JP5696465B2 - ビス(トリフルオロメタンスルホニル)エチル基を有する化合物及び酸触媒、並びにその製造方法 - Google Patents
ビス(トリフルオロメタンスルホニル)エチル基を有する化合物及び酸触媒、並びにその製造方法 Download PDFInfo
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- JP5696465B2 JP5696465B2 JP2010281174A JP2010281174A JP5696465B2 JP 5696465 B2 JP5696465 B2 JP 5696465B2 JP 2010281174 A JP2010281174 A JP 2010281174A JP 2010281174 A JP2010281174 A JP 2010281174A JP 5696465 B2 JP5696465 B2 JP 5696465B2
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- Prior art keywords
- formula
- bis
- reaction
- trifluoromethanesulfonyl
- group
- 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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- 150000001875 compounds Chemical class 0.000 title claims description 53
- -1 bis (trifluoromethanesulfonyl) ethyl group Chemical group 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000003377 acid catalyst Substances 0.000 title description 24
- BFFOGQAVMGLUJF-UHFFFAOYSA-N 1,1,3,3-tetrakis(trifluoromethylsulfonyl)propane Chemical compound FC(F)(F)S(=O)(=O)C(S(=O)(=O)C(F)(F)F)CC(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F BFFOGQAVMGLUJF-UHFFFAOYSA-N 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 19
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- 239000011630 iodine Substances 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 54
- 238000006243 chemical reaction Methods 0.000 description 52
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 239000013078 crystal Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 22
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 21
- 238000005160 1H NMR spectroscopy Methods 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 238000005481 NMR spectroscopy Methods 0.000 description 20
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 239000011734 sodium Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 238000001953 recrystallisation Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 13
- 238000002844 melting Methods 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 238000000023 Kugelrohr distillation Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- QBOFWVRRMVGXIG-UHFFFAOYSA-N trifluoro(trifluoromethylsulfonylmethylsulfonyl)methane Chemical compound FC(F)(F)S(=O)(=O)CS(=O)(=O)C(F)(F)F QBOFWVRRMVGXIG-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 229910052751 metal Chemical class 0.000 description 5
- 239000002184 metal Chemical class 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- GBMVKGRKEQZYEK-UHFFFAOYSA-N 1,1-bis(trifluoromethylsulfonyl)ethene Chemical compound FC(F)(F)S(=O)(=O)C(=C)S(=O)(=O)C(F)(F)F GBMVKGRKEQZYEK-UHFFFAOYSA-N 0.000 description 4
- OOIHWQDHXASARN-UHFFFAOYSA-N 2-[2,2-bis(trifluoromethylsulfonyl)ethyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F)=C1 OOIHWQDHXASARN-UHFFFAOYSA-N 0.000 description 4
- 238000005698 Diels-Alder reaction Methods 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- DPZNOMCNRMUKPS-UHFFFAOYSA-N 1,3-Dimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1 DPZNOMCNRMUKPS-UHFFFAOYSA-N 0.000 description 3
- IOUPPRVFNSCDOP-UHFFFAOYSA-N 2,4,6-tris[2,2-bis(trifluoromethylsulfonyl)ethyl]benzene-1,3,5-triol Chemical compound OC1=C(CC(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F)C(O)=C(CC(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F)C(O)=C1CC(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F IOUPPRVFNSCDOP-UHFFFAOYSA-N 0.000 description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 101150065749 Churc1 gene Proteins 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 3
- 102100038239 Protein Churchill Human genes 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 238000007350 electrophilic reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000269 nucleophilic effect Effects 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 3
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- GSFIZZHILCKLGB-UHFFFAOYSA-N 2,6-bis[2,2-bis(trifluoromethylsulfonyl)ethyl]-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC(CC(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F)=C(O)C(CC(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F)=C1 GSFIZZHILCKLGB-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- SYMIGNCAFCNGGM-UHFFFAOYSA-N 3-[2,2-bis(trifluoromethylsulfonyl)ethyl]-2,6-dimethylphenol Chemical compound CC1=CC=C(CC(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F)C(C)=C1O SYMIGNCAFCNGGM-UHFFFAOYSA-N 0.000 description 2
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- TTYVYRHNIVBWCB-VNQPRFMTSA-N [(1r,2s,5r)-5-methyl-2-propan-2-ylcyclohexyl] benzoate Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1OC(=O)C1=CC=CC=C1 TTYVYRHNIVBWCB-VNQPRFMTSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229940075966 (+)- menthol Drugs 0.000 description 1
- NOOLISFMXDJSKH-AEJSXWLSSA-N (+)-menthol Chemical compound CC(C)[C@H]1CC[C@H](C)C[C@@H]1O NOOLISFMXDJSKH-AEJSXWLSSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- FZJFCCODVWMWAT-UHFFFAOYSA-N 1,1-bis(trifluoromethylsulfonyl)ethane Chemical compound FC(F)(F)S(=O)(=O)C(C)S(=O)(=O)C(F)(F)F FZJFCCODVWMWAT-UHFFFAOYSA-N 0.000 description 1
- CHLICZRVGGXEOD-UHFFFAOYSA-N 1-Methoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1 CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 1
- OXJZWVGQZOPRSP-UHFFFAOYSA-N 1-[2,2-bis(trifluoromethylsulfonyl)ethyl]-2,4-dimethoxybenzene Chemical compound COC1=CC=C(CC(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F)C(OC)=C1 OXJZWVGQZOPRSP-UHFFFAOYSA-N 0.000 description 1
- XDDPHNSTWQXOCU-UHFFFAOYSA-N 1-[2,2-bis(trifluoromethylsulfonyl)ethyl]naphthalen-2-ol Chemical compound C1=CC=CC2=C(CC(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F)C(O)=CC=C21 XDDPHNSTWQXOCU-UHFFFAOYSA-N 0.000 description 1
- CHBXCQHBCCLICW-UHFFFAOYSA-N 1-methyl-4-phenylmethoxybenzene Chemical compound C1=CC(C)=CC=C1OCC1=CC=CC=C1 CHBXCQHBCCLICW-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- FHRJRZSCSVQWJQ-UHFFFAOYSA-N 2,6-bis[2,2-bis(trifluoromethylsulfonyl)ethyl]-4-methylphenol Chemical compound CC1=CC(CC(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F)=C(O)C(CC(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F)=C1 FHRJRZSCSVQWJQ-UHFFFAOYSA-N 0.000 description 1
- ATGFTMUSEPZNJD-UHFFFAOYSA-N 2,6-diphenylphenol Chemical compound OC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 ATGFTMUSEPZNJD-UHFFFAOYSA-N 0.000 description 1
- IOHSAWJCIWNNTR-UHFFFAOYSA-N 2-[2,2-bis(trifluoromethylsulfonyl)ethyl]-1,4-dimethoxybenzene Chemical compound COC1=CC=C(OC)C(CC(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F)=C1 IOHSAWJCIWNNTR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
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- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
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Description
[発明2]
式[1]、[2]、又は[3]で表される化合物のうち、R1がそれぞれ独立に炭素数1〜6の直鎖もしくは分岐鎖のアルキル基であり、R2がそれぞれ独立に水素原子、又は炭素数1〜4の直鎖のアルキル基である、発明1に記載の化合物。
[発明4]
式[1]、[2]、又は[3]で表される化合物のうち、R1がそれぞれ独立に炭素数1〜6の直鎖もしくは分岐鎖のアルキル基であり、R2がそれぞれ独立に水素原子、又は炭素数1〜4の直鎖のアルキル基である、発明3に記載の酸触媒。
発明3又は4に記載の酸触媒を用いたディールズ・アルダー反応、アルドール型反応、フリーデル・クラフツ型反応、又はエステル化反応への使用。
を反応させることを特徴とする、式[1]で表されるビス(トリフルオロメタンスルホニル)エチル基を有する化合物
の製造方法。
を反応させることを特徴とする、式[2]で表されるビス(トリフルオロメタンスルホニル)エチル基を有する化合物
の製造方法。
を反応させることを特徴とする、式[3]で表されるビス(トリフルオロメタンスルホニル)エチル基を有する化合物
の製造方法。
まず、本願発明の対象とする化合物のうち、式[1]〜式[3]で表されるビス(トリフルオロメタンスルホニル)エチル基を有する化合物について説明する。
次に、式[1]〜式[3]で表されるビス(トリフルオロメタンスルホニル)エチル基を有する化合物の、酸触媒としての使用について説明する。
次に、式[1]〜式[3]で表されるビス(トリフルオロメタンスルホニル)エチル基を有する化合物の製造方法について説明する。
<1,1,3,3−テトラキス(トリフルオロメチルスルホニル)プロパン(4)Tf2CHCH2CHTf2の合成例>
塩化メチレン(50ml)に窒素を吹き込みながら攪拌して懸濁させたパラホルムアルデヒド(6.3g)を、窒素雰囲気下、40℃で還流しているビス(トリフルオロメチルスルホニル)メタン(112g,0.4mol)の塩化メチレン(300ml)溶液に、5時間かけてゆっくり加えた。
[実施例1]
1,1,3,3−テトラキス(トリフルオロメチルスルホニル)プロパン(4)(121.6mg,0.21mmol)を、フェノール(22.0mg,0.23mmol)のアセトニトリル(0.21ml)溶液に室温で加え、1時間反応させた。反応溶液を減圧下で濃縮した後、クーゲルロールによる蒸留精製(180−200℃/4mmHg)を経て、オルト/パラ異性体約2.3:1の混合物を得た。2−(2,2−ビス(トリフルオロメチルスルホニル)エチル)フェノール(1a)及び4−(2,2−ビス(トリフルオロメチルスルホニル)エチル)フェノール(1b)の混合物の収率は合計で72%であった(59.5mg,0.15mmol)。
[実施例2]
p−クレゾール(28.1mg,0.27mmol)のアセトニトリル(0.25ml)溶液に、1,1,3,3−テトラキス(トリフルオロメチルスルホニル)プロパン(4)(139.5mg,0.24mmol)を室温で加えた。3時間攪拌した後、反応溶液を減圧下で濃縮した。得られた残渣をクーゲルロール蒸留によって精製し(180−200℃/3mmHg)、2−(2,2−ビス(トリフルオロメチルスルホニル)エチル−4−メチルフェノール(1c)がほぼ定量的な収率で得られた(97.0mg,0.24mmol)。
[実施例3]
2,6−キシレノール(34.1mg,0.28mmol)のアセトニトリル(0.25ml)溶液に、1,1,3,3−テトラキス(トリフルオロメチルスルホニル)プロパン(4)(143.2mg,0.25mmol)を室温で加えた。3時間攪拌した後、反応溶液を減圧下で濃縮した。得られた残渣をクーゲルロール蒸留によって精製し(180−200℃/3mmHg)、4−(2,2−ビス(トリフルオロメチルスルホニル)エチル−2,6−ジメチルフェノール(1d)を収率94%で得た(96.9mg,0.234mmol)。更に、ヘキサンから再結晶して無色結晶を得た。
[実施例4]2,6−キシレノールの代わりに2,4−ジメチルフェノール(33.6mg、0.275mmol)を用いた他は実施例3と操作、条件とも同様に行った。その結果、2−(2,2−ビス(トリフルオロメチルスルホニル)エチル)−4,6−ジメチルフェノール(1e)
[実施例5]2,6−キシレノールの代わりに2−ブロモ−4−メチルフェノール(33.2μL、0.275mmol)を用い、100℃で10時間反応させた他は実施例3と操作、条件とも同様に行った。その結果、2−(2,2−ビス(トリフルオロメチルスルホニル)エチル)−6−ブロモ−4−メチルフェノール(1f)
[実施例6]2,6−キシレノールの代わりにメチル 2−ヒドロキシ−5−メチルベンゾエート(45.7mg、0.275mmol)を用い、100℃で24時間反応させた他は実施例3と操作、条件とも同様に行った。その結果、メチル 3−(2,2−ビス(トリフルオロメチルスルホニル)エチル)−2−ヒドロキシ−5−メチルベンゾエート(1g)
[実施例7]2,6−キシレノールの代わりにtert−ブチルフェノール(49.6mg、0.33mmol)、アセトニトリルを0.50mL用い、80℃で10時間反応させた他は実施例3と操作、条件とも同様に行った。その結果、2,6−ビス(2,2−ビス(トリフルオロメチルスルホニル)エチル)−4−tert−ブチルフェノール(1h)
[実施例8]2,6−キシレノールの代わりに1−メトキシ−4−メチルベンゼン(34.2mg、0.28mmol)を用い、室温で5時間反応させた他は実施例3と操作、条件とも同様に行った。その結果、2−(2,2−ビス(トリフルオロメチルスルホニル)エチル)−1−メトキシ−4−メチルベンゼン(1i)
[実施例9]2,6−キシレノールの代わりに1−(ベンジルオキシ)−4−メチルベンゼン(54.5mg、0.275mmol)を用い、塩化メチレン(50μL)、80℃で6時間反応させた他は実施例3と操作、条件とも同様に行った。その結果、1−(ベンジルオキシ)−2−(2,2−ビス(トリフルオロメチルスルホニル)エチル)−4−メチルベンゼン(1j)
[実施例10]2,6−キシレノールの代わりに1,4−ジメトキシベンゼン(34.5mg、0.25mmol)を用い、アセトニトリル(0.50mL)、室温で5時間反応させた他は実施例3と操作、条件とも同様に行った。その結果、2−(2,2−ビス(トリフルオロメチルスルホニル)エチル)−1,4−ジメトキシベンゼン(1k)
[実施例11]2,6−キシレノールの代わりに1,2−ジメトキシベンゼン(34.5mg、0.25mmol)を用い、アセトニトリルを0.50mL用いた他は実施例3と操作、条件とも同様に行った。その結果、4−(2,2−ビス(トリフルオロメチルスルホニル)エチル)−1,2−ジメトキシベンゼン(1l)
[実施例12]
2−ナフトール(79.0mg,0.55mmol)のアセトニトリル(0.5ml)溶液に、1,1,3,3−テトラキス(トリフルオロメチルスルホニル)プロパン(4)(285.8mg,0.50mmol)を室温で加えた。1時間攪拌した後、クロロホルムから再結晶することによって無色結晶の1−(2,2−ビス(トリフルオロメチルスルホニル)エチル)ナフタレン−2−オール(1m)を収率70%で得た(152.7mg,0.35mmol)。
[実施例13]
1,1,3,3−テトラキス(トリフルオロメチルスルホニル)プロパン(4)(101.7mg,0.18mmol)に対して1.0当量のN,N−ジメチルアニリン(22.5μl,0.18mmol)を、アセトニトリル(0.20ml)中80℃で3時間作用させた後、生成した固体をろ別し、塩化メチレン(約3ml)で洗浄した。減圧下で乾燥することによって分子内で塩を形成したビス(トリフルオロメチルスルホニル)エチル化生成物(2a)を収率95%で得た(70.1mg,0.17mmol)。更に、アセトンから再結晶して無色結晶を得た。
[実施例14]
2,6−ジフェニルフェノール(61.9mg,0.25mmol)のアセトニトリル(0.25ml)溶液に、1,1,3,3−テトラキス(トリフルオロメチルスルホニル)プロパン(4)(157.3mg,0.28mmol)を室温で加えた。9時間攪拌した後、クーゲルロール蒸留によって精製し(120℃/3mmHg)、4−(2,2−ビス(トリフルオロメチルスルホニル)エチル−2,6−ジフェニルフェノール(1n)を収率97%で得た(130.7mg,0.24mmol)。
[実施例15]
4−t−ブチルフェノール(43.6mg,0.29mmol)のアセトニトリル(0.25ml)溶液に、1,1,3,3−テトラキス(トリフルオロメチルスルホニル)プロパン(4)(148.8mg,0.264mmol)を室温で加えた。1時間攪拌した後、反応溶液を減圧下で濃縮した。得られた残渣をクーゲルロール蒸留によって精製し(190−210℃/5mmHg)、2−(2,2−ビス(トリフルオロメチルスルホニル)エチル−4−t−ブチルフェノール(1o)がほぼ定量的な収率で得られた(97.0mg,0.24、mmol)。
[実施例16]
5−メチルビフェニル−2−オール(40.0mg,0.22mmol)のアセトニトリル(0.20ml)溶液に、1,1,3,3−テトラキス(トリフルオロメチルスルホニル)プロパン(4)(113.0mg,0.20mmol)を加えて80℃で2時間攪拌した。反応溶液をクーゲルロール蒸留によって精製し(195−210℃/3mmHg)、3−(2,2−ビス(トリフルオロメチルスルホニル)エチル)−5−メチルビフェニル−2−オール(1p)が収率51%で得られた(48.4mg,0.10mmol)。
[実施例17]
p−クレゾール(21.1mg,0.19mmol)のアセトニトリル(0.20ml)溶液に、1,1,3,3−テトラキス(トリフルオロメチルスルホニル)プロパン(4)(330.4mg,0.58mmol)を加えて80℃で10時間攪拌した。反応溶液をクーゲルロール蒸留によって精製し(210−230℃/3mmHg)、2,6−ビス(2,2−ビス(トリフルオロメチルスルホニル)エチル)−4−メチルフェノール(1q)が収率74%で得られた(97.0mg,0.14mmol)。
[実施例18]
1,3−ジメトキシベンゼン(18)(34.5mg,0.25mmol)のアセトニトリル(0.50ml)溶液に、1,1,3,3−テトラキス(トリフルオロメチルスルホニル)プロパン(4)(172.5mg,0.30mmol)を室温で加えた。2時間攪拌した後、反応溶液をクーゲルロール蒸留によって精製し(180−190℃/3mmHg)、1−(2,2−ビス(トリフルオロメチルスルホニル)エチル)−2,4−ジメトキシベンゼン(1r)を収率80%で得た(86.3mg,0.201mmol)。更に、ベンゼンから再結晶して無色結晶を得た。
[実施例19]
ベンゼン−1,3,5−トリオール(126mg,1.0mmol)のアセトニトリル(1.0ml)溶液に、1,1,3,3−テトラキス(トリフルオロメチルスルホニル)プロパン(4)(1.89g,3.3mmol)を室温で加えた。7時間攪拌した後、ろ別した沈殿をクロロホルム(約5ml)で洗浄した。減圧下で乾燥して2,4,6−トリス(2,2−ビス(トリフルオロメチルスルホニル)エチル)ベンゼン−1,3,5−トリオール(1s)を収率64%で得た(838mg,0.64mmol)。更に、ジエチルエーテルから再結晶して無色結晶を得た。
[実施例20]
<向山アルドール反応触媒への応用>
触媒量の2,4,6−トリス(2,2−ビス(トリフルオロメチルスルホニル)エチル)ベンゼン−1,3,5−トリオール(1s)(0.5mg,0.5μmol)を含んだシクロヘキサノン(98.0mg,1.00mmol)の塩化メチレン(1.0ml)溶液に、2−TBSO−furan(詳細は後述の[表1]内に記述)(218mg,1.10mmol)のクロロホルム(1.0ml)溶液を室温でシリンジポンプを使用して120分かけて加えた。2時間攪拌した後、炭酸水素ナトリウムの飽和水溶液(20ml)を加え、酢酸エチル(20ml)で3回抽出した。有機層を合わせ、無水硫酸マグネシウム上で乾燥した。これを減圧下で濃縮し、シリカゲルのカラムクロマトグラフィー(ヘキサン/酢酸エチル=10:1〜1:1)を用いて精製した。得られた生成物は、シリル化体(8a)と少量の脱シリル化体(8b)を含んでおり、これらの合計として77%の収率で目的物であるアルドール付加体が得られた(227.3mg,0.77mmol)。シリル化体と脱シリル化体の比率は約97:3であった。
(8b):1H−NMR(400MHz,CD3Cl3)δ1.15−1.28(1H,m),1.40−1.76(9H,m),4.85(1H,t,J=1.7Hz),6.81(1H,dd,J=5.8,1.7Hz),7.51(1H,J=5.8,1.7Hz);13C−NMR(100MHz,CD3Cl3)δ21.0and21.1,25.4,33.4and33.5,72.6,89.3,122.7,153.5,173.0.
[実施例21]〜[実施例26]
4−(2,2−ビス(トリフルオロメチルスルホニル)エチル−2,6−ジメチルフェノール(1d)、2−(2,2−ビス(トリフルオロメチルスルホニル)エチル−4−メチルフェノール(1c)、2,6−ビス(2,2−ビス(トリフルオロメチルスルホニル)エチル)−4−tert−ブチルフェノール(1h)を用いて、各種当量を変更した他は、実施例20と同様に行った(なお、実施例21及び実施例26については、各種当量の変更の他に、反応時間を3〜5時間とした)。
<エステル反応触媒への応用>
(+)−メントール( 156mg, 1.0mmol)、安息香酸無水物(339mg, 1.5mmol)、2,4,6−トリス(2,2−ビス(トリフルオロメチルスルホニル)エチル)ベンゼン−1,3,5−トリオール(1s)(30mg, 30μmol)の混合物を、70℃ で3時間攪拌した。反応後、炭酸水素ナトリウムの飽和水溶液(10mL)を加え、酢酸エチル(15mL)で3回抽出した。有機層を飽和食塩水(10mL)で洗浄後、無水硫酸マグネシウムで乾燥した。これを減圧下で濃縮後、シリカゲルのカラムクロマトグラフィー(ヘキサン/酢酸エチル=30:1)で精製し、目的物である安息香酸メンチル(9)を収率は93%(241mg,0.93mmol)で得た。
<エステル反応触媒への応用>
2,4,6−トリス(2,2−ビス(トリフルオロメチルスルホニル)エチル)ベンゼン−1,3,5−トリオール(1s)の代わりに2,6−ビス(2,2−ビス(トリフルオロメチルスルホニル)エチル)−4−tert−ブチルフェノール(1h)を用いた他は、実施例27と同様に行った。その結果、目的物である安息香酸メンチル(9)を、収率は50%で得た。
<2−(2,2−ビス(トリフルオロメチルスルホニル)エチル−4−メチルフェノール(1c)の製造、及び酸触媒回収の例>
実施例2の1cの合成例と同様にして、p−クレゾール(108.1mg,1.00mmol)のアセトニトリル(1.0ml)溶液に、1,1,3,3−テトラキス(トリフルオロメチルスルホニル)プロパン(4)(574.4mg,1.00mmol)を室温で加えた。3時間攪拌した後、反応溶液を減圧下で濃縮した。得られた残渣をクーゲルロール蒸留によって精製し(180−200℃/3mmHg)、2−(2,2−ビス(トリフルオロメチルスルホニル)エチル−4−メチルフェノール(1c)を約90%の収率で得た(359.4mg,0.90mmol)。
Claims (3)
- 式[4]で表される1,1,3,3−テトラキス(トリフルオロメタンスルホニル)プロパン
を反応させることを特徴とする、式[1]で表されるビス(トリフルオロメタンスルホニル)エチル基を有する化合物
の製造方法。 - 式[4]で表される1,1,3,3−テトラキス(トリフルオロメタンスルホニル)プロパン
を反応させることを特徴とする、式[2]で表されるビス(トリフルオロメタンスルホニル)エチル基を有する化合物
の製造方法。 - 式[4]で表される1,1,3,3−テトラキス(トリフルオロメタンスルホニル)プロパン
を反応させることを特徴とする、式[3]で表されるビス(トリフルオロメタンスルホニル)エチル基を有する化合物
の製造方法。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010281174A JP5696465B2 (ja) | 2010-12-17 | 2010-12-17 | ビス(トリフルオロメタンスルホニル)エチル基を有する化合物及び酸触媒、並びにその製造方法 |
US13/994,520 US9314782B2 (en) | 2010-12-17 | 2011-12-08 | Bis(trifluoromethanesulfonyl)ethyl-bearing compound and acid catalyst, and method for preparing same |
DE112011103786T DE112011103786T5 (de) | 2010-12-17 | 2011-12-08 | Bis(Trifluormethansulfonyl)ethyl tragende Verbindung und Säurekatalysator und Verfahren zum Herstellen derselben |
CN201180060777.1A CN103261154B (zh) | 2010-12-17 | 2011-12-08 | 具有双(三氟甲磺酰基)乙基的化合物和酸催化剂及其制造方法 |
PCT/JP2011/078409 WO2012081488A1 (ja) | 2010-12-17 | 2011-12-08 | ビス(トリフルオロメタンスルホニル)エチル基を有する化合物及び酸触媒、並びにその製造方法 |
CN201410320540.8A CN104151215B (zh) | 2010-12-17 | 2011-12-08 | 具有双(三氟甲磺酰基)乙基的化合物的制造方法 |
GB1312783.2A GB2500551A (en) | 2010-12-17 | 2011-12-08 | Bis(trifluoromethanesulfonyl)ethyl-bearing compound and acid catalyst, and method for preparing same |
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US (1) | US9314782B2 (ja) |
JP (1) | JP5696465B2 (ja) |
CN (2) | CN103261154B (ja) |
DE (1) | DE112011103786T5 (ja) |
GB (1) | GB2500551A (ja) |
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JP6167791B2 (ja) * | 2012-09-25 | 2017-07-26 | セントラル硝子株式会社 | ビス(パーフルオロアルキルスルホニル)メチル基を含む化合物および塩の製造方法、それを用いた固体電解質膜 |
JP5998948B2 (ja) * | 2013-01-21 | 2016-09-28 | セントラル硝子株式会社 | ビス(トリフルオロメチルスルホニル)メチル基を有する化合物、その製造方法、およびその酸触媒としての使用方法 |
CN105903489A (zh) * | 2016-05-27 | 2016-08-31 | 北京化工大学 | 用于制备生物基对二甲苯的固体酸催化剂及其制备与应用 |
JP7448571B2 (ja) * | 2022-01-14 | 2024-03-12 | ポリプラスチックス株式会社 | ポリアセタール重合体の製造方法 |
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US3586616A (en) * | 1969-03-14 | 1971-06-22 | Minnesota Mining & Mfg | Bis(perfluoroalkylsulfonyl)methane metal salts in cationic polymerization |
DE2012013C3 (de) * | 1969-03-14 | 1980-09-18 | Minnesota Mining And Manufacturing Co., Saint Paul, Minn. (V.St.A.) | Verfahren zur kationischen Polymerisation von olefinisch ungesättigten Monomeren, von Epoxiverbindungen, Äthyleniminen oder Trioxan in Gegenwart von Polymerisationsinitiatoren |
US4053519A (en) | 1975-03-07 | 1977-10-11 | Minnesota Mining And Manufacturing Company | 1,1,3,3-tetrakis(perfluoroalkylsulfonyl)propanes |
US3962346A (en) | 1975-03-07 | 1976-06-08 | Minnesota Mining And Manufacturing Company | 1,1-Bis(perfluoroalkylsulfonyl)ethenes |
JP3166959B2 (ja) | 1994-03-11 | 2001-05-14 | セントラル硝子株式会社 | ルイス酸触媒 |
JPH0957110A (ja) | 1995-08-28 | 1997-03-04 | Central Glass Co Ltd | ルイス酸触媒 |
JPH09262479A (ja) | 1996-03-29 | 1997-10-07 | Kuraray Co Ltd | ルイス酸触媒 |
JP4127917B2 (ja) | 1999-01-29 | 2008-07-30 | 旭化成株式会社 | トリス(パーフルオロアルキルスルホニル)メチドの金属塩 |
AU2002222644A1 (en) | 2000-12-15 | 2002-06-24 | Japan Science And Technology Corporation | Arylbis (perfluoroalkylsulfonyl) methane, metal salt of the same, and processes for producing these |
CN101323650B (zh) * | 2007-06-13 | 2010-11-03 | 中国石油天然气股份有限公司 | 一种烯烃聚合催化剂及其制备方法和应用 |
CN101970400B (zh) * | 2008-03-13 | 2015-04-22 | 中央硝子株式会社 | 具有含氟碳负离子结构的盐及其衍生物、光产酸剂以及使用其的抗蚀材料和图案形成方法 |
JP5481944B2 (ja) * | 2008-06-12 | 2014-04-23 | セントラル硝子株式会社 | 含フッ素重合体およびそれを用いた帯電防止剤 |
CN101628950B (zh) * | 2009-08-07 | 2011-08-03 | 中国石油天然气股份有限公司 | 含磺酰基化合物的聚丙烯催化剂及其制备方法与应用 |
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- 2011-12-08 CN CN201410320540.8A patent/CN104151215B/zh not_active Expired - Fee Related
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CN103261154B (zh) | 2015-12-16 |
GB2500551A (en) | 2013-09-25 |
DE112011103786T5 (de) | 2013-09-12 |
US20140066659A1 (en) | 2014-03-06 |
US9314782B2 (en) | 2016-04-19 |
CN103261154A (zh) | 2013-08-21 |
JP2012126688A (ja) | 2012-07-05 |
CN104151215B (zh) | 2016-06-29 |
GB201312783D0 (en) | 2013-08-28 |
WO2012081488A1 (ja) | 2012-06-21 |
CN104151215A (zh) | 2014-11-19 |
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