CN117986294A - Preparation method and application of fluorooxyphosphorus compound - Google Patents
Preparation method and application of fluorooxyphosphorus compound Download PDFInfo
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- CN117986294A CN117986294A CN202211386800.2A CN202211386800A CN117986294A CN 117986294 A CN117986294 A CN 117986294A CN 202211386800 A CN202211386800 A CN 202211386800A CN 117986294 A CN117986294 A CN 117986294A
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- -1 fluorooxyphosphorus compound Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 37
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 19
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 44
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 40
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 claims description 35
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 23
- 235000003270 potassium fluoride Nutrition 0.000 claims description 20
- 239000011698 potassium fluoride Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 10
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- AENDXYYGTYFGOX-UHFFFAOYSA-N chloro(difluoro)phosphane Chemical compound FP(F)Cl AENDXYYGTYFGOX-UHFFFAOYSA-N 0.000 claims description 6
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000012467 final product Substances 0.000 description 11
- 239000012535 impurity Substances 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical class [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method and application of a fluorooxyphosphorus compound, wherein the preparation method comprises the following steps: (1) Reacting fluoride with phosphorus trichloride to obtain intermediate gas phosphorus oxychloride; (2) Reacting phosphorus oxychloride obtained in the step (1) with an alcohol compound ROH to obtain the fluorooxyphosphorus compound. The preparation method provided by the invention can be used for efficiently and rapidly preparing the fluoroxyphosphate compound, and has the advantage of high yield.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method and application of a fluoroxyphosphorus compound, in particular to a preparation method and application of a fluoroxyphosphorus compound with high yield.
Background
Fluorine-containing species, such as fluorinated organic molecules, fluorolithium salts, are often used as electrolyte additives due to the electronegativity, strong charge delocalization and ionic dissociation of fluorine. The lithium fluoride salt dissolves in a dipolar aprotic solvent and dissociates in a large amount in a high dielectric constant solvent, thus exhibiting high conductivity in solution. Researches show that the difluoro lithium dioxalate phosphate can improve the low-temperature performance of the lithium ion battery; liDFBOP can not only effectively inhibit the decomposition of electrolyte on the surface of the anode at low temperature, but also reduce the impedance of the SEI film. In addition, the electrolyte with the organic compound containing the epoxy functional group as the additive is used in the field of electrochemical energy storage, and can reduce the battery resistance, prolong the cycle life and improve the high-temperature performance.
WO2022046174A1 discloses a lithium ion battery modification additive comprising a series of fluoroxyphosphorus compounds and a preparation method thereof, wherein the total yield is only 44%, however, chlorine atoms on phosphorus as an intermediate product react with glycidol one by one in the reaction process, resulting in the formation of a large amount of byproducts; in addition, ethylene oxide in glycidol can be phosphorylated by trichloride to form five-membered rings at room temperature, so that reaction intermediate products are destroyed, a large amount of raw materials are lost, the cost is increased, and the method is not suitable for large-scale production.
Therefore, how to provide a preparation method of fluorooxyphosphorus compounds with high yield is a problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method and application of a fluoroxyphosphorus compound, in particular to a preparation method and application of a fluoroxyphosphorus compound with high yield. The preparation method provided by the invention can be used for efficiently and rapidly preparing the fluoroxyphosphate compound, and has the advantage of high yield.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
In one aspect, the invention provides a method for preparing a fluoroxyphosphorus compound, which comprises the following steps:
(1) Reacting fluoride with phosphorus trichloride to obtain intermediate gas phosphorus oxychloride;
(2) Reacting phosphorus oxychloride obtained in the step (1) with an alcohol compound ROH to obtain the fluorooxyphosphorus compound.
The structure of the fluorooxyphosphorus compound is shown as follows:
wherein R is selected from any one of C1-C6 alkyl, C1-C6 alkoxy and C6-C12 aryl.
Compared with the prior art that the alcohol compound reacts with the phosphorus trichloride and then reacts with the antimony trifluoride, the method can effectively avoid the problem that chlorine atoms on intermediate product phosphorus are replaced in the prior art, and meanwhile, the phosphorus trichloride cannot be contacted with the alcohol compound due to separation of a reaction system, so that the reaction process is not influenced, and the yield is remarkably improved.
Wherein C1-C6 respectively means that the structure contains one carbon atom, two carbon atoms, three carbon atoms, four carbon atoms, five carbon atoms or six carbon atoms, C6-C12 respectively means that the structure contains six carbon atoms, seven carbon atoms, eight carbon atoms, nine carbon atoms, ten carbon atoms, eleven carbon atoms or twelve carbon atoms, C1-C6 alkyl can be methyl, ethyl, propyl, n-butyl, tert-butyl and the like, C1-C6 alkoxy can be methoxy, ethoxy, propoxy, 2, 3-epoxypropyl and the like, and C6-C12 aryl can be benzene, biphenyl, naphthalene and the like.
Preferably, the fluoride is batchwise mixed with phosphorus oxychloride prior to reacting with the phosphorus trichloride.
The specific mixing mode can avoid local over fluorination and improve the yield.
Preferably, the molar ratio of fluorine atoms of the fluoride to phosphorus trichloride in step (1) is (3-17): 1, for example, 3:1, 5:1, 7:1, 9:1, 11:1, 13:1, 15:1 or 17:1, etc., but not limited to the values recited above, other non-recited values within the above ranges are equally applicable.
Preferably, the molar ratio of fluorine atoms of the fluoride to phosphorus trichloride in the step (1) is (7-10): 1.
Preferably, the molar ratio of fluorine atoms of the fluoride in the step (1) to phosphorus trichloride is 9:1.
Preferably, the fluoride comprises antimony trifluoride.
Preferably, the fluoride is a combination of potassium fluoride and antimony trifluoride.
The specific fluoride can effectively control the fluorination degree and improve the yield through the combination of potassium fluoride and antimony trifluoride.
Preferably, the molar ratio of potassium fluoride to antimony trifluoride is (0-4.5): 1, e.g., 0:1, 1:1, 2:1, 3:1, 4:1, or 4.5:1, etc., but is not limited to the values recited above, other non-recited values within the above ranges are equally applicable, preferably 2:1; when the fraction of potassium fluoride is 0, it means that the fluoride does not contain potassium fluoride.
Preferably, the temperature of the reaction in step (1) is-10 to 10 ℃, for example, -10 ℃, -8 ℃, -6 ℃, -4 ℃, -2 ℃,0 ℃,2 ℃,4 ℃,6 ℃,8 ℃ or 10 ℃, etc., but is not limited to the values listed above, and other values not listed in the above-mentioned value ranges are equally applicable.
Preferably, the reaction of step (1) is carried out in a solvent including any one or a combination of at least two of dichloromethane, chloroform, dichloroethane, carbon tetrachloride, methyl formate, ethyl formate, methyl acetate, ethyl acetate, diethyl ether, tetrahydrofuran or methyl tert-butyl ether, for example, a combination of dichloromethane and chloroform, a combination of dichloromethane and carbon tetrachloride or a combination of methyl formate and ethyl formate, etc., but not limited to the above-listed combinations, and other non-listed combinations within the above-listed ranges are equally applicable.
Preferably, the step (1) further comprises cooling the intermediate gas phosphorus monochloride difluoride after the intermediate gas phosphorus monochloride difluoride is obtained.
The cooling step can effectively remove impurity gas generated by the reaction of antimony trifluoride and phosphorus trichloride, reduce the interference on subsequent reactions and improve the yield.
Preferably, the cooling is performed by a cooling device, and the set temperature of the cooling device is-30-0 ℃.
Preferably, the molar ratio of the phosphorus trichloride to the alcohol compound ROH is (1-2): 1.
Preferably, the temperature of the reaction in step (2) is from 0 to 20 ℃.
Preferably, the reaction time of step (2) is 1-10 hours.
Wherein the set temperature of the cooling device may be-30 ℃, -25 ℃, -20 ℃, -15 ℃, -10 ℃, -5 ℃ or 0 ℃ and the like, the molar ratio of phosphorus trichloride to the alcohol compound ROH may be 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 or 2:1 and the like, the temperature of the reaction in the step (2) may be 0 ℃,2 ℃,4 ℃,6 ℃,8 ℃,10 ℃,12 ℃, 14 ℃,16 ℃, 18 ℃ or 20 ℃ and the like, and the time of the reaction in the step (2) may be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h and the like, but is not limited to the values listed above, and other non-listed values within the above numerical ranges are equally applicable.
Preferably, the reaction of step (2) is carried out in a solvent comprising any one or a combination of at least two of dichloromethane, chloroform, dichloroethane, carbon tetrachloride, methyl formate, ethyl formate, methyl acetate, ethyl acetate, diethyl ether, tetrahydrofuran or methyl tert-butyl ether, such as a combination of dichloromethane and chloroform, a combination of dichloromethane and carbon tetrachloride or a combination of methyl formate and ethyl formate, etc., but not limited to the combinations listed above, other non-listed combinations within the above ranges are equally applicable, preferably dichloromethane and/or acetonitrile.
In another aspect, the invention also provides the use of the preparation method as described above in the preparation of a battery additive.
Compared with the prior art, the invention has the following beneficial effects:
Compared with the prior art that the alcohol compound reacts with the phosphorus trichloride and then reacts with the antimony trifluoride, the preparation method of the fluorooxyphosphorus compound can effectively avoid the problem that chlorine atoms on intermediate product phosphorus are replaced in the prior art, and meanwhile, the phosphorus trichloride cannot be contacted with the alcohol compound due to the separation of a reaction system, so that the reaction process is not influenced, and the yield is remarkably improved; meanwhile, by utilizing a specific cooling step, impurity gas generated by the reaction of fluoride and phosphorus trichloride can be effectively removed, the interference on subsequent reactions is reduced, and the yield is improved.
Detailed Description
In order to further describe the technical means adopted by the present invention and the effects thereof, the following describes the technical scheme of the present invention in combination with the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
In the following examples, the total yield calculation method was actual yield/theoretical maximum yield (in terms of alcohol compound) ×100%.
Example 1
The embodiment provides a preparation method of a fluorooxyphosphorus compound, which has the following structure:
The method comprises the following specific steps:
(1) Preparing 37g (0.5 mol) of glycidol in 370g of dichloromethane, and uniformly stirring for later use;
(2) 116g (2 mol) of potassium fluoride and 89g (0.5 mol) of antimony trifluoride are added into 1000g of methylene dichloride at the temperature of 0 ℃, then 75.5g (0.55 mol) of phosphorus trichloride is added dropwise, gas is generated, the gas passes through a serpentine cooling tower with the temperature set between-30 ℃ and 0 ℃, the liquid flows back to a reaction container, and the gas is introduced into the reaction liquid prepared in the step (1). After the phosphorus trichloride is added dropwise, 89g (0.5 mol) of antimony trifluoride is added for continuous reaction for 5 hours, and the temperature is raised to 5 ℃ for continuous reaction for 5 hours. The reaction was stopped. Filtering to obtain filtrate, distilling under reduced pressure, heating from 30deg.C, collecting 30-40deg.C distillate as front fraction, 40-60deg.C target product, and 60-125deg.C distillate as rear fraction. Mixing the front fraction and the rear fraction, purifying by secondary distillation, and combining to obtain colorless oily clear liquid, namely 57.1g of product is obtained, and the total yield is 80%. Characterization data are as follows ：1H-NMR(DMSO)δ(ppm);2.54(m,1H),2.35-2.60(m,2H),3.52-3.77(m,2H);13C-NMR(DMSO)δ(ppm);44.2,53.1,65.6.
Example 2
The embodiment provides a preparation method of a fluorooxyphosphorus compound, which comprises the steps of firstly adding 92.8g (1.6 mol) of potassium fluoride and 71.2g (0.4 mol) of antimony trifluoride in the step (2); after the phosphorus trichloride was added dropwise, 71.2g (0.4 mol) of antimony trifluoride was then added thereto for further reaction for 5 hours, and the remainder was the same as in example 1.
54.6G of clear colorless oily liquid are obtained, with a total yield of 77% of the final product.
Example 3
The embodiment provides a preparation method of a fluorooxyphosphorus compound, which comprises the steps of adding 185.6g (6.2 mol) of potassium fluoride and 142.4g (0.8 mol) of antimony trifluoride in the step (2); after the phosphorus trichloride was added dropwise, 142.4g (0.8 mol) of antimony trifluoride was then added and the reaction was continued for 5 hours, the remainder being identical to example 1.
56.1G of clear colorless oily liquid are obtained, with a total yield of 79% of the final product.
Example 4
The embodiment provides a preparation method of a fluorooxyphosphorus compound, which comprises the steps of firstly adding 58.1g (1 mol) of potassium fluoride and 119.3g (0.67 mol) of antimony trifluoride in the step (2); after the phosphorus trichloride was added dropwise, 119.3g (0.67 mol) of antimony trifluoride was then added thereto for further reaction for 5 hours, and the remainder was the same as in example 1.
53.5G of clear colorless oily liquid are obtained, with a total yield of 75% of the final product.
Example 5
The embodiment provides a preparation method of a fluorooxyphosphorus compound, which comprises the steps of firstly adding 174.3g (3 mol) of potassium fluoride and 58.7g (0.33 mol) of antimony trifluoride in the step (2); after the phosphorus trichloride was added dropwise, 58.7g (0.33 mol) of antimony trifluoride was then added thereto for further reaction for 5 hours, and the remainder was the same as in example 1.
53.8G of clear colorless oily liquid are obtained, with a total yield of 76% of the final product.
Example 6
The embodiment provides a preparation method of a fluorooxyphosphorus compound, which comprises the steps of adding 147.7g (0.83 mol) of antimony trifluoride without adding potassium fluoride in the step (2); after the phosphorus trichloride was added dropwise, 147.7g (0.83 mol) of antimony trifluoride was then added and the reaction was continued for 5 hours, the remainder being identical to example 1.
50.9G of clear colorless oily liquid was obtained, the total yield of the final product being 72%.
Example 7
This example provides a process for the preparation of fluorooxyphosphors, which is identical to example 1 except that in step (2), only 290.5g (5 mol) of potassium fluoride is first added, and no antimony trifluoride is added.
The potassium fluoride alone is too low in activity to obtain a product.
Example 8
This example provides a method for preparing a fluorooxyphosphorus compound having the same structure as in example 1, and the experimental procedure was substantially the same as in example 1, except that after 116.2g (2 mol) of potassium fluoride was added, 178.8g (1 mol) of antimony trifluoride was added at a time, and then no antimony trichloride was added, and a gas was generated.
53.8G of clear colorless oily liquid are obtained, with a total yield of 76% of the final product.
Example 9
This example provides a method for preparing a fluorooxyphosphorus compound, which is the same as example 1 except that in step (2), 116.2g (2 mol) of potassium fluoride and 133.5g (0.75 mol) of antimony trifluoride are added first, after the dropwise addition of phosphorus trichloride is completed, 44.5g (0.25 mol) of antimony trifluoride is then added and the reaction is continued for 5 hours.
53.2G of clear colorless oil are obtained in a final product yield of 75%.
Example 10
The present example provides a process for the preparation of fluorooxyphosphorus compounds, in which the procedure is as in example 1 except that in step (1) dichloromethane is replaced with an equal volume of ethyl acetate.
52.5G of clear colorless oil are obtained in a final yield of 74%.
Example 11
The present example provides a process for the preparation of fluorooxyphosphorus compounds, in which the procedure is as in example 1 except that in step (1) dichloromethane is replaced with an equal volume of acetonitrile.
54.6G of clear colorless oily liquid are obtained, with a total yield of 77% of the final product.
Example 12
This example provides a process for the preparation of fluorooxyphosphorus compounds, which is identical to example 1 except that in step (1) a solution of 20.35g (0.275 mol) glycidol in 204g of dichloromethane is prepared.
30.1G of clear colorless oily liquid was obtained, the final yield of the product was 77%.
Example 13
The embodiment provides a preparation method of a fluorooxyphosphorus compound, which has the following structure:
The method comprises the following specific steps:
(1) Preparing 37g of tertiary butanol in 370g of dichloromethane, and uniformly stirring for later use;
(2) 116g (2 mol) of potassium fluoride and 89g (0.5 mol) of antimony trifluoride are added into 1000g of methylene dichloride at the temperature of-10-0 ℃, then 75.5g (0.55 mol) of phosphorus trichloride is added dropwise, gas is generated, the gas passes through a serpentine cooling tower with the temperature set between-30 and 0 ℃, the liquid flows back to a reaction container, and the gas is introduced into the reaction liquid prepared in the step (1). After the phosphorus trichloride was added dropwise, the temperature was raised to 5℃and 89g (0.5 mol) of antimony trifluoride was then added thereto for further reaction for 5 hours. The reaction was stopped. Filtering to obtain filtrate, distilling under reduced pressure, heating from 30deg.C, collecting 10-25deg.C distillate as front fraction, 25-35deg.C target product, and 35-55deg.C distillate as rear fraction. Mixing the front fraction and the rear fraction, purifying by secondary distillation, and combining to obtain colorless oily clear liquid, namely 51.8g of the product, wherein the total yield is 73%. Characterization data are as follows: 1H-NMR(DMSO)δ(ppm);1.2(s,9H).13 C-NMR (DMSO) delta (ppm); 30.6,30.7,30.6, 63.9.
Example 14
The embodiment provides a preparation method of a fluorooxyphosphorus compound, which has the following structure:
The method comprises the following specific steps:
(1) Preparing a 470g dichloromethane solution of 47g phenol, and uniformly stirring for later use;
(2) 116g (2 mol) of potassium fluoride and 89g (0.5 mol) of antimony trifluoride are added into 1000g of methylene dichloride at the temperature of-10-0 ℃, then 75.5g (0.55 mol) of phosphorus trichloride is added dropwise, gas is generated, the gas passes through a serpentine cooling tower with the temperature set between-30 and 0 ℃, the liquid flows back to a reaction container, and the gas is introduced into the reaction liquid prepared in the step (1). After the phosphorus trichloride was added dropwise, the temperature was raised to 5℃and 89g (0.5 mol) of antimony trifluoride was then added thereto for further reaction for 5 hours. The reaction was stopped. Filtering to obtain filtrate, distilling under reduced pressure, heating from 30deg.C, collecting 50-55deg.C distillate as front fraction, 55-62deg.C target product, and 62-70deg.C distillate as rear fraction. The front fraction and the rear fraction are mixed and purified by secondary distillation, and colorless oily clear liquid is obtained by combination, thus 61.5g of product is obtained, and the total yield is 76%. Characterization data are as follows ：1H-NMR(DMSO)δ(ppm);6.81(m,2H),6.9(m,1H),7.22(m,2H).13C-NMR(DMSO)δ(ppm);121,121,124,124,152.
Comparative example 1
The comparative example provides a method for preparing a fluorooxyphosphorus compound, the structure of which is the same as that of example 1, and the specific steps are the same as example 1 except that the gas generated in step (2) is not cooled by a serpentine cooling tower.
22.4G of clear colorless oily liquid was obtained, the total yield of the final product being 32%.
Comparative example 2
This comparative example provides a method for preparing a fluorooxyphosphorus compound, the structure of which is the same as that of example 1, wherein 23.2g (0.4 mol) of potassium fluoride and 17.8g (0.1 mol) of antimony trifluoride are added first, after the dropwise addition of phosphorus trichloride is completed, 17.8g (0.1 mol) of antimony trifluoride is then added for continuous reaction for 5 hours, and the rest is the same as that of example 1.
17.5G of clear colorless oily liquid was obtained, with a total yield of 25% of the final product.
Comparative example 3
The comparative example provides a preparation method of a fluorooxyphosphorus compound, the structure of the compound is consistent with that of the example 1, and the specific steps are as follows:
9.7g of phosphorus trichloride and 29.5g of methylene chloride were added to the reaction flask, and 5.0g of glycidol was slowly added dropwise at 5 ℃. After about 4 hours, stirring was resumed at 20deg.C for 1 hour. Stopping the reaction, and distilling off 12.2g of crude product by rotary distillation at 75 ℃ with 1mmHg to obtain a colorless oily product a,6.8g (55%);
Into another reaction flask, 4.7g of antimony fluoride and 19.1g of hexane were charged, 6.8g of the above colorless oily product a was added dropwise at 5℃and stirring was continued for 2 hours at 20℃to stop the reaction. After spin-drying 4.4g (80%) of the product are obtained as a colourless oil; the overall yield of the final product was 42%.
After the distillation in comparative example 3 is finished, a small amount of liquid remains at the bottom of the kettle, and according to the mass spectrum characterization, the small amount of liquid can be found to be a by-product of grafting a plurality of glycidols on phosphorus; and the corrosion phenomenon occurs in the oil pump because the phosphorus trichloride is dissolved in water and generates hydrochloric acid.
According to the data, the preparation method of the fluoroxyphosphorus compound can be used for effectively synthesizing the fluoroxyphosphorus compound;
As can be seen from comparative examples 1-3 and comparative example 2, the invention can effectively control the generation of intermediate gas phosphorus monochlorodifluoride by controlling the molar ratio of fluorine atoms and phosphorus trichloride in fluoride, reduce the generation of impurity gas and subsequent reaction impurities, and improve the yield;
Comparing example 1 with examples 4-7, the invention can effectively control the generation of intermediate gas phosphorus oxychloride by controlling the mole ratio of potassium fluoride to antimony trifluoride and adopting the combination of the two, thereby reducing the generation of impurity gas and subsequent reaction impurities and improving the yield compared with other mole ratios and fluoride selection;
Comparing example 1 with examples 8-9, it can be found that the invention can effectively control the generation of intermediate gas phosphorus monochloro difluoride by controlling the addition of antimony fluoride in batches twice, thereby improving the yield;
As can be seen from a comparison of examples 1 and examples 10 to 11, the present invention uses methylene chloride to provide the best results, and then acetonitrile, esters, etc., all react but the yield is reduced, and the examples are not exhaustive.
As can be seen from comparative example 1 and comparative example 1, the present invention can effectively remove impurity gas generated by the reaction of antimony fluoride and phosphorus trichloride by cooling the intermediate gas, reduce the interference to subsequent reaction, and improve the yield;
As can be seen from comparative example 1 and comparative example 3, according to the invention, the problem that chlorine atoms on intermediate product phosphorus are replaced in the prior art can be effectively avoided, and meanwhile, the problem of five-membered cyclization caused by contact of phosphorus trichloride and alcohol compounds is avoided, so that the yield is remarkably improved.
The applicant states that the present invention describes the preparation method and application of the fluorooxyphosphorus compound of the present invention by the above examples, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be practiced by the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Claims (10)
1. The preparation method of the fluoroxyphosphorus compound is characterized by comprising the following steps of:
(1) Reacting fluoride with phosphorus trichloride to obtain intermediate gas phosphorus oxychloride;
(2) Reacting phosphorus oxychloride obtained in the step (1) with an alcohol compound ROH to obtain the fluorooxyphosphorus compound;
the structure of the fluorooxyphosphorus compound is shown as follows:
wherein R is selected from any one of C1-C6 alkyl, C1-C6 alkoxy and C6-C12 aryl.
2. The method according to claim 1, wherein the molar ratio of fluorine atoms of the fluoride to phosphorus trichloride in the step (1) is (3-17): 1;
Preferably, the molar ratio of fluorine atoms of the fluoride to phosphorus trichloride in the step (1) is (7-10): 1;
preferably, the molar ratio of fluorine atoms of the fluoride in the step (1) to phosphorus trichloride is 9:1.
3. The production method according to claim 1 or 2, wherein the fluoride comprises antimony trifluoride;
Preferably, the fluoride is a combination of potassium fluoride and antimony trifluoride.
4. A process according to any one of claims 1 to 3, wherein the temperature of the reaction in step (1) is from-10 to 10 ℃.
5. The process of any one of claims 1-4, wherein the reaction of step (1) is carried out in a solvent comprising any one or a combination of at least two of dichloromethane, chloroform, dichloroethane, carbon tetrachloride, acetonitrile, methyl formate, ethyl formate, methyl acetate, ethyl acetate, diethyl ether, tetrahydrofuran, or methyl tert-butyl ether.
6. The method according to any one of claims 1 to 5, wherein the step (1) of obtaining the intermediate gas phosphorus monochlorodifluoride further comprises cooling the intermediate gas phosphorus monochlorodifluoride;
preferably, the cooling is performed by a cooling device, and the set temperature of the cooling device is-30-0 ℃.
7. The process according to any one of claims 1 to 6, wherein the molar ratio of phosphorus trichloride to the alcohol compound ROH is (1-2): 1.
8. The process according to any one of claims 1 to 7, wherein the temperature of the reaction of step (2) is 0 to 20 ℃;
preferably, the reaction time of step (2) is 1-10 hours.
9. The process according to any one of claims 1 to 8, wherein the reaction of step (2) is carried out in a solvent comprising any one or a combination of at least two of dichloromethane, chloroform, dichloroethane, carbon tetrachloride, methyl formate, ethyl formate, methyl acetate, ethyl acetate, diethyl ether, tetrahydrofuran or methyl tert-butyl ether, preferably dichloromethane and/or acetonitrile.
10. Use of a preparation method according to any one of claims 1-9 for the preparation of a battery additive.
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