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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- 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
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- 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
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- 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
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- 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 System
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- 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 System
- C07F3/02—Magnesium compounds
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- 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 System
- C07F3/06—Zinc compounds
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- 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 System
- 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
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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525267A (en) * | 2009-04-24 | 2009-09-09 | 河南工业大学 | Method for preparing hexachlorobutadiene |
| CN105272818A (en) * | 2015-11-19 | 2016-01-27 | 北京宇极科技发展有限公司 | New method for preparing hexafluorobutadiene |
-
2017
- 2017-03-03 CN CN201710123615.7A patent/CN106866355A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525267A (en) * | 2009-04-24 | 2009-09-09 | 河南工业大学 | Method for preparing hexachlorobutadiene |
| CN105272818A (en) * | 2015-11-19 | 2016-01-27 | 北京宇极科技发展有限公司 | New method for preparing hexafluorobutadiene |
Non-Patent Citations (2)
| Title |
|---|
| KOSTIKOV, R. R.: "Product subclass 1: 1,1-dihaloalk-1-enes", 《SCIENCE OF SYNTHESIS》 * |
| TANG, XIAOQING等: "Conversion of ketones into 1,1-disubstituted-2,3,3-trifluoro-2-propen-1-ols with 1,1-dibromo-1,2,2,2-tetrafluoroethane/magnesium reagent", 《CHINESE CHEMICAL LETTERS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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Application publication date: 20170620 |