CN116693371A - Method for synthesizing methyl nonafluoro isobutyl ether - Google Patents
Method for synthesizing methyl nonafluoro isobutyl ether Download PDFInfo
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- CN116693371A CN116693371A CN202310616672.4A CN202310616672A CN116693371A CN 116693371 A CN116693371 A CN 116693371A CN 202310616672 A CN202310616672 A CN 202310616672A CN 116693371 A CN116693371 A CN 116693371A
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- difluoro
- trifluoromethyl
- propane
- methoxy
- catalyst
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- DJXNLVJQMJNEMN-UHFFFAOYSA-N 2-[difluoro(methoxy)methyl]-1,1,1,2,3,3,3-heptafluoropropane Chemical compound COC(F)(F)C(F)(C(F)(F)F)C(F)(F)F DJXNLVJQMJNEMN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000001294 propane Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000005660 chlorination reaction Methods 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000007259 addition reaction Methods 0.000 claims description 6
- 238000006266 etherification reaction Methods 0.000 claims description 6
- 238000003682 fluorination reaction Methods 0.000 claims description 6
- 230000001699 photocatalysis Effects 0.000 claims description 6
- -1 alkyl phosphate Chemical compound 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 20
- 238000004817 gas chromatography Methods 0.000 description 14
- 239000012043 crude product Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000000872 buffer Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910000856 hastalloy Inorganic materials 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- COQIQRBKEGPRSG-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoro-2-(trifluoromethyl)propane Chemical compound FC(F)(F)C(F)(C(F)(F)F)C(F)(F)F COQIQRBKEGPRSG-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical compound FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 1
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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
- C07C41/18—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
- 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
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
-
- 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
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- 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 method for synthesizing methyl nonafluoroisobutyl ether, which comprises the following steps: (1) Carbon tetrachloride (formula CCl 4) and 1, 3-pentafluoropropene (formula cf3ch=cf2) are catalyzed in an aprotic solvent with the aid of a catalyst and a cocatalyst to produce 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethylpropane; (2) Reacting 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethylpropane with methanol (molecular formula CH3 OH) under the action of a catalyst to generate 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane; (3) 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane is subjected to photochlorination reaction to generate 1,2, 3-tetrachloro-3, 3-difluoro-1-methoxy-2- (trifluoromethyl) propane; (4) The 1,2, 3-tetrachloro-3, 3-difluoro-1-methoxy-2- (trifluoromethyl) propane and anhydrous hydrofluoric acid are subjected to gas phase catalysis to synthesize the methyl nonafluoro isobutyl ether under the action of a catalyst. The invention has the advantages of low raw material cost, high reaction yield, good catalyst stability, simple product separation and purification, and the like.
Description
Technical Field
The invention belongs to the field of organic chemical synthesis, and particularly relates to a method for synthesizing methyl nonafluoroisobutyl ether.
Background
In recent years, the trend of global warming has been increasing, and in order to improve this phenomenon, chlorofluorocarbons (CFCs) and Hydrochlorofluorocarbons (HCFCs) which have been widely used have been eliminated or have a serious destruction effect on the ozone layer in the atmosphere. New materials that can be substituted are now being developed.
Methyl nonafluoroisobutyl ether (CAS: 163702-08-7,1,1,2,3,3,3-hexafluoro-1-methoxy-2- (trifluoromethyl) propane) is a colorless liquid having high density, low viscosity, low surface tension, excellent inertness, and simultaneously has the characteristics of non-combustibility, non-toxicity, non-corrosiveness, no residue, zero Ozone Depletion Potential (ODP), low Global Warming Potential (GWP). The methyl nonafluoroisobutyl ether is also an industrial raw material with high industrial added value and has wide application. Can be used for cleaning the circuit board of precise instruments, the electronic instrument and the laser disc surface, and is also an important raw material for synthesizing fluorine-containing medical intermediates. Methyl nonafluoroisobutyl ether is also an excellent solvent diluent, and can replace common solvent diluents such as trichloroethane, carbon tetrachloride and the like. In addition, the methyl nonafluoroisobutyl ether is also an excellent refrigerant, can be used in heat conduction application in the fields of semiconductors, electrons, automobiles, household appliances and the like, and has the characteristics of high efficiency, stability and environmental friendliness. In the comprehensive view, the methyl nonafluoro isobutyl ether has wide application prospect.
At present, the existing synthetic route of methyl nonafluoro isobutyl ether is complex, and the reaction conditions are harsh. In the literature (Synlett, 2000,3, p.343-344) it is described that heptafluoroisopropenyl methyl ether is reacted with cobalt fluoride (trivalent) at a temperature of from-196℃to 20℃to form methyl nonafluoroisobutyl ether in an amount of 70%. Fluorine gas is involved in the reaction process, so that the risk of industrial production is greatly increased. Patent (US 2004192974) reports that 71% of methyl nonafluoroisobutyl ether is synthesized from perfluoroisobutane and a methoxy-containing compound under the action of a catalyst KF, but a large amount of industrial waste liquid is generated. Therefore, the prior art can not meet the requirement of industrial production.
Disclosure of Invention
The invention aims to efficiently prepare methyl nonafluoroisobutyl ether under mild reaction conditions by using a simple reaction system. The raw materials used in the invention are low in price and easy to obtain, the products are easy to separate, and the synthesis process is safe and reliable.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention discloses a method for synthesizing methyl nonafluoroisobutyl ether, which comprises the following steps:
(1) Addition reaction: carbon tetrachloride and 1, 3-pentafluoropropene are catalyzed in an aprotic solvent in an auxiliary manner through a catalyst and a cocatalyst to generate 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethylpropane;
(2) Etherification reaction: reacting 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethyl propane with methanol under the action of a catalyst to generate 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane;
(3) Chlorination reaction: 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane is subjected to photochlorination reaction to generate 1,2, 3-tetrachloro-3, 3-difluoro-1-methoxy-2- (trifluoromethyl) propane;
(4) Fluorination reaction: the 1,2, 3-tetrachloro-3, 3-difluoro-1-methoxy-2- (trifluoromethyl) propane and anhydrous hydrofluoric acid are subjected to gas phase catalysis to synthesize the methyl nonafluoro isobutyl ether under the action of a catalyst.
The synthetic route of the invention is as follows:
preferably, in the step (1), the catalyst is a composite component catalyst of one or more of iron, copper, ferric chloride and cuprous chloride; the cocatalyst is one of alkyl phosphate, alkyl phosphite, ethanolamine, triethylamine, trimethylamine and tributylamine; the aprotic solvent is one of acetonitrile, sulfolane, dimethylformamide, dimethylacetamide, tetrahydrofuran and carbon tetrachloride; the reaction temperature is-30-150 ℃.
Preferably, the aprotic solvent is dimethylformamide or carbon tetrachloride; the reaction temperature is 80-140 ℃;
preferably, in the step (2), the catalyst is one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium methoxide and potassium methoxide; the molar ratio of the 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethyl propane, the methanol and the catalyst is 1: 1-5:1-2, the reaction temperature is 0-100 ℃.
Preferably, the molar ratio of the 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethyl propane, the methanol and the catalyst is 1:1-2:1-1.5; the reaction temperature is 50-100 ℃;
preferably, in the step (3), the photocatalytic chlorination reagent is chlorine gas; the molar ratio of the 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane to the chlorine is 1:1-5, and the reaction temperature is-10-100 ℃.
Preferably, the molar ratio of the 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane to the chlorine is 1:1-2; the reaction temperature is 20-60 ℃;
preferably, the catalyst in the step (4) is a composite component catalyst of one or more of Fe, cu, mn, cr, al, zn, ba and Ni; the molar ratio of the 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane to the anhydrous hydrofluoric acid is as follows: 1:4-20; the reaction temperature is 100-300 ℃.
Preferably, the molar ratio of the 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane to the anhydrous hydrofluoric acid is as follows: 1:10.
Preferably, the reaction temperature is 260 to 280 ℃.
The invention has the beneficial effects that:
1. the raw materials in the invention are low in price and easy to obtain, and the adopted catalyst has good stability and can be reused.
2. The invention has simple process, high reaction yield, simple product separation and purification, safe synthesis process and suitability for industrial production.
Detailed Description
The invention will be further understood by reference to the following examples which are given to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
The embodiment relates to a method for synthesizing methyl nonafluoroisobutyl ether, which comprises the following steps:
(1) Addition reaction
10g of Fe powder, 30g of tributyl phosphate, 730g of dimethylformamide and 154g of carbon tetrachloride are added into a 2L hastelloy high-pressure valve, the temperature is raised to 90-100 ℃, and after magnetic stirring for 1h, 132g of 1, 3-pentafluoropropene is introduced. After 4h of reaction, 310g of an organic matter is obtained by distillation, the content of 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethyl propane is 85% by GC analysis, and a 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethyl propane product with the purity of more than 99% is obtained by rectification and is used for the next reaction.
(2) Etherification reaction
40g of sodium hydroxide and 60g of anhydrous methanol, 285g of 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethyl propane are added into a 1000ml four-port reaction bottle, the temperature is reduced to 50 to 60 ℃, magnetic stirring is carried out for 6 hours, then the crude product 310g is obtained by distillation, GC analysis is carried out, the content of 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane is 87%, and the product with the purity of more than 99% is obtained by rectification and is used for the next reaction.
(3) Chlorination reaction
281g of 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane is added into a photocatalysis reactor, the temperature is kept at 50 ℃, 80g of chlorine gas is continuously introduced, 350g of crude product is obtained by distillation after the reaction is finished, the content of the 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane is 87 percent by GC analysis, and the product with the purity of more than 99 percent is obtained by rectification for the next reaction.
(4) Fluorination reaction
50g of chromium-based composite catalyst is filled into a fixed bed reactor, the temperature is raised to 220-230 ℃, 1g/min of 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane and 0.7g/min of anhydrous hydrogen fluoride are filled into a mixing cavity and fully mixed, a buffer bottle, an alkali liquor bottle, a water washing bottle and a cooling receiving bottle are connected with the reactor, the receiving bottle collects about 550g of product after the experiment is finished, GC analysis is carried out, the content of methyl nonafluoroisobutyl ether is 85%, and the product with the purity of more than 99% is obtained through rectification.
Example 2
The embodiment relates to a method for synthesizing methyl nonafluoroisobutyl ether, which comprises the following steps:
(1) Addition reaction
10g of Cu powder, 30g of triethyl phosphate, 730g of dimethylformamide and 154g of carbon tetrachloride are added into a 2L hastelloy high-pressure valve, the temperature is raised to 90-100 ℃, and after magnetic stirring for 1h, 132g of 1, 3-pentafluoropropene is introduced. After 4h of reaction, the organic matter 284 g is obtained by distillation, the content of 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethyl propane is 81% by GC analysis, and the 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethyl propane product with the purity of more than 99% is obtained by rectification and is used for the next reaction.
(2) Etherification reaction
56g of potassium hydroxide and 285g of 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethylpropane are added into a 1L four-port reaction bottle, the temperature is reduced to 50-60 ℃, after magnetic stirring is carried out for 6 hours, 300g of crude product is obtained by distillation, the content of 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane is 90% by GC analysis, and the product with the purity of more than 99% is obtained by rectification and is used for the next reaction.
(3) Chlorination reaction
Adding 281g of 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane into a photocatalysis reactor, keeping the temperature at 50 ℃, continuously introducing 100g of chlorine, distilling to obtain 350g of crude product after the reaction is finished, carrying out GC analysis, wherein the content of the 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane is 88%, and rectifying to obtain the product with the purity of more than 99% for the next reaction.
(4) Fluorination reaction
50g of chromium-based composite catalyst is filled into a fixed bed reactor, the temperature is raised to 290-300 ℃, 1g/min of 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane and 0.7g/min of anhydrous hydrogen fluoride are filled into a mixing cavity and fully mixed, a buffer bottle, an alkali liquor bottle, a water washing bottle and a cooling receiving bottle are connected with the reactor, the receiving bottle collects about 510g of product after the experiment is finished, GC analysis is carried out, the content of methyl nonafluoroisobutyl ether is 92%, and the product with the purity of more than 99% is obtained through rectification.
Example 3
The embodiment relates to a method for synthesizing methyl nonafluoroisobutyl ether, which comprises the following steps:
(1) Addition reaction
10g of Fe powder, 30g of tributyl phosphate, 730g of dimethylformamide and 154g of carbon tetrachloride are added into a 2L hastelloy high-pressure valve, the temperature is raised to 80-90 ℃, and after magnetic stirring for 1h, 132g of 1, 3-pentafluoropropene is introduced. After 4 hours of reaction, organic matter 322g is obtained by distillation, the content of 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethyl propane is 90% by GC analysis, and 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethyl propane with the purity of more than 99% is obtained by rectification for the next reaction.
(2) Etherification reaction
40g of sodium hydroxide, 48g of absolute methanol, 285g of 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethyl propane and the like are added into a 1L four-port reaction bottle, the temperature is kept between 70 and 80 ℃, after magnetic stirring is carried out for 6 hours, 300g of crude product is obtained by distillation, the content of 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane is 90 percent by GC analysis, and the product with the purity of more than 99 percent is obtained by rectification and is used for the next reaction.
(3) Chlorination reaction
Adding 281g of 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane into a photocatalysis reactor, keeping the temperature at 30 ℃, continuously introducing 100g of chlorine, distilling to obtain 355g of crude product after the reaction is finished, analyzing by GC, wherein the content of 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane is 90%, and rectifying to obtain the product with the purity of more than 99% for the next reaction.
(4) Fluorination reaction
50g of chromium-based composite catalyst is filled into a fixed bed reactor, the temperature is raised to 260-270 ℃, 1g/min of 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane and 0.7g/min of anhydrous hydrogen fluoride are filled into a mixing cavity and fully mixed, a buffer bottle, an alkali liquor bottle, a water washing bottle and a cooling receiving bottle are connected with the reactor, the receiving bottle collects about 545 g of products after the experiment is finished, GC analysis is carried out, the content of methyl nonafluoroisobutyl ether is 92%, and the products with the purity of more than 99% are obtained through rectification.
Example 4
The embodiment relates to a method for synthesizing methyl nonafluoroisobutyl ether, which comprises the following steps:
(1) Addition reaction
10g of Fe powder, 30g of triethyl phosphate and 800g of carbon tetrachloride are added into a 2L hastelloy high-pressure valve, after the temperature is raised to 90-100 ℃ and magnetic stirring is carried out for 1h, 660g of pentafluoropropene is introduced, after 4h of reaction, 1460g of organic matters are obtained, the content of 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethylpropane is 96% by GC analysis, and 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethylpropane with the purity of more than 99% is obtained by rectification for the next reaction.
(2) Etherification reaction
110g of sodium carbonate and 285g of anhydrous methanol, namely 48g of 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethylpropane are added into a 1L four-port reaction bottle, the temperature is kept between 70 and 80 ℃, magnetic stirring is carried out for 6 hours, the crude product 300g is obtained by distillation, GC analysis is carried out, the content of 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane is 85%, and the product with the purity of more than 99% is obtained by rectification and is used for the next reaction.
(3) Chlorination reaction
Adding 281g of 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane into a photocatalysis reactor, keeping the temperature at 30 ℃, continuously introducing 75g of chlorine, distilling to obtain 355g of crude product after the reaction is finished, analyzing by GC, wherein the content of 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane is 90%, and rectifying to obtain the product with the purity of more than 99% for the next reaction.
(4) Fluorination reaction
50g of chromium-based composite catalyst is filled into a fixed bed reactor, the temperature is raised to 260-270 ℃, 1g/min of 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane and 0.7g/min of anhydrous hydrogen fluoride are filled into a mixing cavity and fully mixed, a buffer bottle, an alkali liquor bottle, a water washing bottle and a cooling receiving bottle are connected with the reactor, the receiving bottle is used for collecting about 530g of product after the experiment is finished, GC analysis is carried out, the content of methyl nonafluoroisobutyl ether is 93%, and the product with the purity of more than 99% is obtained through rectification.
Although the specific embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes and modifications without inventive labor may be made within the scope of the present invention without departing from the spirit of the present invention, which is within the scope of the present invention.
Claims (10)
1. A method for synthesizing methyl nonafluoroisobutyl ether, comprising the steps of:
(1) Addition reaction: carbon tetrachloride and 1, 3-pentafluoropropene are catalyzed in an aprotic solvent in an auxiliary manner through a catalyst and a cocatalyst to generate 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethylpropane;
(2) Etherification reaction: reacting 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethyl propane with methanol under the action of a catalyst to generate 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane;
(3) Chlorination reaction: 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane is subjected to photochlorination reaction to generate 1,2, 3-tetrachloro-3, 3-difluoro-1-methoxy-2- (trifluoromethyl) propane;
(4) Fluorination reaction: the 1,2, 3-tetrachloro-3, 3-difluoro-1-methoxy-2- (trifluoromethyl) propane and anhydrous hydrofluoric acid are subjected to gas phase catalysis to synthesize the methyl nonafluoro isobutyl ether under the action of a catalyst.
2. The method for synthesizing methyl nonafluoroisobutyl ether according to claim 1, characterized in that: in the step (1), the catalyst is a composite component catalyst of one or more of iron, copper, ferric chloride and cuprous chloride; the cocatalyst is one of alkyl phosphate, alkyl phosphite, ethanolamine, triethylamine, trimethylamine and tributylamine; the aprotic solvent is one of acetonitrile, sulfolane, dimethylformamide, dimethylacetamide, tetrahydrofuran and carbon tetrachloride; the reaction temperature is-30-150 ℃.
3. The method for synthesizing methyl nonafluoroisobutyl ether according to claim 2, characterized in that: the aprotic solvent is dimethylformamide or carbon tetrachloride; the reaction temperature is 80-140 ℃.
4. The method for synthesizing methyl nonafluoroisobutyl ether according to claim 1, characterized in that: in the step (2), the catalyst is one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium methoxide and potassium methoxide; the molar ratio of the 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethyl propane, the methanol and the catalyst is 1: 1-5:1-2, and the reaction temperature is 0-100 ℃.
5. The method for synthesizing methyl nonafluoroisobutyl ether according to claim 4, wherein: the molar ratio of the 1, 3-tetrachloro-3, 3-difluoro-2-trifluoromethyl propane, the methanol and the catalyst is 1:1-2:1-1.5; the reaction temperature is 50-100 ℃.
6. The method for synthesizing methyl nonafluoroisobutyl ether according to claim 1, characterized in that: in the step (3), the photocatalytic chlorination reagent is chlorine; the molar ratio of the 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane to the chlorine is 1:1-5, and the reaction temperature is-10-100 ℃.
7. The method for synthesizing methyl nonafluoroisobutyl ether according to claim 6, characterized in that: the molar ratio of the 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane to the chlorine is 1:1-2; the reaction temperature is 20-60 ℃.
8. The method for synthesizing methyl nonafluoroisobutyl ether according to claim 1, characterized in that: the catalyst in the step (4) is a composite component catalyst of one or more of Fe, cu, mn, cr, al, zn, ba and Ni; the molar ratio of the 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane to the anhydrous hydrofluoric acid is as follows: 1:4-20; the reaction temperature is 100-300 ℃.
9. The method for synthesizing methyl nonafluoroisobutyl ether according to claim 8, wherein: the molar ratio of the 1, 3-trichloro-3, 3-difluoro-1-methoxy- (2-trifluoromethyl) propane to the anhydrous hydrofluoric acid is as follows: 1:10.
10. The method for synthesizing methyl nonafluoroisobutyl ether according to claim 8, wherein: the reaction temperature is 260-280 ℃.
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