CN116162016A - Preparation method of high-purity pentafluoropentanol - Google Patents
Preparation method of high-purity pentafluoropentanol Download PDFInfo
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- CN116162016A CN116162016A CN202310027867.5A CN202310027867A CN116162016A CN 116162016 A CN116162016 A CN 116162016A CN 202310027867 A CN202310027867 A CN 202310027867A CN 116162016 A CN116162016 A CN 116162016A
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- pentafluoropentanol
- pentafluoropropanol
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- pentafluoropropane
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- QROUUECTKRZFHF-UHFFFAOYSA-N 4,4,5,5,5-pentafluoropentan-1-ol Chemical compound OCCCC(F)(F)C(F)(F)F QROUUECTKRZFHF-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- YLCLKCNTDGWDMD-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoyl fluoride Chemical compound FC(=O)C(F)(F)C(F)(F)F YLCLKCNTDGWDMD-UHFFFAOYSA-N 0.000 claims abstract description 25
- VLHYAWNCTMZTSC-UHFFFAOYSA-N 1,1,3,3,3-pentafluoropropan-1-ol Chemical compound OC(F)(F)CC(F)(F)F VLHYAWNCTMZTSC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012043 crude product Substances 0.000 claims abstract description 8
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006467 substitution reaction Methods 0.000 claims abstract description 5
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 4
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 3
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000010791 quenching Methods 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- COWKRCCNQSQUGJ-UHFFFAOYSA-N 1,1,2,2,3-pentafluoropropan-1-ol Chemical compound OC(F)(F)C(F)(F)CF COWKRCCNQSQUGJ-UHFFFAOYSA-N 0.000 claims description 10
- 230000000171 quenching effect Effects 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 7
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- WMFABESKCHGSRC-UHFFFAOYSA-N propanoyl fluoride Chemical compound CCC(F)=O WMFABESKCHGSRC-UHFFFAOYSA-N 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000001586 (Z)-pent-2-en-1-ol Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- KBOAVUSWPXRQBC-UHFFFAOYSA-N 1,1,1,2,2-pentafluoropentane Chemical compound CCCC(F)(F)C(F)(F)F KBOAVUSWPXRQBC-UHFFFAOYSA-N 0.000 description 1
- NNZZMYIWZFZLHU-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanol Chemical compound OC(F)(F)C(F)(F)F NNZZMYIWZFZLHU-UHFFFAOYSA-N 0.000 description 1
- JRHNUZCXXOTJCA-UHFFFAOYSA-N 1-fluoropropane Chemical compound CCCF JRHNUZCXXOTJCA-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- VWUXBMIQPBEWFH-WCCTWKNTSA-N Fulvestrant Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3[C@H](CCCCCCCCCS(=O)CCCC(F)(F)C(F)(F)F)CC2=C1 VWUXBMIQPBEWFH-WCCTWKNTSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229960002258 fulvestrant Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical compound CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/11—Halogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/27—Halogenation
- C25B3/28—Fluorination
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- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of synthesis of pentafluoropentanol, in particular to a preparation method of high-purity pentafluoropentanol, which comprises the following steps: (1) Electrolytic fluorination reaction is carried out by taking propionyl chloride as raw material to generate perfluoro propionyl fluoride; (2) The perfluoro propionyl fluoride reacts with sodium borohydride and methanol to generate 2, 3-pentafluoropropanol; (3) 2, 3-pentafluoropropanol and phosphorus tribromide undergo substitution reaction, to produce 1-bromo-2, 3-pentafluoropropane; (4) Reacting 1-bromo-2, 3-pentafluoropropane with magnesium powder to generate a Grignard reagent, generating a crude product of pentafluoropentanol with ethylene oxide, and rectifying to obtain high-purity pentafluoropentanol. Compared with the prior art, the method has the advantages of milder reaction, higher safety, reduction of waste, avoidance of heavy metal catalysts and contribution to industrial production. Meanwhile, the raw materials used in the invention are simple and easy to obtain, the raw materials are fully supplied in the raw material market, and compared with the existing process route, the price and cost advantages are obvious.
Description
Technical Field
The invention relates to the technical field of synthesis of pentafluoropentanol, in particular to a preparation method of high-purity pentafluoropentanol.
Background
Pentafluoropentanol, also known as 4, 5-pentafluoropentanol, is an important intermediate for the antitumor drug fulvestrant. The downstream products are intermediates for producing pentafluoroethanol, which has been applied to novel efficient drug synthesis and some drug preparation in recent years, and are also synthetic intermediates in the industries of surfactants, functional materials, inert liquids and dyes, and the application is quite wide.
There are three main processes reported in the literature for the preparation of pentafluoropentanol. The first process route is to take pentafluoroidine and propenol as raw materials, and sodium dithionite/sodium bicarbonate mixture as a free radical initiator to generate 4, 5-pentafluoro-2-iodo-2-penten-1-ol, and generate pentafluoropentanol after hydrogenation dehalogenation with hydrogen under the catalysis of platinum oxide. The disadvantage of this process route is the relatively large catalyst usage and the relatively expensive price. The third process route is to use 1, 2-pentafluoropentane 4, 5-pentafluoro-2-penten-1-ol is produced for the raw material, noble metal is used as a catalyst to generate the pentafluoropentanol through reduction reaction. The process route needs to use noble metals, and has high cost. The third process route uses pentafluoroethane and allyl acetate as raw materials and azodiisobutyronitrile as a catalyst to generate 5-acetoxyl-4-iodo-1, 2-pentafluoropentane; the dehalogenation reaction of 5-acetoxyl-4-iodine-1, 2-pentafluoropentane under the action of tributyl tin hydride, to produce 5-acetoxy-1, 2-pentafluoropentane; the 5-acetoxyl-1, 2-pentafluoropentane is hydrolyzed to generate the pentafluoropentane under the action of alkali, and the disadvantage of the process route is that the reaction process is not easy to control and is difficult to realize industrialization.
Disclosure of Invention
Aiming at the technical problems of high cost and difficult control of the reaction process in the existing preparation method of the pentafluoropentanol, the invention provides a preparation method of high-purity pentafluoropentanol, comprising the preparation of 2, 3-pentafluoropropanol preparation of 1-bromo-2, 3-pentafluoropropane 1-bromo-2, 3-penta preparation of fluoropropane. The preparation method avoids the dangerous reactions such as the application of noble metal catalysts, hydrogenation reaction and the like, has low cost, good safety and good product purity, and can realize industrial production.
The invention provides a preparation method of high-purity pentafluoropentanol, which comprises the following steps:
(1) Taking anhydrous hydrogen fluoride as a solvent and propionyl chloride or propionyl fluoride as an electrolyte to carry out electrolytic fluorination reaction to generate perfluoropropionyl fluoride; (2) The perfluoro propionyl fluoride reacts with sodium borohydride and methanol to generate 2, 3-pentafluoropropanol; (3) 2, 3-pentafluoropropanol and phosphorus tribromide undergo substitution reaction, to produce 1-bromo-2, 3-pentafluoropropane; (4) Reacting 1-bromo-2, 3-pentafluoropropane with magnesium powder to generate a Grignard reagent, generating a crude product of pentafluoropentanol with ethylene oxide, and rectifying to obtain high-purity pentafluoropentanol.
The reaction equation of the preparation method is as follows:
(1) electrolytic fluorination reaction: c (C) 3 H 5 OX+6HF→C 3 F 6 O↑+HX+5H 2 E, -; wherein X is Cl or F.
②C 3 F 6 O+NaBH 4 +2CH 3 OH→C 3 F 5 H 3 O+NaBHF(CH 3 O) 2 ；
③3C 3 F 5 H 3 O+PBr 3 →3C 3 F 5 H 2 Br+H 3 PO 3 ；
(4) Grignard reaction: c (C) 3 F 5 H 2 Br+Mg+C 2 H 4 O→C 5 F 5 H 6 OMgBr；
⑤C 5 F 5 H 6 OMgBr+H 2 O→C 5 F 5 H 6 OH。
Further, the method specifically comprises the following steps: (1) Adding anhydrous hydrogen fluoride and propionyl chloride or propionyl fluoride into a Simons electrolytic tank, generating perfluoropropionyl fluoride gas by electrolysis, freezing and collecting liquid perfluoropropionyl fluoride, introducing perfluoropropionyl fluoride into sodium borohydride suspension, the suspension solvent is a mixed solvent of tetrahydrofuran and methanol, heating and stirring to react to generate 2, 3-pentafluoropropanol, adding water for quenching, and rectifying to obtain 2, 3-pentafluoropropanol;
(2) Adding 2, 3-pentafluoropropanol into a reaction kettle, adding an organic solvent to prepare a pentafluoropropanol solution, then adding phosphorus tribromide, stirring for reaction, and distilling to obtain 1-bromo-2, 3-pentafluoropropane after the reaction is completed;
(3) Adding magnesium powder into anhydrous tetrahydrofuran, adding 1-bromo-2, 3-pentafluoropropane for reaction, cooling after the reaction is finished, introducing ethylene oxide for reaction, adding water for quenching reaction, distilling to obtain a crude product of pentafluoropentanol, and rectifying the crude product of pentafluoropentanol to obtain high-purity pentafluoropentanol.
Further, in the step (1), the anode plate of the Simons electrolytic tank is a nickel plate, the cathode plate is an iron plate, the electrolyte accounts for 3.5-8% of the mass of the solvent, and the current density is controlled to be 2-4A/dm 2 The voltage is controlled at 5-8V, the temperature in the electrolytic tank is maintained at 0-10 ℃, and the consumed anhydrous hydrogen fluoride is periodically replenished.
In the step (2), the mass ratio of the perfluoropropionyl fluoride to the sodium borohydride is 1:0.2-0.4, the mass ratio of the sodium borohydride to the mixed solvent is 1:3-8, the mass ratio of the methanol to the tetrahydrofuran in the mixed solvent is 1:20-30, and the mass of the added water during quenching is 0.1-0.2 times of that of the perfluoropropionyl fluoride.
In the step (2), the temperature of freezing and collecting liquid perfluoropropionyl fluoride is-60 to-80 ℃, the temperature of stirring reaction is controlled to be 50-60 ℃, and the fraction at 80 ℃ is collected during rectification to be pentafluoropropanol.
Further, in the step (3), the organic solvent is 1, 2-dichloroethane or dichloromethane.
Further, in the step (3), the mass concentration of the pentafluoropropanol solution is 10% -50%, the mass ratio of the phosphorus tribromide to the pentafluoropropanol is 0.6-0.8:1, the reaction is stirred for 1-2 hours, and the distillation temperature is 50-60 ℃.
Further, in the step (4), the mass ratio of the magnesium powder to the tetrahydrofuran is 0.1-0.15:1, the mass ratio of the tetrahydrofuran to the 1-bromo-2, 3-pentafluoropropane is 3-8:1, the mass ratio of the ethylene oxide to the tetrahydrofuran is 0.2-0.3:1, and the mass ratio of the water addition amount to the 1-bromo-2, 3-pentafluoropropane during quenching is 0.1-0.2:1.
Further, in the step (4), 1-bromo-2, 3-pentafluoropropane is slowly added at 40 ℃ to initiate reaction, stirring, refluxing and cooling are started, the reaction temperature is controlled to be 40-50 ℃, and 1-bromo-2, 3-pentafluoropropane is introduced.
Further, in the step (4), the temperature is reduced to 0 ℃, ethylene oxide is slowly introduced at the maintained temperature, the reaction is carried out for 1 hour at 20-30 ℃, and then water is added for quenching.
The invention has the beneficial effects that:
the preparation method of high-purity pentafluoropentanol provided by the invention can obtain the pentafluoropentanol with high yield and high purity, greatly reduces the reaction risk, reduces the generation of three wastes, avoids hydrogenation reaction and the use of heavy metal catalysts, and reduces the risk of heavy metal pollution for use in the downstream pharmaceutical field by replacing substrate raw materials. Compared with the prior art, the invention has the advantages of milder temperature and higher safety, and is more beneficial to industrial production. Meanwhile, the raw materials used in the invention are simple and easy to obtain, the raw materials are fully supplied in the raw material market, and compared with the existing process route, the price and cost advantages are obvious.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a gas chromatogram of perfluoropropionyl fluoride in example 1 of the present invention.
FIG. 2 is a gas chromatogram of perfluoropropionyl fluoride in example 2 of the present invention.
FIG. 3 is a gas chromatogram of pentafluoropentanol in example 1 of the present invention.
FIG. 4 is a nuclear magnetic resonance spectrum of pentafluoropentanol 1H-NMR in example 1 of the invention.
FIG. 5 is a nuclear magnetic resonance spectrum of pentafluoropentanol 19F-NMR in example 1 of the invention.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
The preparation method of the high-purity pentafluoropentanol comprises the following steps:
(1) 8kg of anhydrous hydrogen fluoride is added into a 10L Simons electrolytic tank (an anode plate is a nickel plate and a cathode plate is an iron plate), cooling reflux and jacket refrigeration are started above the electrolytic tank, a collecting tank is cooled to-60 ℃, and the temperature in the electrolytic tank is controlled to be 0-5 ℃. Opening a rectifier to supply direct current, stabilizing the voltage for 5.5V, dewatering for 1 hour, adding 290g of propionyl chloride, regulating the rectifier to be in a stabilized voltage mode, controlling the voltage to be 5.5V, electrolyzing for 24 hours at the current of 33-38A, opening a stabilized current mode until the voltage exceeds 8V, stopping electrolysis, and cooling in a collecting tank to obtain 280g of liquid perfluoropropionyl fluoride with the content of 86 percent and the yield of 53 percent;
(2) In a 5L high-pressure reaction kettle, 273g of sodium borohydride is added into 2000g of tetrahydrofuran and 100g of methanol, stirring is carried out uniformly, circulating water is started to control the temperature to 50-55 ℃, 1.2kg of perfluoropropionyl fluoride is slowly introduced while stirring, the reaction is continued for 3 hours, the temperature is reduced to room temperature, the pressure is removed, 120g of water quenching reaction is slowly added while stirring, the obtained solution is rectified in a rectifying tower with the height of 2m and filled with a theta ring of 3mm multiplied by 3mm, and fractions at 80 ℃ are collected and purified to obtain 720g of 2, 3-pentafluoropropanol, and the yield is 66%.
(3) 1000g of pentafluoropropanol is added into a 5L glass bottle, 5kg of 1, 2-dichloroethane is added as a solvent, 600g of phosphorus tribromide is slowly added dropwise at the temperature of 0-10 ℃, the mixture is stirred and reacts for 1 hour at room temperature, the temperature is raised to 50 ℃ and distilled to obtain 1280g of 1-bromo-2, 3-pentafluoropropane, and the yield is 90%;
(4) Adding a condenser and a dropping funnel into a 5L high-pressure reaction kettle, adding 130g of magnesium powder into 1000g of anhydrous tetrahydrofuran, slowly adding 1-bromo-2, 3-pentafluoropropane at 40 ℃ to initiate reaction, starting stirring, refluxing and cooling, the reaction temperature is controlled to be 40-50 ℃, 1-bromo-2, 3-pentafluoropropane is slowly added dropwise to total 1000g, the reaction is continued for 1 hour, the temperature is reduced to 0 ℃, 250g of ethylene oxide is slowly introduced at the maintained temperature, and then the reaction is carried out for 1 hour at 20-30 ℃. Decompressing, adding 100g of water to quench and react, and distilling at 60-70 ℃ to obtain a crude product of the pentafluoropentanol; and (3) rectifying the crude pentafluoropentanol product in a 2m high rectifying tower filled with a theta ring of 3mm multiplied by 3mm, and collecting fractions at 62-64 ℃ to obtain 620g of high-purity pentafluoropentanol with the content of 99% and the yield of 74%.
Example 2
(1) 8kg of anhydrous hydrogen fluoride is added into a 10L Simons electrolytic tank (an anode plate is a nickel plate and a cathode plate is an iron plate), cooling reflux and jacket refrigeration are started above the electrolytic tank, a collecting tank is cooled to-80 ℃, and the temperature in the electrolytic tank is controlled to be 0-5 ℃. Opening a rectifier to supply direct current, stabilizing the voltage for 5.5V, dewatering for 1 hour, adding 390g of propionyl fluoride, regulating the rectifier to be in a stabilized voltage mode, controlling the voltage to be 5.5V, electrolyzing for 24 hours at the current of 33-38A, opening a stabilized current mode until the voltage exceeds 8V, stopping electrolysis, and cooling in a collecting tank to obtain 480g of liquid perfluoropropionyl fluoride with the content of 80 percent and the yield of 56 percent;
(2) In a 5L high-pressure reaction kettle, adding 323g sodium borohydride into 3000g tetrahydrofuran and 150g methanol, stirring uniformly, starting circulating water to control the temperature to 55-60 ℃, slowly introducing 1.2kg of perfluoropropionyl fluoride while stirring, continuing to react for 3 hours, cooling to room temperature, removing pressure, slowly adding 180g of water while stirring to quench reaction, rectifying the obtained solution in a rectifying tower with the height of 2m and filled with a theta ring of 3mm multiplied by 3mm, collecting fraction at 80 ℃, and purifying to obtain 750g of 2, 3-pentafluoropropanol with the yield of 69%.
(3) 1000g of pentafluoropropanol is added into a 5L glass bottle, 5kg of dichloromethane is added as a solvent, 600g of phosphorus tribromide is slowly added dropwise at the temperature of 0-10 ℃, the temperature is raised to room temperature, stirring reaction is carried out for 2 hours, the obtained mother liquor is rectified in a rectifying tower with the height of 2m and filled with a theta ring of 3mm multiplied by 3mm, after dichloromethane is separated out, the temperature is continuously raised to 55 ℃ to distill 780g of 1-bromo-2, 3-pentafluoropropane, and the yield is 55%;
(4) Adding a condenser and a dropping funnel into a 5L high-pressure reaction kettle, adding 150g of magnesium powder into 1200g of anhydrous tetrahydrofuran, slowly adding 1-bromo-2, 3-pentafluoropropane at 40 ℃ to initiate reaction, starting stirring, refluxing and cooling, the reaction temperature is controlled to be 40-50 ℃, 1-bromo-2, 3-pentafluoropropane is slowly added dropwise to total 1000g, the reaction is continued for 1 hour, the temperature is reduced to 0 ℃, 280g ethylene oxide is slowly introduced at the maintained temperature, and then the reaction is carried out for 1 hour at 20-30 ℃. Decompression, adding 150g of water to quench reaction, and distilling at 60-70 ℃ to obtain crude pentafluoropentanol; and (3) rectifying the crude pentafluoropentanol product in a 2m high rectifying tower filled with a theta ring of 3mm multiplied by 3mm, and collecting fractions at 62-64 ℃ to obtain 645g of high-purity pentafluoropentanol with a yield of 77%.
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims.
Claims (9)
1. The preparation method of the high-purity pentafluoropentanol is characterized by comprising the following steps of:
(1) Electrolytic fluorination reaction is carried out by taking propionyl chloride or propionyl fluoride as raw materials to generate perfluoro propionyl fluoride; (2) The perfluoro propionyl fluoride reacts with sodium borohydride and methanol to generate 2, 3-pentafluoropropanol; (3) 2, 3-pentafluoropropanol and phosphorus tribromide undergo substitution reaction, to produce 1-bromo-2, 3-pentafluoropropane; (4) Reacting 1-bromo-2, 3-pentafluoropropane with magnesium powder to generate a Grignard reagent, generating a crude product of pentafluoropentanol with ethylene oxide, and rectifying to obtain high-purity pentafluoropentanol.
2. The preparation method according to claim 1, characterized by comprising the following steps:
(1) Adding anhydrous hydrogen fluoride and propionyl chloride or propionyl fluoride into a Simons electrolytic tank, electrolyzing to generate perfluoropropionyl fluoride gas, and freezing to collect liquid perfluoropropionyl fluoride;
(2) Introducing perfluoro propionyl fluoride into sodium borohydride suspension, wherein the suspension solvent is a mixed solvent of tetrahydrofuran and methanol, heating and stirring to react to generate 2, 3-pentafluoropropanol, adding water for quenching, and rectifying to obtain 2, 3-pentafluoropropanol;
(3) Adding 2, 3-pentafluoropropanol into a reaction kettle, adding an organic solvent to prepare a pentafluoropropanol solution, then adding phosphorus tribromide, stirring for reaction, and distilling to obtain 1-bromo-2, 3-pentafluoropropane after the reaction is completed;
(4) Adding magnesium powder into anhydrous tetrahydrofuran, adding 1-bromo-2, 3-pentafluoropropane for reaction, cooling after the reaction is finished, introducing ethylene oxide for reaction, adding water for quenching reaction, then distilling to obtain a crude product of pentafluoropentanol, and rectifying the crude product of pentafluoropentanol to obtain high-purity pentafluoropentanol.
3. The preparation method as claimed in claim 2, wherein in the step (1), the anode plate of the electrolytic bath is nickel plate, the cathode plate is iron plate, the concentration of the electrolyte is controlled to be 3.5-8% by mass, and the current density is controlled to be 2-4A/dm 2 The voltage is controlled at 5-8V, the temperature in the electrolytic tank is maintained at 0-10 ℃, the consumed anhydrous hydrogen fluoride is periodically replenished, and the temperature of the liquid perfluoropropionyl fluoride collected by freezing is minus 60-minus 80 ℃.
4. The preparation method according to claim 2, wherein in the step (2), the mass ratio of the perfluoropropionyl fluoride to the sodium borohydride is 1:0.2-0.4, the mass ratio of the sodium borohydride to the mixed solvent is 1:3-8, the mass ratio of the methanol to the tetrahydrofuran in the mixed solvent is 1:20-30, and the mass of the added water during quenching is 0.1-0.2 times that of the perfluoropropionyl fluoride.
5. The process according to claim 2, wherein in the step (2), the temperature of the stirring reaction is controlled to be 50 to 60 ℃, and the fraction at 80 ℃ is collected during the rectification to be pentafluoropropanol.
6. The process according to claim 2, wherein in step (3), the organic solvent is 1, 2-dichloroethane or dichloromethane.
7. The preparation method according to claim 2, wherein in the step (3), the mass concentration of the pentafluoropropanol solution is 10% -50%, the mass ratio of the phosphorus tribromide to the pentafluoropropanol is 0.6-0.8:1, the reaction is stirred for 1-2 hours, and the distillation temperature is 50-60 ℃.
8. The process according to claim 2, wherein in the step (4), the mass ratio of the magnesium powder to the tetrahydrofuran is 0.1 to 0.15:1, the mass ratio of the tetrahydrofuran to the 1-bromo-2, 3-pentafluoropropane is 3 to 8:1, the mass ratio of the ethylene oxide to the tetrahydrofuran is 0.2-0.3:1, and the mass ratio of the water addition amount to the 1-bromo-2, 3-pentafluoropropane during quenching is 0.1-0.2:1.
9. The process according to claim 8, wherein in step (4), 1-bromo-2, 3-pentafluoropropane is slowly added at 40℃to initiate the reaction, stirring, refluxing and cooling are started, the reaction temperature is controlled to be 40-50 ℃, and 1-bromo-2, 3-pentafluoropropane is introduced.
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