CN117247368B - Zxfoom zxfoom zxfoom fluorine (F) ester compound is prepared by the preparation method of (2) - Google Patents
Zxfoom zxfoom zxfoom fluorine (F) ester compound is prepared by the preparation method of (2) Download PDFInfo
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- CN117247368B CN117247368B CN202311542067.3A CN202311542067A CN117247368B CN 117247368 B CN117247368 B CN 117247368B CN 202311542067 A CN202311542067 A CN 202311542067A CN 117247368 B CN117247368 B CN 117247368B
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- -1 ester compound Chemical class 0.000 title claims abstract description 54
- 229910052731 fluorine Inorganic materials 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title abstract description 38
- 239000011737 fluorine Substances 0.000 title description 11
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 31
- 239000012025 fluorinating agent Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- PMGNOQUKCGLETL-TYYBGVCCSA-N carbonic acid;(e)-1,2-difluoroethene Chemical compound OC(O)=O.F\C=C\F PMGNOQUKCGLETL-TYYBGVCCSA-N 0.000 claims abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- SZGLVPZZVOKAKA-UHFFFAOYSA-N 3,4-difluoro-2-pyridin-2-ylpyridine Chemical group FC1=CC=NC(C=2N=CC=CC=2)=C1F SZGLVPZZVOKAKA-UHFFFAOYSA-N 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- DEQOKDUASYKHRI-UHFFFAOYSA-N 1-fluoro-2-(1-fluoropyridin-2-ylidene)pyridine Chemical compound FN1C(C=CC=C1)=C1N(C=CC=C1)F DEQOKDUASYKHRI-UHFFFAOYSA-N 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 5
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 claims description 4
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 claims description 2
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000000707 stereoselective effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 10
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- CSJLBAMHHLJAAS-UHFFFAOYSA-N diethylaminosulfur trifluoride Chemical group CCN(CC)S(F)(F)F CSJLBAMHHLJAAS-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 7
- PMGNOQUKCGLETL-UHFFFAOYSA-N carbonic acid 1,2-difluoroethene Chemical compound C(O)(O)=O.FC=CF PMGNOQUKCGLETL-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- APOYTRAZFJURPB-UHFFFAOYSA-N 2-methoxy-n-(2-methoxyethyl)-n-(trifluoro-$l^{4}-sulfanyl)ethanamine Chemical compound COCCN(S(F)(F)F)CCOC APOYTRAZFJURPB-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical class [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 4
- DSMUTQTWFHVVGQ-JCYAYHJZSA-N (4s,5s)-4,5-difluoro-1,3-dioxolan-2-one Chemical compound F[C@@H]1OC(=O)O[C@H]1F DSMUTQTWFHVVGQ-JCYAYHJZSA-N 0.000 description 3
- KNLOWMNWRKBVKP-UHFFFAOYSA-N 1-fluoro-2h-pyridine;trifluoromethanesulfonic acid Chemical compound FN1CC=CC=C1.OS(=O)(=O)C(F)(F)F KNLOWMNWRKBVKP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000012363 selectfluor Substances 0.000 description 3
- IBZKBSXREAQDTO-UHFFFAOYSA-N 2-methoxy-n-(2-methoxyethyl)ethanamine Chemical group COCCNCCOC IBZKBSXREAQDTO-UHFFFAOYSA-N 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 2
- PSCXEUSWZWRCMQ-UHFFFAOYSA-N F[S](F)F Chemical compound F[S](F)F PSCXEUSWZWRCMQ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical group [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical group O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- SSPIBMWEJNSGAF-UHFFFAOYSA-N 4,5-diethyl-1,3-dioxol-2-one Chemical compound CCC=1OC(=O)OC=1CC SSPIBMWEJNSGAF-UHFFFAOYSA-N 0.000 description 1
- QYIOFABFKUOIBV-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxol-2-one Chemical compound CC=1OC(=O)OC=1C QYIOFABFKUOIBV-UHFFFAOYSA-N 0.000 description 1
- LWLOKSXSAUHTJO-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C LWLOKSXSAUHTJO-UHFFFAOYSA-N 0.000 description 1
- QCLFSYYUWPUWQR-UHFFFAOYSA-N 4-(chloromethyl)-5-methyl-1,3-dioxol-2-one Chemical compound CC=1OC(=O)OC=1CCl QCLFSYYUWPUWQR-UHFFFAOYSA-N 0.000 description 1
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 1
- HXXOPVULXOEHTK-UHFFFAOYSA-N 4-methyl-1,3-dioxol-2-one Chemical compound CC1=COC(=O)O1 HXXOPVULXOEHTK-UHFFFAOYSA-N 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- BUPLCMMXKFWTTA-UHFFFAOYSA-N 4-methylidene-1,3-dioxetan-2-one Chemical class C=C1OC(=O)O1 BUPLCMMXKFWTTA-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical group BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- RLKHFSNWQCZBDC-UHFFFAOYSA-N n-(benzenesulfonyl)-n-fluorobenzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)N(F)S(=O)(=O)C1=CC=CC=C1 RLKHFSNWQCZBDC-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 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
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/42—Halogen atoms or nitro radicals
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Zxfoom zxfoom zxfoom New material in particular to an additive which can be used as electrolyte of a lithium ion battery a process for producing a trans-difluoroethylene carbonate compound. Zxfoom zxfoom I zxfoom I sub-carbonic acid of (C) stereoselective preparation by electrophilic fluorination trans-difluoro ethylene carbonate and analogues thereof. The invention has the advantages of convenient and easily obtained raw materials, safe and stable used fluorinating agent, environmental protection, easy operation of the reaction process and high selectivity for preparing the trans-difluoro ethylene carbonate compounds.
Description
Technical Field
The invention relates to the technical field of new material synthesis, in particular to a preparation method of a trans-difluoro ethylene carbonate compound serving as an additive of lithium ion battery electrolyte.
Background
Fluoroethylene carbonate (FEC) is an electrolyte additive of a lithium ion battery, which has excellent performance, can inhibit electrolyte decomposition, forms an SEI film with compact structure and better performance at a negative electrode, reduces battery impedance, improves electrolyte low-temperature performance, improves specific capacity, cycle stability and cycle life of the lithium ion battery, and plays an important role in improving endurance capacity, service life and safety of the lithium ion battery. 4, 5-difluoroethylene carbonate (DFEC) has higher dielectric constant, higher oxidation resistance and structural symmetry stability than 4-fluoroethylene carbonate (FEC), and has more excellent electrochemical performance in improving silica ink negative electrode. During the preparation of FEC, various byproducts of polyfluorination, such as 4, 4-difluoroethylene carbonate, cis-4, 5-difluoroethylene carbonate, trans-4, 5-difluoroethylene carbonate, etc., are usually formed. The separation and purification of each isomer are difficult, and the preparation of a single component is difficult. Therefore, development of a preparation method of a stereospecific difluoro ethylene carbonate compound, wherein the required isomer can be obtained with higher yield, still has very important application value.
In the prior art, the preparation methods of the 4, 5-difluoro ethylene carbonate mainly comprise the following steps: (1) a direct electrochemical fluorination process using ethylene carbonate as a starting material. Literature (j. Fluoroine chem., 2003, 120, 105-110.) and patent JP2000344763 report a direct electrochemical fluorination process (30% F) starting from ethylene carbonate 2 /N 2 ) FEC can be prepared in 70% yield, and continued electrolytic fluorination can yield a mixture of cis-4, 5-difluoroethylene carbonate (11%) and trans-4, 5-difluoroethylene carbonate (59%) and 4, 4-difluoroethylene carbonate (5%). (2) Using vinylene carbonate as raw material and fluorine gas (F) 2 ) The 4, 5-difluoro ethylene carbonate is prepared by direct addition reaction of fluorine source. WO2010128634 discloses a process for preparing 4, 5-dialkyl-4, 5-difluoro-1, 3-dioxolan-2-one compounds from 4, 5-dimethyl-1, 3-dioxolan-2-one by direct fluorination with fluorine gas. (3) The stepwise preparation method is also a method mainly adopted at present, namely, chlorinated ethylene carbonate is obtained firstly, and then halogen exchange is carried out under the action of a fluorinating agent. The halogen exchange method is studied more, for example, patent WO2011048053A1, CN103113346A, CN113896705A, CN115611846A, CN115772150A, CN104529992A and the like disclose that 4, 5-dichloro/bromo-ethylene carbonate and a fluorinating agent are used for generating fluorine-chlorine exchange to prepare 4, 5-difluoro-ethylene carbonate, and the obtained product is a mixture of cis-isomer and trans-isomer; meanwhile, since the fluorine-chlorine exchange reaction generally requires the addition of alkali, byproducts of dechlorination elimination are also formed. Also patent CN110903274a discloses a process for preparing 4, 5-difluoroethylene carbonate from monofluoroethylene carbonate (FEC) as a raw material by a chlorination and fluorination step.
In the method, the direct electrochemical fluorination method has higher requirements on equipment, has no selectivity in the reaction and is easy to obtain polyfluorinated byproducts. The fluorine gas has high activity, strong corrosiveness and high toxicity, so that the fluorine gas is difficult to apply on a large scale, and the direct addition method of the fluorine gas has the problem of very poor selectivity; the fluorohalogenate exchange method is the most used method, but because halogenated substrates are poor in stability, side reactions such as hydrolysis and elimination are easy to occur, so that the fluorination efficiency is low, fluorinated products are also usually polyfluorinated isomer mixtures with various configurations, and the separation difficulty of the products is high. Therefore, researchers have been looking for a fluorination process that is environmentally friendly, highly selective, and gentle in the reaction system.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a process for preparing trans-difluoroethylene carbonate compounds with high stereospecificity and high yield.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a preparation method of a trans-difluoro ethylene carbonate compound, which comprises the following steps:
mixing a vinylene carbonate compound shown in a formula I with a fluorinating agent, and performing electrophilic fluorination reaction to obtain a trans-difluoro ethylene carbonate compound shown in a formula II;
；
wherein the fluorinating agent is difluoro bipyridine substance;
R 1 and R is 2 The same or different are respectively and independently selected from H, C-C6 linear or branched alkyl or C1-C6 linear or branched alkyl containing F, cl or ether bond.
In electrophilic fluorination reaction products, the selectivity of the trans-form products is more than 99 percent.
In another aspect, the present invention provides a trans-difluoroethylene carbonate compound prepared by the preparation method of the present invention.
In another aspect, the invention provides the use of a trans-difluoro ethylene carbonate compound according to the invention in a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for preparing trans-4, 5-difluoroethylene carbonate compounds stereospecifically by taking vinylene carbonate compounds as starting materials and carrying out 1, 2-difluoro addition reaction of olefins under the action of difluorobipyridine fluorination reagents. The method has the characteristics of convenient and easily obtained raw materials, mild reaction conditions, higher operation safety and the like. No by-products such as 4-fluoroethylene carbonate, 4-difluoroethylene carbonate, and cis-4, 5-difluoroethylene carbonate were detected by gas chromatography in the reaction solution of the fluorination reaction. The selectivity of the trans isomer is more than 99%, the product yield can reach 92%, the preparation efficiency of the product is greatly improved, and the separation and purification cost is reduced.
Drawings
FIG. 1 shows trans-4, 5-difluoro-1, 3-dioxolan-2-one (t-DFEC) of the invention 1 H-NMR spectrum.
FIG. 2 shows trans-4, 5-difluoro-1, 3-dioxolan-2-one (t-DFEC) of the invention 13 C-NMR spectrum.
Detailed Description
The following detailed description specifically discloses a method for preparing a trans-difluoroethylene carbonate compound and an embodiment of the trans-difluoroethylene carbonate compound.
The "range" disclosed herein is defined in terms of lower and upper limits, with a given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
As mentioned in the background, in the preparation of 4, 5-difluoroethylene carbonate compounds, a mixture of trans and cis isomers is generally obtained. When used in an electrolyte, the trans form is particularly preferable because it has a lower melting point, higher stability and lower viscosity than the cis-isomer thereof, and can better improve the low-temperature performance of the electrolyte. In order to reduce the difficulty of separation and purification of the later-stage product, the highly selective obtaining of the trans isomer in the synthesis stage is a very effective means. For 4, 5-difluoroethylene carbonate, trans-conformational isomers are more thermodynamically stable and easier to produce due to interactions between adjacent substituents, while yields are also a problem that must be considered for practical industrial production. However, in practice, a highly reactive substrate is used, the reactivity of the reagent is high, the reaction proceeds rapidly, all of the cis-trans isomers tend to be formed rapidly, and the selectivity of the trans-conformation tends to be less than ideal. In the prior art WO2010128634A1, vinylene carbonate is adopted as a substrate, fluorine gas is adopted as a fluorinating agent, the chemical property is very active, the fluorination position and the number of the fluoro are difficult to control in the fluorination process, the trans-selectivity of the obtained product is 70-90%, and the obtained yield is up to 81%.
The inventors of the present invention have found through a number of experiments that the choice of fluorinating agent is critical to further enhance the stereoselectivity of the trans-difluoroethylene carbonate product while simultaneously enhancing the yield. Although in the prior art, fluorine gas (F 2 /N 2 ）、HF、XeF 2 Alkali metal fluoride, N-fluorobenzenesulfonimide, quaternary ammonium cationic fluoride and the like are selected as fluorinating agents in the preparation process of fluoroethylene carbonate, but the problems of poor universality of reaction substrates, high toxicity, strong corrosiveness, difficult post-treatment, poor reaction selectivity, easiness in generation of isomer byproducts and the like exist. The invention uses difluoro bipyridine compound as fluorinating agent and ethylene sulfate structure as substrate, which can be high yield and selectivityThe trans-difluoro ethylene carbonate compounds are prepared under mild reaction conditions, the reaction is easy to control and the operation is simple. On this basis, the present invention has been completed.
Preparation method of trans-difluoro ethylene carbonate compounds
The invention provides a preparation method of trans-difluoro ethylene carbonate compounds, which is obtained by taking ethylene carbonate compounds represented by a formula (I) as a starting material and difluoro bipyridine substances as a fluorinating agent through electrophilic difluoro reaction.
The preparation route of the trans-difluoro ethylene carbonate compound (formula II) is as follows:
；
R 1 and R is 2 The same or different are respectively and independently selected from H, C-C6 linear or branched alkyl or C1-C6 linear or branched alkyl containing F, cl or ether bond.
In the preparation method of the trans-difluoro ethylene carbonate compound, R is optionally selected 1 And R is 2 The same or different are each independently selected from H.
In the preparation method of the trans-difluoro ethylene carbonate compound, R is optionally selected 1 And R is 2 The same or different are independently selected from C1-C6 straight chain or branched alkyl. Examples of the "compound" include methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, t-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl and 2-ethylbutyl groups.
In the preparation method of the trans-difluoro ethylene carbonate compound, R is optionally selected 1 And R is 2 The same or different are independently selected from C1-C6 straight-chain or branched alkyl containing F, cl or ether bond.
The invention provides a trans-difluoro ethylene carbonate compoundIn the preparation method of the compound, optionally, R in vinylene carbonate compounds shown in formula I 1 And R is 2 The same or different, each independently selected from H, methyl, ethyl, chloromethyl, chloroethyl, fluoromethyl or fluoroethyl. Further alternatively, chloromethyl groups include, but are not limited to, -CCl 3 、-CHCl 2 、-CH 2 Cl, chloroethyl groups include, but are not limited to, -CH 2 CCl 3 、-CH 2 CHCl 2 、-CH 2 CH 2 Cl; chloromethyl groups include, but are not limited to, -CF 3 、-CHF 2 、-CH 2 F, performing the process; chloroethyl groups include, but are not limited to, -CH 2 CF 3 、-CH 2 CHF 2 、-CH 2 CH 2 F。
In the preparation method of the trans-difluoro ethylene carbonate compound, optionally, the ethylene carbonate compound represented by the formula (I) is ethylene carbonate, 4, 5-dimethyl-1, 3-dioxole-2-ketone, 4-methyl-1, 3-dioxole-2-ketone, 4-chloromethyl-5-methyl-1, 3-dioxole-2-ketone, 4, 5-diethyl-1, 3-dioxole-2-ketone and the like.
In the preparation method of the trans-difluoro ethylene carbonate compounds, the difluoro bipyridine compounds are N, N '-difluoro-2, 2' -bipyridine compounds, and the general formula of the N, N '-difluoro-2, 2' -bipyridine compounds is as follows:
；
wherein R is 3 、R 4 Each independently selected from H, 4' -diCH 3 、4,4’-diCl、4,4’-diC 6 H 5 、4,4’-diCO 2 CH 3 Or 5,5' -dicaf 3 ；
X is OTf, OMs, BF 4 、PF 6 Or SbF 6 。
Optionally, the difluorobipyridine-based reagent is selected from one or more of N, N '-difluoro-2, 2' -bipyridine bis tetrafluoroborate, N '-difluoro-2, 2' -bipyridine bis-trifluoro-methanesulfonate, or N, N '-difluoro-2, 2' -bipyridine bis-methanesulfonate.
As electrophilic fluorination reagents, difluorobipyridines have the advantages of easy storage, convenient use, mild reaction conditions and the like, and have many literature reports (j. Org. Chem., 1998, 63, 3379-3385; j. Org. Chem., 2002, 67, 6415-6420; j. Florine chem., 2003, 120, 173-183). In prior art CN115772151a, N '-difluoro-2, 2' -bipyridine bis tetrafluoroborate was reacted with ethylene carbonate as a fluorinating agent to give 4-fluoro-1, 3-dioxolan-2-one. In WO2016080484A1, 1 '-difluoro-2, 2' -bipyridinium bis (tetrafluoroborate) is used as a fluorinating agent for fluorinating a fluorinated saturated cyclic carbonate, or a fluorine atom is introduced by electrophilic fluorination reaction on carbanions with ortho positions of electron withdrawing groups, such as beta-diketones and beta-keto esters, which are used as monofluorinating agents, and the high selectivity in space positions is not shown. Electrophilic fluorination on electron-rich aromatic rings has also been reported, and due to factors such as substituents on the aromatic rings, more positional isomerism is considered in fluorination, and selectivity is not shown in the space isomerism, various products such as monofluorination, polyfluorination, fluorinated dearomatization and the like are usually generated.
According to the invention, difluoro bipyridine compounds are used as a fluorinating agent, and vinylidene carbonate compounds are used as starting materials to generate bifluorination reaction of electron-rich olefin substrates, so that trans-4, 5-difluoro ethylene carbonate and analogues thereof are prepared stereoselectively, and similar documents and patent reports are not yet seen at present.
In the preparation method of the trans-difluoro ethylene carbonate compound, the dosage of the fluorinating agent is 1.0 mole equivalent based on the dosage of the compound (I), and the mole ratio of the ethylene carbonate compound shown in the formula I to the fluorinating agent is 1: (1-3). Optionally, the molar ratio of the vinylene carbonate compound shown in formula I to the fluorinating agent may also be 1: (1-2) or 1: (2-3), etc.
As a preferred embodiment of the present invention, the electrophilic fluorination reaction is carried out in the presence of an organic solvent.
；
Wherein R is 1 And R is 2 The selection of (c) is as described above.
The solvent is one or more selected from acetonitrile, dichloromethane, dichloroethane, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethyl acetate and isopropyl acetate.
In the preparation method of the trans-difluoro ethylene carbonate compounds, the temperature of the electrophilic fluorination reaction is 0-100 ℃. Alternatively, the electrophilic fluorination reaction may be carried out at a temperature of, for example, from 0deg.C to 50deg.C, 50 o C～60 o C or 60 o C～100 o C, etc.
In the preparation method of the trans-difluoro ethylene carbonate compounds, the reaction time of the electrophilic fluorination reaction is 1-24 h, the reaction is monitored by gas chromatography until the reaction is completed, and the content of the reactant (I) is less than 5%, namely the reaction is considered to be finished. Optionally, the reaction time of the electrophilic fluorination reaction is 1 h-4 h, 4 h-8 h, 8 h-12 h, 12 h-16 h, 16 h-24 h or the like.
After the reaction is finished, the method also comprises a post-treatment step, wherein the reaction solution is subjected to post-treatment operations such as quenching, extraction, concentration, distillation and the like, so that a trans-difluoro ethylene carbonate crude product can be obtained stereoselectively, and finally, the purity of a trans-isomer can be improved to more than 99.5% through rectification and purification, thereby meeting the requirement of high purity of the lithium ion battery electrolyte additive.
Trans-difluoro ethylene carbonate compounds
In another aspect, the invention provides a trans-difluoroethylene carbonate compound prepared by the preparation method of the first aspect of the invention.
Use of the same
In another aspect, the invention provides the use of the trans-difluoro-ethylene carbonate compound or the trans-difluoro-ethylene carbonate compound crystal form in a lithium ion battery.
Specifically, the trans-difluoro ethylene carbonate can be used as an additive of the nonaqueous electrolyte, has the advantages of forming a stable protective film on an electrode (positive electrode or negative electrode) of a lithium secondary battery, improving the cycle performance and low-temperature performance of the electrolyte, having good flame-retardant effect and improving the safety of the electrolyte.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for preparing trans-4, 5-difluoroethylene carbonate compounds stereospecifically by taking vinylene carbonate compounds as starting materials and carrying out 1, 2-difluoro addition reaction of olefins under the action of difluorobipyridine fluorination reagents. The method has the characteristics of convenient and easily obtained raw materials, mild reaction conditions, higher operation safety and the like. No by-products such as 4-fluoroethylene carbonate, 4-difluoroethylene carbonate, and cis-4, 5-difluoroethylene carbonate were detected by gas chromatography in the reaction solution of the fluorination reaction. The selectivity of the trans isomer is more than 99%, the product yield can reach 92%, the preparation efficiency of the product is greatly improved, and the separation and purification cost is reduced.
The technical solutions of the present application are clearly and completely described below in connection with the embodiments of the present invention. It is noted herein that the following examples are given solely for the purpose of further illustration and are not to be construed as limitations on the scope of the invention, as will be apparent to those skilled in the art in light of the foregoing disclosure.
In the examples described below, reagents, materials and apparatus used are commercially available unless otherwise specified.
The source of the general reaction reagent is not particularly limited in the present invention, and vinylene carbonate, N '-difluoro-2, 2' -bipyridine bistetrafluoroborate, xeF used in the examples of the present invention 2 BAST, BAST, selectfluor% fluorine reagent, 1-fluoropyridine trifluoromethane sulfonate, etc. were purchased from Shanghai Taitan technologies Co., ltd.
The analytical methods used in the examples below were as follows:
(1) NMR spectra were obtained on a BRUKER 400. Unless otherwise stated, noThen solvent CDCl 3 、CD 3 OD and DMSO-d 6 All purchased from Shanghai Taitan technologies Co.
(2) GC data was obtained on Agilent gas chromatograph Agilent 8860 using a chromatographic column: HP-5 30m*0.32mm*0.25um.
EXAMPLE 1 preparation of trans-4, 5-difluoro-1, 3-dioxolan-2-one
300 g of vinylene carbonate and 500mL of anhydrous dichloroethane are added into a 2L three-necked flask under the protection of nitrogen, stirring is started, and the mixture is cooled to 0 o Under C, 500 g of N, N '-difluoro-2, 2' -bipyridine bis tetrafluoroborate was slowly added dropwise to a solution of 500mL of anhydrous dichloromethane using a constant pressure funnel over a period of about 3 hours. After the dripping is finished, naturally heating to room temperature, continuously preserving heat for about 1 hour, and determining that the conversion of the vinylene carbonate raw material is complete through gas chromatography. Adding a small amount of saturated sodium bicarbonate water solution to quench the reaction, separating liquid, separating an organic phase, drying the organic phase by using anhydrous sodium sulfate, filtering the organic phase, and concentrating the obtained filtrate under reduced pressure to obtain a crude product of the difluoroethylene carbonate. And finally, transferring the crude product into a rectifying kettle for vacuum rectification, collecting the distillate 397.7g of finished product (colorless transparent liquid) with the top temperature of 63-75 ℃ and the vacuum degree of 22.5mmHg, wherein the GC content is 99.5 percent and the yield is 92.0 percent.
1 H-NMR (400 MHz, CDCl 3 ) δ 6.20 (d,J= 10.4Hz, 1H), 6.06 (m, d,J= 10.4Hz, 1H)； 13 C-NMR (100 MHz, CDCl 3 ) δ 149.69, 107.42 (d, 1C), 104.54 (d, 1C)。
Comparative example 1
This comparative example provides a process for the preparation of 4, 5-difluoro-1, 3-dioxolan-2-one wherein the fluorinating agent is XeF 2 Other conditions were the same as in example 1. After the reaction was completed, the reaction was checked by GC to find that the product was a mixture of various fluorides and byproducts, in which the trans-4, 5-difluoroethylene carbonate GC content was 43.8%, the cis-4, 5-difluoroethylene carbonate GC content was 18.0%, and the other byproducts content was 38.2%.
Comparative example 2
This comparative example provides a 4, 5-difluoro-1, 3-bisThe preparation method of the oxacyclopentane-2-ketone, wherein the fluorinating agent is diethylaminosulfur trifluoride (DAST), and the reaction temperature is between room temperature and 60 ℃ and is heated o And C, the reaction solvent is anhydrous dichloroethane. GC detects the reaction process, and no target product is detected.
Comparative example 3
This comparative example provides a process for the preparation of 4, 5-difluoro-1, 3-dioxolan-2-one wherein the fluorinating agent is bis (2-methoxyethyl) amine sulfur trifluoride (BAST/Deoxo-Fluro), the solvent is acetonitrile, and the other conditions are the same as in example 1. The reaction temperature is between room temperature and 60 o C, GC detects the reaction process, and no target product is detected.
Comparative example 4
This comparative example provides a process for the preparation of 4, 5-difluoro-1, 3-dioxolan-2-one wherein the fluorinating agent is 1-fluoropyridine triflate and the other conditions are the same as in example 1. The reaction temperature is between room temperature and 60 o C, GC detects the reaction process, and no target product is detected.
Comparative example 5
This comparative example provides a process for the preparation of 4, 5-difluoro-1, 3-dioxolan-2-one wherein the fluorinating agent is 1-chloromethyl-4-fluoro-1, 4-diazabicyclo [2.2.2]Octane bis (tetrafluoroborate) (Selectfluor) salt at room temperature to 60 deg.f o And C, the reaction solvent is anhydrous dichloroethane. At the end of the reaction, GC detects 21.0% of trans-4, 5-difluoroethylene carbonate content and 61.5% of other various byproducts.
As can be seen by comparing the example 1 of the present invention with the comparative examples 1 to 5, the difluorobipyridine type fluorination reagent selected in the present invention can undergo a bifluorination addition reaction of vinylene carbonate, the reaction yield is high, the stereoselectivity is high, and the formation of fluorinated byproducts such as 4-fluoroethylene carbonate, 4-difluoroethylene carbonate, cis-4, 5-difluoroethylene carbonate, etc. is not detected by gas chromatography during the reaction. By XeF 2 As a fluorinating agent, the mixture of cis-isomer and trans-isomer is prepared by reaction, and the reaction yield is lower due to the fact that cis-isomer is taken as a main component. Diethylaminosulfur trifluoride (DAST),Bis (2-methoxyethyl) amine sulfur trifluoride (BAST/Deoxo-Fluro) and 1-fluoropyridine trifluoromethane sulfonate were used as fluorinating agents, and no formation of the target product was detected. The trans-difluorinated product is obtained by utilizing the Selectfluor reagent reaction, but the yield is lower.
EXAMPLE 2 preparation of trans-4, 5-difluoro-4, 5-methyl-1, 3-dioxolan-2-one
80 g of 4, 5-dimethyl-1, 3-dioxol-2-one are dissolved in 200mL of anhydrous dichloroethane under nitrogen and cooled to 0 o About C, 400 g of N, N '-difluoro-2, 2' -bipyridine bis-mesylate was slowly added dropwise thereto in 200mL of an anhydrous methylene chloride solution for about 2 hours. After the dripping is finished, slowly heating to 50 o And C, keeping the temperature for about 2 hours, and tracking the reaction progress through gas chromatography until the raw material is completely converted. After the reaction is finished, cooling to room temperature, adding a small amount of saturated sodium hydrogen aqueous solution to quench the reaction, separating the solution, drying the lower organic phase by using anhydrous sodium sulfate, filtering, concentrating under reduced pressure to remove the organic solvent, transferring the residue into a rectifying device for vacuum pump rectification, collecting the fraction with the top temperature of 60 ℃ -65 ℃ (20 mmHg), namely the trans isomer, wherein the product weight is 72 g, the GC content is 99.0%, and the yield is 68.0%.
EXAMPLE 3 preparation of trans-4, 5-difluoro-4-methyl-1, 3-dioxolan-2-one
120 g of 4-methyl-1, 3-dioxol-2-one are dissolved in 250mL of anhydrous dichloroethane under nitrogen and cooled to 0 o About C, 700 g of N, N '-difluoro-2, 2' -bipyridine bis tetrafluoroborate was slowly added dropwise thereto in 300mL of an anhydrous dichloromethane solution for about 2 hours. After the dripping is finished, slowly heating to 50 o And C, keeping the temperature for about 2 hours, and tracking the reaction progress through gas chromatography until the raw material is completely converted. After the reaction is finished, cooling to room temperature, adding a small amount of saturated sodium hydrogen aqueous solution to quench the reaction, separating liquid, drying the lower organic phase by using anhydrous sodium sulfate, filtering, concentrating under reduced pressure to remove the organic solvent, transferring the residue into a rectifying device to carry out vacuum pump rectification, collecting the fraction with the top temperature of 60-65 ℃ (10 mmHg) to obtain 130 g, namely trans-4, 5-difluoro-4-methyl-1, 3-dioxaCyclopentane-2-one, GC content was 98.6% yield 78.5%.
Example 4: preparation of trans-4, 5-difluoro-4-chloromethyl-5-methyl-1, 3-dioxolan-2-one
100 g of 4-chloromethyl-5-methyl-1, 3-dioxol-2-one are dissolved in 200mL of anhydrous dichloroethane under nitrogen, cooled to 0 o About C, 320 g of N, N '-difluoro-2, 2' -bipyridine bis tetrafluoroborate was slowly added dropwise thereto in 200mL of an anhydrous dichloromethane solution for about 2 hours. After the dripping is finished, slowly heating to 50 o And C, keeping the temperature for about 3 hours, and tracking the reaction progress through gas chromatography until the raw material is completely converted. After the reaction is finished, cooling to room temperature, adding a small amount of saturated sodium hydrogen aqueous solution to quench the reaction, separating the solution, drying the lower organic phase by using anhydrous sodium sulfate, filtering, concentrating under reduced pressure to remove the organic solvent, transferring the residue into a rectifying device for vacuum pump rectification, collecting the fraction with the top temperature of 70-75 ℃ (10 mmHg) to weigh 91 g, namely trans-4, 5-difluoro-4-chloromethyl-5-methyl-1, 3-dioxolane-2-one, wherein the GC content is 99.0%, and the yield is 71.6%.
EXAMPLE 5 preparation of trans-4, 5-difluoro-4, 5-diethyl-1, 3-dioxolan-2-one
140 g of 4, 5-diethyl-1, 3-dioxol-2-one are dissolved in 200mL of anhydrous dichloroethane under nitrogen and cooled to 0 o About C, 470 g of N, N '-difluoro-2, 2' -bipyridine bis-mesylate was slowly added dropwise thereto in 250mL of an anhydrous dichloromethane solution over a period of about 2 hours. After the dripping is finished, slowly heating to 50 o And C, keeping the temperature for about 2 hours, and tracking the reaction progress through gas chromatography until the raw material is completely converted. After the reaction is finished, cooling to room temperature, adding a small amount of saturated sodium hydrogen aqueous solution to quench the reaction, separating liquid, drying the lower organic phase by using anhydrous sodium sulfate, filtering, concentrating under reduced pressure to remove the organic solvent, transferring the residue into a rectifying device for vacuum pump rectification, collecting the fraction product with the top temperature of 70-75 ℃ (10 mmHg) to weigh 152 g, namely trans-4, 5-difluoro-4, 5-diethyl-1, 3-dioxolan-2-one, wherein the GC content is 99.2%, and the yield is 85.7%.
The foregoing description of the embodiments is provided to facilitate the understanding and application of the present application by those of ordinary skill in the art. It will be apparent to those skilled in the art that various modifications can be made to these embodiments and that the general principles described herein may be applied to other embodiments without the use of inventive faculty. Accordingly, the present application is not limited to the embodiments herein, and those skilled in the art, based on the present disclosure, may make improvements and modifications within the scope and spirit of the present application.
Claims (7)
1. A method for preparing a trans-difluoro ethylene carbonate compound, which is characterized by comprising the following steps:
mixing a vinylene carbonate compound shown in a formula I with a fluorinating agent, and performing electrophilic fluorination reaction to obtain a trans-difluoro ethylene carbonate compound shown in a formula II;
；
wherein the fluorinating agent is difluoro bipyridine substance; the difluoro bipyridine compound is an N, N '-difluoro-2, 2' -bipyridine compound, and the general formula of the N, N '-difluoro-2, 2' -bipyridine compound is as follows:
；
III
wherein R is 3 、R 4 Each independently selected from H;
x is OMs, BF 4 ；
R 1 And R is 2 The same or different are respectively and independently selected from C1-C6 straight-chain or branched-chain alkyl or C1-C6 straight-chain or branched-chain alkyl containing F, cl.
2. The method for producing trans-difluoroethylene carbonate according to claim 1, wherein the difluorobipyridine-based reagent is one or more selected from the group consisting of N, N '-difluoro-2, 2' -bipyridine bis tetrafluoroborate and N, N '-difluoro-2, 2' -bipyridine bis methanesulfonate.
3. The method for producing a trans-difluoroethylene carbonate compound according to claim 1, wherein R in the ethylene carbonate compound represented by formula I 1 And R is 2 The same or different, each independently selected from methyl, ethyl, chloromethyl, chloroethyl, fluoromethyl or fluoroethyl.
4. The method for producing a trans-difluoroethylene carbonate compound according to claim 1, wherein the molar ratio of the ethylene carbonate compound represented by formula I to the fluorinating agent is 1: (1-3);
and/or, the temperature of the electrophilic fluorination reaction is 0-100 ℃;
and/or the reaction time of the electrophilic fluorination reaction is 1-24 h.
5. The method for producing a trans-difluoroethylene carbonate compound according to claim 1, wherein the electrophilic fluorination reaction further comprises a solvent selected from one or more of acetonitrile, methylene chloride, dichloroethane, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, ethyl acetate, isopropyl acetate.
6. The method for producing a trans-difluoroethylene carbonate compound according to claim 1, further comprising a post-treatment comprising quenching, extracting, concentrating, distilling the reaction liquid to obtain a crude product, and rectifying and purifying the crude product.
7. The method for producing a trans-difluoroethylene carbonate compound according to claim 1, wherein the trans-difluoroethylene carbonate compound represented by formula II has a selectivity of 99% or more.
Priority Applications (1)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002030004A (en) * | 2000-07-14 | 2002-01-29 | Daikin Ind Ltd | Fluorinating agent and method for manufacturing fluorine compound |
| WO2003008364A1 (en) * | 2001-07-13 | 2003-01-30 | Daikin Industries Ltd. | Fluorination process |
| WO2010128634A1 (en) * | 2009-05-07 | 2010-11-11 | ダイキン工業株式会社 | Process for producing 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one |
| CN115772151A (en) * | 2022-11-25 | 2023-03-10 | 山东东岳高分子材料有限公司 | Preparation method of 4-fluoro-1,3-dioxolane-2-one |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002030004A (en) * | 2000-07-14 | 2002-01-29 | Daikin Ind Ltd | Fluorinating agent and method for manufacturing fluorine compound |
| WO2003008364A1 (en) * | 2001-07-13 | 2003-01-30 | Daikin Industries Ltd. | Fluorination process |
| WO2010128634A1 (en) * | 2009-05-07 | 2010-11-11 | ダイキン工業株式会社 | Process for producing 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one |
| CN115772151A (en) * | 2022-11-25 | 2023-03-10 | 山东东岳高分子材料有限公司 | Preparation method of 4-fluoro-1,3-dioxolane-2-one |
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