CN108484452A - 一种氟烷基磺酰腙的制备方法 - Google Patents
一种氟烷基磺酰腙的制备方法 Download PDFInfo
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- CN108484452A CN108484452A CN201810237625.8A CN201810237625A CN108484452A CN 108484452 A CN108484452 A CN 108484452A CN 201810237625 A CN201810237625 A CN 201810237625A CN 108484452 A CN108484452 A CN 108484452A
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- -1 sulfonyl hydrazone Chemical class 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 239000003863 metallic catalyst Substances 0.000 claims abstract description 7
- ISNKSXRJJVWFIL-UHFFFAOYSA-N (sulfonylamino)amine Chemical compound NN=S(=O)=O ISNKSXRJJVWFIL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000013110 organic ligand Substances 0.000 claims description 28
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims description 2
- 125000001313 C5-C10 heteroaryl group Chemical group 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 2
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229930016911 cinnamic acid Natural products 0.000 claims description 2
- 235000013985 cinnamic acid Nutrition 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- UQXKXGWGFRWILX-UHFFFAOYSA-N ethylene glycol dinitrate Chemical compound O=N(=O)OCCON(=O)=O UQXKXGWGFRWILX-UHFFFAOYSA-N 0.000 claims 1
- 150000007857 hydrazones Chemical class 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 235000015424 sodium Nutrition 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 abstract description 2
- 235000002639 sodium chloride Nutrition 0.000 description 16
- ZBNXZQCRRMUUPB-UHFFFAOYSA-N 2,2-difluoro-N-(sulfonylamino)ethanimine Chemical compound S(=O)(=O)=NN=CC(F)F ZBNXZQCRRMUUPB-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- WJATUBJLYUOLNM-UHFFFAOYSA-N 2,2-difluoroacetaldehyde;hydrate Chemical compound O.FC(F)C=O WJATUBJLYUOLNM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 229910000144 sodium(I) superoxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 238000006186 Bamford-Stevens reaction Methods 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000006882 Shapiro reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000001055 magnesium Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- UORYAOZFMGBGAC-UHFFFAOYSA-N n-methylbenzenesulfonohydrazide Chemical compound CN(N)S(=O)(=O)C1=CC=CC=C1 UORYAOZFMGBGAC-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种温和的氟烷基磺酰腙制备方法,该方法包括如下步骤:将氟烷基醛或水合物与磺酰肼衍生物在金属催化剂和添加物的存在下进行反应得到氟烷基磺酰腙衍生物。本方法反应条件温和,底物范围广,官能团耐受性好,在实验室能够安全的实现数十克数量级的合成,具有进一步工业化应用的潜力。
Description
技术领域
本发明涉及有机合成领域,尤其涉及一种氟烷基磺酰腙的制备方法。
技术背景
磺酰腙是有机合成中一类非常有用的合成子,同时具有较好的稳定性,容易储存,多数情况下为结晶化合物并易于纯化。磺酰腙类化合物在有机合成中的应用最早可以追溯到二十世纪五十年代,它们早期的应用主要是经由重氮或烯基锂中间体用于合成多种多样的烯烃。在此间发展的两个重要转化:Bamford-Stevens反应和Shapiro反应在合成中具有非常高的实用价值。到目前为止,磺酰腙在有机合成化学中已经取得了巨大的进展,它不仅可以作为环加成和其它环化反应中良好的1,3-偶极前体,同时它也是非常有价值的重氮前体,并参与到各种卡宾或类卡宾反应中。
选择性地在有机分子中引入含氟砌块,能够极大的提高分子的生物活性,医药作用和材料强度。由于氟烷基具有很强的吸电子性、亲脂性和含有稳定的C-F键等特性,在有机分子中能够显著地改变化合物的物化性质和生物学特性。因此,发展一类氟烷基磺酰腙衍生物作为新型的氟烷基化试剂参与环加成反应或卡宾类反应,不仅能为氟化基元的构建提供新的方法,同时也为官能化磺酰腙的合成与应用提供新的思路。
发明内容
有鉴于此,本发明的目的在于提供一种温和氟烷基磺酰腙的制备方法,以廉价易得的氟烷基醛、酯或其水合物出发,在金属催化剂和添加物的存在下与磺酰肼衍生物发生反应得到氟烷基磺酰腙。该方法反应条件温和,底物范围广,官能团耐受性好,在实验室能够安全的实现1-50克数量级的合成,具有进一步工业化应用的潜力。
为了实现上述发明目的,本发明提供以下技术方案:
本发明提供了一种氟烷基磺酰腙的制备方法,其特征在于包括以下步骤:
(1)将具有式I所示结构的氟烷基醛水合物和具有式II所示结构的磺酰肼衍生物在金属催化剂和添加剂的存在下进行反应,得到具有式III所示结构的磺酰腙衍生物。
所述R基团选自下组:取代或未取代的的烷基、取代或未取代的C3-C30的环烷基、取代或未取代的C3-C8的杂环基、取代或未取代的C2-C30的烯基、取代或未取代的C2-C30的炔基、取代或未取代的C6-C10的芳基、取代或未取代的C5-C10的杂芳基;所述R基团的取代基选自下组:H、卤素、硝基、氰基、酯基、C1-C8的烷基、C1-C8的氟烷基、C1-C4的烷氧基;
Rf基团选自下组:F1-F3取代的甲基、F1-F5取代的乙基、F1-F7取代的丙基、F1-F9取代的丁基、F1-F2n+1取代的n+1个碳链长度的氟烷基。
所述步骤(1)中金属催化剂选自下组:铜的氧化物、无机盐类化合物及含有有机配体的配合物;铁的氧化物、无机盐类化合物及含有有机配体的配合物;金的无机盐类化合物及含有有机配体的配合物;镍的无机盐类化合物及含有有机配体的配合物;钯的氧化物、无机盐类化合物及含有有机配体的配合物;锌的氧化物、无机盐类化合物及含有有机配体的配合物;铬的氧化物、无机盐类化合物及含有有机配体的配合物;铑的无机盐类化合物及含有有机配体的配合物;铱的无机盐类化合物及含有有机配体的配合物;钌的无机盐类化合物及含有有机配体的配合物;钪的氧化物、无机盐类化合物及含有有机配体的配合物;钇的氧化物、无机盐类化合物及含有有机配体的配合物;钴的氧化物、无机盐类化合物及含有有机配体的配合物;锆的氧化物、无机盐类化合物及含有有机配体的配合物;汞的氧化物、无机盐类化合物及含有有机配体的配合物;锰的氧化物、无机盐类化合物及含有有机配体的配合物。
所述步骤(1)中添加剂选自下组:五氧化二磷、三氯氧磷、五氯化磷、氧化钡、氧化镁、硫酸钠、硫酸镁、氯化锌、二环己基碳二亚胺、浓硫酸、醋酸、特戊酸、三氟甲磺酸、甲酸、盐酸、丁酸、肉桂酸、三氟化硼乙醚、水杨酸、酒石酸、异丁酸、三氟乙酸、全氟丙酸中的一种或几种;
所述步骤(1)中的溶剂选自下组:甲苯、乙腈、二氯甲烷、四氢呋喃、乙醚、乙二醇二甲醚、二氧六环、DMF、DMSO、乙酸乙酯、水等常见溶剂中的一种或几种的组合。
所述步骤(1)中的反应温度为-20-60℃,优选为20-30℃;
所述具有式II结构的磺酰肼衍生物与氟烷基醛水合物的摩尔比为1:1-5.0。
有益技术效果:
本发明开发了一种以氟烷基醛、酯或其水合物为原料,使用过渡金属催化,制备氟烷基磺酰腙衍生物的方法;
本发明制备的氟烷基磺酰腙衍生物为白色固体,热稳定性好,不易吸潮,无腐蚀性,便于保存,便于运输,便于空气中使用,原料易得,适合大规模生产。
说明书附图:
图1为氟烷基磺酰腙的制备路线图;
图2为实施例1中二氟乙醛磺酰腙3a的1H核磁共振谱图;
图3为实施例1中二氟乙醛磺酰腙3a的13C核磁共振谱图;
图4为实施例1中二氟乙醛磺酰腙3a的19F核磁共振谱图;
图5为实施例2中二氟乙醛磺酰腙3b的1H核磁共振谱图;
图6为实施例2中二氟乙醛磺酰腙3b的13C核磁共振谱图;
图7为实施例2中二氟乙醛磺酰腙3b的19F核磁共振谱图;
具体实施方式
下面结合实施例对本发明提供的氟烷基磺酰腙的合成进行详细的说明,但是不能把它们理解为对本发明保护范围的限定。
实施例1二氟乙醛磺酰腙3a的制备
实施例1反应式如下所示:
氮气条件下,向250mL的反应瓶中加入邻三氟甲基苯磺酰肼2a(9.6g,40mmol) 和溶剂1,2-二氯乙烷(80mL),搅拌至溶解,冰水浴降温至0℃,加入金属催化剂氯化铜(68.0mg,1mmol%),滴加添加剂冰乙酸20滴,加入二氟乙醛水合物1a(5.88g,60mmol), 0℃反应至薄层色谱监测邻三氟甲基苯磺酰2a肼消失,旋转蒸发除去溶剂。然后再加入溶剂溶解并在氮气保护条件下加入添加剂二环己基碳二亚胺(2.06g,10mmol),常温搅拌 24h,用饱和氯化钠水溶液洗涤2次,无水硫酸镁干燥,浓缩至20mL左右,将体系滴入 200mL正己烷中,逐渐有白色固体析出,抽滤,得到白色固体3a(10.27g,产率85%), 其结构表征如图2、图3、图4及以下数据所示:
白色固体,m.p 125-126℃;1H-NMR(600MHz,DMSO)δ12.72(s,1H),8.10(d,J =7.8Hz,1H),8.05(d,J=7.8Hz,1H),7.96(t,J=7.8Hz,1H),7.92(t,J= 7.8Hz,1H),7.48(d,J=4.2Hz,1H),6.40(td,J=53.4Hz,J=4.8Hz,1H).13C-NMR (150MHz,DMSO)δ140.07(t,J=31.4Hz),137.77,134.45,133.99,131.74,129.15 (q,J=6.0Hz),126.84(q,J=32.7Hz),123.14(q,J=272.1Hz),113.04(t,J =232.1Hz).19F-NMR(565MHz,DMSO)δ-56.50,-117.03(dd,J=53.7Hz,J=3.4 Hz).HRMS(ESI)m/z calculated for C9H7F5N2NaO2S[M+Na]+325.0046,found 325.0042.
实施例1二氟乙醛磺酰腙3b的制备
实施例2反应式如下图所示:
氮气条件下,向250mL的反应瓶中加入对甲基苯磺酰肼2b(9.3g,50mmol)和溶剂乙酸乙酯(90mL),搅拌至溶解,冰水浴降温至0℃,加入金属催化剂硝酸铁(120mg,1 mmol%),滴加添加剂浓硫酸20滴,加入二氟乙醛水合物1a(7.35g,75mmol),0℃反应至薄层色谱监测对甲基苯磺酰2b肼消失,旋转蒸发除去溶剂。然后再加入溶剂溶解并在氮气保护条件下加入添加剂三氟化硼乙醚(1.42g,10mmol),常温搅拌24h,用饱和氯化钠水溶液洗涤2次,无水硫酸镁干燥,浓缩至20mL左右,将体系滴入200mL正己烷中,逐渐有白色固体析出,抽滤,得到白色固体3b(11.16g,产率90%),其结构表征如图5、图6、图7及以下数据所示:
白色固体,m.p 125-126℃;1H-NMR(600MHz,DMSO)δ12.09(s,1H),7.70(d,J =8.4Hz,2H),7.43(d,J=7.8Hz,2H),7.32(q,J=4.2Hz,1H),6.37(td,J= 53.4Hz,J=4.8Hz,1H),2.39(s,3H).13C-NMR(150MHz,DMSO)δ144.47,139.94 (t,J=31.2Hz),136.06,130.35,127.59,113.12(t,J=231.8Hz),21.49.19F-NMR (565MHz,DMSO)δ-116.75(dd,J=54.2Hz,J=4.0Hz).HRMS(ESI)m/z calculated for C9H10F2N2NaO2S[M+Na]+271.0329,found 271.0335.
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (2)
1.一种氟烷基磺酰腙的制备方法,其特征在于包括以下步骤:
(1)将具有式I所示结构的氟烷基醛水合物和具有式II所示结构的磺酰肼衍生物在金属催化剂和添加剂的存在下进行反应,得到具有式III所示结构磺酰腙的衍生物。
所述R基团选自下组:取代或未取代的的烷基、取代或未取代的C3-C30的环烷基、取代或未取代的C3-C8的杂环基、取代或未取代的C2-C30的烯基、取代或未取代的C2-C30的炔基、取代或未取代的C6-C10的芳基、取代或未取代的C5-C10的杂芳基;所述R基团的取代基选自下组:H、卤素、硝基、氰基、酯基、C1-C8的烷基、C1-C8的氟烷基、C1-C4的烷氧基;
Rf基团选自下组:F1-F3取代的甲基、F1-F5取代的乙基、F1-F7取代的丙基、F1-F9取代的丁基、F1-F2n+1取代的n+1个碳链长度的氟烷基。
2.根据权利要求1所述的制备方法,其特征在于,所述步骤(1)中的反应温度为-20-60℃;
所述具有式II结构的磺酰肼衍生物与氟烷基醛水合物的摩尔比为1:1-5.0。
所述步骤(1)中金属催化剂选自下组:铜的氧化物、无机盐类化合物及含有有机配体的配合物;铁的氧化物、无机盐类化合物及含有有机配体的配合物;金的无机盐类化合物及含有有机配体的配合物;镍的无机盐类化合物及含有有机配体的配合物;钯的氧化物、无机盐类化合物及含有有机配体的配合物;锌的氧化物、无机盐类化合物及含有有机配体的配合物;铬的氧化物、无机盐类化合物及含有有机配体的配合物;铑的无机盐类化合物及含有有机配体的配合物;铱的无机盐类化合物及含有有机配体的配合物;钌的无机盐类化合物及含有有机配体的配合物;钪的氧化物、无机盐类化合物及含有有机配体的配合物;钇的氧化物、无机盐类化合物及含有有机配体的配合物;钴的氧化物、无机盐类化合物及含有有机配体的配合物;锆的氧化物、无机盐类化合物及含有有机配体的配合物;汞的氧化物、无机盐类化合物及含有有机配体的配合物;锰的氧化物、无机盐类化合物及含有有机配体的配合物。
所述步骤(1)中添加剂选自下组:五氧化二磷、三氯氧磷、五氯化磷、氧化钡、氧化镁、硫酸钠、硫酸镁、氯化锌、二环己基碳二亚胺、浓硫酸、醋酸、特戊酸、三氟甲磺酸、甲酸、盐酸、丁酸、肉桂酸、三氟化硼乙醚、水杨酸、酒石酸、异丁酸、三氟乙酸、全氟丙酸中的一种或几种;
所述步骤(1)中的溶剂选自下组:甲苯、乙腈、二氯甲烷、四氢呋喃、乙醚、乙二醇二甲醚、二氧六环、DMF、DMSO、乙酸乙酯、水等常见溶剂中的一种或几种的组合。
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CN110964200A (zh) * | 2019-12-19 | 2020-04-07 | 新纳奇材料科技江苏有限公司 | 一种基于聚硅氧烷馏出物的羟基封端聚硅氧烷的制备方法 |
CN115448841A (zh) * | 2022-10-19 | 2022-12-09 | 东北师范大学 | 一种利用氨水合成伯胺的方法 |
CN114539107B (zh) * | 2022-03-31 | 2023-09-15 | 平顶山学院 | 一种芳香磺酰基修饰的二氟甲基反应砌块及其合成方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1475471A (zh) * | 2003-06-27 | 2004-02-18 | 中国科学院上海有机化学研究所 | 一种1-芳基-2全氟或多氟苯基乙烯及其衍生物、其合成和应用 |
US20040186295A1 (en) * | 2001-10-04 | 2004-09-23 | Cosford Nicholas D P | Heteroaryl substituted tetrazole modulators of metabotrophic glutamate receptor-5 |
CN106608788A (zh) * | 2016-11-18 | 2017-05-03 | 东北师范大学 | 一种温和的重氮甲烷衍生物的制备方法 |
CN107739317A (zh) * | 2017-11-16 | 2018-02-27 | 东北师范大学 | 一种全氟烷基重氮甲烷的制备方法及其应用 |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040186295A1 (en) * | 2001-10-04 | 2004-09-23 | Cosford Nicholas D P | Heteroaryl substituted tetrazole modulators of metabotrophic glutamate receptor-5 |
CN1475471A (zh) * | 2003-06-27 | 2004-02-18 | 中国科学院上海有机化学研究所 | 一种1-芳基-2全氟或多氟苯基乙烯及其衍生物、其合成和应用 |
CN106608788A (zh) * | 2016-11-18 | 2017-05-03 | 东北师范大学 | 一种温和的重氮甲烷衍生物的制备方法 |
CN107739317A (zh) * | 2017-11-16 | 2018-02-27 | 东北师范大学 | 一种全氟烷基重氮甲烷的制备方法及其应用 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110964200A (zh) * | 2019-12-19 | 2020-04-07 | 新纳奇材料科技江苏有限公司 | 一种基于聚硅氧烷馏出物的羟基封端聚硅氧烷的制备方法 |
CN114539107B (zh) * | 2022-03-31 | 2023-09-15 | 平顶山学院 | 一种芳香磺酰基修饰的二氟甲基反应砌块及其合成方法 |
CN115448841A (zh) * | 2022-10-19 | 2022-12-09 | 东北师范大学 | 一种利用氨水合成伯胺的方法 |
CN115448841B (zh) * | 2022-10-19 | 2024-04-09 | 东北师范大学 | 一种利用氨水合成伯胺的方法 |
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