dimethyl ether, benzene, toluene, xylene, or a combination thereof.
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| CN108997135A (en) * | 2018-07-18 | 2018-12-14 | 张金河 | A kind of method and device producing the chloro- 4- fluoroaniline of 3- |
| CN112500313A (en) * | 2020-12-04 | 2021-03-16 | 阜新睿光氟化学有限公司 | Method for replacing fluorination reaction of halogenated aromatic hydrocarbon |
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