CN106866355A - It is a kind of to synthesize the method containing trifluoro-ethylene group compound - Google Patents
It is a kind of to synthesize the method containing trifluoro-ethylene group compound Download PDFInfo
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- CN106866355A CN106866355A CN201710123615.7A CN201710123615A CN106866355A CN 106866355 A CN106866355 A CN 106866355A CN 201710123615 A CN201710123615 A CN 201710123615A CN 106866355 A CN106866355 A CN 106866355A
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- 238000000034 method Methods 0.000 title claims abstract description 22
- -1 trifluoro-ethylene group compound Chemical class 0.000 title claims abstract description 17
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 238000005859 coupling reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000011149 active material Substances 0.000 abstract 1
- 230000002508 compound effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 5
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachloro-1,3-butadiene Chemical class ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- AFNVSCFNCGXMQC-UHFFFAOYSA-N trimethyl(1,2,2-trifluoroethenyl)silane Chemical class C[Si](C)(C)C(F)=C(F)F AFNVSCFNCGXMQC-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- SUTQSIHGGHVXFK-UHFFFAOYSA-N 1,2,2-trifluoroethenylbenzene Chemical compound FC(F)=C(F)C1=CC=CC=C1 SUTQSIHGGHVXFK-UHFFFAOYSA-N 0.000 description 1
- CTWHEJYDDHMKDI-UHFFFAOYSA-N 1-ethenyl-2,3,4-trifluorobenzene Chemical compound FC1=CC=C(C=C)C(F)=C1F CTWHEJYDDHMKDI-UHFFFAOYSA-N 0.000 description 1
- GCTYSZBOAURZCV-UHFFFAOYSA-N 5-ethenyl-5,6,6-trifluorocyclohexa-1,3-diene Chemical class FC1(F)C=CC=CC1(F)C=C GCTYSZBOAURZCV-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UXZRTSMSPBYEET-UHFFFAOYSA-N FC(=C(F)F)[Cd] Chemical compound FC(=C(F)F)[Cd] UXZRTSMSPBYEET-UHFFFAOYSA-N 0.000 description 1
- WLMZXTVPENQUEZ-UHFFFAOYSA-N FC(=C(F)F)[Mg] Chemical compound FC(=C(F)F)[Mg] WLMZXTVPENQUEZ-UHFFFAOYSA-N 0.000 description 1
- AFLIPEBFYDIRNJ-UHFFFAOYSA-N FC(F)=C(F)[Zn] Chemical compound FC(F)=C(F)[Zn] AFLIPEBFYDIRNJ-UHFFFAOYSA-N 0.000 description 1
- UMXSHEUZMQMOHJ-UHFFFAOYSA-K F[Sn](C=C)(F)F Chemical compound F[Sn](C=C)(F)F UMXSHEUZMQMOHJ-UHFFFAOYSA-K 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- PUPKPAZSFZOLOR-UHFFFAOYSA-N n,n-dimethylformamide;toluene Chemical compound CN(C)C=O.CC1=CC=CC=C1 PUPKPAZSFZOLOR-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 229940094989 trimethylsilane Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/2632—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions involving an organo-magnesium compound, e.g. Grignard synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
Synthesize the method containing trifluoro-ethylene group compound the present invention relates to a kind of, be that, with 1,1- bis- bromo- 1,2,2,2- HFC-134as are raw material, under metal or metallic compound effect, obtain corresponding trifluoro-ethylene based metal complex.There is coupling reaction in this trifluoro-ethylene based metal complex, obtain containing trifluoro-ethylene group compound under the effect such as catalyst with active material.The inventive method raw material is easy to get, and method is easy, and production safety is a method which be suitable for industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method containing trifluoro-ethylene group compound, belong to organic chemical synthesis technology neck
Domain.
Background technology
Can assign molecule some special functions containing trifluoro-ethylene group in molecular structure, such as trifluoro vinyl benzene
(also known as trifluorostyrene), can be used to prepare proton exchange resins, be the core material of fuel cell barrier film；Trifluoro second for another example
Alkenyl trimethyl silane, is a kind of good organosilicon synthetic material and modifying agent etc..
The synthesis of these trifluoro-ethylene based compounds is usually the method for using trifluoro-ethylene based metal complex, and trifluoro
It is raw material preparation that ethene based metal complex then typically uses trifluoro iodoethylene, bromotrifluoroethylene or CTFE, but
These three expensive raw material prices, and property is unstable, transports and using difficult, causes the production containing trifluoro-ethylene based compound
It is very restricted with application.
The content of the invention
The problem to be solved in the present invention is to provide a kind of new easy bromo- 1,2,2,2- of fluorine-containing raw material 1,1- bis- for obtaining of conforming to the principle of simplicity
HFC-134a sets out and prepares the method containing trifluoro-ethylene based compound, including first prepares trifluoro-ethylene based metal complex, then
The various compounds containing trifluoro-ethylene group are prepared using this trifluoro-ethylene based metal complex.
A kind of method containing trifluoro-ethylene group compound for synthesizing formula (I),
(1) when R is MX, wherein M includes magnesium, zinc, lithium, tin and cadmium；When X represents one or more in bromine, chlorine and fluorine, with
1,1- bis- bromo- 1,2,2,2- HFC-134as are raw material, with M metal simple-substances or M metallic compounds stirring reaction in a solvent, are obtained
Trifluoro-ethylene based metal complex formula (II), the solvent is toluene, DMF, THF；
(2) when R is for substitution and unsubstituted alkyl, silane, alkenyl, alkynyl, aromatic rings and heterocyclic group；With 1,1- bis-
Bromo- 1,2,2,2- HFC-134as are raw material, with M metal simple-substances or M metallo-organic compounds stirring reaction in a solvent, obtain three
Fluoride-based metal complex；There is coupling reaction to being directly added into M2 catalyst and X1-R in the mixture of reaction products again
Obtain formula (I) compound, wherein M2 catalyst is one or more in iron content, copper, palladium, phosphorus compound, X1 represent with it is organic
The functional group of metallic compound reaction, the solvent is toluene, DMF, THF.
The M metallic compounds are M metal halides or M metallo-organic compounds.
The stirring reaction temperature is -100 DEG C -50 DEG C, and the stirring reaction time is 20-25 hours.
The X1 is iodine, bromine, chlorine, silane or ketone.
The X1 is halogen.
The M2 catalyst and X1-R are first dissolved in adding in solvent in mixture of reaction products.
The coupling reaction temperature is 0 DEG C -50 DEG C, and the stirring reaction time is 4-20 hours.
It with the bromo- 1,2,2,2- HFC-134as of the 1,1- bis- of safety and stability is raw material by trifluoro-ethylene Base Metal that the present invention is
The process of complex compound synthesizes various trifluoro-ethylene based compounds, and synthetic reaction formula can be exemplified below：
M1 is expressed as the simple substance or metallic compound of magnesium metal, zinc, lithium and cadmium in formula, and M2 represents catalyst, including iron,
The compound of copper, palladium, phosphorus etc., X1 represent can organo-metallic compound reaction functional group.
Using the method for the present invention, at a certain temperature, 1,1- bis- bromo- 1,2,2,2- HFC-134as first with metal simple-substance or
Metallic compound reacts, and is just readily available trifluoro-ethylene based metal complex (being probably various mixtures).This reaction needs
Carry out in the solution, be trifluoro vinyl metal complex solution because obtained from.This solution be not required to separate, can be used directly into
The synthesis of row next step, you can the directly various substitutions with activation of catalyst and unsubstituted alkyl, alkenyl, alkynyl, aromatic rings
There is coupling reaction with heterocyclic compound, obtain the compound containing trifluoro vinyl.
Prepare trifluoro-ethylene based metal complex and finally give using the method for the present invention and contain trifluoro vinyl
Compound, not only raw material is easy to get, and method is easy, and production safety can be adapted to the method for industrialized production.
Specific implementation method
Following embodiments will be described in further detail to the present invention, but the invention is not restricted to these instantiations.
Embodiment 1：The synthesis of 1,2,2- trifluorostyrenes
1,1- bis- bromo- 1,2,2,2- HFC-134as (260mg), zinc powder (150mg), toluene 10mL are added into belt stirrer
In the there-necked flask of condenser pipe, nitrogen displacement.45 DEG C of stirring reactions are reacted completely after 24 hours, obtain the complexing of trifluoro vinyl zinc
Thing solution.Bromobenzene (160mg) and four (triphenyl) phosphines palladium (11.5mg) are added in solution, continues stirring reaction 6 hours, then
Colourless liquid, yield 80% are obtained after crossing post with n-hexane.1H NMR (300MHz, CDCl3, 293K, TMS) δ 7.54-7.38 (m,
5H)ppm；19F NMR (282MHz, CDCl3, 293K, TMS) and δ -100.12 (dd, J=54.1,25.1Hz, 1F), -114.94
(dd, J=82.1,53.6Hz, 1F), -176.952 (dd, J=82.1,24.8Hz, 1F) ppm.MS(EI)：M/z (%) 158
(100)。
Embodiment 2：The synthesis of 2- (1,2,2- trifluoro vinyls) naphthalene
1,1- bis- bromo- 1,2,2,2- HFC-134as (260mg), magnesium powder (50mg), tetrahydrofuran 10mL are added into band stirring
In the there-necked flask of device and condenser pipe, nitrogen displacement.5 DEG C of stirring reactions are reacted completely after 24 hours, obtain trifluoro vinyl magnesium network
Polymer solution.Solution is warmed up to 40 DEG C, adds 2- iodine naphthalene (300mg) and four (triphenyl) phosphines palladium (11.5mg), continues to stir anti-
Answer 6 hours, colourless liquid, yield 90% are obtained after then crossing post with n-hexane.1H NMR (300MHz, CDCl3,293K, TMS) δ
7.94 (s, 1H), 7.87-7.81 (m, 3H), 7.56-7.50 (m, 3H) ppm；19F NMR (282MHz, CDCl3,293K, TMS) δ-
99.14 (dd, J=52.1,23.4Hz, 1F), -114.33 (dd, J=81.5,52.7Hz, 1F), -176.20 (dd, J=81.5,
24.3Hz, 1F) ppm；MS(EI)：M/z (%) 208 (100).
Embodiment 3：The synthesis of 1,1,2,3,4,4- hexachlorobutadienes
The there-necked flask of belt stirrer and condenser pipe is taken, nitrogen displacement is simultaneously protected.Take anhydrous zinc chloride 4.2g and 30mL anhydrous
THF, obtains suspension.Suspension is cooled to -100 DEG C, is slowly added to 1,1- bis- bromo- 1,2,2,2- HFC-134a 7.2g.Then
The 1.8M solution of 64mmol diisopropylamine lithiums is slowly added to syringe, 0 DEG C or so is slowly warmed up to, is evacuated down to oil-free
100mmHg, while the DMF solution of catalyst iron chloride is added dropwise, collects the outlet of oilless vacuum pump, and liquid nitrogen cooling obtains 1,1,
2,3,4,4- hexachlorobutadienes, colourless liquid, 6 DEG C of boiling point.Yield 70%.
Embodiment 4：The synthesis of 1,2,2- trifluoro vinyl trimethyl silanes
1,1- bis- bromo- 1,2,2,2- HFC-134as (260mg), cadmium powder (200mg), DMF 10mL are added into belt stirrer
In the there-necked flask of condenser pipe, nitrogen displacement.30 DEG C of stirring reactions are reacted completely after 24 hours, obtain the complexing of trifluoro vinyl cadmium
Thing solution.Solution is warmed up to 40 DEG C, adds 360mg trim,ethylchlorosilanes and 30mg cuprous bromides.Successive reaction overnight, by essence
Evaporate, obtain the trifluoro vinyl trimethyl silane of product 1,2,2-, colourless liquid, boiling point DEG C.75% yield.19F NMR(CDCl3
solvent,CFCl3reference):- 88.7ppm (dd, J=71Hz, J=25Hz, 1F)；- 117.6ppm (dd, J=
115Hz, J=71Hz, 1F)；- 199.5ppm (dd, J=115Hz, J=25Hz, 1F).
Embodiment 5：The synthesis of the chloro- 4- of 1- [2,3,3- tri- fluoro- 1- (2- methoxyethyls) -2- acrylic]-benzene
Under nitrogen protective condition, by 1,1- bis- bromo- 1,2,2,2- HFC-134as (67mg), organotin (95mg), DMF toluene
In the there-necked flask of 150mL, addition belt stirrer and condenser pipe, nitrogen displacement.45 DEG C of stirring reactions are reacted completely after 24 hours, are obtained
To trifluoro vinyl tin complex solution.3- (4- chlorphenyls) -3- bromopropyls methyl ether (17.06g) is dissolved in 10mLDMF,
It is slowly dropped in above-mentioned complex solution, is then slowly added dropwise the DMF solution 50mL of copper bromide (29.83g), keeping temperature continues
Reaction is overnight.After reaction completely, saturated aqueous ammonium chloride is added, and extracted with hexane, merge organic phase, steamed solvent and obtain
The chloro- 4- of brown liquid 12g, as 1- [2,3,3- tri- fluoro- 1- (2- methoxyethyls) -2- acrylic]-benzene.
Claims (7)
1. it is a kind of synthesize formula (I) the method containing trifluoro-ethylene group compound,
(1) wherein R is MX, and M is the one kind in magnesium, zinc, lithium, tin and cadmium；When X represents one or more in bromine, chlorine and fluorine, with
1,1- bis- bromo- 1,2,2,2- HFC-134as are raw material, with M metal simple-substances or M metallic compounds stirring reaction in a solvent, are obtained
Trifluoro-ethylene based metal complex formula (II), the solvent is toluene, DMF, THF；
(2) when wherein R is substituted or unsubstituted alkyl, silane, alkenyl, alkynyl, aromatic rings and heterocyclic group；With 1,1- bis-
Bromo- 1,2,2,2- HFC-134as are raw material, with M metal simple-substances or M metallic compounds stirring reaction in a solvent, obtain trifluoro second
Alkenyl metal complex；Obtain to being directly added into M2 catalyst and X1-R in the mixture of reaction products coupling reaction occurs again
Formula (I) compound, wherein M2 catalyst are one or more in iron content, copper, palladium, phosphorus compound, and X1 is represented and organic metal
The functional group of compound reaction, the solvent is toluene, DMF, THF.
2. method according to claim 1, the M metallic compounds are M metal halides or M metallo-organic compounds.
3. method according to claim 1, the stirring reaction temperature is -100 DEG C -50 DEG C, and the stirring reaction time is
20-25 hours.
4. method according to claim 1, the X1 is iodine, bromine, chlorine, silane or ketone.
5. method according to claim 4, the X1 is halogen.
6. method according to claim 1, the M2 catalyst and X1-R are first dissolved in adding product in solvent and mix
In compound.
7. method according to claim 1, the coupling reaction temperature is 0 DEG C -50 DEG C, and the stirring reaction time is 4-20
Hour.
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| CN111320526A (en) * | 2018-12-14 | 2020-06-23 | 浙江蓝天环保高科技股份有限公司 | Method for preparing hexafluorobutadiene |
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| CN111320526B (en) * | 2018-12-14 | 2023-09-05 | 浙江蓝天环保高科技股份有限公司 | Method for preparing hexafluorobutadiene |
| CN111187145A (en) * | 2020-01-08 | 2020-05-22 | 广东电网有限责任公司电力科学研究院 | Preparation method of hexafluorobutadiene |
| CN111187145B (en) * | 2020-01-08 | 2023-01-24 | 广东电网有限责任公司电力科学研究院 | Preparation method of hexafluorobutadiene |
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