JP6735278B2 - ハロゲン化s−(パーフルオロアルキル)ジベンゾチオフェニウム塩およびその生成方法 - Google Patents
ハロゲン化s−(パーフルオロアルキル)ジベンゾチオフェニウム塩およびその生成方法 Download PDFInfo
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- JP6735278B2 JP6735278B2 JP2017534695A JP2017534695A JP6735278B2 JP 6735278 B2 JP6735278 B2 JP 6735278B2 JP 2017534695 A JP2017534695 A JP 2017534695A JP 2017534695 A JP2017534695 A JP 2017534695A JP 6735278 B2 JP6735278 B2 JP 6735278B2
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- Japan
- Prior art keywords
- perfluoroalkyl
- dibenzothiophenium
- fluorinated
- salt
- 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 20
- 238000000034 method Methods 0.000 claims description 95
- 239000000203 mixture Substances 0.000 claims description 61
- 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 claims description 56
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 47
- 239000011541 reaction mixture Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 150000003839 salts Chemical class 0.000 claims description 24
- 229910052731 fluorine Inorganic materials 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 17
- 125000001153 fluoro group Chemical group F* 0.000 claims description 16
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 235000010290 biphenyl Nutrition 0.000 claims description 13
- 239000004305 biphenyl Substances 0.000 claims description 13
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical class C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 claims description 8
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 7
- 239000007848 Bronsted acid Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000006477 desulfuration reaction Methods 0.000 claims description 5
- 230000023556 desulfurization Effects 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- HHBZZTKMMLDNDN-UHFFFAOYSA-N 2-butan-2-yloxybutane Chemical compound CCC(C)OC(C)CC HHBZZTKMMLDNDN-UHFFFAOYSA-N 0.000 claims description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000003455 sulfinic acids Chemical class 0.000 claims 3
- 230000021615 conjugation Effects 0.000 claims 1
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical class [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 238000005481 NMR spectroscopy Methods 0.000 description 77
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 71
- 238000006243 chemical reaction Methods 0.000 description 50
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 48
- 239000000047 product Substances 0.000 description 45
- 239000000243 solution Substances 0.000 description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- -1 sodium tetrafluoroborate Chemical compound 0.000 description 27
- 239000003153 chemical reaction reagent Substances 0.000 description 26
- 238000001914 filtration Methods 0.000 description 20
- GAYJHUJLHJWCTH-UHFFFAOYSA-N 1-fluoro-3-(3-fluorophenyl)benzene Chemical group FC1=CC=CC(C=2C=C(F)C=CC=2)=C1 GAYJHUJLHJWCTH-UHFFFAOYSA-N 0.000 description 16
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 230000003595 spectral effect Effects 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 15
- WLVWCXRDONBKDB-UHFFFAOYSA-M 2,8-difluoro-5-(trifluoromethyl)dibenzothiophen-5-ium trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.Fc1ccc2[S+](c3ccc(F)cc3-c2c1)C(F)(F)F WLVWCXRDONBKDB-UHFFFAOYSA-M 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 14
- 239000011737 fluorine Substances 0.000 description 13
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 12
- 238000001819 mass spectrum Methods 0.000 description 12
- KAVUKAXLXGRUCD-UHFFFAOYSA-M sodium trifluoromethanesulfinate Chemical compound [Na+].[O-]S(=O)C(F)(F)F KAVUKAXLXGRUCD-UHFFFAOYSA-M 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 11
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 11
- 239000007858 starting material Substances 0.000 description 11
- 238000010626 work up procedure Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000000921 elemental analysis Methods 0.000 description 10
- 150000002894 organic compounds Chemical class 0.000 description 10
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 238000010183 spectrum analysis Methods 0.000 description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 239000012258 stirred mixture Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- UVFIXEGOSUKAPD-UHFFFAOYSA-N 5-(trifluoromethyl)dibenzothiophen-5-ium Chemical class C1=CC=C2[S+](C(F)(F)F)C3=CC=CC=C3C2=C1 UVFIXEGOSUKAPD-UHFFFAOYSA-N 0.000 description 7
- QULYNCCPRWKEMF-UHFFFAOYSA-N parachlorobenzotrifluoride Chemical compound FC(F)(F)C1=CC=C(Cl)C=C1 QULYNCCPRWKEMF-UHFFFAOYSA-N 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- OSDMDUISKPVVEC-UHFFFAOYSA-M 2,3,7,8-tetrafluoro-5-(trifluoromethyl)dibenzothiophen-5-ium trifluoromethanesulfonate Chemical compound FC(S(=O)(=O)[O-])(F)F.FC1=CC2=C([S+](C3=C2C=C(C(=C3)F)F)C(F)(F)F)C=C1F OSDMDUISKPVVEC-UHFFFAOYSA-M 0.000 description 6
- QDVBPRHCDXJHMH-UHFFFAOYSA-N 4-fluoro-2-(3-fluorophenyl)-1-(trifluoromethylsulfinyl)benzene Chemical group FC=1C=C(C(=CC=1)S(=O)C(F)(F)F)C1=CC(=CC=C1)F QDVBPRHCDXJHMH-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006692 trifluoromethylation reaction Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 5
- REXSZQOQQIMKHL-UHFFFAOYSA-N 2,8-difluoro-5-(trifluoromethyl)dibenzothiophen-5-ium Chemical compound FC1=CC2=C([S+](C3=C2C=C(C=C3)F)C(F)(F)F)C=C1 REXSZQOQQIMKHL-UHFFFAOYSA-N 0.000 description 5
- KAZGCDLQXWEKEL-UHFFFAOYSA-M 2,8-difluoro-5-(trifluoromethyl)dibenzothiophen-5-ium chloride Chemical compound [Cl-].FC1=CC2=C([S+](C3=C2C=C(C=C3)F)C(F)(F)F)C=C1 KAZGCDLQXWEKEL-UHFFFAOYSA-M 0.000 description 5
- ZFSHDTLSXRUGFP-UHFFFAOYSA-N 4-(3,4-difluorophenyl)-1,2-difluorobenzene Chemical group C1=C(F)C(F)=CC=C1C1=CC=C(F)C(F)=C1 ZFSHDTLSXRUGFP-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- AWBAEJYMKODJAE-UHFFFAOYSA-N 2,3,7,8-tetrafluorodibenzothiophene Chemical compound FC1=CC2=C(SC3=C2C=C(C(=C3)F)F)C=C1F AWBAEJYMKODJAE-UHFFFAOYSA-N 0.000 description 4
- 0 CC=Cc1c(C=*)c2ccccc2[s]1 Chemical compound CC=Cc1c(C=*)c2ccccc2[s]1 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical group OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 150000008282 halocarbons Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- PZDAAZQDQJGXSW-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)benzene Chemical group C1=CC(F)=CC=C1C1=CC=C(F)C=C1 PZDAAZQDQJGXSW-UHFFFAOYSA-N 0.000 description 3
- IOYLIZCLDSMERO-UHFFFAOYSA-N 2,6-difluorodibenzothiophene Chemical compound FC1=CC2=C(SC3=C2C=CC=C3F)C=C1 IOYLIZCLDSMERO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- YBKCOFSJGXNOKP-UHFFFAOYSA-N methyl 3-oxo-1,2-dihydroindene-2-carboxylate Chemical compound C1=CC=C2C(=O)C(C(=O)OC)CC2=C1 YBKCOFSJGXNOKP-UHFFFAOYSA-N 0.000 description 3
- PIPFYXGPIBROMU-UHFFFAOYSA-N methyl 3-oxo-2-(trifluoromethyl)-1h-indene-2-carboxylate Chemical compound C1=CC=C2C(=O)C(C(=O)OC)(C(F)(F)F)CC2=C1 PIPFYXGPIBROMU-UHFFFAOYSA-N 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 230000003389 potentiating effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000013074 reference sample Substances 0.000 description 3
- ZFRKQXVRDFCRJG-UHFFFAOYSA-N skatole Chemical compound C1=CC=C2C(C)=CNC2=C1 ZFRKQXVRDFCRJG-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 3
- QXXHXTRTGZBOGD-UHFFFAOYSA-M trifluoromethanesulfonate;5-(trifluoromethyl)dibenzothiophen-5-ium Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=C2[S+](C(F)(F)F)C3=CC=CC=C3C2=C1 QXXHXTRTGZBOGD-UHFFFAOYSA-M 0.000 description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- JNZFHLGRUWVTGK-UHFFFAOYSA-N 1-(3,5-difluorophenyl)-3,5-difluorobenzene Chemical group FC1=CC(F)=CC(C=2C=C(F)C=C(F)C=2)=C1 JNZFHLGRUWVTGK-UHFFFAOYSA-N 0.000 description 2
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- CBINVWSQQQCRLY-UHFFFAOYSA-N 2,8-difluorodibenzothiophene Chemical compound C1=C(F)C=C2C3=CC(F)=CC=C3SC2=C1 CBINVWSQQQCRLY-UHFFFAOYSA-N 0.000 description 2
- UFHJPDAMFQMMJU-UHFFFAOYSA-N 2-fluoro-4-(3-fluorophenyl)-1-(trifluoromethylsulfinyl)benzene Chemical group FC=1C=C(C=CC=1S(=O)C(F)(F)F)C1=CC(=CC=C1)F UFHJPDAMFQMMJU-UHFFFAOYSA-N 0.000 description 2
- ZQTPBODDVRYHSY-UHFFFAOYSA-N 3-methyl-2-(trifluoromethyl)-1h-indole Chemical compound C1=CC=C2C(C)=C(C(F)(F)F)NC2=C1 ZQTPBODDVRYHSY-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- CGDXUTMWWHKMOE-UHFFFAOYSA-N difluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)F CGDXUTMWWHKMOE-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- WXACOVNAZWPSJM-UHFFFAOYSA-N diphenyl(trifluoromethyl)phosphane Chemical compound C=1C=CC=CC=1P(C(F)(F)F)C1=CC=CC=C1 WXACOVNAZWPSJM-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MDKXBBPLEGPIRI-UHFFFAOYSA-N ethoxyethane;methanol Chemical compound OC.CCOCC MDKXBBPLEGPIRI-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- IKGLACJFEHSFNN-UHFFFAOYSA-N hydron;triethylazanium;trifluoride Chemical compound F.F.F.CCN(CC)CC IKGLACJFEHSFNN-UHFFFAOYSA-N 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
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- AMFRKRKTBYNSMP-UHFFFAOYSA-M lithium;trifluoromethanesulfinate Chemical compound [Li+].[O-]S(=O)C(F)(F)F AMFRKRKTBYNSMP-UHFFFAOYSA-M 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- OYIZLPKQAMHVMI-UHFFFAOYSA-N methyl 4-(2,2,2-trifluoroethyl)benzoate Chemical compound COC(=O)C1=CC=C(CC(F)(F)F)C=C1 OYIZLPKQAMHVMI-UHFFFAOYSA-N 0.000 description 1
- NLWBJPPMPLPZIE-UHFFFAOYSA-N methyl 4-(bromomethyl)benzoate Chemical compound COC(=O)C1=CC=C(CBr)C=C1 NLWBJPPMPLPZIE-UHFFFAOYSA-N 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- PHWISQNXPLXQRU-UHFFFAOYSA-N n,n-dimethylcarbamothioyl chloride Chemical compound CN(C)C(Cl)=S PHWISQNXPLXQRU-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 description 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- ZXUCBXRTRRIBSO-UHFFFAOYSA-L tetrabutylazanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC ZXUCBXRTRRIBSO-UHFFFAOYSA-L 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 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
- UPGBQYFXKAKWQC-UHFFFAOYSA-N trifluoromethylsulfonylbenzene Chemical compound FC(F)(F)S(=O)(=O)C1=CC=CC=C1 UPGBQYFXKAKWQC-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Description
本発明は、有用な求電子性パーフルオロアルキル化剤である新規なS−(パーフルオロアルキル)ジベンゾチオフェニウム塩、およびその生成方法に関する。
パーフルオロアルキル基は、非常に有用な官能基である。なぜなら、これは、高い電気陰性度、高い安定性、および高い親油性などの、独特の特性を有するからである(例えば、P.Kirsch,「Modern Fluoroorganic Chemistry,Synthesis,Reactivity,Applications」,Wiley−VCH Verlag GmbH & Co.KGaA,Weinheim,2004を参照のこと)。パーフルオロアルキル基のうちでもとりわけ、1個〜4個の炭素の低級パーフルオロアルキル基、特に、トリフルオロメチル基は、有効な医薬、農薬、および他の有用な物質を開発するために重要である。従って、トリフルオロメチル基を有する多くの有用な医薬および農薬が開発されている(例えば、K.L.Kirk,J.Fluorine Chem.2006,127,1013−1029;S.Purser et al.,Chem.Soc.Rev.,2008,37,237−432;G.Theodoridis,「Fluorine and the environment」,Vol.2,Chapter 4,pp 121−175(2006)(ISSN 1872−0358)を参照のこと)。従って、これらの製造プロセスを改善し、そしてより有効な医薬、農薬、および他のものを作製する目的で、パーフルオロアルキル化有機化合物を調製するための新規な方法を作製するための活発な研究および開発が続けられている(例えば、J.−A.Ma,D.Cahard,Journal of Fluorine Chemistry,2007,128,975−996;G.K.S.Prakash,A.K.Yudin,Chem.Rev.,1997,97,757−786;T.Umemoto,Chem.Rev.,1996,96,1757−1778を参照のこと)。これらのうちでもとりわけ、求電子性のトリフルオロメチル化剤が特に有用である。なぜなら、これらは、求核性有機分子を直接トリフルオロメチル化することができるからである。従って、トリフルオロメチル化有機化合物を生成するための、多くの求電子性トリフルオロメチル化剤が報告されている(例えば、S.Barata−Vallejo,B.Lantano,A.Postigo,Chem.Eur.J.2014,12,16806−16829;Y.Mace,E.Magnier,Eur.J.Org.Chem.2012,2479−2494;N.Shibata et al.,Beilstein J.Org.Chem.,2010,6,No.65を参照のこと)。
本発明は、強力な求電子性パーフルオロアルキル化剤として有用な、新規なハロゲン化S−(パーフルオロアルキル)ジベンゾチオフェニウム塩を提供すること、およびその費用効果的かつ環境保護を考慮した生成方法を提供することである。
上記課題を解決するために、本発明者らは、上記条件の全てを満足し得る、新規な特定のS−(パーフルオロアルキル)ジベンゾチオフェニウム塩を作製する考えを徹底的に研究した。その結果、本発明者らは、上記条件の全てを満足し得る、新規なハロゲン化S−(パーフルオロアルキル)ジベンゾチオフェニウム塩を作製することに成功した。
によって表される化合物であり得る。
方法2
この方法2のために使用可能な、X’=CF3SO3であるハロゲン化S−(パーフルオロアルキル)ジベンゾチオフェニウム塩は、上記方法1によって調製され得る。この方法2のために使用可能な、CF3SO3とは異なるX’を有するハロゲン化S−(パーフルオロアルキル)ジベンゾチオフェニウム塩は、X’=CF3SO3であるハロゲン化S−(パーフルオロアルキル)ジベンゾチオフェニウム塩から、対陰イオン置換反応によって調製され得る。好ましいX’として、CF3SO3、Cl、Br、およびHSO4が例示される。
本発明の、上記一般式(I)によって表されるハロゲン化S−(パーフルオロアルキル)ジベンゾチオフェニウム塩は、パーフルオロアルキル化有機化合物を調製するための広範な用途の、有用な求電子性パーフルオロアルキル化剤である(以下の実施例17〜30を参照のこと)。
実施形態(実施例)
2,8−ジフルオロ−S−(トリフルオロメチル)ジベンゾチオフェニウム塩(0.75mmol)を、1−オキソ−2−インダンカルボン酸メチル(0.5mmol)、K2CO3(1.5mmol)、およびテトラブチルアンモニウムヨージド(0.025mmol)の、5mLのN,N−ジメチルホルムアミド(DMF)中の撹拌溶液に窒素雰囲気下室温で添加した。この混合物を1時間撹拌した。この反応混合物を、4−クロロベンゾトリフルオリドを標準物質として使用する19F NMRによって分析した。2,8−ジフルオロ−S−(トリフルオロメチル)ジベンゾチオフェニウム塩として、2,8−ジフルオロ−S−(トリフルオロメチル)ジベンゾチオフェニウムトリフルオロメタンスルホネート(実施例18)、2,8−ジフルオロ−S−(トリフルオロメチル)ジベンゾチオフェニウムクロリド(実施例19)、および2,8−ジフルオロ−S−(トリフルオロメチル)ジベンゾチオフェニウムテトラフルオロボレート(実施例20)を使用した。この19F NMR分析は、トリフルオロメチル化生成物である1−オキソ−2−(トリフルオロメチル)インダン−2−カルボン酸メチルが、実施例18、19、および20においてそれぞれ、85%、91%、および100%の収率で生成したことを示した(表2を参照のこと)。CF3−生成物を標準的な後処理により単離し、そしてスペクトル解析により同定した:19F NMR (376.5 MHz, CDCl3) δ -69.3 (s, CF3)。
ハロゲン化S−(トリフルオロメチル)ジベンゾチオフェニウム塩(1mmol)、アニリン(2mmol)、および4−クロロベンゾトリフルオリド(1mmol)のN,N−ジメチルホルムアミド(DMF)(2mL)中の混合物を、窒素雰囲気下30℃で3時間撹拌した。ハロゲン化S−(トリフルオロメチル)ジベンゾチオフェニウム塩として、2,3,7,8−テトラフルオロ−S−(トリフルオロメチル)ジベンゾチオフェニウムトリフルオロメタンスルホネート(実施例22)、2,8−ジフルオロ−S−(トリフルオロメチル)ジベンゾチオフェニウムトリフルオロメタンスルホネート(実施例23)、および2,6−ジフルオロ−S−(トリフルオロメチル)ジベンゾチオフェニウムトリフルオロメタンスルホネート(実施例24)を使用した、アニリン(2mmol)の半分(1mmol)を、この反応のための塩基として使用した。なぜなら、この反応は、1mmolのトリフルオロメタンスルホン酸を生成したからである。4−コロベンゾトリフルオリド(4-Chorobenzotrifluoride)が、19F NMR分析のための標準物質であった。反応混合物の各々を、19F NMRによって分析した。その結果を表3に示す。生成物である2−および4−(トリフルオロメチル)アニリンを、基準試料とのスペクトル比較により同定した。
アニリンと、S−(トリフルオロメチル)ジベンゾチオフェニウムトリフルオロメタンスルホネート(梅本試薬)との反応を、梅本試薬をハロゲン化S−(トリフルオロメチル)ジベンゾチオフェニウム塩の代わりに使用したこと以外は実施例22〜24と同じ方法で行った。その結果を表3に示す。
Claims (19)
- Rfは、トリフルオロメチル(CF3)基である、請求項1に記載のフッ素化S−(パーフルオロアルキル)ジベンゾチオフェニウム塩。
- R 2 =R 7 =F、R 3 =R 4 =R 5 =R 6 =Hである、または、R 3 =R 6 =F、R 2 =R 4 =R 5 =R 7 =Hである、または、R 2 =R 5 =F、R 3 =R 4 =R 6 =R 7 =Hである、または、R 2 =R 3 =R 6 =R 7 =F、R 4 =R 5 =Hである、請求項1に記載のフッ素化S−(パーフルオロアルキル)ジベンゾチオフェニウム塩。
- X−は、CF3SO3 −、Cl−、Br−、BF4 −、PF6 −、またはHSO4 −である、請求項1に記載のフッ素化S−(パーフルオロアルキル)ジベンゾチオフェニウム塩。
- 一般式(Ia’):
によって表されるフッ素化S−(パーフルオロアルキル)ジベンゾチオフェニウム塩を調製する方法であって、該方法は、一般式(IIa)によって表されるフッ素化ビフェニルを、一般式RfSO2Mによって表されるパーフルオロアルカンスルフィン酸塩と、トリフルオロメタンスルホン酸無水物[(CF3SO2)2O]、トリフルオロメタンスルホン酸(CF3SO3H)、および/または一般式(RCO)2Oによって表されるカルボン酸無水物との任意の組み合わせ物と反応させる工程:
を包含し、ここでRfは、1個〜4個の炭素を有するパーフルオロアルキル基であり;R2、R3、R4、R5、R6 およびR7の各々は、水素原子またはフッ素原子であり、ただし、R 2〜7 のフッ素原子の総数は2〜4であり;Mは、金属原子またはアンモニウム部分であり;そしてRは、1個〜4個の炭素を有するアルキル基またはハロアルキル基である、方法。 - 前記方法は、前記フッ素化ビフェニルを、前記パーフルオロアルカンスルフィン酸塩およびトリフルオロメタンスルホン酸無水物と反応させる工程を包含する、請求項5に記載の方法。
- 前記方法は、前記フッ素化ビフェニルを、前記パーフルオロアルカンスルフィン酸塩、トリフルオロメタンスルホン酸無水物、および前記カルボン酸無水物と反応させる工程を包含する、請求項5に記載の方法。
- 前記方法は、前記フッ素化ビフェニルを、前記パーフルオロアルカンスルフィン酸塩、トリフルオロメタンスルホン酸、および前記カルボン酸無水物と反応させる工程を包含する、請求項5に記載の方法。
- 前記方法は、前記フッ素化ビフェニルを、前記パーフルオロアルカンスルフィン酸塩、トリフルオロメタンスルホン酸無水物、トリフルオロメタンスルホン酸、および前記カルボン酸無水物と反応させる工程を包含する、請求項5に記載の方法。
- 前記方法は、(第一の工程)前記パーフルオロアルカンスルフィン酸塩をトリフルオロメタンスルホン酸無水物と混合する工程;および(第二の工程)前記フッ素化ビフェニルを該第一の工程の混合物と混合する工程を包含する、請求項5に記載の方法。
- Rfはトリフルオロメチル(CF3)基である、請求項5〜10に記載の方法。
- 前記有機溶媒は、ジエチルエーテル、ジプロピルエーテル、ジ(イソプロピル)エーテル、ジブチルエーテル、ジ(イソブチル)エーテル、ジ(sec−ブチル)エーテル、tert−ブチルメチルエーテル、1,2−ジメトキシエタン、1,2−ジエトキシエタン、ジオキサン、ジグリム、酢酸エチル、酢酸プロピル、酢酸イソプロピル、プロピオン酸エチル、ジクロロメタン、クロロホルム、四塩化炭素、ジクロロエタン、ベンゼン、トルエン、キシレン、クロロベンゼン、ジクロロベンゼン、フルオロベンゼン、ベンゾトリフルオリド、n−ペンタンおよびその異性体、n−ヘキサンおよびその異性体、n−ヘプタンおよびその異性体、ならびにn−オクタンおよびその異性体の群から選択される、請求項13〜14に記載のプロセス。
- 一般式(Ia):
によって表されるフッ素化S−(パーフルオロアルキル)ジベンゾチオフェニウム塩を調製する方法であって、該方法は、一般式(Ia”):
によって表されるフッ素化S−(パーフルオロアルキル)ジベンゾチオフェニウム塩を、(M’)+X−と反応させる工程を包含し、
ここでRfは、1個〜4個の炭素を有するパーフルオロアルキル基であり;R2、R3、R4、R5、R6およびR7の各々は、水素原子またはフッ素原子であり、ただし、R 2〜7 のフッ素原子の総数は2〜4であり;M’は、水素原子、金属原子、またはアンモニウム部分であり;そしてX−および(X’)−の各々は、ブレンステッド酸の共役塩基であり、ただし、X−と(X’)−とは異なる、方法。 - M’は、H、Li、Na、K、またはAgであり、そしてX’は、CF3SO3、Cl、Br、またはHSO4である、請求項16に記載の方法。
- Rfはトリフルオロメチル(CF3)基である、請求項18に記載のフッ素化2−[(パーフルオロアルキル)スルフィニル]ビフェニル。
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