CN115710206B - Synthesis method and application of trifluoromethyl sulfoxide reagent - Google Patents
Synthesis method and application of trifluoromethyl sulfoxide reagent Download PDFInfo
- Publication number
- CN115710206B CN115710206B CN202211550947.0A CN202211550947A CN115710206B CN 115710206 B CN115710206 B CN 115710206B CN 202211550947 A CN202211550947 A CN 202211550947A CN 115710206 B CN115710206 B CN 115710206B
- Authority
- CN
- China
- Prior art keywords
- trifluoromethyl
- reaction
- reagent
- added
- cdcl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 83
- OCOTWWSGPAHHQW-UHFFFAOYSA-N trifluoro(trifluoromethylsulfinyl)methane Chemical compound FC(F)(F)S(=O)C(F)(F)F OCOTWWSGPAHHQW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 206
- -1 sulfonate compound Chemical class 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 14
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims abstract description 11
- OFHCXWMZXQBQMH-UHFFFAOYSA-N trifluoro(trifluoromethylsulfanyl)methane Chemical compound FC(F)(F)SC(F)(F)F OFHCXWMZXQBQMH-UHFFFAOYSA-N 0.000 claims abstract description 11
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 10
- MWKJTNBSKNUMFN-UHFFFAOYSA-N trifluoromethyltrimethylsilane Chemical compound C[Si](C)(C)C(F)(F)F MWKJTNBSKNUMFN-UHFFFAOYSA-N 0.000 claims abstract description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 claims abstract description 7
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 7
- 239000001632 sodium acetate Substances 0.000 claims abstract description 5
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 75
- 239000002904 solvent Substances 0.000 claims description 57
- 229910052757 nitrogen Inorganic materials 0.000 claims description 55
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 38
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 19
- 229910052786 argon Inorganic materials 0.000 claims description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims description 4
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims description 3
- FQTIYMRSUOADDK-UHFFFAOYSA-N ethyl 3-bromopropanoate Chemical compound CCOC(=O)CCBr FQTIYMRSUOADDK-UHFFFAOYSA-N 0.000 claims description 3
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 3
- KQEVIFKPZOGBMZ-UHFFFAOYSA-N methyl 3-bromopropanoate Chemical group COC(=O)CCBr KQEVIFKPZOGBMZ-UHFFFAOYSA-N 0.000 claims description 3
- KQNJUTDIDREYGN-UHFFFAOYSA-N propan-2-yl 3-bromopropanoate Chemical compound CC(C)OC(=O)CCBr KQNJUTDIDREYGN-UHFFFAOYSA-N 0.000 claims description 3
- RMWVUWLBLWBQDS-UHFFFAOYSA-N tert-butyl 3-bromopropanoate Chemical compound CC(C)(C)OC(=O)CCBr RMWVUWLBLWBQDS-UHFFFAOYSA-N 0.000 claims description 3
- CQZIEDXCLQOOEH-UHFFFAOYSA-N 3-bromopropanenitrile Chemical compound BrCCC#N CQZIEDXCLQOOEH-UHFFFAOYSA-N 0.000 claims description 2
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 claims description 2
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 claims description 2
- WPFIDAHMRZVKKN-UHFFFAOYSA-N fluoro(fluoromethylsulfinyl)methane Chemical compound FCS(=O)CF WPFIDAHMRZVKKN-UHFFFAOYSA-N 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 39
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 7
- 238000004440 column chromatography Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000005486 sulfidation Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 162
- 239000012074 organic phase Substances 0.000 description 89
- 239000012299 nitrogen atmosphere Substances 0.000 description 68
- 239000012043 crude product Substances 0.000 description 55
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 48
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 46
- 239000000243 solution Substances 0.000 description 42
- 239000000047 product Substances 0.000 description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 37
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 37
- 238000010898 silica gel chromatography Methods 0.000 description 37
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 36
- 239000012300 argon atmosphere Substances 0.000 description 33
- 239000007788 liquid Substances 0.000 description 32
- 238000002390 rotary evaporation Methods 0.000 description 28
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 28
- 239000000203 mixture Substances 0.000 description 25
- 239000011541 reaction mixture Substances 0.000 description 23
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 22
- 229910000024 caesium carbonate Inorganic materials 0.000 description 22
- 239000008346 aqueous phase Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 14
- 238000001704 evaporation Methods 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 9
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 238000005086 pumping Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 239000012039 electrophile Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000012038 nucleophile Substances 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000012434 nucleophilic reagent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- CRUILBNAQILVHZ-UHFFFAOYSA-N 1,2,3-trimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1OC CRUILBNAQILVHZ-UHFFFAOYSA-N 0.000 description 2
- NQMUGNMMFTYOHK-UHFFFAOYSA-N 1-methoxynaphthalene Chemical compound C1=CC=C2C(OC)=CC=CC2=C1 NQMUGNMMFTYOHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000005520 diaryliodonium group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000003375 sulfoxide group Chemical group 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 description 1
- QGRPVMLBTFGQDQ-UHFFFAOYSA-N 1-chloro-2-methoxybenzene Chemical compound COC1=CC=CC=C1Cl QGRPVMLBTFGQDQ-UHFFFAOYSA-N 0.000 description 1
- MLZBESJTTHZAST-UHFFFAOYSA-N 1-chloro-3-(1-phenylethenyl)benzene Chemical compound ClC1=CC=CC(C(=C)C=2C=CC=CC=2)=C1 MLZBESJTTHZAST-UHFFFAOYSA-N 0.000 description 1
- QRSXZQQKWIHIHY-UHFFFAOYSA-N 1-chloro-4-(1-phenylethenyl)benzene Chemical compound C1=CC(Cl)=CC=C1C(=C)C1=CC=CC=C1 QRSXZQQKWIHIHY-UHFFFAOYSA-N 0.000 description 1
- NLWCWEGVNJVLAX-UHFFFAOYSA-N 1-methoxy-2-phenylbenzene Chemical group COC1=CC=CC=C1C1=CC=CC=C1 NLWCWEGVNJVLAX-UHFFFAOYSA-N 0.000 description 1
- DOLKMMRRGVRVFW-UHFFFAOYSA-N 1-methoxy-4-(1-phenylethenyl)benzene Chemical compound C1=CC(OC)=CC=C1C(=C)C1=CC=CC=C1 DOLKMMRRGVRVFW-UHFFFAOYSA-N 0.000 description 1
- QJQCPPAIBVNVHW-UHFFFAOYSA-N 1-methyl-2-(1-phenylethenyl)benzene Chemical compound CC1=CC=CC=C1C(=C)C1=CC=CC=C1 QJQCPPAIBVNVHW-UHFFFAOYSA-N 0.000 description 1
- OCINXEZVIIVXFU-UHFFFAOYSA-N 1-methyl-3-[3-methyl-4-[4-(trifluoromethylthio)phenoxy]phenyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(N2C(N(C)C(=O)NC2=O)=O)=CC=C1OC1=CC=C(SC(F)(F)F)C=C1 OCINXEZVIIVXFU-UHFFFAOYSA-N 0.000 description 1
- LUZDYPLAQQGJEA-UHFFFAOYSA-N 2-Methoxynaphthalene Chemical compound C1=CC=CC2=CC(OC)=CC=C21 LUZDYPLAQQGJEA-UHFFFAOYSA-N 0.000 description 1
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical group ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 1
- FPWNLURCHDRMHC-UHFFFAOYSA-N 4-chlorobiphenyl Chemical group C1=CC(Cl)=CC=C1C1=CC=CC=C1 FPWNLURCHDRMHC-UHFFFAOYSA-N 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- ZOCSXAVNDGMNBV-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile Chemical compound NC1=C(S(=O)C(F)(F)F)C(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LSRGXLRLWFDKNR-UHFFFAOYSA-N FC(F)(F)[S] Chemical compound FC(F)(F)[S] LSRGXLRLWFDKNR-UHFFFAOYSA-N 0.000 description 1
- 239000005899 Fipronil Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000282887 Suidae Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000001165 anti-coccidial effect Effects 0.000 description 1
- 230000036528 appetite Effects 0.000 description 1
- 235000019789 appetite Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 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
- 229940013764 fipronil Drugs 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005543 phthalimide group Chemical group 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 125000004591 piperonyl group Chemical group C(C1=CC=2OCOC2C=C1)* 0.000 description 1
- 238000002600 positron emission tomography Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 229960000898 toltrazuril Drugs 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method and application of a trifluoromethyl sulfoxide reagent. Firstly, reacting sodium toluenesulfonate with bromide to obtain sulfonate compound; then, a sulfonate compound reacts with trifluoromethyl trimethylsilane under the condition of sodium acetate to obtain trifluoro methyl sulfide substances; finally, the trifluoromethyl sulfoxide reagent is obtained by utilizing the reaction of trifluoromethyl sulfide substances under the condition of m-chloroperoxybenzoic acid. The invention also provides application of the prepared trifluoromethyl sulfoxide reagent as a trifluoromethyl sulfoxide reagent and a trifluoromethyl sulfidation reagent, wherein the application substrate is a diaryl iodide salt derivative, a 1, 1-stilbene derivative or an electron-rich aromatic hydrocarbon. The method has the advantages of low synthesis cost and simple reaction, the trifluoromethyl sulfoxide reagent can be obtained without complicated column chromatography separation, and the structure is adjustable and the activity is controllable by introducing the trifluoromethyl sulfoxide reagents with different leaving groups.
Description
Technical Field
The invention belongs to the technical field of chemistry, relates to a synthesis method and application of a trifluoromethyl sulfoxide reagent, in particular to a synthesis method of a compound containing trifluoromethyl sulfoxide capable of performing double functionalization, which is applied to the preparation of trifluoromethyl sulfide or trifluoromethyl sulfoxide products by reacting with different electrophiles and nucleophiles under different reaction conditions.
Background
Fluorine atoms play an important role in organic drugs. The addition of fluorine atoms improves the properties of the drug, such as enhancing the cell membrane permeability, target specificity and metabolic stability, and isotopes of the drug 18 F is also used for positron emission tomography. Wherein the trifluoromethyl Sulfur (SCF) in the fluorine-containing group 3 ) And a trifluoromethyl sulfoxide group (S (O) CF) 3 ) Has wide potential application prospect. Like the trifluoromethylthio group, has the highest known Hansch lipophilic parameter, with values up to pi=1.44. The compound containing trifluoromethyl thio substitution has higher biological activity and has wide application in the fields of agricultural chemicals and organic synthesis. In agricultural chemistry, fipronil is a strong pesticide, has a wide insecticidal range, and has contact killing and certain systemic effect on pests; toltrazuril is a commonly used anticoccidial drug for birds and pigs; teflupirtine inhibits appetite.
The current methods for synthesizing trifluoromethyl sulfoxide compounds mainly comprise three methods: firstly, m-CPBA or hydrogen peroxide is used for oxidizing trifluoromethylthio, but the method needs to control the dosage of an oxidant, otherwise, the oxidant is easy to excessively oxidize into sulfonyl; secondly, the perfluoroalkyl group is carried out by nucleophilic or electrophilic trifluoromethyl groups, and the method has the defects that the precursor is not stable enough, has larger toxicity and is more harsh to the reaction conditions; thirdly, the trifluoromethyl sulfoxide group is directly introduced, the reaction quantity can be well controlled by the method, the reaction operation is simple and quick, and the reaction range is wider. However, such agents are currently less developed.
The reagents are also mainly divided into three types, the first is free radical reagent, so that the research is less at present, and few reports are made; the second is trifluoromethyl sulfoxide electrophile, which has imperfect development. The applicant has created an electrophilic trifluoromethyl sulfoxide reagent with phthalimide structure, and the reagent has simple synthesis, stable structure and high activity. On this basis, it is desirable to synthesize more challenging nucleophiles. Such agents develop less and are more difficult to produce than electrophiles. And because of the strong electronegativity of oxygen atoms and trifluoromethyl groups, the electron distribution is more prone to generate sulfur positive ions, so that sulfoxide anions alone are difficult to exist, are not easy to generate and are unstable, and therefore, few researches are conducted. To overcome this difficulty, it is desirable to design the reagent structure so that the highly active trifluoromethyl sulfoxide nucleophile can be generated in situ during the reaction.
The corresponding sulfoxide trifluoromethylated aryl groups can only be obtained by looking for reactions with non-fluorine containing sulfoxide groups, such as methyl sulfoxide with diaryliodonium salts, but this requires a strong base to do (Yu, h.; li, z.; bolm, c.org. lett.2018, 20, 7104-7106 and Wang, l.; chen, m.j.; zhang, j.l. org. chem. Front.2019,6, 32-35.).
In recent years, the development of trifluoromethylthio reagent has been more advanced than that of trifluoromethylsulfoxide reagent. Most of these reagents are linked to a molecule structure that is easily removed, such as a nitrogen atom or an oxygen atom, by a trifluoromethylthio group. In 2020, the Procter group developed a novel trifluoromethyl sulfoxide reagent, which was different from other reagents in the method of forming a trifluoromethylthio group by combining a trifluoromethyl group with a sulfoxide group. However, the low temperatures and long reaction times required for the present studies of the trifluoromethylthiolation reaction have resulted in severe reaction conditions (D.Wang, C.G.Carlton, M.Tayu, J.J.W.McDouall, G.J.P.Perry, D.J.Procter, angew.Chem.Int.Ed.2020, 59, 15918.). These agents all have good activity, but they all only undergo trifluoromethylthiolation. The applicant has combined the two to develop a fluorine-containing sulfoxide reagent capable of performing difunctional.
According to the preparation method, based on the trifluoromethyl sulfoxide reagent with the structure, under the condition of alkali promotion, reverse Michael addition occurs, so that alkali attacks hydrogen on beta position, after electron transfer, a byproduct of the reverse Michael addition can be removed, the olefin is stable in property and easy to leave, the reaction is facilitated, and finally, a nucleophilic reagent can attack the nucleophilic reagent to obtain a corresponding trifluoromethyl sulfoxide compound. In contrast, when used as an electrophile, the present application utilizes trifluoromethanesulfonic anhydride to activate a reactant to form an electrophilic intermediate. The intermediate is then reacted with an arene-interrupted pummers to form a sulfur salt. Finally, selectively removing leaving groups through alkali to form electrophiles, and then obtaining the trifluoromethylthio compound under the selective attack of different nucleophiles.
Therefore, the cheap and easily available methyl 3-bromopropionate is used as a starting material, a new synthesis method of a double-functionalization reagent with adjustable structure and controllable activity is developed, and meanwhile, the compound is researched and developed, and has important significance in high-efficiency direct introduction of trifluoromethyl thio or trifluoromethyl sulfoxide groups, and experiment conditions are simple and easy to operate.
Disclosure of Invention
The invention aims to provide a method for synthesizing a trifluoromethyl sulfoxide reagent.
The method of the invention is as follows:
adding sodium paratoluenesulfonate into a container in the step (1), adding bromide and a first organic solvent, and reacting for 12-24 hours at normal temperature under the protection of nitrogen or argon to obtain sulfonate compound; in the reaction system, the molar ratio of the sodium paratoluenesulfonate to the sodium benzenesulfonate is 1:1, and 1-10 liters of the first organic solvent is added per mole of sodium benzenesulfonate. The structural formula of the sodium p-toluenesulfonate isThe bromide has the structural formula->The reaction formula is as follows:
the bromide is 3-methyl bromopropionate, and the structural formula isOr ethyl 3-bromopropionate having the structural formula +.>Or tert-butyl 3-bromopropionate of the formula +.>Or isopropyl 3-bromopropionate having the formula +.>Or 3-bromopropionitrile of the formula +.>
The first organic solvent is N, N-dimethylformamide solvent DMF or N, N-dimethylacetamide solvent DMAc, and the concentration is 0.1-1.0M.
Adding a sulfonate compound into a container in the step (2), and then adding sodium acetate and trifluoromethyl trimethylsilane TMSCF 3 And a second organic solvent, and reacting for 6-18 hours at the temperature of minus 10 ℃ to minus 30 ℃ under the protection of nitrogen or argon to obtain trifluoro methyl sulfide substances; in the reaction system, sulfonate compound, sodium acetate, trifluoromethyl trimethylsilane TMSCF 3 The molar ratio of (2) is 1:3:3, and 1-10 liters of the second organic solvent is added per mole of the sulfonate compound. The reaction formula is as follows:
the volume ratio of the second organic solvent is 0.5-1.2: 1 and redistilled dimethyl sulfoxide DMSO at a concentration of 0.1-1.0M.
Adding a trifluoro methyl sulfide substance, m-chloroperoxybenzoic acid and a third organic solvent into a container, and reacting for 10-16 hours at normal temperature under the protection of nitrogen or argon to obtain a trifluoro methyl sulfoxide reagent, wherein the structure is thatWherein EWG is COOMe, COOEt, COO i Pr、COO t Bu, CN. In the reaction system, the molar ratio of the m-chloroperoxybenzoic acid to the trifluormethyl sulfide is 1:1, and 1-10 liters of the third organic solvent is added per mole of trifluormethyl sulfide. The reaction formula is as follows:
the concentration of the third organic solvent is 0.1-1.0M for the redistilled dichloromethane DCM.
It is another object of the present invention to provide the use of the above process for preparing a trifluoromethyl sulfoxide reagent as a trifluoromethyl sulfoxide reagent and a trifluoromethyl sulfide reagent, wherein the substrate is a diaryliodonium derivative, a 1, 1-stilbene derivative or an electron-rich aromatic hydrocarbon.
The diaryl iodized salt derivative is diphenyl trifluoro methyl sulfonate iodized salt derivative, and the structural formula isSubstituent R 1 And R is R 2 In the same case, the catalyst is one of hydrogen, p-bromine, p-chlorine, p-methoxy, o-methyl, o-chlorine and m-methyl; substituent R 1 And R is R 2 When not identical, substituent R 1 Is hydrogen, substituent R 2 Is mesityl or o-methyl.
The structure of the 1, 1-stilbene derivative is thatSubstituent R 3 And R is R 4 In the same case, p-fluoro, p-bromo, p-chloro, p-methylAn oxy group, one of a para-methyl group; substituent R 3 And R is R 4 When not identical, substituent R 3 Is hydrogen, substituent R 4 Is one of p-methoxy, p-phenyl, 3, 4-dimethyl, p-chloro, m-chloro and o-methyl.
The structure of the electron-rich aromatic hydrocarbon isThe substituent R is one of methoxy, o-dimethoxy, m-dimethoxy, mesityl, 1-chloro-2-methoxy, 1-bromo-2-methoxy, 1,2, 3-trimethoxy and 1, 2-methylenedioxy; the main structure of the arene is benzene or naphthalene.
The method overcomes the defects of expensive initial raw materials and complicated reagent synthesis in the prior method, uses the bromide which is cheap and easy to obtain as an initial material to prepare the trifluoromethyl sulfoxide reagent, and further realizes the regulation and control of the reaction activity of the reagent by adjusting different groups in the reagent skeleton. Meanwhile, the reagent can perform a difunctional reaction, is used as a nucleophilic reagent to react with diaryl iodized salt derivatives, and is used as an electrophilic reagent to react with 1, 1-stilbene derivatives and electron-rich aromatic hydrocarbon.
The invention has the following beneficial effects:
(1) The cost is low, and the trifluoromethyl sulfoxide reagent can be obtained through simple three-step reaction from bromide without complicated column chromatographic separation.
(2) The trifluoromethyl sulfoxide reagent with different leaving groups introduced into the reagent skeleton is prepared, and the structure is adjustable and the activity is controllable.
(3) The reaction of the trifluoromethyl sulfoxide reagent and diaryl iodized salt realizes C (sp 2 )-S(O)CF 3 Constructing chemical bonds; the trifluoromethyl sulfoxide reagent reacts with the 1, 1-stilbene derivative and the electron-rich aromatic hydrocarbon to realize C (sp 2 )-SCF 3 Construction of chemical bonds.
Detailed Description
The present invention is further described below with reference to specific examples, which are intended to be illustrative only and not to be limiting of the scope of the present invention, since modifications of the invention in various equivalent forms will occur to those skilled in the art upon reading the present invention, which are within the scope of the claims appended hereto.
In the examples of the present invention, the normal temperature is 20 to 25℃unless otherwise specified.
Firstly, preparing a sulfonate compound by adopting the existing method, then preparing a trifluoro methyl sulfide substance, and finally synthesizing a trifluoro methyl sulfoxide reagent, wherein the structure is as follows
Preparation example 1.
The specific operation steps are as follows: firstly, a 200mL round bottom flask which is baked in an oven at 100 ℃ for 2 hours is cooled, then a magnet is placed, air is pumped three times under the atmosphere of nitrogen or argon, 50mmol of 4-toluene sodium thiosulfate is added, 50mmol of methyl 3-bromopropionate and 1.0M of super-dry N, N-dimethylformamide solvent are added, stirring reaction is carried out for 24 hours at normal temperature, the reaction liquid is poured into 50mL of water, an organic phase is extracted by ethyl acetate (50 mL multiplied by 3), the combined organic phases are back extracted by water for 5 times, then the mixture is dried by anhydrous sodium sulfate for 15 minutes, then a sand core funnel is used for filtering, the organic phases are combined, and the solvent is removed by spin evaporation. Finally, the crude product was recrystallized from methylene chloride and petroleum ether to give the desired product 1a as a white solid in 84% isolated yield. 1 H NMR(400MHz，CDCl 3 )δ7.81(2H，d，J＝8.3Hz)，7.35(2H，d，J＝8.1Hz)，3.67(3H，s)，3.18(2H，t，J＝7.0Hz)，2.73(2H，t，J＝7.0Hz)，2.45(3H，s)；
Then a 200mL round bottom flask with a branch port is taken and baked in a baking oven at 100 ℃ for 2 hours, cooled, then magnetons are put in, air is pumped three times under the atmosphere of nitrogen or argon, 40mmol of 1a and 120mmol of NaOAc are mixed at-20 ℃ in a volume ratio of 0.1M of 1:2 re-distilled dichloromethane and dimethyl sulfoxide, and 120mmol of trimethyl trifluoromethyl silicon was added dropwise thereto, after reacting for 12 hours, 50mL of saline was poured into the reaction solution, the organic phase was extracted with dichloromethane (50 ml×3), the combined organic phases were back-extracted 5 times with saturated saline, then dried with anhydrous sodium sulfate for 15 minutes, then filtered with a sand core funnel, the organic phases were combined, and the solvent was removed by spin evaporation to obtain a crude product 2a.
Finally, a 100mL round bottom flask baked for 2 hours in a 100 ℃ oven is taken, a magnet is placed after cooling, air is pumped three times under the atmosphere of nitrogen or argon, 40mmol of M-chloroperoxybenzoic acid is added into 0.2M dichloromethane, the crude product 2a is directly added after dissolution, and the reaction is carried out for 12 hours at normal temperature. After the reaction was completed, an appropriate amount of saturated sodium carbonate solution was poured into the reaction solution, then the organic phase was extracted with methylene chloride (50 ml×3), the combined organic phases were back-extracted 3 times with saturated brine, then dried over anhydrous sodium sulfate for 15min, then filtered with a sand core funnel, and the organic phases were combined and the solvent was removed by rotary evaporation to obtain a crude product. The crude product was distilled under reduced pressure to give purer 3a in 65% yield. The 3a can also be subjected to column chromatography separation to further purify the 3a. 1 H NMR(400MHz，CDCl 3 )δ3.75(3H，s)，3.28–3.24(2H，m)，3.03–2.79(m，2H)。
Preparation example 2.
The specific operation steps are as follows: firstly, a 200mL round bottom flask which is baked in an oven at 150 ℃ for 1 hour is cooled, then a magnet is placed, air is pumped three times under the atmosphere of nitrogen or argon, 15mmol of 4-toluene sodium thiosulfate is added, 15mmol of ethyl 3-bromopropionate and 0.5M super-dry N, N-dimethylformamide solvent are added, stirring reaction is carried out for 12 hours at normal temperature, reaction liquid is poured into 30mL of water, an organic phase is extracted by ethyl acetate (30 mL multiplied by 3), the combined organic phases are back extracted by water for 3 times, then dried by anhydrous sodium sulfate for 15 minutes, then a sand core funnel is used for filtering, the organic phases are combined, and the solvent is removed by spin evaporation. The final crude product can be separated by silica gel column chromatography by 78%Yield was obtained as white solid target product 1b. 1 H NMR(400MHz，CDCl 3 )δ7.81(2H，d，J＝8.3Hz)，7.35(2H，d，J＝8.3Hz)，4.13(2H，q，J＝7.1Hz)，3.18(2H，t，J＝7.0Hz)，2.71(2H，t，J＝7.0Hz)，2.45(3H，s)，1.24(3H，t，J＝7.1Hz)。
Then a 100mL round bottom flask with a branch port is taken and baked in an oven at 150 ℃ for 1 hour, a magnet is placed after cooling, air is pumped three times under the atmosphere of nitrogen or argon, 10mmol of 1b and 30mmol of NaOAc are mixed in 4-5 volume percent of 0.5M methylene dichloride and dimethyl sulfoxide at-10 ℃, 30mmol of trimethyl trifluoromethyl silicon is added dropwise into the mixture, 50mL of saline is poured into the reaction solution after reaction for 6 hours, the organic phase is extracted by methylene dichloride (50 mL multiplied by 3), the combined organic phase is back extracted by saturated saline for 5 times, then dried by anhydrous sodium sulfate for 15 minutes, then a sand core funnel is used for filtering, the organic phase is combined, and the solvent is removed by rotary evaporation, thus obtaining a crude product 2b.
Finally, a 100mL round bottom flask baked for 1 hour in an oven at 150 ℃ is taken, a magnet is placed after cooling, air is pumped three times under the atmosphere of nitrogen or argon, 10mmol of M-chloroperoxybenzoic acid is added into 0.5M dichloromethane, the crude product 2b is directly added after dissolution, and the reaction is carried out for 10 hours at normal temperature. After the reaction was completed, an appropriate amount of saturated sodium carbonate solution was poured into the reaction solution, then the organic phase was extracted with methylene chloride (30 ml×3), the combined organic phases were back-extracted with saturated brine 3 times, then dried over anhydrous sodium sulfate for 15min, then filtered with a sand core funnel, and the organic phases were combined and the solvent was removed by rotary evaporation to obtain a crude product. Column chromatography of 3b gave a purified 3b yield of 51.6%. 1 H NMR(400MHz，CDCl 3 )δ4.20(2H，q，J＝7.1Hz)，3.29–3.24(2H，m)，3.03–2.78(2H，m)，1.28(3H，t，J＝7.1Hz)。
Preparation example 3.
The specific operation steps are as follows: 200mL of the mixture was first baked in an oven at 120℃for 1.5 hoursThe round bottom flask was cooled, put into a magneton, pumped three times under nitrogen or argon atmosphere, added with 15mmol of 4-toluene sodium thiosulfate, added with 15mmol of isopropyl 3-bromopropionate and 0.1M of super-dry N, N-dimethylacetamide solvent, stirred at normal temperature for reaction for 18h, poured into 300mL of water, the organic phase was extracted with ethyl acetate (300 mL. Times.3), the combined organic phases were back extracted with water for 3 times, then dried with anhydrous sodium sulfate for 15min, filtered with a sand core funnel, the organic phases were combined, and the solvent was removed by rotary evaporation. Finally, the crude product is subjected to silica gel column chromatography to obtain a colorless liquid target product 1c with a separation yield of 61%. 1 H NMR(400MHz，CDCl 3 )δ7.81(2H，d，J＝8.2Hz)，7.35(2H，d，J＝8.0Hz)，3.17(2H，t，J＝7.0Hz)，2.67(2H，t，J＝7.0Hz)，2.45(3H，s)，1.21(3H，s)，1.20(3H，s)。
Then a 100mL round bottom flask with a branch port is taken and baked in an oven at 120 ℃ for 1.5 hours, a magnet is placed after cooling, the air is pumped three times under the atmosphere of nitrogen or argon, 10mmol of 1c and 30mmol of NaOAc are mixed at-18 ℃ in a volume ratio of 0.8M of 1:1 re-distilled dichloromethane and dimethyl sulfoxide, and 30mmol of trimethyl trifluoromethyl silicon was added dropwise thereto, after reacting for 18 hours, 50mL of saline was poured into the reaction solution, the organic phase was extracted with dichloromethane (50 ml×3), the combined organic phases were back-extracted 5 times with saturated saline, then dried over anhydrous sodium sulfate for 15 minutes, then filtered with a sand core funnel, the organic phases were combined, and the solvent was removed by spin evaporation to obtain a crude product 2c.
Finally, a 100mL round bottom flask baked for 1.5 hours in an oven at 120 ℃ is taken, a magnet is placed after cooling, air is pumped three times under the atmosphere of nitrogen or argon, 10mmol of M-chloroperoxybenzoic acid is added into 0.1M dichloromethane, the crude product 2c is directly added after dissolution, and the reaction is carried out for 16 hours at normal temperature. After the reaction was completed, an appropriate amount of saturated sodium carbonate solution was poured into the reaction solution, then the organic phase was extracted with methylene chloride (30 ml×3), the combined organic phases were back-extracted with saturated brine 3 times, then dried over anhydrous sodium sulfate for 15min, then filtered with a sand core funnel, and the organic phases were combined and the solvent was removed by rotary evaporation to give a crude product 3c. Subjecting 3c to column chromatography to obtain purified 3c with yield of 53.2％。 1 H NMR(400MHz，CDCl 3 )δ5.06(1H，m，J＝6.2Hz)，3.28–3.23(2H，m)，3.01–2.74(2H，m)，1.27(3H，s)，1.25(3H，s)。
Preparation example 4.
The specific operation steps are as follows: firstly, a 200mL round bottom flask which is baked in an oven at 120 ℃ for 1 hour is cooled, then a magnet is placed, air is pumped three times under the atmosphere of nitrogen or argon, 20mmol of 4-toluene sodium thiosulfate salt is added, 20mmol of 3-bromopropionic acid tert-butyl ester and 0.4M super-dry N, N-dimethylformamide solvent are added, stirring reaction is carried out for 15 hours at normal temperature, reaction liquid is poured into 40mL of water, an organic phase is extracted by ethyl acetate (30 mL multiplied by 3), the combined organic phases are back extracted by water for 3 times, then dried by anhydrous sodium sulfate for 15 minutes, then a sand core funnel is used for filtering, the organic phases are combined, and the solvent is removed by spin evaporation. Finally, the crude product is subjected to silica gel column chromatography to obtain a colorless liquid target product 1d with a separation yield of 67.9%. 1 H NMR(400MHz，CDCl 3 )δ7.81(2H，d，J＝8.1Hz)，7.34(2H，d，J＝8.1Hz)，3.13(2H，t，J＝7.0Hz)，2.62(2H，t，J＝6.9Hz)，2.45(3H，s)，1.41(9H，s).
Then a 100mL round bottom flask with a branch port is taken and baked in an oven at 120 ℃ for 1 hour, cooled, then magnetons are put in, air is pumped three times under the atmosphere of nitrogen or argon, 10mmol of 1d and 30mmol of NaOAc are mixed at-30 ℃ in a volume ratio of 1.0M of 6:5 redistilled dichloromethane and dimethyl sulfoxide, and 30mmol of trimethyltrifluoromethyl silicon was added dropwise thereto, after reacting for 12 hours, 50mL of saline was poured into the reaction solution, the organic phase was extracted with dichloromethane (50 mL. Times.3), the combined organic phases were back-extracted 5 times with saturated saline, then dried over anhydrous sodium sulfate for 15 minutes, then filtered with a sand core funnel, the organic phases were combined, and the solvent was removed by rotary evaporation to give a crude product 2d.
Finally, a 100mL round bottom flask baked for 1 hour in a baking oven at 120 ℃ is taken, cooled and then put into a magnet, and the magnet is replaced under the atmosphere of nitrogen or argon10mmol of M-chloroperoxybenzoic acid was dissolved in 1.0M dichloromethane three times and the crude product was added directly to 2d and reacted at room temperature for 14h. After the reaction was completed, an appropriate amount of saturated sodium carbonate solution was poured into the reaction solution, then the organic phase was extracted with methylene chloride (30 ml×3), the combined organic phases were back-extracted with saturated brine 3 times, then dried over anhydrous sodium sulfate for 15min, then filtered with a sand core funnel, the organic phases were combined, and the solvent was removed by rotary evaporation to obtain a crude product 3d. Column chromatography separation was performed on 3d to give purified 3d in 65.9% yield. 1 H NMR(400MHz，CDCl 3 )δ3.29–3.16(2H，m)，2.94–2.71(2H，m)，1.47(9H，s)。
Preparation example 5.
The specific operation steps are as follows: firstly, a 200mL round bottom flask which is baked in an oven at 120 ℃ for 2 hours is cooled, then a magnet is placed, air is pumped three times under the atmosphere of nitrogen or argon, 20mmol of 4-toluene sodium thiosulfate is added, 20mmol of 3-bromopropionic acid propionitrile and 0.8M super-dry N, N-dimethylacetamide solvent are added, stirring reaction is carried out for 20 hours at normal temperature, reaction liquid is poured into 40mL of water, an organic phase is extracted by ethyl acetate (30 mL multiplied by 3), the combined organic phase is back extracted by water for 3 times, then the mixture is dried by anhydrous sodium sulfate for 15 minutes, then a sand core funnel is used for filtering, the organic phase is combined, and the solvent is removed by spin evaporation. Finally, the crude product is subjected to silica gel column chromatography to obtain a colorless liquid target product 1e with a separation yield of 42.2%. 1 H NMR(400MHz，CDCl 3 )δ7.82(2H，d，J＝8.3Hz)，7.38(2H，d，J＝8.0Hz)，3.18(2H，t，J＝7.2Hz)，2.81(2H，t，J＝7.2Hz)，2.47(3H，s).
Then a 100mL round bottom flask with a branch port is taken and baked in an oven at 120 ℃ for 2 hours, a magneton is placed after cooling, and air is pumped out three times under the nitrogen atmosphere, 8.4mmol of 1e and 25.2mmol of NaOAc are mixed at-25 ℃ in a volume ratio of 0.4M of 3:5 redistilled dichloromethane and dimethyl sulfoxide, and 25.2mmol of trimethyl trifluoromethyl silicon was added dropwise thereto, after reacting for 15 hours, 50mL of saline was poured into the reaction solution, the organic phase was extracted with dichloromethane (30 mL. Times.3), the combined organic phases were back-extracted 5 times with saturated saline, then dried over anhydrous sodium sulfate for 15 minutes, then filtered with a sand core funnel, the organic phases were combined, and the solvent was removed by rotary evaporation to give a crude product 2e.
Finally, a 100mL round bottom flask baked for 2 hours in a baking oven at 120 ℃ is taken, a magnet is placed after cooling, and air is pumped out three times under the nitrogen atmosphere, 8.4mmol of M-chloroperoxybenzoic acid is added into 0.8M methylene dichloride, the crude product 2e is directly added after dissolution, and the reaction is carried out for 11 hours at normal temperature. After the reaction was completed, an appropriate amount of saturated sodium carbonate solution was poured into the reaction solution, then the organic phase was extracted with methylene chloride (20 ml×3), the combined organic phases were back-extracted with saturated brine 3 times, then dried over anhydrous sodium sulfate for 15min, then filtered with a sand core funnel, and the organic phases were combined and the solvent was removed by rotary evaporation to give a crude product 3e. Column chromatography separation was performed on 3e to give purified 3e in 36.7% yield. 1 H NMR(400MHz，CDCl 3 )δ3.40–3.20(2H，m)，3.08–2.84(2H，m)。
The use of trifluoromethyl sulfoxides prepared according to the methods of examples 1-5 as reagents for trifluoromethyl sulfoxides and trifluormethylation using diaryl iodide derivatives or 1, 1-stilbene derivatives or electron rich aromatic hydrocarbons as substrates.
Application example 1.
The specific operation steps are as follows: 25.0mL of the tube was sealed after being baked in an oven at 120℃for 1.5 hours, the tube was put into a magnet and cooled, the gas was evacuated three times under a nitrogen atmosphere, 0.550mmol of diphenyl trifluoromethanesulfonic acid iodide salt and 1.50mmol of cesium carbonate were added, the gas was evacuated three times under a nitrogen or argon atmosphere, 5.00mL of ultra-dry 1, 4-dioxane and 0.500mmol of the reagent were added, the reaction solution was stirred at room temperature for reaction for 12 hours, the reaction solution was poured into 20mL of saturated saline, the aqueous phase was extracted with methylene chloride (20 mL. Times.3), the combined organic phase was back extracted with saturated saline for 5 times, then dried with anhydrous sodium sulfate for 15 minutes, then filtered with a sand core funnel, the organic phase was combined, and the solvent was removed by spin evaporation. Finally, 0.500mmol of benzotrifluoride is added to the crude product, and the reaction yield is 85% as proved by fluorine spectrum yield, and the product can be proved by GC-MS.
Application example 2.
The specific operation steps are as follows: 25.0mL of the reaction solution is sealed after being baked in an oven at 120 ℃ for 1 hour, the reaction solution is cooled and then put into a magnet, the mixture is pumped out and discharged three times under the nitrogen atmosphere, 0.550mmol of p-chlorodiphenyl trifluoro methanesulfonate iodized salt and 1.50mmol of cesium carbonate are added, the mixture is pumped out and discharged three times under the nitrogen or argon atmosphere, 5.00mL of ultra-dry 1, 4-dioxane and 0.500mmol of reagent are added, the reaction solution is stirred and reacted for 12 hours at normal temperature, the reaction solution is poured into 20mL of saturated saline solution, the aqueous phase is extracted with dichloromethane (20 mL multiplied by 3), the combined organic phase is back extracted with saturated saline solution for 5 times, then dried with anhydrous sodium sulfate for 15 minutes, then a sand core funnel is used for filtering, the organic phase is combined, the solvent is removed by spin evaporation, and finally the crude product can be separated into a colorless liquid target product with a separation yield of 81 percent through silica gel column chromatography. 1 H NMR(500MHz，CDCl 3 )δ7.73(2H，d，J＝8.2Hz)，7.59(2H，d，J＝8.6Hz)； 13 C NMR(101MHz，CDCl 3 )δ140.4，134.1，130.1，127.4，124.6(q，J C-F ＝336.5Hz)； 19 FNMR(471MHz，CDCl 3 )δ–74.9。
Application example 3.
The specific operation steps are as follows: sealing a tube with 25.0mL which has been baked in an oven at 120deg.C for 2 hours, cooling, adding a magnet, pumping out air three times under nitrogen atmosphere, adding 0.550mmol of p-bromodiphenyl trifluoro methanesulfonate iodide and 1.50mmol of cesium carbonate, pumping out air three times under nitrogen or argon atmosphere, adding 5.00mL of ultra-dry 1,4Dioxa-hexacyclic ring and 0.500mmol of reagent are reacted for 12h under stirring at normal temperature, the reaction solution is poured into 20mL of saturated saline, the aqueous phase is extracted with dichloromethane (20 mL. Times.3), the combined organic phases are back extracted with saturated saline for 5 times, then dried with anhydrous sodium sulfate for 15min, filtered with a sand core funnel, the organic phases are combined, the solvent is removed by rotary evaporation, and finally the crude product can be obtained as a colorless liquid target product with a separation yield of 79% by silica gel column chromatography. 1 H NMR(400MHz，CDCl 3 )δ7.75(2H，d，J＝8.6Hz)，7.65(2H，d，J＝8.4Hz)； 13 C NMR(101MHz，CDCl 3 )δ134.7，133.0，128.8，127.4，124.4(q，J C-F ＝336.5Hz)； 19 F NMR(471MHz，CDCl 3 )δ–74.4。
Application example 4.
The specific operation steps are as follows: 25.0mL of the reaction solution is sealed after being baked in an oven at 100 ℃ for 2 hours, the reaction solution is cooled and then put into a magnet, the mixture is pumped out for three times under the nitrogen atmosphere, 0.550mmol of o-methyl diphenyl trifluoro methanesulfonate iodized salt and 1.50mmol of cesium carbonate are added, the mixture is pumped out for three times under the nitrogen or argon atmosphere, 5.00mL of ultra-dry 1, 4-dioxane and 0.500mmol of reagent are added, the reaction solution is stirred and reacted for 12 hours at normal temperature, the reaction solution is poured into 20mL of saturated saline, the water phase is extracted with dichloromethane (20 mL multiplied by 3), the combined organic phase is back extracted with saturated saline for 5 times, then dried with anhydrous sodium sulfate for 15 minutes, then a sand core funnel is used for filtering, the organic phase is combined, the solvent is removed by spin evaporation, and finally the crude product can be separated into a colorless liquid target product with a separation yield of 78 percent through silica gel column chromatography. 1 H NMR(400MHz，CDCl 3 )δ8.00(1H，d，J＝7.7Hz)，7.54–7.42(2H，m)，7.29(1H，d，J＝7.5Hz)，2.45(3H，s)； 13 C NMR(101MHz，CDCl 3 )δ138.0，134.2，133.2，131.4，127.3，125.9，125.3(q，J C-F ＝337.1Hz)，18.3； 19 F NMR(471MHz，CDCl 3 )δ–73.6。
Application example 5.
The specific operation steps are as follows: 25.0mL of the reaction solution is sealed after being baked in an oven at 100 ℃ for 1 hour, the reaction solution is cooled and then put into a magnet, the mixture is pumped out for three times under the nitrogen atmosphere, 0.550mmol of o-methoxy diphenyl trifluoro methanesulfonate iodized salt and 1.50mmol of cesium carbonate are added, the mixture is pumped out for three times under the nitrogen or argon atmosphere, 5.00mL of ultra-dry 1, 4-dioxane and 0.500mmol of reagent are added, the reaction solution is stirred and reacted for 12 hours at normal temperature, the reaction solution is poured into 20mL of saturated saline, the water phase is extracted with dichloromethane (20 mL multiplied by 3), the combined organic phase is back extracted with saturated saline for 5 times, then dried with anhydrous sodium sulfate for 15 minutes, then a sand core funnel is used for filtering, the organic phase is combined, the solvent is removed by spin evaporation, and finally the crude product can be separated into a colorless liquid target product with 85 percent separation yield through silica gel column chromatography. IR (thin film) 2874 (w), 2756 (w), 1590 (m), 1479(s), 1278(s), 1247 (m), 1173(s), 1130(s), 1075(s), 1049(s), 1016(s), 795 (m), 755(s); 1 H NMR(400MHz，CDCl 3 )δ7.89(1H，d，J＝9.1Hz)，7.19(1H，dd，J＝8.5，8.9Hz)，7.19(1H，dd，J＝7.8，7.4Hz)，6.99(1H，d，J＝8.3Hz)，3.88(3H，s)； 13 C NMR(101MHz，CDCl 3 )δ157.8，134.9，126.8，125.2(q，J C-F ＝340.2Hz)，123.5，121.8，111.5，56.1； 19 F NMR(471MHz，CDCl 3 )δ–74.0；H RMS(ESI+)[M+H]+calc’dforC 8 H 7 F 3 O 2 SNa:247.0011，found:247.0014。
application example 6.
The specific operation steps are as follows: sealing the tube with 25.0mL which has been baked in an oven at 100deg.C for 1.5 hours, cooling, adding the magnet, pumping out the gas three times under nitrogen atmosphere, adding 0.550mmol of p-methoxy diphenyl trifluoro methanesulfonic acid iodine Salt and 1.50mmol of cesium carbonate are pumped three times under nitrogen or argon atmosphere, 5.00mL of ultra-dry 1, 4-dioxane and 0.500mmol of reagent are added, stirring reaction is carried out for 12h at normal temperature, the reaction solution is poured into 20mL of saturated saline, the aqueous phase is extracted with dichloromethane (20 mL multiplied by 3), the combined organic phases are back extracted with saturated saline for 5 times, then dried with anhydrous sodium sulfate for 15min, then filtered by a sand core funnel, the organic phases are combined, the solvent is removed by rotary evaporation, and finally the crude product can be obtained as a colorless liquid target product with a separation yield of 95% through silica gel column chromatography. 1 H NMR(400MHz，CDCl 3 )δ7.68(2H，d，J＝8.7Hz)，7.04(2H，d，J＝8.9Hz)，3.82(3H，s)； 13 C NMR(101MHz，CDCl 3 )δ164.0，128.1，126.1，124.7(q，J C-F ＝336.0Hz)，115.2，55.6； 19 F NMR(471MHz，CDCl 3 )δ–75.4。
Application example 7.
The specific operation steps are as follows: 25.0mL of the reaction solution is sealed after being baked in an oven at 150 ℃ for 1 hour, the reaction solution is cooled and then put into a magnet, the mixture is pumped out for three times under the nitrogen atmosphere, 0.550mmol of o-chlorodiphenyl trifluoro methanesulfonate iodized salt and 1.50mmol of cesium carbonate are added, the mixture is pumped out for three times under the nitrogen or argon atmosphere, 5.00mL of ultra-dry 1, 4-dioxane and 0.500mmol of reagent are added, the reaction solution is stirred and reacted for 12 hours at normal temperature, the reaction solution is poured into 20mL of saturated saline, the water phase is extracted with dichloromethane (20 mL multiplied by 3), the combined organic phase is back extracted with saturated saline for 5 times, then dried with anhydrous sodium sulfate for 15 minutes, then a sand core funnel is used for filtering, the organic phase is combined, the solvent is removed by spin evaporation, and finally the crude product can be separated into a colorless liquid target product with 58% of separation yield through silica gel column chromatography. 1 H NMR(400MHz，CDCl 3 )δ8.06–7.99(1H，m)，7.61–7.57(2H，m)，7.52–7.46(1H，m)； 13 C NMR(101MHz，CDCl 3 )δ134.7，134.6，133.4，130.5，128.2，127.9，125.2(q，J C - F ＝339.4Hz)； 19 F NMR(471MHz，CDCl 3 )δ–72.7。
Application example 8.
The specific operation steps are as follows: 25.0mL of the reaction solution is sealed after being baked in an oven at 150 ℃ for 2 hours, the reaction solution is cooled and then put into a magnet, the mixture is pumped out for three times under the nitrogen atmosphere, 0.550mmol of m-methyl diphenyl trifluoro methanesulfonate iodized salt and 1.50mmol of cesium carbonate are added, the mixture is pumped out for three times under the nitrogen or argon atmosphere, 5.00mL of ultra-dry 1, 4-dioxane and 0.500mmol of reagent are added, the reaction solution is stirred and reacted for 12 hours at normal temperature, the reaction solution is poured into 20mL of saturated saline, the water phase is extracted with dichloromethane (20 mL multiplied by 3), the combined organic phase is back extracted with saturated saline for 5 times, then dried with anhydrous sodium sulfate for 15 minutes, then a sand core funnel is used for filtering, the organic phase is combined, the solvent is removed by spin evaporation, and finally the crude product can be separated into a colorless liquid target product with 96% of separation yield through silica gel column chromatography. 1 H NMR(400MHz，CDCl 3 )δ7.60(1H，s)，7.56(1H，d，J＝7.0Hz)，7.56(2H，m)，2.44(3H，s)； 13 C NMR(101MHz，CDCl 3 )δ140.1，135.5，134.5，129.5，126.1，124.8(q，J C-F ＝336.3Hz)，123.2，21.4； 19 F NMR(471MHz，CDCl 3 )δ–74.。
Application example 9.
The specific operation steps are as follows: sealing a tube with 25.0mL which has been baked in an oven at 150 ℃ for 1.5 hours, cooling, putting the tube into a magnet, pumping out the gas three times under nitrogen atmosphere, adding 0.550mmol of 1-o-methyldiphenyl-1-phenyl trifluoro-methanesulfonate iodine salt and 1.50mmol of cesium carbonate, pumping out the gas three times under nitrogen or argon atmosphere, adding 5.00mL of ultra-dry 1, 4-dioxane and 0.500mmol of reagent, stirring the mixture at normal temperature for reacting for 12 hours, pouring the reaction solution into 20mL of saturated saline, and adding water The phases were extracted with dichloromethane (20 ml×3), the combined organic phases were back-extracted 5 times with saturated brine, then dried over anhydrous sodium sulfate for 15min, then filtered with a sand core funnel, the organic phases were combined, the solvent was removed by rotary evaporation, and finally the crude product was purified by silica gel column chromatography to give the desired product as a colorless liquid in 68.4% isolation yield. 1 H NMR(500MHz，CDCl 3 )δ8.00(2H，d，J＝7.8Hz)，7.51(1H，dd，J＝6.2，7.4Hz)，7.46(1H，dd，J＝7.3，7.4Hz)，7.29(1H，d，J＝7.5Hz)，2.46(3H，s)； 13 C NMR(101MHz，CDCl 3 )δ138.0，134.2，133.3，131.4，127.4，125.9，125.3(q，J C-F ＝337.1Hz)，18.3； 19 F NMR(471MHz，CDCl 3 )δ–73.6。
Application example 10.
The specific operation steps are as follows: 25.0mL of the mixture is sealed after being baked in an oven at 110 ℃ for 1 hour, the mixture is cooled and then put into a magnet, the mixture is pumped and deflated three times under the nitrogen atmosphere, 0.550mmol of 1-mesityl-1-phenyl trifluoro methanesulfonate and 1.50mmol of cesium carbonate are added, the mixture is pumped and deflated three times under the nitrogen or argon atmosphere, 5.00mL of ultra-dry 1, 4-dioxane and 0.500mmol of reagent are added, the mixture is stirred and reacted for 12 hours at normal temperature, the reaction solution is poured into 20mL of saturated saline, the aqueous phase is extracted with dichloromethane (20 mL multiplied by 3), the combined organic phase is back extracted with saturated saline for 5 times, then dried with anhydrous sodium sulfate for 15 minutes, then a sand core funnel is used for filtering, the organic phase is combined, the solvent is removed by rotary evaporation, and finally the crude product can be separated into a colorless liquid target product with 91 percent of separation yield through silica gel column chromatography. 1 H NMR(400MHz，CDCl 3 )δ6.92(2H，s)，2.54(6H，bs)，2.31(3H，s)； 13 C NMR(101MHz，CDCl 3 )δ143.7，131.6，128.3，126.2(q，J C-F ＝262.6Hz)，121.6，21.2，19.2； 19 F NMR(471MHz，CDCl 3 )δ–70.1。
Application example 11.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in an oven at 110 ℃ for 2 hours is cooled, then a magneton is placed in the reaction tube, and under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of 1, 1-stilbene and 0.750mmol of reagent are added in the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred at normal temperature for 1 hour, then 1.50mmol of cesium carbonate is added, and the reaction tube is reacted at normal temperature for 6 hours. After the completion of the reaction, 20mL of saturated brine and 20mL of methylene chloride were added to the reaction mixture, the aqueous phase was extracted with methylene chloride (20 mL. Times.3), the combined organic phases were back-extracted 3 times with saturated brine, then dried over anhydrous sodium sulfate for 15min, then filtered through a sand core funnel, and the combined organic phases were spin-distilled to remove the solvent. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 83%. 1 H NMR(400MHz，CDCl 3 )δ7.51–7.44(3H，m)，7.38(3H，d，J＝4.4Hz)，7.31(4H，dd，J＝7.1，6.8Hz)，6.79(1H，s). 13 C NMR(101MHz，CDCl 3 )δ146.5，140.4，138.2，130.0(q，J C-F ＝308.9Hz)，129.5，128.8，128.7，128.6，128.5，127.5，112.3(q，J C-F ＝3.3Hz). 19 F NMR(471MHz，CDCl 3 )δ–42.5。
Application example 12.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked for 1.5 hours in a 110 ℃ oven is cooled, then magnetons are placed in the reaction tube, the reaction tube is deflated three times under a nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of 1, 1-p-chlorostilbene and 0.750mmol of reagent are added under a nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred at normal temperature for reaction for 1 hour, then 1.50mmol of cesium carbonate is added, and the reaction tube is reacted at normal temperature for 6 hours. After the reaction is finished To the reaction solution were added 20mL of saturated brine and 20mL of dichloromethane, the aqueous phase was extracted with dichloromethane (20 ml×3), and the combined organic phases were back-extracted 3 times with saturated brine, followed by drying over anhydrous sodium sulfate for 15min, then filtration over a sand core funnel, the combined organic phases were filtered, and the solvent was removed by rotary evaporation. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 78%. 1 H NMR(400MHz，CDCl 3 )δ7.42(2H，d，J＝8.4Hz)，7.31(2H，d，J＝8.5Hz)，7.18(4H，d，J＝8.4Hz)，6.73(1H，s). 13 C NMR(101MHz，CDCl 3 )δ144.1，138.5，136.1，134.9，134.7，130.8，129.7(q，J C-F ＝309.2Hz)，129.2，128.9，128.7，113.4(q，J C-F ＝113.4Hz). 19 F NMR(471MHz，CDCl 3 )δ–42.6。
Application example 13.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in an oven at 130 ℃ for 2 hours is cooled, then a magneton is placed in the reaction tube, the reaction tube is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of 1, 1-p-methyl stilbene and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred and reacted for 1 hour at normal temperature, then 1.50mmol of cesium carbonate is added, and the reaction tube is reacted for 6 hours at normal temperature. After the completion of the reaction, 20mL of saturated brine and 20mL of methylene chloride were added to the reaction mixture, the aqueous phase was extracted with methylene chloride (20 mL. Times.3), the combined organic phases were back-extracted 3 times with saturated brine, then dried over anhydrous sodium sulfate for 15min, then filtered through a sand core funnel, and the combined organic phases were spin-distilled to remove the solvent. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 90%. 1 H NMR(500MHz，CDCl 3 )δ7.28(2H，d，J＝7.8Hz)，7.24–7.13(6H，m)，6.69(1H，s)，2.46(3H，s)，2.41(3H，s). 13 C NMR(101MHz，CDCl 3 )δ146.8，138.6，138.4，137.9，135.4，130.0(q，J C-F ＝309.0Hz)，129.4，129.3，127.5，110.7(q，J C-F ＝3.3Hz)，21.5，21.3. 19 F NMR(471MHz，CDCl 3 )δ–42.7。
Application example 14.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in a baking oven at 130 ℃ for 1 hour is cooled, then a magneton is placed in the reaction tube, the reaction tube is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of 1, 1-p-bromostilbene and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred and reacted for 1 hour at normal temperature, then 1.50mmol of cesium carbonate is added, and the reaction tube is reacted for 6 hours at normal temperature. After the completion of the reaction, 20mL of saturated brine and 20mL of methylene chloride were added to the reaction mixture, the aqueous phase was extracted with methylene chloride (20 mL. Times.3), the combined organic phases were back-extracted 3 times with saturated brine, then dried over anhydrous sodium sulfate for 15min, then filtered through a sand core funnel, and the combined organic phases were spin-distilled to remove the solvent. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 76%. 1 H NMR(400MHz，CDCl 3 )δ7.58(2H，d，J＝8.4Hz)，7.46(2H，d，J＝8.5Hz)，7.11(4H，d，J＝8.3Hz)，6.73(1H，s). 13 C NMR(101MHz，CDCl 3 )δ144.1，138.8，136.4，132.2，131.9，131.1，129.6(q，J C - F ＝309.3Hz)，129.0，123.2，123.0，113.5(q，J C-F ＝3.4Hz). 19 F NMR(471MHz，CDCl 3 )δ–42.3。
Application example 15.
The specific operation steps are as follows: drying in a 130 ℃ oven for 1.5 hours to obtain 25.0mL branch reaction tube, cooling, adding a magnet, and pumping out the gas three times under nitrogen atmosphere2.50mL of carbon tetrachloride, 0.500mmol of 1, 1-p-fluorostilbene and 0.750mmol of reagent are added under the atmosphere of nitrogen or argon, then 0.750mmol of trifluoromethanesulfonic anhydride is added dropwise, the mixture is stirred at normal temperature for reaction for 1h, then 1.50mmol of cesium carbonate is added, and the mixture is reacted at normal temperature for 6 h. After the completion of the reaction, 20mL of saturated brine and 20mL of methylene chloride were added to the reaction mixture, the aqueous phase was extracted with methylene chloride (20 mL. Times.3), the combined organic phases were back-extracted 3 times with saturated brine, then dried over anhydrous sodium sulfate for 15min, then filtered through a sand core funnel, and the combined organic phases were spin-distilled to remove the solvent. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 90%. 1 H NMR(400MHz，CDCl 3 )δ7.21–7.17(4H，m)，7.10(2H，dd，J＝8.6，8.7Hz)，7.00(2H，dd，J＝8.5，8.7Hz)，6.64(1H，s). 13 C NMR(101MHz，CDCl 3 )δ164.2(d，J C-F ＝14.5Hz)，161.7(d，J C-F ＝14.4Hz)，144.8，136.5(d，J C-F ＝3.2Hz)，134.0(d，J C-F ＝3.5Hz)，131.4(d，J C-F ＝8.2Hz)，129.8(q，J C-F ＝309.1Hz)，129.3(d，J C-F ＝8.4Hz)，115.9(d，J C-F ＝31.6Hz)，115.7(d，J C-F ＝31.6Hz)，112.4. 19 F NMR(471MHz，CDCl 3 )δ–42.6，–112.1，–112.9。
Application example 16.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in an oven at 140 ℃ for 1 hour is cooled, then a magneton is placed in the reaction tube, the reaction tube is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of 1, 1-p-methoxystilbene and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred and reacted for 1 hour at normal temperature, then 1.50mmol of cesium carbonate is added, and the reaction tube is reacted for 6 hours at normal temperature. After completion of the reaction, 20mL of saturated brine and 20mL of methylene chloride were added to the reaction mixture, and methylene chloride was used as the aqueous phaseAlkane extraction (20 ml×3), combined organic phases were back extracted 3 times with saturated brine, then dried over anhydrous sodium sulfate for 15min, then filtered through a sand funnel, combined organic phases and solvent removed by rotary evaporation. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 89%. 1 H NMR(400MHz，CDCl 3 )δ7.24–7.18(4H，m)，6.98(2H，d，J＝8.5Hz)，6.88(2H，d，J＝8.7Hz)，6.57(1H，s)，3.87(3H，s)，3.84(3H，s). 13 C NMR(101MHz，CDCl 3 )δ160.0，159.8，146.8，133.4，130.9，130.6，130.0(q，J C-F ＝308.8Hz)，129.0，114.0，113.9，109.1(q，J C-F ＝3.1Hz)，55.3，55.3. 19 F NMR(471MHz，CDCl 3 )δ–43.9。
Application example 17.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in an oven at 140 ℃ for 2 hours is cooled, then a magneton is placed in the reaction tube, the reaction tube is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of 1-p-chlorophenyl-1-phenylethene and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is added dropwise, the reaction tube is stirred and reacted for 1 hour at normal temperature, then 1.50mmol of cesium carbonate is added, and the reaction tube is reacted for 6 hours at normal temperature. After the completion of the reaction, 20mL of saturated brine and 20mL of methylene chloride were added to the reaction mixture, the aqueous phase was extracted with methylene chloride (20 mL. Times.3), the combined organic phases were back-extracted 3 times with saturated brine, then dried over anhydrous sodium sulfate for 15min, then filtered through a sand core funnel, and the combined organic phases were spin-distilled to remove the solvent. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 85%. 1 H NMR(400MHz，CDCl 3 )δ7.41–7.36(2H，m)，7.31–7.25(2H，m)，7.22–7.14(5H，m)，6.68(1H，s). 13 C NMR(101MHz，CDCl 3 )δ145.1，140.1，137.8，134.7，134.5，129.9(q，J C-F ＝309.2Hz)，129.4，128.9，128.8，127.5，112.9(q，J C-F ＝3.2Hz). 19 F NMR(471MHz，CDCl 3 )δ–42.5。
Application example 18.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked for 1.5 hours in a 140 ℃ oven is cooled, then magnetons are placed in the reaction tube, the mixture is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of 1-p-methoxyphenyl-1-phenylethene and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is added dropwise, the mixture is stirred and reacted for 1 hour at normal temperature, then 1.50mmol of cesium carbonate is added, and the reaction is carried out for 6 hours at normal temperature. After the completion of the reaction, 20mL of saturated brine and 20mL of methylene chloride were added to the reaction mixture, the aqueous phase was extracted with methylene chloride (20 mL. Times.3), the combined organic phases were back-extracted 3 times with saturated brine, then dried over anhydrous sodium sulfate for 15min, then filtered through a sand core funnel, and the combined organic phases were spin-distilled to remove the solvent. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 91%. 1 H NMR(400MHz，CDCl 3 )δ7.40–7.33(2H，m)，7.29–7.13(4H，m)，6.82(2H，d，J＝8.7Hz)，6.59(1H，s)，3.76(3H，s). 13 C NMR(101MHz，CDCl 3 )δ160.0，147.0，138.4，133.1，130.9，130.0(q，J C-F ＝308.8Hz)，129.5，128.8，128.7，113.9，109.8(q，J C-F ＝3.1Hz)，55.3. 19 FNMR(471MHz，CDCl 3 )δ–42.7。
Application example 19.
The specific operation steps are as follows: the 25.0mL branch reaction tube which is baked in an oven at 120 ℃ for 80 minutes is cooled and then put into a magnet, the air is pumped out three times under the nitrogen atmosphere, and 2.50mL of tetrachloro is added under the nitrogen or argon atmosphere Carbon, 0.500mmol of 1-biphenyl-1-phenylethene and 0.750mmol of reagent are added dropwise, then 0.750mmol of trifluoromethanesulfonic anhydride is added dropwise, stirring reaction is carried out for 1h at normal temperature, then 1.50mmol of cesium carbonate is added, and reaction is carried out for 6 h at normal temperature. After the completion of the reaction, 20mL of saturated brine and 20mL of methylene chloride were added to the reaction mixture, the aqueous phase was extracted with methylene chloride (20 mL. Times.3), the combined organic phases were back-extracted 3 times with saturated brine, then dried over anhydrous sodium sulfate for 15min, then filtered through a sand core funnel, and the combined organic phases were spin-distilled to remove the solvent. Finally, the crude product can be subjected to silica gel column chromatography to obtain a white solid target product with a separation yield of 73 percent. M.p. =75.7-76.4 ℃; IR (thin film) 3003 (w), 3000 (w), 1598 (w), 1497 (w), 1432 (w), 1107(s), 758(s), 690(s). 1 H NMR(400MHz，CDCl 3 )δ7.75–7.59(4H，m)，7.56–7.31(10H，m)，6.85(1H，s). 13 C NMR(101MHz，CDCl 3 )δ146.1，142.3，140.4，139.2，138.1，130.0(q，J C-F ＝309.1Hz)，129.5，129.0，128.7，128.6，127.9，127.7，127.7，127.4，127.3，127.1，112.2(q，J C-F ＝3.4Hz). 19 F NMR(471MHz，CDCl 3 )δ–42.5。
Application example 20.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in an oven at 120 ℃ for 100 minutes is cooled, then a magneton is placed in the reaction tube, the reaction tube is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of 1-biphenyl-1-phenylethene and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred and reacted for 1 hour at normal temperature, then 1.50mmol of cesium carbonate is added, and the reaction tube is reacted for 6 hours at normal temperature. After the reaction, 20mL of saturated saline and 20mL of methylene chloride were added to the reaction mixture, the aqueous phase was extracted with methylene chloride (20 mL. Times.3), the combined organic phases were back-extracted 3 times with saturated saline, then dried over anhydrous sodium sulfate for 15min, then filtered through a sand core funnel, and the combined organic phases were removed by rotary evaporation Removing the solvent. Finally, the crude product can be subjected to silica gel column chromatography to obtain a white solid target product with a separation yield of 73 percent. IR (thin film) 3026 (w), 2925 (w), 1504 (m), 1444 (m), 1159 (m), 1103(s), 755(s), 697(s). 1 H NMR(400MHz，CDCl 3 )δ7.49–7.42(5H，m)，7.36–7.31(3H，m)，6.72(1H，s)，2.32(3H，s)，2.29(3H，s). 13 C NMR(101MHz，CDCl 3 )δ147.1，140.7，138.5，137.3，136.8，130.0(q，J C-F ＝308.8Hz)，130.0，129.5，128.7，128.5，127.6，125.1，111.0(q，J C-F ＝3.1Hz)，19.9，19.6. 19 F NMR(471MHz，CDCl 3 )δ–42.6.HRMS(APCI)[M+H]+calc’dforC17H16F3S:309.0919，found:309.0921。
Application example 21.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in an oven at 120 ℃ for 110 minutes is cooled, then a magneton is placed in the reaction tube, the reaction tube is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of 1-m-chlorophenyl-1-phenylethene and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred and reacted for 1 hour at normal temperature, then 1.50mmol of cesium carbonate is added, and the reaction tube is reacted for 6 hours at normal temperature. After the completion of the reaction, 20mL of saturated brine and 20mL of methylene chloride were added to the reaction mixture, the aqueous phase was extracted with methylene chloride (20 mL. Times.3), the combined organic phases were back-extracted 3 times with saturated brine, then dried over anhydrous sodium sulfate for 15min, then filtered through a sand core funnel, and the combined organic phases were spin-distilled to remove the solvent. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 69%. IR (thin film) 3203 (w), 1587 (w), 1103(s), 773 (m), 753 (m), 694 (m). 1 H NMR(400MHz，CDCl 3 )δ7.48–7.33(5H，m)，7.28–7.24(3H，m)，7.18–7.15(1H，m)，6.77(1H，s). 13 C NMR(101MHz，CDCl 3 )δ145.2，142.2，139.8，134.8，130.1，129.8(q，J C-F ＝309.1Hz)，129.4，129.0，128.8，127.7，127.5，125.7，113.2(q，J C-F ＝3.1Hz). 19 F NMR(471MHz，CDCl 3 )δ–42.2.
Application example 22.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in an oven at 120 ℃ for 70 minutes is cooled, then a magneton is placed in the reaction tube, the reaction tube is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of 1-o-methylphenyl-1-phenylethene and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred and reacted for 1 hour at normal temperature, then 1.50mmol of cesium carbonate is added, and the reaction tube is reacted for 6 hours at normal temperature. After the completion of the reaction, 20mL of saturated brine and 20mL of methylene chloride were added to the reaction mixture, the aqueous phase was extracted with methylene chloride (20 mL. Times.3), the combined organic phases were back-extracted 3 times with saturated brine, then dried over anhydrous sodium sulfate for 15min, then filtered through a sand core funnel, and the combined organic phases were spin-distilled to remove the solvent. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 62%. IR (thin film) 2923 (m), 2802 (m), 1572 (w), 1465 (w), 1112(s), 751 (m), 731 (m), 694 (m). 1 H NMR(400MHz，CDCl 3 )δ7.43–7.17(9H，m)，6.94(1H，s)，2.17(3H，s). 13 C NMR(101MHz，CDCl 3 )δ145.3，138.7，137.3，136.3，130.8，130.0(q，J C-F ＝309.0Hz)，129.6，128.8，128.5，128.4，126.4，126.2，113.0(q，J C-F ＝3.3Hz)； 19 F NMR(471MHz，CDCl 3 )δ–42.2.
Application example 23.
The specific operation steps are as follows: the 25.0mL branch reaction tube which is baked in an oven at 130 ℃ for 80 minutes is cooled and then putAdding magneton, pumping out and discharging gas three times under nitrogen atmosphere, adding 2.50mL of carbon tetrachloride, 0.500mmol of anisole and 0.750mmol of reagent under nitrogen or argon atmosphere, then dropwise adding 0.750mmol of trifluoromethanesulfonic anhydride, stirring and reacting for 1h at normal temperature, then adding 1.50mmol of triethylamine, and reacting for 6 h at normal temperature. After the completion of the reaction, the solvent was removed by rotary evaporation from the reaction mixture. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with 82% of separation yield. 1 H NMR(400MHz，CDCl 3 )δ7.58(2H，d，J＝8.7Hz)，6.93(2H，d，J＝8.9Hz)，3.84(3H，s). 13 C NMR(101MHz，CDCl 3 )δ162.0，138.4，129.8(q，J C-F ＝309.3Hz)，115.1，114.9(q，J C-F ＝2.0Hz)，55.5. 19 F NMR(471MHz，CDCl 3 )δ–44.0。
Application example 24.
The specific operation steps are as follows: the 25.0mL branch reaction tube which is baked in a baking oven at 130 ℃ for 70 minutes is cooled and then put into a magnet, and is pumped out and deflated three times under nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of o-bromoanisole and 0.750mmol of reagent are added under nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is added dropwise, stirring is carried out at normal temperature for reaction for 1 hour, then 1.50mmol of triethylamine is added, and reaction is carried out at normal temperature for 6 hours. After the completion of the reaction, the solvent was removed by rotary evaporation from the reaction mixture. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 63%. 1 H NMR(400MHz，CDCl 3 )δ7.83(1H，s)，7.56(1H，d，J＝8.6Hz)，6.90(1H，d，J＝8.6Hz)，3.91(3H，s). 13 C NMR(101MHz，CDCl 3 )δ158.3，141.0，137.4，129.5(q，J C-F ＝309.5Hz)，116.1(d，J C-F ＝2.1Hz)，112.3，56.4. 19 F NMR(471MHz，CDCl 3 )δ–43.6。
Application example 25.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in a baking oven at 130 ℃ for 100 minutes is cooled, then a magneton is placed in the reaction tube, the reaction tube is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of o-diphenyl methyl ether and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred and reacted for 1 hour at normal temperature, then 1.50mmol of triethylamine is added, and the reaction tube is reacted for 6 hours at normal temperature. After the completion of the reaction, the solvent was removed by rotary evaporation from the reaction mixture. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 98%. 1 H NMR(400MHz，CDCl 3 )δ7.22(1H，dd，J＝8.3，2.0Hz)，7.09(1H，d，J＝1.9Hz)，6.85(1H，d，J＝8.4Hz)，3.87(3H，s)，3.87(3H，s). 13 C NMR(101MHz，CDCl 3 )δ151.6，149.3，130.2，129.7(q，J C-F ＝309.4Hz)，118.9，114.9(q，J C-F ＝2.0Hz)，111.5，56.1，55.9. 19 F NMR(471MHz，CDCl 3 )δ–43.8。
Application example 26.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in a baking oven at 130 ℃ for 110 minutes is cooled, then a magnet is placed in the reaction tube, the reaction tube is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of piperonyl and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred and reacted for 1 hour at normal temperature, then 1.50mmol of triethylamine is added, and the reaction tube is reacted for 6 hours at normal temperature. After the completion of the reaction, the solvent was removed by rotary evaporation from the reaction mixture. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 70%. 1 H NMR(400MHz，CDCl 3 )δ7.17(1H，d，J＝9.2Hz)，7.09(1H，s)，6.83(1H，d，J＝8.1Hz)，6.04(2H，s). 13 C NMR(101MHz，CDCl 3 )δ150.5，148.4，131.7，129.7(q，J C-F ＝309.4Hz)，116.4，116.1(q，J C-F ＝2.0Hz)，109.2，102.1. 19 F NMR(471MHz，CDCl 3 )δ–43.9。
Application example 27.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in an oven at 140 ℃ for 80 minutes is cooled, then a magneton is placed in the reaction tube, the reaction tube is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of mesitylene and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred and reacted for 1 hour at normal temperature, then 1.50mmol of triethylamine is added, and the reaction tube is reacted for 6 hours at normal temperature. After the completion of the reaction, the solvent was removed by rotary evaporation from the reaction mixture. Finally, the crude product can be subjected to silica gel column chromatography to obtain a white solid target product with a separation yield of 94%. 1 H NMR(400MHz，CDCl 3 )δ6.13(2H，s)，3.84(3H，s)，3.81(3H，s). 13 C NMR(101MHz，CDCl 3 )δ164.6，163.5，129.6(q，J C-F ＝311.7Hz)，91.4(q，J C-F ＝1.8Hz)，91.0，56.2，55.4. 19 F NMR(471MHz，CDCl 3 )δ–43.5。
Application example 28.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in an oven at 140 ℃ for 70 minutes is cooled, then a magnet is placed in the reaction tube, the reaction tube is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of mesitylene and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred and reacted for 1 hour at normal temperature, then 1.50mmol of triethylamine is added, and the reaction tube is reacted for 6 hours at normal temperature. ReactionAfter completion, the solvent was removed by rotary evaporation from the reaction mixture. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 48%. 1 H NMR(400MHz，CDCl 3 )δ7.03(2H，s)，2.56(6H，s)，2.32(3H，s). 13 C NMR(101MHz，CDCl 3 )δ145.4，141.5，130.3(q，J C-F ＝310.4Hz)，129.7，120.2(d，J C-F ＝1.3Hz)，22.2，21.3. 19 F NMR(471MHz，CDCl 3 )δ–41.9。
Application example 29.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in an oven at 140 ℃ for 100 minutes is cooled, then a magnet is placed in the reaction tube, the reaction tube is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of 1, 3-diphenyl methyl ether and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred and reacted for 1 hour at normal temperature, and then 1.50mmol of triethylamine is added and reacted for 6 hours at normal temperature. After the completion of the reaction, the solvent was removed by rotary evaporation from the reaction mixture. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 98%. 1 H NMR(400MHz，CDCl 3 )δ7.52(1H，d，J＝9.2Hz)，6.52–6.50(2H，m)，3.87(3H，s)，3.82(3H，s). 13 C NMR(101MHz，CDCl 3 )δ164.1，162.2，140.3，129.7(q，J C-F ＝310.3Hz)，105.7，103.1(d，J C-F ＝1.3Hz)，99.3，56.0，55.5. 19 F NMR(471MHz，CDCl 3 )δ–43.7。
Application example 30.
The specific operation steps are as follows: 25.0mL of the branch reaction tube which is baked in an oven at 140 ℃ for 110 minutes is cooled and then put into a magnet, under the nitrogen atmosphere,the gas is pumped out three times, 2.50mL of carbon tetrachloride, 0.500mmol of 1-methoxynaphthalene and 0.750mmol of reagent are added under the atmosphere of nitrogen or argon, then 0.750mmol of trifluoromethanesulfonic anhydride is added dropwise, the mixture is stirred and reacted for 1h at normal temperature, then 1.50mmol of triethylamine is added, and the reaction is carried out for 6 h at normal temperature. After the completion of the reaction, the solvent was removed by rotary evaporation from the reaction mixture. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 78%. 1 H NMR(400MHz，CDCl 3 )δ8.46(1H，d，J＝8.5Hz)，8.29(1H，d，J＝8.4Hz)，7.85(1H，d，J＝8.1Hz)，7.62(1H，dd，J＝7.1，7.2Hz)，7.52(1H，dd，J＝8.1，7.1Hz)，6.76(1H，d，J＝8.1Hz)，3.96(3H，s). 13 C NMR(101MHz，CDCl 3 )δ158.8，139.1，136.3，129.9(q，J C-F ＝310.8Hz)，128.2，126.5，126.1，125.8，122.7，112.3(d，J C-F ＝1.5Hz)，104.0，55.8. 19 F NMR(471MHz，CDCl 3 )δ–43.2。
Application example 31.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in an oven at 110 ℃ for 80 minutes is cooled, then a magneton is placed in the reaction tube, the reaction tube is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of 2-methoxynaphthalene and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred and reacted for 1 hour at normal temperature, then 1.50mmol of triethylamine is added, and the reaction tube is reacted for 6 hours at normal temperature. After the completion of the reaction, the solvent was removed by rotary evaporation from the reaction mixture. Finally, the crude product can be subjected to silica gel column chromatography to obtain a white solid target product with a separation yield of 54%. 1 H NMR(400MHz，CDCl 3 )δ8.56(1H，d，J＝8.6Hz)，8.00(1H，d，J＝9.1Hz)，7.81(1H，d，J＝8.1Hz)，7.64(1H，dd，J＝8.2，8.2Hz)，7.44(1H，dd，J＝7.8，7.1Hz)，7.31(1H，d，J＝9.1Hz)，4.04(3H，s). 13 C NMR(101MHz，CDCl 3 )δ160.8，137.0，134.3，129.8(q，J C-F ＝311.7Hz)，128.4，128.3，125.1，124.4，113.1，105.2(d，J C-F ＝1.2Hz)，56.9. 19 F NMR(471MHz，CDCl 3 )δ–41.8。
Application example 32.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in an oven at 110 ℃ for 70 minutes is cooled, then a magnet is placed in the reaction tube, the reaction tube is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of naphthalene and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred and reacted for 1 hour at normal temperature, then 1.50mmol of triethylamine is added, and the reaction tube is reacted for 6 hours at normal temperature. After the completion of the reaction, the solvent was removed by rotary evaporation from the reaction mixture. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 64%. 1 H NMR(400MHz，CDCl 3 )δ8.58(1H，d，J＝8.5Hz)，8.01(2H，dd，J＝9.4，8.3Hz)，7.91(1H，d，J＝8.2Hz)，7.68(1H，dd，J＝8.1，7.3Hz)，7.59(1H，dd，J＝7.1，7.1Hz)，7.52(1H，dd，J＝7.6，7.9Hz). 13 C NMR(101MHz，CDCl 3 )δ138.0，135.5，134.4，132.5，130.4(q，J C-F ＝311.7Hz)，128.7，126.9，126.0，125.7，121.7(d，J C-F ＝1.6Hz). 19 F NMR(471MHz，CDCl 3 )δ–42.2。
Application example 33.
The specific operation steps are as follows: the 25.0mL branch reaction tube which is baked in a baking oven at 110 ℃ for 100 minutes is cooled and then put into a magnet, and is pumped out and discharged three times under nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of 1,2, 3-trimethoxybenzene and 0.750mmol of reagent are added under nitrogen or argon atmosphere, and then 0.750mmol of trifluoromethanesulfonic acid is added dropwiseThe anhydride was reacted at room temperature with stirring for 1 hour, and then 1.50mmol of triethylamine was added thereto, followed by reaction at room temperature for 6 hours. After the completion of the reaction, the solvent was removed by rotary evaporation from the reaction mixture. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 90%. 1 H NMR(400MHz，CDCl 3 )δ7.33(1H，d，J＝8.8Hz)，6.69(1H，d，J＝8.8Hz)，3.94(3H，s)，3.87(3H，s)，3.85(3H，s). 13 C NMR(101MHz，CDCl 3 )δ156.9，156.0，142.9，133.4，129.6(q，J C-F ＝309.9Hz)，109.3(d，J C-F ＝1.5Hz)，107.7，61.5，60.9，56.1. 19 F NMR(471MHz，CDCl 3 )δ–43.3。
Application example 34.
The specific operation steps are as follows: a25.0 mL branch reaction tube which is baked in an oven at 110 ℃ for 110 minutes is cooled, then a magneton is placed in the reaction tube, the reaction tube is pumped out and deflated three times under the nitrogen atmosphere, 2.50mL of carbon tetrachloride, 0.500mmol of o-chloroanisole and 0.750mmol of reagent are added under the nitrogen or argon atmosphere, then 0.750mmol of trifluoromethanesulfonic anhydride is dropwise added, the reaction tube is stirred and reacted for 1 hour at normal temperature, then 1.50mmol of triethylamine is added, and the reaction tube is reacted for 6 hours at normal temperature. After the completion of the reaction, the solvent was removed by rotary evaporation from the reaction mixture. Finally, the crude product can be subjected to silica gel column chromatography to obtain a colorless liquid target product with a separation yield of 79%. 1 H NMR(400MHz，CDCl 3 )δ7.67(1H，d，J＝2.1Hz)，7.53(1H，dd，J＝8.6，2.1Hz)，6.95(1H，d，J＝8.6Hz)，3.94(3H，s). 13 C NMR(101MHz，CDCl 3 )δ157.5，138.1，136.7，129.5(q，J C-F ＝309.8Hz)，123.4，115.7(d，J C-F ＝2.1Hz)，112.5，56.4. 19 F NMR(471MHz，CDCl 3 )δ–43.6。
Claims (7)
1. Application of trifluoromethyl sulfoxide reagent as trifluoromethyl sulfoxide reagent, wherein the application substrate is diaryl iodide salt derivative; the three areThe structure of the fluoromethyl sulfoxide reagent isWherein EWG is COOMe, COOEt, COO i Pr、COO t Bu or CN;
the diaryl iodized salt derivative is diphenyl trifluoro methyl sulfonate iodized salt derivative, and the structural formula isThe specific application is as follows:
2. the application of the trifluoromethyl sulfoxide reagent as a trifluoromethyl vulcanizing reagent adopts 1, 1-stilbene derivative as an application substrate; the structure of the trifluoromethyl sulfoxide reagent is that Wherein EWG is COOMe, COOEt, COO i Pr、COO t Bu or CN;
the structure of the 1, 1-stilbene derivative is thatThe specific application is as follows:
3. the use according to claim 1 or 2, wherein the method for synthesizing the trifluoromethyl sulfoxide reagent is as follows:
adding sodium paratoluenesulfonate into a container in the step (1), adding bromide and a first organic solvent, and reacting for 12-24 hours at normal temperature under the protection of nitrogen or argon to obtain sulfonate compound; in the reaction system, the molar ratio of the sodium paratoluenesulfonate to the sodium benzenesulfonate is 1:1, and 1 to 10 liters of first organic solvent with the concentration of 0.1 to 1.0M is added into each mole of sodium benzenesulfonate;
the structural formula of the sodium p-toluenesulfonate isThe bromide has the structural formula->The reaction formula is as follows:
adding a sulfonate compound into a container in the step (2), and then adding sodium acetate and trifluoromethyl trimethylsilane TMSCF 3 And a second organic solvent, and reacting for 6-18 hours at the temperature of minus 10 ℃ to minus 30 ℃ under the protection of nitrogen or argon to obtain trifluoro methyl sulfide substances; in the reaction system, sulfonate compound, sodium acetate, trifluoromethyl trimethylsilane TMSCF 3 The molar ratio of the sulfonate compound is 1:3:3, and 1 to 10 liters of second organic solvent with the concentration of 0.1 to 1.0M is added per mole of sulfonate compound; the reaction formula is as follows:
Adding a trifluoro methyl sulfide substance, m-chloroperoxybenzoic acid and a third organic solvent into a container in the step (3), and reacting at normal temperature under the protection of nitrogen or argonThe trifluoromethyl sulfoxide reagent is obtained after 10 to 16 hours and has the structure thatIn the reaction system, the molar ratio of the M-chloroperoxybenzoic acid to the trifluoro-methyl sulfide is 1:1, and 1 to 10 liters of a third organic solvent with the concentration of 0.1 to 1.0M is added into each mole of trifluoro-methyl sulfide; the reaction formula is as follows:
4. a use according to claim 3, wherein: in the step (1), the bromide is 3-bromopropionic acid methyl ester, and the structural formula isOr ethyl 3-bromopropionate having the structural formula +.>Or tert-butyl 3-bromopropionate of the formula +.>Or isopropyl 3-bromopropionate having the formula +.>Or 3-bromopropionitrile of the formula
5. A use according to claim 3, wherein: in the step (1), the first organic solvent is N, N-dimethylformamide solvent DMF or N, N-dimethylacetamide solvent DMAc.
6. A use according to claim 3, wherein: in the step (2), the volume ratio of the second organic solvent is 0.5-1.2: 1 and redistilled dimethyl sulfoxide DMSO.
7. A use according to claim 3, wherein: in step (3), the third organic solvent is redistilled dichloromethane DCM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211550947.0A CN115710206B (en) | 2022-12-05 | 2022-12-05 | Synthesis method and application of trifluoromethyl sulfoxide reagent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211550947.0A CN115710206B (en) | 2022-12-05 | 2022-12-05 | Synthesis method and application of trifluoromethyl sulfoxide reagent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115710206A CN115710206A (en) | 2023-02-24 |
| CN115710206B true CN115710206B (en) | 2024-04-12 |
Family
ID=85235581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211550947.0A Active CN115710206B (en) | 2022-12-05 | 2022-12-05 | Synthesis method and application of trifluoromethyl sulfoxide reagent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115710206B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105985280A (en) * | 2015-01-30 | 2016-10-05 | 中国科学院上海有机化学研究所 | Difluoromethylthiolation reagent, and preparation method and application thereof |
| CN108569942A (en) * | 2018-05-30 | 2018-09-25 | 丽水学院 | A kind of preparation method of α-trifluoromethylthio substituted acetophenone class compound |
| CN113527158A (en) * | 2021-04-21 | 2021-10-22 | 华东师范大学 | Method for constructing fluorine-containing methyl sulfone compound by multi-component coupling |
| CN114957086A (en) * | 2022-06-30 | 2022-08-30 | 杭州师范大学 | Synthesis method and application of N-trifluoromethylsulfonyl phthalimide |
-
2022
- 2022-12-05 CN CN202211550947.0A patent/CN115710206B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105985280A (en) * | 2015-01-30 | 2016-10-05 | 中国科学院上海有机化学研究所 | Difluoromethylthiolation reagent, and preparation method and application thereof |
| CN108569942A (en) * | 2018-05-30 | 2018-09-25 | 丽水学院 | A kind of preparation method of α-trifluoromethylthio substituted acetophenone class compound |
| CN113527158A (en) * | 2021-04-21 | 2021-10-22 | 华东师范大学 | Method for constructing fluorine-containing methyl sulfone compound by multi-component coupling |
| CN114957086A (en) * | 2022-06-30 | 2022-08-30 | 杭州师范大学 | Synthesis method and application of N-trifluoromethylsulfonyl phthalimide |
Non-Patent Citations (3)
| Title |
|---|
| General, practical and selective oxidation protocol for CF3S into CF3S(O) group;Sokolenko, Liubov V.;Molecules;第24卷(第7期);1249 * |
| Perfluoroalkylation of Thiosulfonates: Synthesis of Per fluoroalkyl Sulfides;Ziwei Luo等;Org. Lett.;第22卷;P6155−6159 * |
| Trifluoromethyl Sulfoxides: Reagents for Metal-Free C-H Trifluoromethylthiolation;Dong Wang, C. Grace Carlton等;Angew. Chem.;第132卷;P16052 –16056 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115710206A (en) | 2023-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI586843B (en) | Electrochemical coupling of two phenols of different oxidation potential | |
| Wang et al. | Copper-catalyzed hydroxylation of aryl halides: efficient synthesis of phenols, alkyl aryl ethers and benzofuran derivatives in neat water | |
| Kareem et al. | Vicinal halo-trifluoromethylation of alkenes | |
| Yagupolskii et al. | A new method for the synthesis of trifluoromethylating agents—Diaryltrifluoromethylsulfonium salts | |
| ES2701808T3 (en) | Method of preparation of vitamin K2 of type MK-7 | |
| CN109336860B (en) | Preparation method of 3-methylsulfonyl-2-substituted benzothiophene compound | |
| CN107540598B (en) | Method for preparing N-difluoromethylthio phthalimide compound | |
| Liu et al. | β-Trifluorosulfinylesters: tuneable reagents for switchable trifluoromethylsulfinylation and C–H trifluoromethylthiolation | |
| CN115710206B (en) | Synthesis method and application of trifluoromethyl sulfoxide reagent | |
| CN111269074A (en) | Preparation method of α -halogenated trifluoromethyl substituted alkane | |
| Hu et al. | Defluorinative Multi‐Functionalization of Fluoroaryl Sulfoxides Enabled by Fluorine‐Assisted Temporary Dearomatization | |
| Liu et al. | Reagents for direct trifluoromethylthiolation | |
| CN114957086B (en) | Synthesis method and application of N-trifluoromethyl sulfonyl phthalimide | |
| CN113880737B (en) | Application of novel persulfate reagent in synthesis of asymmetric polysulfide | |
| CN102190581A (en) | Process for preparing 4'-halogenalkyl-biphenyl-2-carboxylic acids | |
| CA2140610C (en) | Method of selective fluorination | |
| CN113214124B (en) | Monofluoromethylselenated reagent and preparation method and application thereof | |
| CN114573438A (en) | Mono-fluorine chlorine/bromoacetone compound and preparation method thereof | |
| CN112457340A (en) | Tri/difluoroethylation reagent and preparation method and application thereof | |
| CN114716353A (en) | Synthesis method of 4-iodine-2, 3-diene sulfone compound | |
| US11028105B2 (en) | Difluoromethyl and difluoromethylene transfer reagents | |
| BR112018014326B1 (en) | PROCESS FOR PREPARATION OF SUBSTITUTED 2-ARYL ETHANOLS | |
| CN106631926A (en) | Method for selectively compounding aryl methyl sulphone and belta-hydroxy sulphone derivative | |
| Iaroshenko et al. | Synthesis of trifluoromethyl-substituted salicylates by cyclocondensation of 1, 3-bis (silyloxy)-1, 3-butadienes with 4, 4-dimethylthio-1, 1, 1-trifluorobut-3-en-2-one | |
| CN114920636B (en) | Synthesis method of alpha chloro-aryl-ethanone compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |