CN105503548A - Synthesizing method of fluorine halogenated vinyl ether - Google Patents
Synthesizing method of fluorine halogenated vinyl ether Download PDFInfo
- Publication number
- CN105503548A CN105503548A CN201610053628.7A CN201610053628A CN105503548A CN 105503548 A CN105503548 A CN 105503548A CN 201610053628 A CN201610053628 A CN 201610053628A CN 105503548 A CN105503548 A CN 105503548A
- Authority
- CN
- China
- Prior art keywords
- reaction
- fluorine
- ether
- haloalkene
- synthetic method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- 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
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
-
- 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
- C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesizing method of fluorine halogenated vinyl ether. The method includes the steps of firstly, adding alcohol, solvent and a catalyst into a reaction still, continuously introducing olefin for reaction, controlling the pressure of the reaction still by adjusting the introduction amount of olefin in the reaction process, stopping the introduction of olefin when the introduction flow of olefin is 0.5-1.5% of the initial introduction flow, and fine distilling reaction liquid to obtain fluorine-containing vinyl ether, wherein at least one of alcohol and olefin contains fluorine; secondly, making fluorine-containing vinyl ether and elemental halide react under illumination, and conducting alkaline washing and liquid separating on reaction liquid to obtain fluorine halogenated ether; thirdly, adding fluorine halogenated ether to a triethylamine solution of sodium alkoxide to react, and conducting liquid separating and fine distilling on reaction liquid to obtain fluorine halogenated vinyl ether. The method has the advantages that raw materials are easy to obtain, reaction conditions are mild and yield is high.
Description
Technical field
The present invention relates to fluorine technical field of fine, particularly relate to a kind of synthetic method of fluorine haloalkene ether.
Background technology
Fluorine haloalkene ether, particularly end group has the fluorine haloalkene ether replaced by halogen atom, both there is the active group of end group and double bond, there is again the advantages such as fluorine-containing chemicals low surface tension, high stability, playing an important role in organic synthesis, is important medicine, pesticide intermediate and replacement fluorine Leon compound.The fluorine haloalkene ether that end group has by halogen atom replaces also has important purposes in organic chemical industry and pharmaceutical synthesis process, and its synthetic method is the focus of current research.
As China Patent Publication No. CN1660740A; publication date on August 31st, 2005; denomination of invention: the method preparing fluorohalogenethers; this application case discloses a kind of preparation method of fluorohalogenethers, in glass reactor, under the temperature of reaction of-70 DEG C; the fluorine gas of perfluor polyether diacyl fluorine and helium dilution and CFCl=CFCl reaction; prepare fluorohalogenethers, wherein the two adduct selectivity of acyl group is 55.3%, and acyl group list adduct selectivity is 1.1%.Weak point is that reaction raw materials perfluor polyether diacyl fluorine is difficult to obtain, and expensive; Reaction need be carried out at very low temperatures, long reaction time, and severe reaction conditions, selectivity of product is low.
Summary of the invention
Instant invention overcomes the defect of prior art, the synthetic method of the fluorine haloalkene ether that a kind of raw material is easy to get, reaction conditions gentle, yield is high is provided.
For achieving the above object, the technical solution used in the present invention is: a kind of synthetic method of fluorine haloalkene ether, comprises the following steps:
(1) after adding alcohol, solvent and catalyzer in a kettle., pass into alkene continuously to react, by regulating the intake control reactor pressure of alkene to be 0.2 ~ 1.5MPa in reaction process, in described alcohol and alkene, at least one is fluorine-containing, the mol ratio of described alcohol, solvent, catalyzer is 1:1 ~ 4:1 ~ 3, temperature of reaction is 60 ~ 200 DEG C, when passing into when flow is initially pass into flow 0.5 ~ 1.5% of alkene stops passing into alkene, reaction solution rectifying is obtained containing fluroxene;
(2) reacted under light illumination 1:1 ~ 2 in molar ratio containing fluroxene and simple substance halogen by obtained for step (1), described temperature of reaction is 20 ~ 100 DEG C, and the reaction times is 0.5 ~ 5 hour, and reaction solution obtains fluorohalogenethers through alkali cleaning, separatory;
(3) fluorohalogenethers obtained for step (2) is added in the triethylamine solution of sodium alkoxide or potassium alcoholate react, the mol ratio of fluorohalogenethers, sodium alkoxide, triethylamine is 1:1 ~ 2:1 ~ 5, temperature of reaction is 80 ~ 120 DEG C, reaction times is 0.5 ~ 1.5 hour, and reaction solution obtains fluorine haloalkene ether through separatory, rectifying.
In the present invention, the chain of alkene or alcohol is longer, more easily generates alkene ether products.Alcohol described in step (1) is preferably the one in methyl alcohol, ethanol, propyl alcohol, trifluoroethanol, C3-Fluoroalcohol, three fluoro butanols.Alkene described in step (1) is preferably the one in trifluoro propene, tetrafluoeopropene, tetrafluoroethylene, vinylidene, ethene, propylene.
Solvent described in step (1) is preferably the one in tetramethylene sulfone, DMF (DMF), NMP (N-Methyl pyrrolidone), DMSO (dimethyl sulfoxide (DMSO)).
Catalyzer described in step (1) is preferably the one in deacidite, sodium ethylate, potassium hydroxide or sodium hydroxide.
The mol ratio of the alcohol described in step (1), solvent, catalyzer is preferably 1:1.5 ~ 2.5:1.2 ~ 2, and temperature of reaction is preferably 90 ~ 150 DEG C, and reaction pressure is preferably 0.5 ~ 1.0MPa.
Simple substance halogen described in step (2) is preferably the one in simple substance chlorine, simple substance bromine or iodine.
Alkene ether described in step (2) and preferred 1:1.2 ~ 1.5 of simple substance halogen mol ratio, temperature of reaction is preferably 30 ~ 50 DEG C, and the reaction times is preferably 1.5 ~ 3 hours.
Sodium alkoxide described in step (3) or potassium alcoholate are preferably the one in sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium tert-butoxide, potassium tert.-butoxide.
The mol ratio of the fluorohalogenethers described in step (3), sodium alkoxide, triethylamine is preferably 1:1.2 ~ 1.5:2.5 ~ 4, and temperature of reaction is preferably 90 ~ 110 DEG C, and the reaction times is preferably 0.8 ~ 1.2 hour.
Catalyzer described in step of the present invention (1) can select the one in deacidite, sodium ethylate, potassium hydroxide or sodium hydroxide.Sodium ethylate, NaOH, KOH are as catalyzer, and alkalescence is strong, and reaction is fast, but by product is relatively many, and product color is dark.Make spent ion exchange resin, reaction temperature and, product color is good, but the reaction times is relatively long.
In step of the present invention (1) described reaction, the amount of solvent is larger, and catalytic amount is more, and speed of response is faster, and transformation efficiency is higher.But catalytic amount is too much unsuitable, otherwise causes by-product impurity to increase, selectivity reduces.Therefore, the mol ratio of the alcohol described in the present invention, solvent, catalyzer is 1:1 ~ 4:1 ~ 3, is preferably 1:1.5 ~ 2.5:1.2 ~ 2.
In the present invention, in step (1) described reaction, temperature of reaction is higher, and speed of response is faster, and transformation efficiency is higher, but selectivity reduces.Therefore, it is 60 ~ 200 DEG C that temperature of reaction controls, preferably 90 ~ 150 DEG C.In step of the present invention (1), reaction pressure is higher, and the solubleness of alkene in system is larger, and speed of response is faster, transformation efficiency is higher, but too high reaction pressure can cause reacting the amount terminating rear unreacted alkene to be increased, and this part alkene generally cannot reclaim, and makes unit consumption increase.Therefore, it is 0.2 ~ 1.5MPa, preferably 0.5 ~ 1.0MPa that the reaction pressure in step of the present invention (1) controls.
In the present invention in the described halogenating reaction process of step (2), the usage quantity of simple substance halogen is more, and speed of response is faster, and effect is better, but too much simple substance halogen use also can increase post-processing difficulty.Reaction must be carried out under light illumination, and temperature is higher, and the reaction times is longer, and reaction effect is higher.But temperature is too high or the reaction times is oversize, simple substance halogen gasifies, and affects light efficiency, and then affects halogenation effect.Therefore react under light illumination 1:1 ~ 2 in molar ratio containing fluroxene and simple substance halogen in the present invention, described temperature of reaction is 20 ~ 100 DEG C, and the reaction times is 0.5 ~ 5 hour.Alkene ether and preferred 1:1.2 ~ 1.5 of simple substance halogen mol ratio, temperature of reaction is preferably 30 ~ 50 DEG C, and the reaction times is preferably 1.5 ~ 3 hours.
Sodium alkoxide in invention described in step (3) or potassium alcoholate are the one in sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium tert-butoxide, potassium tert.-butoxide.
The dehydrochlorination reaction of the dihalogenated ether in invention described in step (3) is more difficult, carries out under needing higher temperature and stronger alkali condition.Triethylamine uses as solvent and acid binding agent.Therefore in the present invention, the mol ratio of fluorohalogenethers, sodium alkoxide, triethylamine is 1:1 ~ 2:1 ~ 5, temperature of reaction is 80 ~ 120 DEG C, reaction times is 0.5 ~ 1.5 hour, the mol ratio of fluorohalogenethers, sodium alkoxide, triethylamine is preferably 1:1.2 ~ 1.5:2.5 ~ 4, temperature of reaction is preferably 90 ~ 110 DEG C, and the reaction times is preferably 0.8 ~ 1.2 hour.
Compared with prior art, advantage of the present invention is:
1, the present invention is raw materials used cheap and easy to get, and technical process is short, and product is easily separated, and reaction conditions is gentle;
2, yield is high, good product quality, and product purity is more than 99.6%.
Embodiment
By the following examples more specific description is carried out to the present invention, but the present invention is not limited to described embodiment.
Embodiment 1
C3-Fluoroalcohol 2mol is dropped in 2L stainless steel autoclave, DMSO (dimethyl sulfoxide (DMSO)) 4mol, NaOH3mol, be warming up to 100 DEG C, pass into tetrafluoroethylene under stirring continuously to react, by regulating the flow that passes into of tetrafluoroethylene to keep reacting kettle inner pressure to be 0.8MPa in reaction process, temperature of reaction 100 DEG C is controlled by chuck refrigerant, when passing into when flow is initially pass into flow 0.5% of tetrafluoroethylene stops passing into tetrafluoroethylene, rectifying separation obtains trifluoro-propenyl tetrafluoro ethyl ether (CF
2=CFCH
2oCF
2cF
2h) 1.828 moles, purity 99.9%, yield is 91.4%.
In the 1000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the trifluoro-propenyl tetrafluoro ethyl ether (CF that back obtains
2=CFCH
2oCF
2cF
2h) 1.828mol, and bromine 2.376mol, under stirring, illumination, 45 DEG C of reaction 2h, reaction solution obtains dibromo trifluoro propyl tetrafluoro ethyl ether (CF through alkali cleaning, separatory
2brCFBrCH
2oCF
2cF
2h) 1.792mol, purity 99.9%, yield 98.0%.
In the 2000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the dibromo trifluoro propyl tetrafluoro ethyl ether (CF that back obtains
2brCFBrCH
2oCF
2cF
2h) 1.792mol and sodium ethylate 2.33mol, triethylamine 6.272mol, 100 DEG C of reaction 1h, reaction solution obtains bromine trifluoro-propenyl tetrafluoro ethyl ether (CF through separatory, rectifying
2brCF=CHOCF
2cF
2h) 1.708mol, purity 99.8%, yield 95.3%.
Embodiment 2
C3-Fluoroalcohol 2mol is dropped in 2L stainless steel autoclave, DMF (N, dinethylformamide) 3mol, KOH2.4mol, be warming up to 90 DEG C, pass into ethene under stirring continuously to react, by regulating the flow that passes into of ethene to keep reacting kettle inner pressure to be 1.0MPa in reaction process, temperature of reaction 90 DEG C is controlled by chuck refrigerant, when passing into when flow is initially pass into flow 0.6% of ethene stops passing into ethene, reaction solution rectifying separation is obtained trifluoro propene benzyl ethyl ether (CF
2=CFCH
2oCH
2cH
3) 1.74mol, purity 99.8%, yield is 87.0%.
In the 1000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the trifluoro propene benzyl ethyl ether (CF that back obtains
2=CFCH
2oCH
2cH
3) 1.74mol, and iodine 2.088mol, under stirring, illumination, 30 DEG C of reaction 1.5h, reaction solution obtains diiodo-trifluoro propyl ethyl ether (CF through alkali cleaning, separatory
2iCFICH
2oCH
2cH
3) 1.709mol, purity 99.9%, yield 98.2%.
In the 2000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the diiodo-trifluoro propyl ethyl ether (CF that back obtains
2iCFICH
2oCH
2cH
3) 1.709mol and sodium methylate 2.051mol, triethylamine 6.836mol, 90 DEG C of reaction 0.8h, reaction solution obtains iodine trifluoro propene benzyl ethyl ether (CF through separatory, rectifying
2iCF=CHOCH
2cH
3) 1.659mol, purity 99.9%, yield 97.1%.
Embodiment 3
Three fluoro butanol 2mol are dropped in 2L stainless steel autoclave, DMF (N, dinethylformamide) 5mol, sodium ethylate 4mol, be warming up to 150 DEG C, pass into vinylidene under stirring continuously to react, by regulating the flow that passes into of vinylidene to keep reacting kettle inner pressure to be 0.5MPa in reaction process, temperature of reaction 150 DEG C is controlled by chuck refrigerant, when passing into when flow is initially pass into flow 0.7% of vinylidene stops passing into vinylidene, reaction solution rectifying separation is obtained difluoro butenyl difluoro ethyl ether (CF
2=CHCH
2cH
2oCF
2cH
3) 1.696mol, purity 99.5%, yield is 84.8%.
In the 1000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the difluoro butenyl difluoro ethyl ether (CF that back obtains
2=CHCH
2cH
2oCF
2cH
3) 1.696mol, and bromine 2.544mol, under stirring, illumination, 50 DEG C of reaction 3h, reaction solution obtains dibromo difluorobutyl groups difluoro ethyl ether (CF through alkali cleaning, separatory
2brCFBrCH
2cH
2oCF
2cH
3) 1.65mol, purity 99.7%, yield 97.3%.
In the 2000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the dibromo difluorobutyl groups difluoro ethyl ether (CF that back obtains
2brCFBrCH
2cH
2oCF
2cH
3) 1.65mol and potassium ethylate 1.981mol, triethylamine 4.125mol, 110 DEG C of reaction 1.2h, reaction solution obtains bromine difluoro butenyl difluoro ethyl ether (CF through separatory, rectifying
2brCF=CHCH
2oCF
2cH
3) 1.591mol, purity 99.6%, yield 96.4%.
Embodiment 4
Trifluoroethanol 2mol is dropped in 2L stainless steel autoclave, NMP (N-Methyl pyrrolidone) 2mol, NaOH5mol, be warming up to 60 DEG C, pass into trifluoro propene under stirring continuously to react, by regulating the flow that passes into of trifluoro propene to keep reacting kettle inner pressure to be 0.2MPa in reaction process, temperature of reaction 60 DEG C is controlled by chuck refrigerant, when passing into when flow is initially pass into flow 0.8% of trifluoro propene stops passing into trifluoro propene, reaction solution rectifying separation is obtained difluoropropenes base trifluoroethyl ether (CF
2=CHCH
2oCH
2cF
3) 1.836mol, purity 99.8%, yield is 91.8%.
In the 1000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the difluoropropenes base trifluoroethyl ether (CF that back obtains
2=CHCH
2oCH
2cF
3) 1.836mol, and bromine 3.672mol, under stirring, illumination, 20 DEG C of reaction 5h, reaction solution obtains dibromo two fluoropropyl trifluoroethyl ether (CF through alkali cleaning, separatory
2brCHBrCH
2oCH
2cF
3) 1.833mol, purity 99.8%, yield 98.4%.
In the 2000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the dibromo two fluoropropyl trifluoroethyl ether (CF that back obtains
2brCHBrCH
2oCH
2cF
3) 1.833mol and potassium tert.-butoxide 3.666mol, triethylamine 1.833mol, 120 DEG C of reaction 1.5h, reaction solution obtains bromine difluoropropenes base trifluoroethyl ether (CF through separatory, rectifying
2brCH=CHOCH
2cF
3) 1.591mol, purity 99.6%, yield 96.4%.
Embodiment 5
Methyl alcohol 2mol is dropped in 2L stainless steel autoclave, DMF (N, dinethylformamide) 3mol, deacidite 6mol, be warming up to 200 DEG C, pass into trifluoro propene under stirring continuously to react, by regulating the flow that passes into of trifluoro propene to keep reacting kettle inner pressure to be 0.5MPa in reaction process, temperature of reaction 200 DEG C is controlled by chuck refrigerant, when passing into when flow is initially pass into flow 0.9% of trifluoro propene stops passing into trifluoro propene, reaction solution rectifying separation is obtained difluoropropenes ylmethyl ether (CF
2=CHCH
2oCH
3) 1.864mol, purity 99.9%, yield is 93.2%.
In the 1000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the difluoropropenes ylmethyl ether (CF that back obtains
2=CHCH
2oCH
3) 1.864mol, and bromine 2.051mol, under stirring, illumination, 100 DEG C of reaction 0.5h, reaction solution obtains dibromo difluoro propyl methyl ether (CF through alkali cleaning, separatory
2brCHBrCH
2oCH
3) 1.829mol, purity 99.8%, yield 98.1%.
In the 2000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the dibromo difluoro propyl methyl ether (CF that back obtains
2brCHBrCH
2oCH
3) 1.829mol and sodium tert-butoxide 3.656mol, triethylamine 9.145mol, 80 DEG C of reaction 1.5h, reaction solution obtains bromine difluoropropenes ylmethyl ether (CF through separatory, rectifying
2brCH=CHOCH
3) 1.577mol, purity 99.6%, yield 86.2%.
Embodiment 6
Ethanol 2mol is dropped in 2L stainless steel autoclave, DMSO (dimethyl sulfoxide (DMSO)) 8mol, KOH3.5mol, be warming up to 170 DEG C, pass into trifluoro propene under stirring continuously to react, by regulating the flow that passes into of trifluoro propene to keep reacting kettle inner pressure to be 0.7MPa in reaction process, temperature of reaction 170 DEG C is controlled by chuck refrigerant, when passing into when flow is initially pass into flow 1% of trifluoro propene stops passing into trifluoro propene, reaction solution rectifying separation is obtained difluoropropenes benzyl ethyl ether (CF
2=CHCH
2oCH
2cH
3) 1.824mol, purity 99.9%, yield is 91.2%.
In the 1000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the difluoropropenes benzyl ethyl ether (CF that back obtains
2=CHCH
2oCH
2cH
3) 1.824mol, and chlorine 2.736mol, under stirring, illumination, 60 DEG C of reaction 1h, reaction solution obtains dichlorodifluoro ethyl ether (CF through alkali cleaning, separatory
2clCHClCH
2oCH
2cH
3) 1.527mol, purity 99.8%, yield 83.7%.
In the 2000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the dichlorodifluoro ethyl ether (CF that back obtains
2clCHClCH
2oCH
2cH
3) 1.527mol and potassium methylate 1.985mol, triethylamine 4.581mol, 100 DEG C of reaction 1.0h, reaction solution obtains chlorine difluoropropenes benzyl ethyl ether (CF through separatory, rectifying
2clCH=CHOCH
2cH
3) 1.367mol, purity 99.7%, yield 89.5%.
Embodiment 7
Propyl alcohol 2mol is dropped in 2L stainless steel autoclave, NMP (N-Methyl pyrrolidone) 6mol, NaOH4mol, be warming up to 130 DEG C, pass into tetrafluoeopropene under stirring continuously to react, by regulating the flow that passes into of tetrafluoeopropene to keep reacting kettle inner pressure to be 0.6MPa in reaction process, temperature of reaction 130 DEG C is controlled by chuck refrigerant, when passing into when flow is initially pass into flow 1.1% of tetrafluoeopropene stops passing into tetrafluoeopropene, reaction solution rectifying separation is obtained trifluoro-propenyl propyl ether (CF
2=CHCHFOCH
2cH
2cH
3) 1.834mol, purity 99.7%, yield is 91.7%.
In the 1000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the trifluoro-propenyl propyl ether (CF that back obtains
2=CHCHFOCH
2cH
2cH
3) 1.834mol, and bromine 2.568mol, under stirring, illumination, 60 DEG C of reaction 1h, reaction solution obtains dibromo trifluoro propyl propyl ether (CF through alkali cleaning, separatory
2brCHBrCHFOCH
2cH
2cH
3) 1.698mol, purity 99.8%, yield 92.6%.
In the 2000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the dibromo trifluoro propyl propyl ether (CF that back obtains
2brCHBrCHFOCH
2cH
2cH
3) 1.698mol and potassium ethylate 2.377mol, triethylamine 5.094mol, 100 DEG C of reaction 1.0h, reaction solution obtains bromine trifluoro-propenyl propyl ether (CF through separatory, rectifying
2brCH=CFOCH
2cH
2cH
3) 1.554mol, purity 99.8%, yield 91.5%.
Embodiment 8
C3-Fluoroalcohol 2mol is dropped in 2L stainless steel autoclave, DMSO (dimethyl sulfoxide (DMSO)) 3mol, KOH2.6mol, be warming up to 120 DEG C, pass into propylene under stirring continuously to react, by regulating the flow that passes into of propylene to keep reacting kettle inner pressure to be 0.6MPa in reaction process, temperature of reaction 120 DEG C is controlled by chuck refrigerant, when passing into when flow is initially pass into flow 1.5% of propylene stops passing into propylene, reaction solution rectifying separation is obtained trifluoro-propenyl propyl ether (CF
2=CFCH
2oCH
2cH
2cH
3) 1.78mol, purity 99.8%, yield is 89.0%.
In the 1000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the trifluoro-propenyl propyl ether (CF that back obtains
2=CFCH
2oCH
2cH
2cH
3) 1.78mol, and iodine 2.314mol, under stirring, illumination, 35 DEG C of reaction 1.0h, reaction solution obtains diiodo-trifluoro propyl propyl ether (CF through alkali cleaning, separatory
2iCFICH
2oCH
2cH
2cH
3) 1.757mol, purity 99.9%, yield 98.7%.
In the 2000ml four-hole boiling flask of band mechanical stirring, reflux condensing tube, add the diiodo-trifluoro propyl propyl ether (CF that back obtains
2iCFICH
2oCH
2cH
2cH
3) 1.757mol and sodium ethylate 1.933mol, triethylamine 7.907mol, 95 DEG C of reaction 0.6h, reaction solution obtains iodine trifluoro-propenyl propyl ether (CF through separatory, rectifying
2iCF=CHOCH
2cH
2cH
3) 1.725mol, purity 99.8%, yield 98.2%.
Claims (10)
1. a synthetic method for fluorine haloalkene ether, is characterized in that comprising the following steps:
(1) after adding alcohol, solvent and catalyzer in a kettle., pass into alkene continuously to react, by regulating the intake control reactor pressure of alkene to be 0.2 ~ 1.5MPa in reaction process, in described alcohol and alkene, at least one is fluorine-containing, the mol ratio of described alcohol, solvent, catalyzer is 1:1 ~ 4:1 ~ 3, temperature of reaction is 60 ~ 200 DEG C, when passing into when flow is initially pass into flow 0.5 ~ 1.5% of alkene stops passing into alkene, reaction solution rectifying is obtained containing fluroxene;
(2) reacted under light illumination 1:1 ~ 2 in molar ratio containing fluroxene and simple substance halogen by obtained for step (1), described temperature of reaction is 20 ~ 100 DEG C, and the reaction times is 0.5 ~ 5 hour, and reaction solution obtains fluorohalogenethers through alkali cleaning, separatory;
(3) fluorohalogenethers obtained for step (2) is added in the triethylamine solution of sodium alkoxide or potassium alcoholate react, the mol ratio of fluorohalogenethers, sodium alkoxide, triethylamine is 1:1 ~ 2:1 ~ 5, temperature of reaction is 80 ~ 120 DEG C, reaction times is 0.5 ~ 1.5 hour, and reaction solution obtains fluorine haloalkene ether through separatory, rectifying.
2. the synthetic method of fluorine haloalkene ether according to claim 1, the alcohol that it is characterized in that described in step (1) is the one in methyl alcohol, ethanol, propyl alcohol, trifluoroethanol, C3-Fluoroalcohol, three fluoro butanols.
3. the synthetic method of fluorine haloalkene ether according to claim 1, the alkene that it is characterized in that described in step (1) is the one in trifluoro propene, tetrafluoeopropene, tetrafluoroethylene, vinylidene, ethene, propylene.
4. the synthetic method of fluorine haloalkene ether according to claim 1, the solvent that it is characterized in that described in step (1) is the one in tetramethylene sulfone, DMF, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO).
5. the synthetic method of fluorine haloalkene ether according to claim 1, the catalyzer that it is characterized in that described in step (1) is the one in deacidite, sodium ethylate, potassium hydroxide or sodium hydroxide.
6. the synthetic method of fluorine haloalkene ether according to claim 1, it is characterized in that the mol ratio of the alcohol described in step (1), solvent, catalyzer is 1:1.5 ~ 2.5:1.2 ~ 2, temperature of reaction is 90 ~ 150 DEG C, and reaction pressure is 0.5 ~ 1.0MPa.
7. the synthetic method of fluorine haloalkene ether according to claim 1, the simple substance halogen that it is characterized in that described in step (2) is the one in simple substance chlorine, simple substance bromine or iodine.
8. the synthetic method of fluorine haloalkene ether according to claim 1, it is characterized in that the alkene ether described in step (2) and simple substance halogen mol ratio 1:1.2 ~ 1.5, temperature of reaction is 30 ~ 50 DEG C, and the reaction times is 1.5 ~ 3 hours.
9. the synthetic method of fluorine haloalkene ether according to claim 1, is characterized in that sodium alkoxide described in step (3) or potassium alcoholate are the one in sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium tert-butoxide, potassium tert.-butoxide.
10. the synthetic method of fluorine haloalkene ether according to claim 1, it is characterized in that the mol ratio of the fluorohalogenethers described in step (3), sodium alkoxide, triethylamine is 1:1.2 ~ 1.5:2.5 ~ 4, temperature of reaction is 90 ~ 110 DEG C, and the reaction times is 0.8 ~ 1.2 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610053628.7A CN105503548A (en) | 2016-01-26 | 2016-01-26 | Synthesizing method of fluorine halogenated vinyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610053628.7A CN105503548A (en) | 2016-01-26 | 2016-01-26 | Synthesizing method of fluorine halogenated vinyl ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105503548A true CN105503548A (en) | 2016-04-20 |
Family
ID=55711925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610053628.7A Pending CN105503548A (en) | 2016-01-26 | 2016-01-26 | Synthesizing method of fluorine halogenated vinyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105503548A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906489A (en) * | 2016-05-05 | 2016-08-31 | 巨化集团技术中心 | Method for synchronously preparing hydrofluoroether and fluorine-containing olefine ether |
| CN112898121A (en) * | 2021-01-23 | 2021-06-04 | 四川上氟科技有限公司 | Preparation method of perfluoroalkyl alcohol |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2409274A (en) * | 1943-04-23 | 1946-10-15 | Du Pont | Polyfluoro organic ethers and their preparation |
| US5536885A (en) * | 1993-05-21 | 1996-07-16 | E. I. Du Pont De Nemours And Company | Production of perfluoro(alkyl vinyl ethers) |
| WO2001046108A1 (en) * | 1999-12-22 | 2001-06-28 | Dyneon Llc | Fluorine containing allylethers and higher homologs |
| US20060074264A1 (en) * | 2004-10-06 | 2006-04-06 | Fuji Photo Film Co., Ltd. | Method of producing a flourine-containing vinyl ether compound |
| CN1986511A (en) * | 2005-12-22 | 2007-06-27 | 索尼维索莱克西斯公司 | Process for preparing fluorohalogenethers |
| CN102115428A (en) * | 2010-12-27 | 2011-07-06 | 锦州惠发天合化学有限公司 | Method for synthesizing hydrofluoro ether |
| CN103189342A (en) * | 2010-09-14 | 2013-07-03 | 优迈特株式会社 | Novel fluorinated vinyl ether compound and manufacturing method therefor |
| CN103254041A (en) * | 2013-05-03 | 2013-08-21 | 巨化集团技术中心 | Preparation method of hydrofluoroether |
-
2016
- 2016-01-26 CN CN201610053628.7A patent/CN105503548A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2409274A (en) * | 1943-04-23 | 1946-10-15 | Du Pont | Polyfluoro organic ethers and their preparation |
| US5536885A (en) * | 1993-05-21 | 1996-07-16 | E. I. Du Pont De Nemours And Company | Production of perfluoro(alkyl vinyl ethers) |
| WO2001046108A1 (en) * | 1999-12-22 | 2001-06-28 | Dyneon Llc | Fluorine containing allylethers and higher homologs |
| US20060074264A1 (en) * | 2004-10-06 | 2006-04-06 | Fuji Photo Film Co., Ltd. | Method of producing a flourine-containing vinyl ether compound |
| CN1986511A (en) * | 2005-12-22 | 2007-06-27 | 索尼维索莱克西斯公司 | Process for preparing fluorohalogenethers |
| CN103189342A (en) * | 2010-09-14 | 2013-07-03 | 优迈特株式会社 | Novel fluorinated vinyl ether compound and manufacturing method therefor |
| CN102115428A (en) * | 2010-12-27 | 2011-07-06 | 锦州惠发天合化学有限公司 | Method for synthesizing hydrofluoro ether |
| CN103254041A (en) * | 2013-05-03 | 2013-08-21 | 巨化集团技术中心 | Preparation method of hydrofluoroether |
Non-Patent Citations (1)
| Title |
|---|
| PAUL TARRANT ET AL.: "Free-radical additions involving fluorine compounds. VII. Addition of perhaloalkanes to vinyl ethyl ether and vinyl 2,2,2-trifluoroethyl ether", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906489A (en) * | 2016-05-05 | 2016-08-31 | 巨化集团技术中心 | Method for synchronously preparing hydrofluoroether and fluorine-containing olefine ether |
| CN112898121A (en) * | 2021-01-23 | 2021-06-04 | 四川上氟科技有限公司 | Preparation method of perfluoroalkyl alcohol |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5946410B2 (en) | Process for producing 2-chloro-3,3,3-trifluoropropene | |
| KR101967822B1 (en) | Bis(1,1-dichloro-3,3,3-trifluoropropyl)ether and method for producing same | |
| US7795477B2 (en) | Process for preparing fluorohalogenethers | |
| JP5267561B2 (en) | Method for producing fluorine-containing ether | |
| US11655199B2 (en) | Methods for producing halogenated alkene compound and fluorinated alkyne compound | |
| CN105503548A (en) | Synthesizing method of fluorine halogenated vinyl ether | |
| KR101431926B1 (en) | Method for producing perfluorosulfonic acid having ether structure and derivative thereof, and surfactant containing fluorine-containing ether sulfonic acid compound and derivative thereof | |
| JP4640175B2 (en) | Method for producing fluorine-containing alkyl ether | |
| CN102701919B (en) | Method for synthesizing fluorine halogenated ether | |
| JP2017226617A (en) | Methods for producing acid fluoride and perfluoroalkyl vinyl ether | |
| JP2008044863A (en) | Perfluoro-organic peroxide, its manufacturing method and manufacturing method of polymer | |
| CN106279290B (en) | A kind of oxa- short-chain perfluoroaldyl vinyl ethers and preparation method thereof | |
| US10975053B2 (en) | Production methods for 1,3-dioxolane compound and perfluoro(2,2-dimethyl-1,3-dioxole) | |
| EP2637995B1 (en) | Process for the preparation of difluoroacetic acid | |
| US20210363127A1 (en) | Process for the preparation of 2,2-difluoro-1,3-benzodioxole and intermediates thereof | |
| JP5862252B2 (en) | Method for producing perfluoroalkyl divinyl ether | |
| JP6610625B2 (en) | Method for producing 1,2-dichloro-1,2-difluoroethane (HCFC-132), method for producing 1-chloro-1,2-difluoroethylene (HCFO-1122a), and method for separating HCFC-132 | |
| RU2793785C2 (en) | Method for producing halogenated alkene compound and fluorinated alkyne compound | |
| CN117326926A (en) | Difluoro acetic acid synthesis method | |
| RU2179548C2 (en) | Method of synthesis of perfluorinated ethers with terminal functional groups | |
| JP6027883B2 (en) | Method for producing allyl fluoroalkyl ether | |
| JP2005225816A (en) | Production method for fluorine-containing allyl ether | |
| CN105949030A (en) | Method for preparing perfluoroheptene isomers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160420 |