JP5898419B2 - Method for producing (trifluoromethylsulfonyl) benzene derivative - Google Patents
Method for producing (trifluoromethylsulfonyl) benzene derivative Download PDFInfo
- Publication number
- JP5898419B2 JP5898419B2 JP2011126997A JP2011126997A JP5898419B2 JP 5898419 B2 JP5898419 B2 JP 5898419B2 JP 2011126997 A JP2011126997 A JP 2011126997A JP 2011126997 A JP2011126997 A JP 2011126997A JP 5898419 B2 JP5898419 B2 JP 5898419B2
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- JP
- Japan
- Prior art keywords
- μmol
- group
- copper
- trifluoromethylsulfonyl
- general formula
- 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.)
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- 238000004519 manufacturing process Methods 0.000 title claims description 21
- UPGBQYFXKAKWQC-UHFFFAOYSA-N trifluoromethylsulfonylbenzene Chemical class FC(F)(F)S(=O)(=O)C1=CC=CC=C1 UPGBQYFXKAKWQC-UHFFFAOYSA-N 0.000 title claims description 21
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 66
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 10
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- SFEBPWPPVGRFOA-UHFFFAOYSA-M trifluoromethanesulfinate Chemical compound [O-]S(=O)C(F)(F)F SFEBPWPPVGRFOA-UHFFFAOYSA-M 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- YNYHGRUPNQLZHB-UHFFFAOYSA-M copper(1+);trifluoromethanesulfonate Chemical compound [Cu+].[O-]S(=O)(=O)C(F)(F)F YNYHGRUPNQLZHB-UHFFFAOYSA-M 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims 3
- 239000005749 Copper compound Substances 0.000 claims 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims 2
- 150000001880 copper compounds Chemical class 0.000 claims 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 177
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 177
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 65
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 58
- 239000000243 solution Substances 0.000 description 52
- 238000010898 silica gel chromatography Methods 0.000 description 30
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 29
- 239000012300 argon atmosphere Substances 0.000 description 29
- 239000012043 crude product Substances 0.000 description 29
- 239000010410 layer Substances 0.000 description 29
- 239000012046 mixed solvent Substances 0.000 description 29
- 239000012044 organic layer Substances 0.000 description 29
- 229920006395 saturated elastomer Polymers 0.000 description 29
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 29
- 235000017557 sodium bicarbonate Nutrition 0.000 description 29
- 229910052938 sodium sulfate Inorganic materials 0.000 description 29
- 235000011152 sodium sulphate Nutrition 0.000 description 29
- KAVUKAXLXGRUCD-UHFFFAOYSA-M sodium trifluoromethanesulfinate Chemical compound [Na+].[O-]S(=O)C(F)(F)F KAVUKAXLXGRUCD-UHFFFAOYSA-M 0.000 description 29
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 29
- -1 aryl (trifluoromethyl) sulfide Chemical compound 0.000 description 28
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- YPXIWAYTZKFRIU-UHFFFAOYSA-N 1-chloro-3-(trifluoromethylsulfonyl)benzene Chemical compound FC(F)(F)S(=O)(=O)C1=CC=CC(Cl)=C1 YPXIWAYTZKFRIU-UHFFFAOYSA-N 0.000 description 3
- QWDXSKWKKPIBPA-UHFFFAOYSA-N 1-methyl-3-(trifluoromethylsulfonyl)benzene Chemical compound CC1=CC=CC(S(=O)(=O)C(F)(F)F)=C1 QWDXSKWKKPIBPA-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012230 colorless oil Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- CKIITVIMJSJBQV-UHFFFAOYSA-N methyl 4-(trifluoromethylsulfonyl)benzoate Chemical compound COC(=O)C1=CC=C(S(=O)(=O)C(F)(F)F)C=C1 CKIITVIMJSJBQV-UHFFFAOYSA-N 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- IAXVRHAQVODOIL-UHFFFAOYSA-N 1-(trifluoromethyl)-3-(trifluoromethylsulfonyl)benzene Chemical compound FC(F)(F)C1=CC=CC(S(=O)(=O)C(F)(F)F)=C1 IAXVRHAQVODOIL-UHFFFAOYSA-N 0.000 description 2
- GSCYBSQLEFYNJT-UHFFFAOYSA-N 1-(trifluoromethyl)-4-(trifluoromethylsulfonyl)benzene Chemical compound FC(F)(F)C1=CC=C(S(=O)(=O)C(F)(F)F)C=C1 GSCYBSQLEFYNJT-UHFFFAOYSA-N 0.000 description 2
- BRNFLBCPGQCBQQ-UHFFFAOYSA-N 1-bromo-4-(trifluoromethylsulfonyl)benzene Chemical compound FC(F)(F)S(=O)(=O)C1=CC=C(Br)C=C1 BRNFLBCPGQCBQQ-UHFFFAOYSA-N 0.000 description 2
- PVPZMAOFUOXVHI-UHFFFAOYSA-N 1-chloro-4-(trifluoromethylsulfonyl)benzene Chemical compound FC(F)(F)S(=O)(=O)C1=CC=C(Cl)C=C1 PVPZMAOFUOXVHI-UHFFFAOYSA-N 0.000 description 2
- YZMRPUPSJOQDBS-UHFFFAOYSA-N 1-methoxy-4-(trifluoromethylsulfonyl)benzene Chemical compound COC1=CC=C(S(=O)(=O)C(F)(F)F)C=C1 YZMRPUPSJOQDBS-UHFFFAOYSA-N 0.000 description 2
- PWMRBWJPWBWEMD-UHFFFAOYSA-N 1-methyl-2-(trifluoromethylsulfonyl)benzene Chemical compound CC1=CC=CC=C1S(=O)(=O)C(F)(F)F PWMRBWJPWBWEMD-UHFFFAOYSA-N 0.000 description 2
- OYROYVXGFZPCGD-UHFFFAOYSA-N 1-methyl-4-(trifluoromethylsulfonyl)benzene Chemical compound CC1=CC=C(S(=O)(=O)C(F)(F)F)C=C1 OYROYVXGFZPCGD-UHFFFAOYSA-N 0.000 description 2
- 0 Cc(cc1C)cc(*)c1[I+]c1cccc(Cl)c1 Chemical compound Cc(cc1C)cc(*)c1[I+]c1cccc(Cl)c1 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- BTPAEZGPNPDPAI-UHFFFAOYSA-M (2-acetylphenyl)-phenyliodanium trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC(=O)C1=CC=CC=C1[I+]C1=CC=CC=C1 BTPAEZGPNPDPAI-UHFFFAOYSA-M 0.000 description 1
- QFMYCPNBAGXLDL-UHFFFAOYSA-M (2-methylphenyl)-(2,4,6-trimethylphenyl)iodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC1=CC(C)=CC(C)=C1[I+]C1=CC=CC=C1C QFMYCPNBAGXLDL-UHFFFAOYSA-M 0.000 description 1
- PYSWXUHXKTWION-UHFFFAOYSA-M (2-nitrophenyl)-phenyliodanium trifluoromethanesulfonate Chemical compound [O-][N+](C(C=CC=C1)=C1[I+]C1=CC=CC=C1)=O.[O-]S(C(F)(F)F)(=O)=O PYSWXUHXKTWION-UHFFFAOYSA-M 0.000 description 1
- KEEKMOIRJUWKNK-CABZTGNLSA-N (2S)-2-[[2-[(4R)-4-(difluoromethyl)-2-oxo-1,3-thiazolidin-3-yl]-5,6-dihydroimidazo[1,2-d][1,4]benzoxazepin-9-yl]amino]propanamide Chemical compound FC([C@H]1N(C(SC1)=O)C=1N=C2N(CCOC3=C2C=CC(=C3)N[C@H](C(=O)N)C)C=1)F KEEKMOIRJUWKNK-CABZTGNLSA-N 0.000 description 1
- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 1
- JFTSJYFKINVLMA-UHFFFAOYSA-M (3-methylphenyl)-(2,4,6-trimethylphenyl)iodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC1=CC=CC([I+]C=2C(=CC(C)=CC=2C)C)=C1 JFTSJYFKINVLMA-UHFFFAOYSA-M 0.000 description 1
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- NYNZQNWKBKUAII-KBXCAEBGSA-N (3s)-n-[5-[(2r)-2-(2,5-difluorophenyl)pyrrolidin-1-yl]pyrazolo[1,5-a]pyrimidin-3-yl]-3-hydroxypyrrolidine-1-carboxamide Chemical compound C1[C@@H](O)CCN1C(=O)NC1=C2N=C(N3[C@H](CCC3)C=3C(=CC=C(F)C=3)F)C=CN2N=C1 NYNZQNWKBKUAII-KBXCAEBGSA-N 0.000 description 1
- OTMXSMDJCLTCNC-UHFFFAOYSA-M (4-bromophenyl)-(2,4,6-trimethylphenyl)iodanium trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC1=CC(C)=CC(C)=C1[I+]C1=CC=C(Br)C=C1 OTMXSMDJCLTCNC-UHFFFAOYSA-M 0.000 description 1
- MPWRPWNXMQSKNQ-UHFFFAOYSA-M (4-chlorophenyl)-(2,4,6-trimethylphenyl)iodanium trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC1=CC(C)=CC(C)=C1[I+]C1=CC=C(Cl)C=C1 MPWRPWNXMQSKNQ-UHFFFAOYSA-M 0.000 description 1
- YLYSMRZNIKDMQG-UHFFFAOYSA-M (4-methoxycarbonylphenyl)-phenyliodanium trifluoromethanesulfonate Chemical compound COC(C(C=C1)=CC=C1[I+]C1=CC=CC=C1)=O.[O-]S(C(F)(F)F)(=O)=O YLYSMRZNIKDMQG-UHFFFAOYSA-M 0.000 description 1
- KVLSSMIQFXWHII-UHFFFAOYSA-M (4-methylphenyl)-(2,4,6-trimethylphenyl)iodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(C)=CC=C1[I+]C1=C(C)C=C(C)C=C1C KVLSSMIQFXWHII-UHFFFAOYSA-M 0.000 description 1
- UNBYRDXFZSZZIO-UHFFFAOYSA-M (4-nitrophenyl)-(2,4,6-trimethylphenyl)iodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC1=CC(C)=CC(C)=C1[I+]C1=CC=C([N+]([O-])=O)C=C1 UNBYRDXFZSZZIO-UHFFFAOYSA-M 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NXZFXDLCZKKNCX-UHFFFAOYSA-N 1-fluoro-2-(trifluoromethylsulfonyl)benzene Chemical compound FC1=CC=CC=C1S(=O)(=O)C(F)(F)F NXZFXDLCZKKNCX-UHFFFAOYSA-N 0.000 description 1
- HNEGJTWNOOWEMH-UHFFFAOYSA-N 1-fluoropropane Chemical group [CH2]CCF HNEGJTWNOOWEMH-UHFFFAOYSA-N 0.000 description 1
- KEBPUJYVEYARGZ-UHFFFAOYSA-N 1-nitro-2-(trifluoromethylsulfonyl)benzene Chemical compound [O-][N+](=O)C1=CC=CC=C1S(=O)(=O)C(F)(F)F KEBPUJYVEYARGZ-UHFFFAOYSA-N 0.000 description 1
- XCDAHECADGUHPH-UHFFFAOYSA-N 1-nitro-4-(trifluoromethylsulfonyl)benzene Chemical compound [O-][N+](=O)C1=CC=C(S(=O)(=O)C(F)(F)F)C=C1 XCDAHECADGUHPH-UHFFFAOYSA-N 0.000 description 1
- ZIHYNXVUDCBRRZ-UHFFFAOYSA-N 1-phenyl-2-(trifluoromethylsulfonyl)ethanone Chemical compound FC(F)(F)S(=O)(=O)CC(=O)C1=CC=CC=C1 ZIHYNXVUDCBRRZ-UHFFFAOYSA-N 0.000 description 1
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 1
- KJUCPVIVNLPLEE-UHFFFAOYSA-N 2,6-difluoro-n-[2-fluoro-5-[5-[2-[(6-morpholin-4-ylpyridin-3-yl)amino]pyrimidin-4-yl]-2-propan-2-yl-1,3-thiazol-4-yl]phenyl]benzenesulfonamide Chemical compound S1C(C(C)C)=NC(C=2C=C(NS(=O)(=O)C=3C(=CC=CC=3F)F)C(F)=CC=2)=C1C(N=1)=CC=NC=1NC(C=N1)=CC=C1N1CCOCC1 KJUCPVIVNLPLEE-UHFFFAOYSA-N 0.000 description 1
- ZSDGHWLLLGYAJV-AHEHSYJASA-N 2-[(E)-[(E)-3-[1-(2-nitrophenyl)pyrrol-2-yl]prop-2-enylidene]amino]guanidine Chemical compound NC(N)=N\N=C\C=C\C1=CC=CN1C1=CC=CC=C1[N+]([O-])=O ZSDGHWLLLGYAJV-AHEHSYJASA-N 0.000 description 1
- SSORSZACHCNXSJ-UHFFFAOYSA-N 2-[2-(3,4-dichlorophenyl)-3-[2-(2-hydroxypropylamino)pyrimidin-4-yl]imidazol-4-yl]acetonitrile Chemical compound ClC=1C=C(C=CC=1Cl)C=1N(C(=CN=1)CC#N)C1=NC(=NC=C1)NCC(C)O SSORSZACHCNXSJ-UHFFFAOYSA-N 0.000 description 1
- KDDPNNXAZURUGP-UHFFFAOYSA-N 2-[2-(3,4-dichlorophenyl)-3-[2-(piperidin-3-ylamino)pyrimidin-4-yl]imidazol-4-yl]acetonitrile Chemical compound ClC=1C=C(C=CC=1Cl)C=1N(C(=CN=1)CC#N)C1=NC(=NC=C1)NC1CNCCC1 KDDPNNXAZURUGP-UHFFFAOYSA-N 0.000 description 1
- DILISPNYIVRDBP-UHFFFAOYSA-N 2-[3-[2-(2-hydroxypropylamino)pyrimidin-4-yl]-2-naphthalen-2-ylimidazol-4-yl]acetonitrile Chemical compound OC(CNC1=NC=CC(=N1)N1C(=NC=C1CC#N)C1=CC2=CC=CC=C2C=C1)C DILISPNYIVRDBP-UHFFFAOYSA-N 0.000 description 1
- DWKNOLCXIFYNFV-HSZRJFAPSA-N 2-[[(2r)-1-[1-[(4-chloro-3-methylphenyl)methyl]piperidin-4-yl]-5-oxopyrrolidine-2-carbonyl]amino]-n,n,6-trimethylpyridine-4-carboxamide Chemical compound CN(C)C(=O)C1=CC(C)=NC(NC(=O)[C@@H]2N(C(=O)CC2)C2CCN(CC=3C=C(C)C(Cl)=CC=3)CC2)=C1 DWKNOLCXIFYNFV-HSZRJFAPSA-N 0.000 description 1
- 125000005999 2-bromoethyl group Chemical group 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- BVGDAZBTIVRTGO-UONOGXRCSA-N 3-[(1r)-1-(2,6-dichloro-3-fluorophenyl)ethoxy]-5-[4-methoxy-6-[(2s)-2-methylpiperazin-1-yl]pyridin-3-yl]pyridin-2-amine Chemical compound C1([C@@H](C)OC=2C(N)=NC=C(C=2)C2=CN=C(C=C2OC)N2[C@H](CNCC2)C)=C(Cl)C=CC(F)=C1Cl BVGDAZBTIVRTGO-UONOGXRCSA-N 0.000 description 1
- UHCGSMMNICMDIX-UHFFFAOYSA-N 4-(trifluoromethylsulfonyl)benzonitrile Chemical compound FC(F)(F)S(=O)(=O)C1=CC=C(C#N)C=C1 UHCGSMMNICMDIX-UHFFFAOYSA-N 0.000 description 1
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- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 238000012746 preparative thin layer chromatography Methods 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
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- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical compound OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- OEBIHOVSAMBXIB-SJKOYZFVSA-N selitrectinib Chemical compound C[C@@H]1CCC2=NC=C(F)C=C2[C@H]2CCCN2C2=NC3=C(C=NN3C=C2)C(=O)N1 OEBIHOVSAMBXIB-SJKOYZFVSA-N 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- SFEBPWPPVGRFOA-UHFFFAOYSA-N trifluoromethanesulfinic acid Chemical compound OS(=O)C(F)(F)F SFEBPWPPVGRFOA-UHFFFAOYSA-N 0.000 description 1
- FKQZCCNYTGBVPK-UHFFFAOYSA-M trifluoromethanesulfonate;[3-(trifluoromethyl)phenyl]-(2,4,6-trimethylphenyl)iodanium Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC1=CC(C)=CC(C)=C1[I+]C1=CC=CC(C(F)(F)F)=C1 FKQZCCNYTGBVPK-UHFFFAOYSA-M 0.000 description 1
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- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Description
本発明は、医農薬、機能材料及びそれらの製造中間体として有用な（トリフルオロメチルスルホニル）ベンゼン誘導体の製造方法に関する。 The present invention relates to a method for producing a (trifluoromethylsulfonyl) benzene derivative useful as a medical pesticide, a functional material, and a production intermediate thereof.
（トリフルオロメチルスルホニル）ベンゼン誘導体は医農薬、機能材料及びそれらの製造中間体として有用である（特許文献１）。従来の（トリフルオロメチルスルホニル）ベンゼン誘導体の製造方法として、アリール（トリフルオロメチル）スルフィドの酸化による製造方法が開示されている（非特許文献１）が、毒性の高い試薬を必要とし工業的な製法とはいえない。また、ベンゼンスルホン酸誘導体のトリフルオロメチル化による製造方法が開示されている（非特許文献２）が、高価な反応試薬が必要であり経済的な製造方法とは言いがたい。さらに、特許文献２には、アリール（２−フルオロフェニル）ヨードニウム塩とトリフルオロメタンスルフィン酸塩から１−フルオロ−２−（トリフルオロメチルスルホニル）ベンゼンを合成する方法が開示されている。しかし、収率の記載はなく、また、他の（トリフルオロメチルスルホニル）ベンゼン誘導体を製造できるかは明らかではない。 (Trifluoromethylsulfonyl) benzene derivatives are useful as medical pesticides, functional materials, and production intermediates thereof (Patent Document 1). As a conventional method for producing a (trifluoromethylsulfonyl) benzene derivative, a method for producing aryl (trifluoromethyl) sulfide is disclosed (Non-patent Document 1), which requires a highly toxic reagent and is industrial. It is not a manufacturing method. Moreover, although the manufacturing method by the trifluoromethylation of a benzenesulfonic acid derivative is disclosed (nonpatent literature 2), an expensive reaction reagent is required and it cannot be said that it is an economical manufacturing method. Furthermore, Patent Document 2 discloses a method for synthesizing 1-fluoro-2- (trifluoromethylsulfonyl) benzene from an aryl (2-fluorophenyl) iodonium salt and a trifluoromethanesulfinate. However, there is no description of the yield, and it is not clear whether other (trifluoromethylsulfonyl) benzene derivatives can be produced.
従来の（トリフルオロメチルスルホニル）ベンゼン誘導体の製造方法は、毒性の高い反応試薬や高価な反応試薬が必要であり、また、基質一般性の乏しい製造方法であった。本発明の課題は、（トリフルオロメチルスルホニル）ベンゼン誘導体を効率的に製造する方法を提供することにある。 A conventional method for producing a (trifluoromethylsulfonyl) benzene derivative requires a highly toxic reaction reagent or an expensive reaction reagent, and has a poor substrate generality. An object of the present invention is to provide a method for efficiently producing a (trifluoromethylsulfonyl) benzene derivative.
本発明者らは、上記課題を鑑み鋭意検討を重ねた結果、銅（Ｉ）塩存在下、ジアリールヨードニウム塩とトリフルオロメチルスルフィン酸塩との反応により、（トリフルオロメチルスルホニル）ベンゼン誘導体が簡便に製造できることを見出し、本発明を完成するに至った。
すなわち本発明は、一般式（１）
As a result of intensive studies in view of the above-mentioned problems, the inventors of the present invention made (trifluoromethylsulfonyl) benzene derivatives simple by the reaction of diaryliodonium salt and trifluoromethylsulfinate in the presence of a copper (I) salt. As a result, the present invention was completed.
That is, the present invention provides the general formula (1)
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９及びＲ１０は各々独立に水素原子、炭素数１から６のアルキル基、炭素数１から６のハロアルキル基、炭素数１から６のアルコキシ基、炭素数２から６のアシル基、（炭素数１から５のアルコキシ）カルボニル基、ニトロ基、シアノ基、塩素原子又は臭素原子を表す。）で表されるジアリールヨードニウム塩を、銅（Ｉ）塩の存在下、一般式（２） Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, carbon A haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, (alkoxy having 1 to 5 carbon atoms) carbonyl group, nitro group, cyano group, chlorine atom or bromine atom; A diaryl iodonium salt represented by the general formula (2) in the presence of a copper (I) salt.
（式中、Ｍはアルカリ金属原子を表す。）で表されるトリフルオロメタンスルフィン酸塩と反応させることを特徴とする、一般式（３） (Wherein M represents an alkali metal atom), and is reacted with a trifluoromethanesulfinate represented by the general formula (3)
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４及びＲ５は前記と同じ意味を表す。）で表される（トリフルオロメチルスルホニル）ベンゼン誘導体及び／または一般式（４） (Wherein R 1 , R 2 , R 3 , R 4 and R 5 have the same meaning as described above) and (trifluoromethylsulfonyl) benzene derivative represented by the general formula (4)
（式中、Ｒ６、Ｒ７、Ｒ８、Ｒ９及びＲ１０は前記と同じ意味を表す。）で表される（トリフルオロメチルスルホニル）ベンゼン誘導体の製造方法に関するものである。 (Wherein R 6 , R 7 , R 8 , R 9 and R 10 have the same meanings as described above). This relates to a method for producing a (trifluoromethylsulfonyl) benzene derivative represented by:
本発明により、医農薬、機能材料及びその製造中間体として有用な（トリフルオロメチルスルホニル）ベンゼン誘導体を簡便に製造することができる。 According to the present invention, a (trifluoromethylsulfonyl) benzene derivative useful as a medical pesticide, a functional material, and a production intermediate thereof can be easily produced.
以下に、本発明を詳細に説明する。
Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９及びＲ１０で表される炭素数１から６のアルキル基としては、直鎖状、環状又は分岐状のいずれであってもよく、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、シクロプロピル基、シクロプロピルメチル基、ペンチル基、ヘキシル基等を例示することができる。
Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９及びＲ１０で表される炭素数１から６のハロアルキル基としては、ブロモメチル基、２−ブロモエチル基、３−ブロモプロピル基、４−ブロモブチル基、５−ブロモペンチル基、６−ブロモヘキシル基、ヨードメチル基、２−ヨードエチル基、３−ヨードプロピル基、４−ヨードブチル基、５−ヨードペンチル基、６−ヨードヘキシル基、フルオロメチル基、２−フルオロエチル基、３−フルオロプロピル基、４−フルオロブチル基、５−フルオロペンチル基、６−フルオロヘキシル基、トリブロモメチル基、トリクロロメチル基、トリフルオロメチル基等を例示することができる。
The present invention is described in detail below.
Examples of the alkyl group having 1 to 6 carbon atoms represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 include linear, cyclic or It may be any one of branched, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopropyl group, cyclopropylmethyl group, pentyl group, A hexyl group etc. can be illustrated.
Examples of the haloalkyl group having 1 to 6 carbon atoms represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 include a bromomethyl group, 2-bromoethyl group Group, 3-bromopropyl group, 4-bromobutyl group, 5-bromopentyl group, 6-bromohexyl group, iodomethyl group, 2-iodoethyl group, 3-iodopropyl group, 4-iodobutyl group, 5-iodopentyl group, 6-iodohexyl, fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, tribromomethyl, trichloromethyl, tri A fluoromethyl group etc. can be illustrated.
Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９及びＲ１０で表される炭素数１から６のアルコキシ基としては、直鎖状、環状又は分岐状のいずれであってもよく、メトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、シクロプロピルオキシ基、ブトキシ基、イソブチルオキシ基、ｓｅｃ−ブチルオキシ基、ｔｅｒｔ−ブチルオキシ基、ヘキシルオキシ基、シクロブチルオキシ基、シクロプロピルメチルオキシ基、シクロペンチルオキシ基、シクロヘキシルオキシ基等を例示することができる。
Ｒ１、Ｒ１ａ、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９及びＲ１０で表される炭素数２から６のアシル基としては、直鎖状又は分岐状のいずれであってもよく、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、バレリル基、イソバレリル基、ピバロイル基、アクリロイル基、クロトノイル基等を例示することができる。
Ｒ１、Ｒ１ａ、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９及びＲ１０で表される（炭素数１から５のアルコキシ）カルボニル基としては、メトキシカルボニル基、エトキシカルボニル基、ｔｅｒｔ−ブトキシカルボニル基等を例示することができる。
Ｒ６、Ｒ８及びＲ１０は、経済性の観点からメチル基又は水素原子が好ましく、水素原子がさらに好ましい。
Examples of the alkoxy group having 1 to 6 carbon atoms represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 include linear, cyclic or It may be any one of branched, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, cyclopropyloxy group, butoxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, hexyloxy group, Examples thereof include a cyclobutyloxy group, a cyclopropylmethyloxy group, a cyclopentyloxy group, a cyclohexyloxy group and the like.
The acyl group having 2 to 6 carbon atoms represented by R 1 , R 1a , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is linear. Alternatively, it may be branched, and examples thereof include an acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, acryloyl group, and crotonoyl group.
Examples of the carbonyl group represented by R 1 , R 1a , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 (alkoxy having 1 to 5 carbon atoms) include A methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, etc. can be illustrated.
R 6 , R 8 and R 10 are preferably a methyl group or a hydrogen atom, and more preferably a hydrogen atom, from the viewpoint of economy.
Ｒ７及びＲ９は、経済性の観点から水素原子が好ましい。 R 7 and R 9 are preferably hydrogen atoms from the viewpoint of economy.
Ｍで表されるアルカリ金属原子としては、リチウム、ナトリウム又はカリウムを例示することができる。収率がよい点で、ナトリウムが好ましい。 Examples of the alkali metal atom represented by M include lithium, sodium, and potassium. Sodium is preferred in terms of good yield.
次に、本発明の製造方法について詳しく述べる。
本発明の製造方法の原料であるジアリールヨードニウム塩（１）は、一部市販されているが、文献記載の方法（Ａｄｖａｎｃｅｄ Ｓｙｎｔｈｅｓｉｓ ＆ Ｃａｔａｌｙｓｉｓ，３４９巻，２６１０−２６１８ページ，２００７年）により対応するヨードベンゼン誘導体から調製することができる。
Next, the production method of the present invention will be described in detail.
The diaryliodonium salt (1), which is a raw material for the production method of the present invention, is partially commercially available, but the corresponding iodine can be obtained by a method described in the literature (Advanced Synthesis & Catalysis, 349, 2610-2618, 2007). It can be prepared from benzene derivatives.
本発明の製造方法の原料であるトリフルオロメタンスルフィン酸塩（２）は市販されている。 The trifluoromethanesulfinate (2), which is a raw material for the production method of the present invention, is commercially available.
本発明の製造方法では、銅（Ｉ）塩を用いることが必須である。用いることのできる銅（Ｉ）塩としては、塩化銅（Ｉ）、臭化銅（Ｉ）、臭化銅（Ｉ）ジメチルスルフィド錯体、酢酸銅（Ｉ）、ヨウ化銅（Ｉ）、シアン化銅（Ｉ）、トリフルオロメタンスルホン酸銅（Ｉ）、酸化銅（Ｉ）等を例示することができる。収率が良い点で、酸化銅（Ｉ）を用いることが好ましい。
銅（Ｉ）塩の使用量は特に制限はないが、いわゆる触媒量でも反応は進行する。具体的には、ジアリールヨードニウム塩（１）に対して０．１〜１０モル％程度用いれば十分である。
In the production method of the present invention, it is essential to use a copper (I) salt. Copper (I) salts that can be used include copper (I) chloride, copper (I) bromide, copper (I) bromide dimethyl sulfide complex, copper (I) acetate, copper (I) iodide, cyanide Examples thereof include copper (I), copper (I) trifluoromethanesulfonate, and copper (I) oxide. From the viewpoint of good yield, it is preferable to use copper (I) oxide.
The amount of copper (I) salt used is not particularly limited, but the reaction proceeds even with a so-called catalytic amount. Specifically, it is sufficient to use about 0.1 to 10 mol% with respect to the diaryliodonium salt (1).
本発明の製造方法は溶媒中で行ってもよく、その際、用いることのできる溶媒としては、反応を阻害しない溶媒であれば良く、具体的には、テトラヒドロフラン、ジエチルエーテル、１，４−ジオキサン、メチル−ｔｅｒｔ−ブチルエーテル、１，２−ジメトキシエタン、シクロペンチルメチルエーテル等のエーテル系溶媒、ヘキサン、ペンタン、ヘプタン、シクロヘキサン等の炭化水素系溶媒、ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶媒、ジクロロメタン、クロロホルム、四塩化炭素、１，２−ジクロロエタン等のハロゲン系溶媒、酢酸エチル、酢酸ブチル等のエステル系溶媒、アセトニトリル、ジメチルスルホキシド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチル−２−ピロリドン、１，３−ジメチル−３，４，５，６−テトラヒドロ−２（１Ｈ）−ピリミジノン等の非プロトン性極性溶媒を例示することができ、これらの溶媒のうち２種類以上を混合して用いても差し支えない。 The production method of the present invention may be carried out in a solvent, and the solvent that can be used in this case may be any solvent that does not inhibit the reaction, and specifically, tetrahydrofuran, diethyl ether, 1,4-dioxane. , Ether solvents such as methyl tert-butyl ether, 1,2-dimethoxyethane, cyclopentyl methyl ether, hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene, xylene Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, ester solvents such as ethyl acetate and butyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, N-methyl-2-pyrrolidone 1,3-dimethyl-3,4,5,6- Torahidoro -2 (IH) - aprotic polar solvents such as pyrimidinone can be exemplified, no problem be used as a mixture of two or more of these solvents.
ジアリールヨードニウム塩（１）とトリフルオロメタンスルフィン酸塩（２）とのモル比は特に制限はないが、１：１から１：５が好ましく、収率が良い点で１：１から１：２がさらに好ましい。 The molar ratio of diaryliodonium salt (1) to trifluoromethanesulfinate (2) is not particularly limited, but is preferably 1: 1 to 1: 5, and 1: 1 to 1: 2 in terms of good yield. Further preferred.
反応温度は、−７８℃から１００℃の範囲から適宜選ばれた温度で行うことができる。収率が良い点で０℃から５０℃の範囲が好ましい。
必要に応じて反応後の溶液から目的物を精製することができる。精製する方法には特に限定はないが、溶媒抽出、シリカゲルカラムクロマトグラフィー、分取薄層クロマトグラフィー、分取液体クロマトグラフィー、再結晶または昇華等の汎用的な方法で目的物を精製することができる。
The reaction temperature can be carried out at a temperature appropriately selected from the range of −78 ° C. to 100 ° C. A range of 0 ° C. to 50 ° C. is preferable in terms of good yield.
If necessary, the desired product can be purified from the solution after the reaction. The purification method is not particularly limited, but the target product may be purified by a general-purpose method such as solvent extraction, silica gel column chromatography, preparative thin layer chromatography, preparative liquid chromatography, recrystallization or sublimation. it can.
次に本発明を実施例によってさらに詳細に説明するが、本発明はこれらに限定されるものではない。
実施例−１
EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to these.
Example-1
アルゴン雰囲気下、トリフルオロメタンスルホン酸ジフェニルヨードニウム（１２９ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝５０：１）により精製し、（トリフルオロメチルスルホニル）ベンゼン（３９．８ｍｇ，１８９μｍｏｌ，６３％）を無色油状物質として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ８．０６（２Ｈ，ｄ，Ｊ＝７．６Ｈｚ），７．８５（１Ｈ，ｍ），７．６９（２Ｈ，ｍ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−７８．９（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１３６．６，１３１．２，１３０．６，１２９．９，１１９．８（ｑ，Ｊ＝３２５．７Ｈｚ）．
実施例−２
In an argon atmosphere, N, N-dimethylformamide (1 mg of diphenyliodonium trifluoromethanesulfonate (129 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) (1 0.5 mL), the solution was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1) to obtain (trifluoromethylsulfonyl) benzene (39.8 mg, 189 μmol, 63%) as a colorless oily substance.
1 H-NMR (400 MHz, CDCl 3 ) δ 8.06 (2H, d, J = 7.6 Hz), 7.85 (1H, m), 7.69 (2H, m); 19 F-NMR (376 MHz, CDCl 3 ) δ-78.9 (3F); 13 C-NMR (100 MHz, CDCl 3 ) δ 136.6, 131.2, 130.6, 129.9, 119.8 (q, J = 325.7 Hz) .
Example-2
アルゴン雰囲気下、トリフルオロメタンスルホン酸ビス［４−（メトキシカルボニル）フェニル］ヨードニウム（１６４ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝５０：１〜４０：１）により精製し、４−（トリフルオロメチルスルホニル）安息香酸メチル（６６．６ｍｇ，２４８μｍｏｌ，８３％）を白色固体として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ８．３２（２Ｈ，ｄ，Ｊ＝８．５Ｈｚ），８．１３（２Ｈ，ｄ，Ｊ＝８．５Ｈｚ），４．００（３Ｈ，ｓ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−７８．５（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１６４．９，１３７．４，１３５．１，１３０．８，１３０．８，１１９．６（ｑ，Ｊ＝３２５．９Ｈｚ），５３．０．
実施例−３
Under argon atmosphere, bis [4- (methoxycarbonyl) phenyl] iodonium trifluoromethanesulfonate (164 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) Of N, N-dimethylformamide (1.5 mL) was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was mixed with a mixed solvent (hexane: ethyl acetate = 1: 1). Extracted. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1 to 40: 1), and methyl 4- (trifluoromethylsulfonyl) benzoate (66.6 mg, 248 μmol, 83%). Was obtained as a white solid.
1 H-NMR (400 MHz, CDCl 3 ) δ 8.32 (2H, d, J = 8.5 Hz), 8.13 (2H, d, J = 8.5 Hz), 4.00 (3H, s); 19 F-NMR (376 MHz, CDCl 3 ) δ-78.5 (3F); 13 C-NMR (100 MHz, CDCl 3 ) δ 164.9, 137.4, 135.1, 130.8, 130.8, 119. 6 (q, J = 325.9 Hz), 53.0.
Example-3
アルゴン雰囲気下、トリフルオロメタンスルホン酸ビス［４−（トリフルオロメチル）フェニル］ヨードニウム（１７０ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−（トリフルオロメチル）−４−（トリフルオロメチルスルホニル）ベンゼン（６１．７ｍｇ，２２２μｍｏｌ，７４％）を白色固体として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ８．２１（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ），７．９６（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−６４．１（３Ｆ），−７８．４（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１３８．０（ｑ，Ｊ＝３３．６Ｈｚ），１３５．１，１３１．５，１２７．０（ｑ，Ｊ＝３．６Ｈｚ），１２２．７（ｑ，Ｊ＝２７３．５Ｈｚ），１１９．６（ｑ，Ｊ＝３２５．９Ｈｚ）．
実施例−４
Under argon atmosphere, bis [4- (trifluoromethyl) phenyl] iodonium trifluoromethanesulfonate (170 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) ) Solution of N, N-dimethylformamide (1.5 mL) at room temperature for 3 days, cooled to 0 ° C., added saturated aqueous sodium hydrogen carbonate solution, and the aqueous layer was mixed solvent (hexane: ethyl acetate = 1: 1). Extracted with. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1) to give 1- (trifluoromethyl) -4- (trifluoromethylsulfonyl) benzene (61.7 mg, 222 μmol, 74 %) As a white solid.
1 H-NMR (400 MHz, CDCl 3 ) δ 8.21 (2H, d, J = 8.3 Hz), 7.96 (2H, d, J = 8.3 Hz); 19 F-NMR (376 MHz, CDCl 3 ) δ-64.1 (3F), -78.4 (3F); 13 C-NMR (100 MHz, CDCl 3 ) δ138.0 (q, J = 33.6 Hz), 135.1, 131.5, 127. 0 (q, J = 3.6 Hz), 122.7 (q, J = 273.5 Hz), 119.6 (q, J = 325.9 Hz).
Example-4
アルゴン雰囲気下、トリフルオロメタンスルホン酸ビス（４−メトキシフェニル）ヨードニウム（１４７ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝３０：１〜１０：１）により精製し、４−（トリフルオロメチルスルホニル）アニソール（６４．５ｍｇ，２６８μｍｏｌ，８９％）を無色油状物質として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ７．９４（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ），７．１０（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ），３．９３（３Ｈ，ｓ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−７９．４（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１６６．２，１３３．２，１２１．９，１１９．９（ｑ，Ｊ＝３２５．５Ｈｚ），１１５．２，５５．９．
実施例−５
Under an argon atmosphere, bis (4-methoxyphenyl) iodonium trifluoromethanesulfonate (147 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) in N, The N-dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 30: 1 to 10: 1), and 4- (trifluoromethylsulfonyl) anisole (64.5 mg, 268 μmol, 89%) was colorless. Obtained as an oil.
1 H-NMR (400 MHz, CDCl 3 ) δ 7.94 (2H, d, J = 8.3 Hz), 7.10 (2H, d, J = 8.3 Hz), 3.93 (3H, s); 19 F-NMR (376 MHz, CDCl 3 ) δ-79.4 (3F); 13 C-NMR (100 MHz, CDCl 3 ) δ 166.2, 133.2, 121.9, 119.9 (q, J = 325. 5Hz), 115.2, 55.9.
Example-5
アルゴン雰囲気下、トリフルオロメタンスルホン酸ビス（４−クロロフェニル）ヨードニウム（１４９ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−クロロ−４−（トリフルオロメチルスルホニル）ベンゼン（５８．２ｍｇ，２３７μｍｏｌ，７９％）を白色固体として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ７．９８（２Ｈ，ｄ，Ｊ＝８．６Ｈｚ），７．６７（２Ｈ，ｄ，Ｊ＝８．６Ｈｚ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−７８．８（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１４４．０，１３２．１，１３０．４，１２９．７，１１９．７（ｑ，Ｊ＝３２５．７Ｈｚ）．
実施例−６
Under argon atmosphere, N, N of bis (4-chlorophenyl) iodonium trifluoromethanesulfonate (149 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) -The dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C, saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1), and 1-chloro-4- (trifluoromethylsulfonyl) benzene (58.2 mg, 237 μmol, 79%) was white. Obtained as a solid.
1 H-NMR (400 MHz, CDCl 3 ) δ 7.98 (2H, d, J = 8.6 Hz), 7.67 (2H, d, J = 8.6 Hz); 19 F-NMR (376 MHz, CDCl 3 ) δ-78.8 (3F); 13 C-NMR (100 MHz, CDCl 3 ) δ 144.0, 132.1, 130.4, 129.7, 119.7 (q, J = 325.7 Hz).
Example-6
アルゴン雰囲気下、トリフルオロメタンスルホン酸ビス（４−ブロモフェニル）ヨ−ドニウム（１７６ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−ブロモ−４−（トリフルオロメチルスルホニル）ベンゼン（７２．１ｍｇ，２４９μｍｏｌ，８３％）を白色固体として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ７．８９（２Ｈ，ｄ，Ｊ＝８．６Ｈｚ），７．８３（２Ｈ，ｄ，Ｊ＝８．６Ｈｚ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−７８．８（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１３３．４，１３２．８，１３２．０，１３０．３，１１９．６（ｑ，Ｊ＝３２５．８Ｈｚ）．
実施例−７
Under argon atmosphere, bis (4-bromophenyl) iodonium trifluoromethanesulfonate (176 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol). The N, N-dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C., a saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). did. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1), and 1-bromo-4- (trifluoromethylsulfonyl) benzene (72.1 mg, 249 μmol, 83%) was white. Obtained as a solid.
1 H-NMR (400 MHz, CDCl 3 ) δ 7.89 (2H, d, J = 8.6 Hz), 7.83 (2H, d, J = 8.6 Hz); 19 F-NMR (376 MHz, CDCl 3 ) δ-78.8 (3F); 13 C-NMR (100 MHz, CDCl 3 ) δ 133.4, 132.8, 132.0, 130.3, 119.6 (q, J = 325.8 Hz).
Example-7
アルゴン雰囲気下、トリフルオロメタンスルホン酸ビス（４−メチルフェニル）ヨードニウム（１３７ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−メチル−４−（トリフルオロメチルスルホニル）ベンゼン（５３．９ｍｇ，２４０μｍｏｌ，８０％）を白色固体として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ７．９２（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ），７．４７（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ），２．５２（３Ｈ，ｓ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−７９．２（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１４８．３，１３０．８，１３０．５，１２８．２，１１９．８（ｑ，Ｊ＝３２５．７Ｈｚ），２１．９．
実施例−８
Under an argon atmosphere, bis (4-methylphenyl) iodonium trifluoromethanesulfonate (137 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) in N, The N-dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1), and 1-methyl-4- (trifluoromethylsulfonyl) benzene (53.9 mg, 240 μmol, 80%) was white. Obtained as a solid.
1 H-NMR (400 MHz, CDCl 3 ) δ 7.92 (2H, d, J = 8.3 Hz), 7.47 (2H, d, J = 8.3 Hz), 2.52 (3H, s); 19 F-NMR (376 MHz, CDCl 3 ) δ-79.2 (3F); 13 C-NMR (100 MHz, CDCl 3 ) δ 148.3, 130.8, 130.5, 128.2, 119.8 (q, J = 325.7 Hz), 21.9.
Example-8
アルゴン雰囲気下、トリフルオロメタンスルホン酸ビス（３−メチルフェニル）ヨードニウム（１３７ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−メチル−３−（トリフルオロメチルスルホニル）ベンゼン（５６．６ｍｇ，２５２μｍｏｌ，８４％）を白色固体として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ７．８２−７．８６（２Ｈ，ｍ），７．６４（１Ｈ，ｍ），７．５５（１Ｈ，ｍ），２．４９（３Ｈ，ｓ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−７９．０（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１４０．４，１３７．４，１３１．２，１３０．８，１２９．７，１２７．９，１１９．８（ｑ，Ｊ＝３２５．９Ｈｚ），２１．２．
実施例−９
Under an argon atmosphere, bis (3-methylphenyl) iodonium trifluoromethanesulfonate (137 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) in N, The N-dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1), and 1-methyl-3- (trifluoromethylsulfonyl) benzene (56.6 mg, 252 μmol, 84%) was white. Obtained as a solid.
1 H-NMR (400 MHz, CDCl 3 ) δ 7.82-7.86 (2H, m), 7.64 (1H, m), 7.55 (1H, m), 2.49 (3H, s); 19 F-NMR (376 MHz, CDCl 3 ) δ-79.0 (3F); 13 C-NMR (100 MHz, CDCl 3 ) δ 140.4, 137.4, 131.2, 130.8, 129.7, 127 .9, 119.8 (q, J = 325.9 Hz), 21.2.
Example-9
アルゴン雰囲気下、トリフルオロメタンスルホン酸ビス［３−（トリフルオロメチル）フェニル］ヨードニウム（１７０ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−（トリフルオロメチル）−３−（トリフルオロメチルスルホニル）ベンゼン（５９．９ｍｇ，２１５μｍｏｌ，７２％）を無色油状物質として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ８．３１（１Ｈ，ｓ），８．２６（１Ｈ，ｄ，Ｊ＝８．０Ｈｚ），８．１１（１Ｈ，ｄ，Ｊ＝７．９Ｈｚ），７．８７（１Ｈ，ｄｄ，Ｊ＝８．０，７．９Ｈｚ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−６３．５（３Ｆ），−７８．４（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１３４．０，１３３．２（ｑ，Ｊ＝３．４Ｈｚ），１３２．９（ｑ，Ｊ＝３４．４Ｈｚ），１３２．９，１３０．９，１２７．７（ｑ，Ｊ＝３．７Ｈｚ），１２２．７（ｑ，Ｊ＝２７３．１Ｈｚ），１１９．６（ｑ，Ｊ＝３２５．７Ｈｚ）．
実施例−１０
Under argon atmosphere, bis [3- (trifluoromethyl) phenyl] iodonium trifluoromethanesulfonate (170 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) ) Solution of N, N-dimethylformamide (1.5 mL) at room temperature for 3 days, cooled to 0 ° C., added saturated aqueous sodium hydrogen carbonate solution, and the aqueous layer was mixed solvent (hexane: ethyl acetate = 1: 1). Extracted with. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1), and 1- (trifluoromethyl) -3- (trifluoromethylsulfonyl) benzene (59.9 mg, 215 μmol, 72 %) As a colorless oil.
1 H-NMR (400 MHz, CDCl 3 ) δ 8.31 (1H, s), 8.26 (1H, d, J = 8.0 Hz), 8.11 (1H, d, J = 7.9 Hz), 7 .87 (1H, dd, J = 8.0, 7.9 Hz); 19 F-NMR (376 MHz, CDCl 3 ) δ-63.5 (3F), −78.4 (3F); 13 C-NMR ( 100 MHz, CDCl 3 ) δ 134.0, 133.2 (q, J = 3.4 Hz), 132.9 (q, J = 34.4 Hz), 132.9, 130.9, 127.7 (q, J = 3.7 Hz), 122.7 (q, J = 273.1 Hz), 119.6 (q, J = 325.7 Hz).
Example-10
アルゴン雰囲気下、トリフルオロメタンスルホン酸ビス（３−クロロフェニル）ヨードニウム（１４９ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−クロロ−３−（トリフルオロメチルスルホニル）ベンゼン（５８．８ｍｇ，２４０μｍｏｌ，８０％）を無色油状物質として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ８．０３（１Ｈ，ｍ），７．９５（１Ｈ，ｂｒｄ，Ｊ＝７．９Ｈｚ），７．８１（１Ｈ，ｄｄｄ，Ｊ＝７．９，２．１，１．０Ｈｚ），７．６４（１Ｈ，ｔ，Ｊ＝７．９Ｈｚ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−７８．５（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１３６．７，１３６．３，１３３．１，１３１．１，１３０．５，１２８．８，１１９．６（ｑ，Ｊ＝３２５．９Ｈｚ）．
実施例−１１
Under argon atmosphere, N, N of bis (3-chlorophenyl) iodonium trifluoromethanesulfonate (149 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) -The dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C, saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1), and 1-chloro-3- (trifluoromethylsulfonyl) benzene (58.8 mg, 240 μmol, 80%) was colorless. Obtained as an oil.
1 H-NMR (400 MHz, CDCl 3 ) δ 8.03 (1H, m), 7.95 (1H, brd, J = 7.9 Hz), 7.81 (1H, ddd, J = 7.9, 2. 11.0 Hz), 7.64 (1 H, t, J = 7.9 Hz); 19 F-NMR (376 MHz, CDCl 3 ) δ-78.5 (3F); 13 C-NMR (100 MHz, CDCl 3 ) 136.7, 136.3, 133.1, 131.1, 130.5, 128.8, 119.6 (q, J = 325.9 Hz).
Example-11
アルゴン雰囲気下、トリフルオロメタンスルホン酸ビス（２−メチルフェニル）ヨードニウム（１３７ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−メチル−２−（トリフルオロメチルスルホニル）ベンゼン（４４．０ｍｇ，１９６μｍｏｌ，６５％）を無色油状物質として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ８．０８（１Ｈ，ｄ，Ｊ＝８．０Ｈｚ），７．６８（１Ｈ，ｄｔ，Ｊ＝７．６，１．４Ｈｚ），７．４２−７．５０（２Ｈ，ｍ），２．７４（３Ｈ，ｓ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−７８．８（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１４２．２，１３６．４，１３３．５，１３３．３，１２９．８，１２７．２，１２０．１（ｑ，Ｊ＝３２６．５Ｈｚ），２０．６（ｑ，Ｊ＝１．３Ｈｚ）．
実施例−１２
Under argon atmosphere, bis (2-methylphenyl) iodonium trifluoromethanesulfonate (137 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) in N, The N-dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1), and 1-methyl-2- (trifluoromethylsulfonyl) benzene (44.0 mg, 196 μmol, 65%) was colorless. Obtained as an oil.
1 H-NMR (400 MHz, CDCl 3 ) δ 8.08 (1H, d, J = 8.0 Hz), 7.68 (1H, dt, J = 7.6, 1.4 Hz), 7.42-7. 50 (2H, m), 2.74 (3H, s); 19 F-NMR (376 MHz, CDCl 3 ) δ-78.8 (3F); 13 C-NMR (100 MHz, CDCl 3 ) δ 142.2, 136 4, 133.5, 133.3, 129.8, 127.2, 120.1 (q, J = 326.5 Hz), 20.6 (q, J = 1.3 Hz).
Example-12
アルゴン雰囲気下、トリフルオロメタンスルホン酸メシチル（フェニル）ヨードニウム（１４２ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝５０：１）により精製し、（トリフルオロメチルスルホニル）ベンゼン（３８．８ｍｇ，１８４μｍｏｌ，６１％）を無色油状物質として得た。
実施例−１３
Under argon atmosphere, mesityl (phenyl) iodonium trifluoromethanesulfonate (142 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) in N, N-dimethyl The formamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1) to obtain (trifluoromethylsulfonyl) benzene (38.8 mg, 184 μmol, 61%) as a colorless oily substance.
Example-13
アルゴン雰囲気下、トリフルオロメタンスルホン酸メシチル［４−（メトキシカルボニル）フェニル］ヨードニウム（１５９ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝５０：１）により精製し、４−（トリフルオロメチルスルホニル）安息香酸メチル（６８．６ｍｇ，２５６μｍｏｌ，８５％）を白色固体として得た。
実施例−１４
Under argon atmosphere, mesityl [4- (methoxycarbonyl) phenyl] iodonium trifluoromethanesulfonate (159 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) Of N, N-dimethylformamide (1.5 mL) was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was mixed with a mixed solvent (hexane: ethyl acetate = 1: 1). Extracted. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1), and methyl 4- (trifluoromethylsulfonyl) benzoate (68.6 mg, 256 μmol, 85%) as a white solid. Obtained.
Example-14
アルゴン雰囲気下、トリフルオロメタンスルホン酸メシチル［４−（トリフルオロメチル）フェニル］ヨードニウム（１６２ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−（トリフルオロメチル）−４−（トリフルオロメチルスルホニル）ベンゼン（５１．４ｍｇ，１８５μｍｏｌ，６２％）を白色固体として得た。
実施例−１５
Under an argon atmosphere, mesityl [4- (trifluoromethyl) phenyl] iodonium trifluoromethanesulfonate (162 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) ) Solution of N, N-dimethylformamide (1.5 mL) at room temperature for 3 days, cooled to 0 ° C., added saturated aqueous sodium hydrogen carbonate solution, and the aqueous layer was mixed solvent (hexane: ethyl acetate = 1: 1). Extracted with. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1), and 1- (trifluoromethyl) -4- (trifluoromethylsulfonyl) benzene (51.4 mg, 185 μmol, 62 %) As a white solid.
Example-15
アルゴン雰囲気下、トリフルオロメタンスルホン酸メシチル（４−メトキシフェニル）ヨードニウム（１５１ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝３０：１〜１０：１）により精製し、４−（トリフルオロメチルスルホニル）アニソール（６３．２ｍｇ，２６３μｍｏｌ，８８％）を無色油状物質として得た。
実施例−１６
Under an argon atmosphere, mesityl (4-methoxyphenyl) iodonium trifluoromethanesulfonate (151 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) N, The N-dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 30: 1 to 10: 1), and 4- (trifluoromethylsulfonyl) anisole (63.2 mg, 263 μmol, 88%) was colorless. Obtained as an oil.
Example-16
アルゴン雰囲気下、トリフルオロメタンスルホン酸（４−クロロフェニル）（メシチル）ヨードニウム（１５２ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−クロロ−４−（トリフルオロメチルスルホニル）ベンゼン（６０．２ｍｇ，２４６μｍｏｌ，８２％）を白色固体として得た。
実施例−１７
N of trifluoromethanesulfonic acid (4-chlorophenyl) (mesityl) iodonium (152 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) under an argon atmosphere , N-dimethylformamide (1.5 mL) was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). . The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1), and 1-chloro-4- (trifluoromethylsulfonyl) benzene (60.2 mg, 246 μmol, 82%) was white. Obtained as a solid.
Example-17
アルゴン雰囲気下、トリフルオロメタンスルホン酸（４−ブロモフェニル）（メシチル）ヨードニウム（１６５ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−ブロモ−４−（トリフルオロメチルスルホニル）ベンゼン（７１．８ｍｇ，２４８μｍｏｌ，８３％）を白色固体として得た。
実施例−１８
Under an argon atmosphere, trifluoromethanesulfonic acid (4-bromophenyl) (mesityl) iodonium (165 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) The N, N-dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C., a saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). did. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1), and 1-bromo-4- (trifluoromethylsulfonyl) benzene (71.8 mg, 248 μmol, 83%) was white. Obtained as a solid.
Example-18
アルゴン雰囲気下、トリフルオロメタンスルホン酸メシチル（４−メチルフェニル）ヨードニウム（１４６ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−メチル−４−（トリフルオロメチルスルホニル）ベンゼン（５８．７ｍｇ，２６２μｍｏｌ，８７％）を白色固体として得た。
実施例−１９
Under an argon atmosphere, mesityl (4-methylphenyl) iodonium trifluoromethanesulfonate (146 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) N, The N-dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1), and 1-methyl-4- (trifluoromethylsulfonyl) benzene (58.7 mg, 262 μmol, 87%) was white. Obtained as a solid.
Example-19
アルゴン雰囲気下、トリフルオロメタンスルホン酸メシチル（３−メチルフェニル）ヨードニウム（１４６ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−メチル−３−（トリフルオロメチルスルホニル）ベンゼン（５３．４ｍｇ，２３８μｍｏｌ，７９％）を白色固体として得た。
実施例−２０
Under an argon atmosphere, mesityl (3-methylphenyl) iodonium trifluoromethanesulfonate (146 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) N, The N-dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1), and 1-methyl-3- (trifluoromethylsulfonyl) benzene (53.4 mg, 238 μmol, 79%) was white. Obtained as a solid.
Example-20
アルゴン雰囲気下、トリフルオロメタンスルホン酸メシチル［３−（トリフルオロメチル）フェニル］ヨードニウム（１６２ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−（トリフルオロメチル）−３−（トリフルオロメチルスルホニル）ベンゼン（５０．３ｍｇ，１８１μｍｏｌ，６０％）を無色油状物質として得た。
実施例−２１
Under argon atmosphere, mesityl [3- (trifluoromethyl) phenyl] iodonium trifluoromethanesulfonate (162 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) ) Solution of N, N-dimethylformamide (1.5 mL) at room temperature for 3 days, cooled to 0 ° C., added saturated aqueous sodium hydrogen carbonate solution, and the aqueous layer was mixed solvent (hexane: ethyl acetate = 1: 1). Extracted with. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1) to give 1- (trifluoromethyl) -3- (trifluoromethylsulfonyl) benzene (50.3 mg, 181 μmol, 60 %) As a colorless oil.
Example-21
アルゴン雰囲気下、トリフルオロメタンスルホン酸（３−クロロフェニル）（メシチル）ヨードニウム（１５２ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−クロロ−３−（トリフルオロメチルスルホニル）ベンゼン（６１．５ｍｇ，２５１μｍｏｌ，８３％）を無色油状物質として得た。
実施例−２２
N of trifluoromethanesulfonic acid (3-chlorophenyl) (mesityl) iodonium (152 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) under an argon atmosphere , N-dimethylformamide (1.5 mL) was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). . The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1), and 1-chloro-3- (trifluoromethylsulfonyl) benzene (61.5 mg, 251 μmol, 83%) was colorless. Obtained as an oil.
Example-22
アルゴン雰囲気下、トリフルオロメタンスルホン酸メシチル（２−メチルフェニル）ヨードニウム（１４６ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１）により精製し、１−メチル−２−（トリフルオロメチルスルホニル）ベンゼン（４９．５ｍｇ，２２１μｍｏｌ，７３％）を無色油状物質として得た。
実施例−２３
Under an argon atmosphere, mesityl (2-methylphenyl) iodonium trifluoromethanesulfonate (146 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) N, The N-dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1), and 1-methyl-2- (trifluoromethylsulfonyl) benzene (49.5 mg, 221 μmol, 73%) was colorless. Obtained as an oil.
Example-23
アルゴン雰囲気下、トリフルオロメタンスルホン酸メシチル（４−ニトロフェニル）ヨードニウム（１５５ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１００：１〜５０：１）により精製し、１−ニトロ−４−（トリフルオロメチルスルホニル）ベンゼン（６７．０ｍｇ，２６２μｍｏｌ，８７％）を白色固体として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ８．５２（２Ｈ，ｄ，Ｊ＝９．０Ｈｚ），８．２８（２Ｈ，ｄ，Ｊ＝９．０Ｈｚ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−７８．１（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１５２．５，１３７．０，１３２．３，１２４．９，１１９．５（ｑ，Ｊ＝３２５．９Ｈｚ）．
実施例−２４
Under an argon atmosphere, mesityl (4-nitrophenyl) iodonium trifluoromethanesulfonate (155 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) N, The N-dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1 to 50: 1), and 1-nitro-4- (trifluoromethylsulfonyl) benzene (67.0 mg, 262 μmol, 87). %) As a white solid.
1 H-NMR (400 MHz, CDCl 3 ) δ 8.52 (2H, d, J = 9.0 Hz), 8.28 (2H, d, J = 9.0 Hz); 19 F-NMR (376 MHz, CDCl 3 ) δ-78.1 (3F); 13 C-NMR (100 MHz, CDCl 3 ) δ152.5, 137.0, 132.3, 124.9, 119.5 (q, J = 325.9 Hz).
Example-24
アルゴン雰囲気下、トリフルオロメタンスルホン酸（４−シアノフェニル）（メシチル）ヨードニウム（１４９ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝５０：１〜３０：１）により精製し、４−（トリフルオロメチルスルホニル）ベンゾニトリル（６０．１ｍｇ，２５５μｍｏｌ，８５％）を白色固体として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ８．１９（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ），７．９９（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−７８．１（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１３５．５，１３３．５，１３１．３，１２０．３，１１９．５（ｑ，Ｊ＝３２６．２Ｈｚ），１１６．４．
実施例−２５
Under an argon atmosphere, trifluoromethanesulfonic acid (4-cyanophenyl) (mesityl) iodonium (149 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) The N, N-dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C., a saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). did. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1-30: 1) to give 4- (trifluoromethylsulfonyl) benzonitrile (60.1 mg, 255 μmol, 85%). Obtained as a white solid.
1 H-NMR (400 MHz, CDCl 3 ) δ 8.19 (2H, d, J = 8.3 Hz), 799 (2H, d, J = 8.3 Hz); 19 F-NMR (376 MHz, CDCl 3 ) δ-78.1 (3F); 13 C-NMR (100 MHz, CDCl 3 ) δ135.5, 133.5, 131.3, 120.3, 119.5 (q, J = 326.2 Hz), 116. 4).
Example-25
アルゴン雰囲気下、トリフルオロメタンスルホン酸メシチル［４−（メトキシカルボニル）−２−メチルフェニル］ヨードニウム（１６３ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝５０：１）により精製し、３−メチル−４−（トリフルオロメチルスルホニル）安息香酸メチル（４８．２ｍｇ，１７１μｍｏｌ，５７％）を白色固体として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ８．１６（１Ｈ，ｄ，Ｊ＝８．４Ｈｚ），８．０６−８．１０（２Ｈ，ｍ），３．９８（３Ｈ，ｓ），２．７９（３Ｈ，ｓ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−７８．４（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１６５．０，１４２．５，１３６．９，１３４．３，１３３．６，１３３．５，１２７．８，１２０．０（ｑ，Ｊ＝３２６．７Ｈｚ），５２．９，２０．６（ｑ，Ｊ＝１．２Ｈｚ）．
実施例−２６
Under an argon atmosphere, mesityl [4- (methoxycarbonyl) -2-methylphenyl] iodonium trifluoromethanesulfonate (163 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2. 1 mg, 15 μmol) of N, N-dimethylformamide (1.5 mL) was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was mixed with a mixed solvent (hexane: ethyl acetate = 1). 1). The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1), and methyl 3-methyl-4- (trifluoromethylsulfonyl) benzoate (48.2 mg, 171 μmol, 57%). Was obtained as a white solid.
1 H-NMR (400 MHz, CDCl 3 ) δ 8.16 (1H, d, J = 8.4 Hz), 8.06-8.10 (2H, m), 3.98 (3H, s), 2.79 (3H, s); 19 F-NMR (376 MHz, CDCl 3 ) δ-78.4 (3F); 13 C-NMR (100 MHz, CDCl 3 ) δ 165.0, 142.5, 136.9, 134.3 , 133.6, 133.5, 127.8, 120.0 (q, J = 326.7 Hz), 52.9, 20.6 (q, J = 1.2 Hz).
Example-26
アルゴン雰囲気下、トリフルオロメタンスルホン酸［２−（メトキシカルボニル）フェニル］（フェニル）ヨードニウム（１４６ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２０：１〜５：１）により精製し、２−（トリフルオロメチルスルホニル）安息香酸メチル（６９．８ｍｇ，２６０μｍｏｌ，８６％）を無色油状物質として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ８．１３（１Ｈ，ｄ，Ｊ＝８．０Ｈｚ），７．８７（１Ｈ，ｄｔ，Ｊ＝７．６，１．２Ｈｚ），７．７２−７．７８（２Ｈ，ｍ），３．９７（３Ｈ，ｓ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−７５．６（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１６６．３，１３６．３，１３６．１，１３２．７，１３１．２，１３０．０，１２９．９，１１９．８（ｑ，Ｊ＝３２７．８Ｈｚ），５３．４．
実施例−２７
Under argon atmosphere, trifluoromethanesulfonic acid [2- (methoxycarbonyl) phenyl] (phenyl) iodonium (146 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) of N, N-dimethylformamide (1.5 mL) was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was mixed with a mixed solvent (hexane: ethyl acetate = 1: 1). ). The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1 to 5: 1), and methyl 2- (trifluoromethylsulfonyl) benzoate (69.8 mg, 260 μmol, 86%). Was obtained as a colorless oil.
1 H-NMR (400 MHz, CDCl 3 ) δ 8.13 (1H, d, J = 8.0 Hz), 7.87 (1H, dt, J = 7.6, 1.2 Hz), 7.72-7. 78 (2H, m), 3.97 (3H, s); 19 F-NMR (376 MHz, CDCl 3 ) δ-75.6 (3F); 13 C-NMR (100 MHz, CDCl 3 ) δ 166.3, 136 3, 136.1, 132.7, 131.2, 130.0, 129.9, 119.8 (q, J = 327.8 Hz), 53.4.
Example-27
アルゴン雰囲気下、トリフルオロメタンスルホン酸（２−アセチルフェニル）（フェニル）ヨードニウム（１４２ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２０：１〜５：１）により精製し、２−（トリフルオロメチルスルホニル）アセトフェノン（６９．７ｍｇ，２７６μｍｏｌ，９２％）を無色油状物質として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ８．０８（１Ｈ，ｄ，Ｊ＝８．０Ｈｚ），７．８７（１Ｈ，ｄｔ，Ｊ＝７．６，１．２Ｈｚ），７．７１（１Ｈ，ｍ），７．４７（１Ｈ，ｄｄ，Ｊ＝７．６，１．０Ｈｚ），２．６３（３Ｈ，ｓ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−７７．２（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ２００．６，１４５．６，１３６．６，１３２．６，１３０．３，１２８．０，１２７．１，１１９．６（ｑ，Ｊ＝３２７．０Ｈｚ），３１．５．
実施例−２８
Under an argon atmosphere, trifluoromethanesulfonic acid (2-acetylphenyl) (phenyl) iodonium (142 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) The N, N-dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C., a saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). did. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1 to 5: 1), and 2- (trifluoromethylsulfonyl) acetophenone (69.7 mg, 276 μmol, 92%) was colorless. Obtained as an oil.
1 H-NMR (400 MHz, CDCl 3 ) δ 8.08 (1H, d, J = 8.0 Hz), 7.87 (1H, dt, J = 7.6, 1.2 Hz), 7.71 (1H, m), 7.47 (1H, dd, J = 7.6, 1.0 Hz), 2.63 (3H, s); 19 F-NMR (376 MHz, CDCl 3 ) δ-77.2 (3F); 13 C-NMR (100 MHz, CDCl 3 ) δ 200.6, 145.6, 136.6, 132.6, 130.3, 128.0, 127.1, 119.6 (q, J = 327.0 Hz) 31.5.
Example-28
アルゴン雰囲気下、トリフルオロメタンスルホン酸（２−ニトロフェニル）（フェニル）ヨードニウム（１４２ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２０：１〜３：１）により精製し、１−ニトロ−２−（トリフルオロメチルスルホニル）ベンゼン（３９．２ｍｇ，１５４μｍｏｌ，５１％）を黄褐色固体として得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）δ８．２５（１Ｈ，ｄｄ，Ｊ＝７．７，１．４Ｈｚ），８．００（１Ｈ，ｍ），７．８７−７．９３（２Ｈ，ｍ）；１９Ｆ−ＮＭＲ（３７６ＭＨｚ，ＣＤＣｌ３）δ−７３．８（３Ｆ）；１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１４９．９，１３７．８，１３４．０，１３２．８，１２５．８，１２５．４，１１９．７（ｑ，Ｊ＝３２７．９Ｈｚ）．
実施例−２９
Under an argon atmosphere, trifluoromethanesulfonic acid (2-nitrophenyl) (phenyl) iodonium (142 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) The N, N-dimethylformamide (1.5 mL) solution was stirred at room temperature for 3 days, cooled to 0 ° C., a saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was extracted with a mixed solvent (hexane: ethyl acetate = 1: 1). did. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1-3: 1) to give 1-nitro-2- (trifluoromethylsulfonyl) benzene (39.2 mg, 154 μmol, 51 %) As a tan solid.
1 H-NMR (400 MHz, CDCl 3 ) δ 8.25 (1H, dd, J = 7.7, 1.4 Hz), 8.00 (1H, m), 7.87-7.93 (2H, m) 19 F-NMR (376 MHz, CDCl 3 ) δ-73.8 (3F); 13 C-NMR (100 MHz, CDCl 3 ) δ 149.9, 137.8, 134.0, 132.8, 125.8, 125.4, 119.7 (q, J = 327.9 Hz).
Example-29
アルゴン雰囲気下、トリフルオロメタンスルホン酸（４−メトキシカルボニルフェニル）（フェニル）ヨードニウム（１４６ｍｇ，３００μｍｏｌ）、トリフルオロメタンスルフィン酸ナトリウム（７０．２ｍｇ，４５０μｍｏｌ）及び酸化銅（Ｉ）（２．１ｍｇ，１５μｍｏｌ）のＮ，Ｎ−ジメチルホルムアミド（１．５ｍＬ）溶液を室温で３日間攪拌後、０℃に冷却し飽和炭酸水素ナトリウム水溶液を加え、水層を混合溶媒（ヘキサン：酢酸エチル＝１：１）で抽出した。得られた有機層を飽和食塩水で洗浄後、硫酸ナトリウムで乾燥、減圧濃縮した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２０：１〜３：１）により精製し、１Ｈ−ＮＭＲ及び１９Ｆ−ＮＭＲより４−（トリフルオロメチルスルホニル）安息香酸メチル（収率：４８％）及び（トリフルオロメチルスルホニル）ベンゼン（収率：３０％）の生成を確認した。 Under argon atmosphere, trifluoromethanesulfonic acid (4-methoxycarbonylphenyl) (phenyl) iodonium (146 mg, 300 μmol), sodium trifluoromethanesulfinate (70.2 mg, 450 μmol) and copper (I) oxide (2.1 mg, 15 μmol) Of N, N-dimethylformamide (1.5 mL) was stirred at room temperature for 3 days, cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, and the aqueous layer was mixed with a mixed solvent (hexane: ethyl acetate = 1: 1). Extracted. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1-3: 1), and methyl 4- (trifluoromethylsulfonyl) benzoate from 1 H-NMR and 19 F-NMR. Formation of (yield: 48%) and (trifluoromethylsulfonyl) benzene (yield: 30%) was confirmed.
Claims (7)
The method for producing a (trifluoromethylsulfonyl) benzene derivative according to any one of claims 1 to 6, wherein the copper compound is copper (I) oxide.
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