WO2012081488A1 - 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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- WO2012081488A1 WO2012081488A1 PCT/JP2011/078409 JP2011078409W WO2012081488A1 WO 2012081488 A1 WO2012081488 A1 WO 2012081488A1 JP 2011078409 W JP2011078409 W JP 2011078409W WO 2012081488 A1 WO2012081488 A1 WO 2012081488A1
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- formula
- reaction
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- arbitrary integer
- alkyl group
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 59
- -1 Bis(trifluoromethanesulfonyl)ethyl Chemical group 0.000 title claims abstract description 37
- 239000003377 acid catalyst Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 238000005698 Diels-Alder reaction Methods 0.000 claims abstract description 6
- 238000005886 esterification reaction Methods 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 26
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 23
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 12
- 229910052740 iodine Inorganic materials 0.000 claims description 12
- 239000011630 iodine Substances 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 24
- 239000003054 catalyst Substances 0.000 abstract description 22
- 150000002989 phenols Chemical class 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 7
- 239000002841 Lewis acid Substances 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 150000007517 lewis acids Chemical class 0.000 abstract description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract description 2
- 238000006845 Michael addition reaction Methods 0.000 abstract description 2
- 238000006053 organic reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 54
- 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
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 21
- 238000005160 1H NMR spectroscopy Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 238000005481 NMR spectroscopy Methods 0.000 description 19
- 239000011734 sodium Substances 0.000 description 19
- 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
- 238000001953 recrystallisation Methods 0.000 description 14
- 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
- 230000008018 melting Effects 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 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
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 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
- 230000008569 process Effects 0.000 description 6
- 150000003839 salts Chemical class 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
- 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
- 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
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-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
- 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
- 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
- 0 C=*C(C(CC=I)C=I)=*C=*1NC1 Chemical compound C=*C(C(CC=I)C=I)=*C=*1NC1 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
- 239000003446 ligand Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material 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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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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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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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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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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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
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- B01J2231/326—Diels-Alder or other [4+2] cycloadditions, e.g. hetero-analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/10—Non-coordinating groups comprising only oxygen beside carbon or hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a compound having a bis (trifluoromethanesulfonyl) ethyl group, an acid catalyst, and a method for producing the same.
- solid acid catalysts have been developed.
- solid acid catalysts have also been used for aromatic alkylation where aluminum chloride has been mainly used.
- Most of the synthesis processes of ethylbenzene and cumene are zeolite catalysts (MCM-22 (MWW)), etc.
- MCM-22 (MWW) zeolite catalysts
- MCM-22 (MWW) zeolite catalysts
- the advantages of the solid catalyst are fully utilized for the synthesis reaction of an organic compound having a relatively simple structure to which a flow-type high temperature process can be applied.
- These solid acid catalysts are also referred to as heterogeneous catalysts, and are particularly useful for synthesizing basic chemical products and purifying exhaust gases of automobile engines, and are used in large quantities.
- organometallic complexes and organic acids have been used as catalysts in organic synthesis reactions under various conditions. Since these compounds with catalytic action are easily soluble in various organic solvents, they are very useful for organic synthesis and polymer synthesis in the liquid phase, and have a sulfonic acid skeleton like the conventionally known sulfuric acid and methanesulfonic acid. Molecules have also been developed as catalysts.
- an organic acid substituted with a trifluoromethanesulfonyl group (trifuryl, CF 3 SO 2 ) group showing very strong electron withdrawing property is known as a super strong acid having an acidity higher than that of sulfuric acid.
- Bis (trifluoromethanesulfonyl) methane having two trifuryl groups on the same carbon and tris (trifluoromethanesulfonyl) methide having three trifuryl groups on the same carbon are also examples of compounds showing strong acidity.
- Patent Document 1 discloses arylbis (perfluoroalkylsulfonyl) methane and a metal salt thereof, and a production method thereof.
- Patent Document 2 discloses a Lewis acid catalyst having an increased catalytic activity in an organic synthesis reaction by an electrophilic reaction as a general formula M [RfSO 2 —N—SO 2 Rf ′] n or M [RfSO 2 —N —SO 2 Rf ′] n ⁇ mH 2 O (Rf and Rf ′ represent a perfluoroalkyl group having 1 to 8 carbon atoms, M is an alkali metal, alkaline earth metal, transition metal, lead, arsenic, antimony Represents an element selected from bismuth, selenium, and tellurium, n represents an integer of the same number as the valence of the corresponding metal, and m represents a natural number of 0.5 to 20.)
- a complex having various perfluoroalkanesulfonylimide groups and an organic synthesis reaction by various electrophilic reactions using the complex as a catalyst are disclosed.
- Patent Document 4 discloses a general formula M + (X 1 ⁇ ) q (wherein M represents at least one metal selected from the group consisting of Group IIIA to VB elements of the periodic table, and X 1 Represents a halogen atom, q represents the same integer as the valence number of M), and can be used even in the presence of water, consisting of a specific metal halide and a quaternary salt type anion exchange resin.
- a highly active Lewis acid catalyst is disclosed.
- Patent Document 6 discloses 1,1,3,3-tetrakis (trifluoromethanesulfonyl) propane ((CF 3 SO 2 ) 2 as an acid catalyst useful for a carbon-carbon bond forming reaction.
- CHCH 2 CH (SO 2 CF 3 ) 2 ; Tf 2 CHCH 2 CHTf 2 ) is disclosed
- Patent Document 7 discloses 1,1-bis (trifluoromethanesulfonyl) ethene ((CF 3 SO 2 ) 2 C ⁇ CH 2 ) is disclosed.
- Non-Patent Document 1 also discloses a method for producing 1,1-bis ((trifluoromethyl) sulfonyl) ethane and 1,1-bis ((trifluoromethyl) sulfonyl) phenylethane.
- Non-Patent Document 2 discloses various carbon-carbon skeleton formation reactions using the above-mentioned 1,1,3,3-tetrakis (trifluoromethanesulfonyl) propane as an acid catalyst.
- a catalyst with excellent catalytic activity and selectivity can essentially simplify the manufacturing process.
- Design is desired.
- the above-described synthesis reaction using an organometallic complex as a catalyst can exhibit high catalytic activity and selectivity under mild conditions by skillfully combining a central metal, a ligand, a reaction solvent, and the like.
- organometallic complexes are less thermally stable than heterogeneous catalysts, and control of side reactions such as catalyst degradation, demetalization, and ligand decomposition in the catalyst separation process must be considered. It has the disadvantage that the separation process becomes complicated.
- An object of the present invention is to provide a carbon acid compound having a bis (trifluoromethanesulfonyl) ethyl group as an acid catalyst in various organic synthesis reactions that reduce waste and that does not corrode and have no toxicity. There is to do.
- the present inventors have intensively studied to solve the above problems. As a result, a specific phenol compound having a bis (trifluoromethanesulfonyl) ethyl group has been found.
- this compound can be used as an acid catalyst in various organic synthesis reactions such as Diels-Alder reaction, Friedel-Crafts reaction, Michael addition reaction, esterification reaction and the like.
- the present invention provides the following [Invention 1] to [Invention 8].
- [Invention 1] A compound having a bis (trifluoromethanesulfonyl) ethyl group represented by the following formula [1], [2], or [3].
- each R 1 independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aromatic hydrocarbon group, or a halogen atom.
- a part of hydrogen atoms of the alkyl group or the aromatic hydrocarbon group may contain a halogen (fluorine, chlorine, bromine, and iodine), an oxygen atom, or a carbonyl bond.
- R 2 , R 3 , and R 4 each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms.
- l is an arbitrary integer of 0 to 2
- n is independently an arbitrary integer of 1 to 5
- m is independently an arbitrary integer of 0 to 4
- o is independent
- n is each independently an arbitrary integer of 1 to 5
- m is independently an arbitrary integer of 0 to 4
- o is independently an arbitrary integer of 1 to 3 and It satisfies m + n + o ⁇ 5.
- R 1 and R 2 and R 3 and R 4 they may be the same or different.
- R 1 is each independently a linear or branched alkyl group having 1 to 6 carbon atoms
- R 2 is independently The compound according to invention 1, which is a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms.
- An acid catalyst comprising a compound having a bis (trifluoromethanesulfonyl) ethyl group represented by the following formula [1], [2], or [3].
- each R 1 independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aromatic hydrocarbon group, or a halogen atom.
- a part of hydrogen atoms of the alkyl group or the aromatic hydrocarbon group may contain a halogen (fluorine, chlorine, bromine, and iodine), an oxygen atom, or a carbonyl bond.
- R 2 , R 3 , and R 4 each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms.
- l is an arbitrary integer of 0 to 2
- n is independently an arbitrary integer of 1 to 5
- m is independently an arbitrary integer of 0 to 4
- o is independent
- n is each independently an arbitrary integer of 1 to 5
- m is independently an arbitrary integer of 0 to 4
- o is independently an arbitrary integer of 1 to 3 and It satisfies m + n + o ⁇ 5.
- R 1 and R 2 and R 3 and R 4 they may be the same or different.
- R 1 is each independently a linear or branched alkyl group having 1 to 6 carbon atoms
- R 2 is independently The acid catalyst according to invention 3, which is a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms.
- each R 1 independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group, and the alkyl group or the aromatic hydrocarbon group A part of hydrogen atoms may contain a halogen (fluorine, chlorine, bromine, and iodine), an oxygen atom, or a carbonyl bond.
- R 2 each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms.
- R 1 and R 2 s are an arbitrary integer of 0 to 2
- n is independently an arbitrary integer of 1 to 5
- m is independently an arbitrary integer of 0 to (6-n).
- R 1 and R 2 s may be the same or different.
- o independently represents an arbitrary integer of 1 to 3, and satisfies m + n + o ⁇ 6.
- each R 1 independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aromatic hydrocarbon group, and the alkyl group or the aromatic hydrocarbon group A part of hydrogen atoms may contain a halogen (fluorine, chlorine, bromine, and iodine), an oxygen atom, or a carbonyl bond.
- R 3 and R 4 each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms.
- R 1 and R 2 and R 3 and R 4 are independently an arbitrary integer of 1 to 5
- m is independently an arbitrary integer of 0 to (6-n).
- R 1 and R 2 and R 3 and R 4 they may be the same or different.
- o independently represents an arbitrary integer of 1 to 3, and satisfies m + n + o ⁇ 6.
- each R 1 independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aromatic hydrocarbon group, and the alkyl group or the aromatic hydrocarbon group.
- a part of the hydrogen atom may contain a halogen (fluorine, chlorine, bromine, and iodine), an oxygen atom, or a carbonyl bond.
- R 2 each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms.
- n independently represents an arbitrary integer of 1 to 5
- m independently represents an arbitrary integer of 0 to (5-n).
- R 1 and R 2 s may be the same or different.
- o represents an arbitrary integer of 1 to 3, and satisfies m + n + o ⁇ 5.
- the reaction can be carried out in a homogeneous system, and has a suitable acidity and corresponding conjugate. Since the nucleophilicity of the base is low, it is difficult to cause a decomposition reaction of the raw material and the target product, and separation of the target product and the catalyst after the reaction is simple. In addition, since the compound targeted by the present invention can be produced even at a relatively low temperature around normal temperature, it is highly useful as an industrial production method.
- each R 1 is independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aromatic hydrocarbon group, or a halogen atom (fluorine, chlorine, bromine, And iodine).
- R 1 Specific examples of the straight chain, branched chain or cyclic alkyl group having 1 to 12 carbon atoms in R 1 include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group.
- T-butyl group n-pentyl group, i-pentyl group, n-hexyl group, i-hexyl group, n-heptyl group, n-octyl group, i-octyl group, n-nonyl group, n-decyl group N-dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantylmethyl group and the like.
- aromatic hydrocarbon group examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, and a 1-phenanthryl group.
- halogen fluorine, chlorine, bromine, and iodine
- an oxygen atom and a carbonyl bond
- a part of hydrogen atoms of the alkyl group or the aromatic hydrocarbon group can be substituted for a part of hydrogen atoms of the alkyl group or the aromatic hydrocarbon group.
- R 2 each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. Regarding the specific structure of the alkyl group, the above-mentioned contents (definition of R 1 in formula [1]) can be similarly applied.
- l is an arbitrary integer of 0 to 2
- n is independently an arbitrary integer of 1 to 5
- m is independently an arbitrary integer of 0 to 4
- o is independent
- n in the formula [3] is independently an arbitrary integer of 1 to 5
- m is independently an arbitrary integer of 0 to 4
- o is independently an arbitrary integer of 1 to 3
- substituents substituted on the aromatic ring specifically, “(R 1 ) m ”, “(OR 2 ) n ”, “(NR 3 R 4 ) n )
- the position of “(CH 2 CH (CF 3 SO 2 ) 2 ) o ”) is not particularly limited, and these substituents may be present within a possible structure range.
- the compound having a bis (trifluoromethanesulfonyl) ethyl group represented by the formulas [1] to [3] targeted in the present invention acts as an acid catalyst in various organic synthesis reactions.
- reaction solvent is not particularly limited, and a general-purpose organic solvent can be used.
- the compound of the present invention can be used as an acid catalyst in various organic synthesis reactions such as aldol-type reaction, Friedel-Crafts-type reaction, Diels-Alder reaction, Michael reaction, ene reaction, and esterification reaction.
- aldol-type reaction Friedel-Crafts-type reaction
- Diels-Alder reaction Diels-Alder reaction
- Michael reaction Michael reaction
- ene reaction ene reaction
- esterification reaction esterification reaction.
- the present invention exhibits particularly excellent performance as an acid catalyst in aldol-type reactions and esterification reactions, and that the reaction proceeds efficiently with a very small amount of catalyst for a specific substrate. This is one of the preferred embodiments of the invention.
- an acid catalyst in various organic synthesis reactions, it may be carried out by a liquid phase reaction as in the case of using a normal solid catalyst.
- the solvent is not particularly limited as long as it does not participate in the reaction.
- saturated hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane, and aromatic hydrocarbons such as benzene, toluene and xylene.
- Ethers such as diethyl ether, tetrahydrofuran and dioxane, halogenated hydrocarbons such as dichloromethane, dichloroethane and chloroform, alkyl ketones such as acetone, acetonitrile, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) And aprotic polar solvents such as hexamethylphosphoric triamide (HMPA).
- Ethers such as diethyl ether, tetrahydrofuran and dioxane
- halogenated hydrocarbons such as dichloromethane, dichloroethane and chloroform
- alkyl ketones such as acetone, acetonitrile, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO)
- aprotic polar solvents such as hexamethylphosphoric triamide (HMPA).
- the addition amount of the compound as an acid catalyst is usually 0.001 times to 10 times mol, preferably 0.01 times to 5 times mol, more preferably 0 to mol of the reaction substrate. It is 0.01 times mole to 3 times mole.
- the yield of the target reaction product is reduced even when the specific acid catalyst is used in an amount of 0.05-fold mol with respect to the substrate.
- the industrially superior knowledge that the desired product can be produced in a high yield without any occurrence was obtained.
- reaction temperature varies depending on the reaction substrate and the amount of catalyst to be added, but it can be usually in the range of ⁇ 50 to 100 ° C.
- reaction vessel There is no particular limitation on the reaction vessel, and a reaction vessel that can withstand the pressure used during the reaction or a material that does not affect the reaction can be used.
- the reaction may be at normal pressure or under pressure, and can be appropriately adjusted by those skilled in the art depending on the type of reaction.
- reaction may be performed while circulating an inert gas such as nitrogen gas or argon gas.
- reaction time is not particularly limited, it may usually be performed within a range of 24 hours.
- the progress of the reaction is traced by analytical means such as gas chromatography, liquid chromatography, and NMR, and the raw material substrate is almost lost.
- the time point is preferably the end point.
- Patent Document 6 described above describes a method of synthesizing 1,1,3,3-tetrakis (trifluoromethanesulfonyl) propane by reaction of bis (trifluoromethanesulfonyl) methane and paraformaldehyde (see the following scheme). ).
- the phenolic compounds targeted by the present invention are 1,1,3,3-tetrakis (trifluoromethanesulfonyl) propane and various organic compounds at room temperature. It can be produced by dissolving in a solvent and reacting with a phenolic compound that is a nucleophilic species.
- 1,1,3,3-tetrakis (trifluoromethanesulfonyl) propane is reversibly decomposed into 1,1-bis (trifluoromethanesulfonyl) ethylene and bis (trifluoromethanesulfonyl) methane in the reaction system. It is assumed that 1,1-bis (trifluoromethanesulfonyl) ethylene, which is a highly electrophilic reaction acceptor, was obtained by reacting with a phenolic nucleophilic species.
- the compound can be produced in the presence of a solvent.
- the reaction solvent is not particularly limited as long as it does not participate in the reaction.
- saturated hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane, and aromatics such as benzene, toluene and xylene.
- Hydrocarbons such as diethyl ether, tetrahydrofuran and dioxane, halogenated hydrocarbons such as dichloromethane, dichloroethane and chloroform, alkyl ketones such as acetone, acetonitrile, N, N-dimethylformamide (DMF), dimethyl sulfoxide ( Examples thereof include aprotic polar solvents such as DMSO) and hexamethylphosphoric triamide (HMPA).
- ethers such as diethyl ether, tetrahydrofuran and dioxane
- halogenated hydrocarbons such as dichloromethane, dichloroethane and chloroform
- alkyl ketones such as acetone, acetonitrile, N, N-dimethylformamide (DMF), dimethyl sulfoxide
- Examples thereof include aprotic polar solvents such as DMSO) and hexamethylphosphoric triamide (HMPA).
- reaction raw material or reaction reagent when liquid at room temperature or melts at the reaction temperature, it also serves as a solvent itself, so there is no need to use a separate solvent, and this is an industrial burden. This is economical and preferable.
- the reaction temperature in the method for producing the compound is usually about 20 ° C. to 150 ° C., but can be appropriately adjusted by those skilled in the art within this temperature range according to the boiling point of the reaction solvent and according to the progress of the reaction.
- acetonitrile is used as the organic solvent, the reaction proceeds sufficiently even at room temperature (about 25 ° C.) (see Examples described later). This is one of the particularly preferred embodiments in the present invention.
- the target compound can be sufficiently produced even in the one-pot reaction, by-products other than the target product (diarylmethane, etc.) are also generated at the same time, and thus the 1,1,3,3-tetrakis (trifluoromethanesulfonyl) propane described above is produced.
- the reaction conditions using is a more useful method for obtaining the target product with high selectivity and high yield.
- the post-treatment method in the production method of the present application is not particularly limited, and the treatment of the reaction product after completion of the reaction may be performed based on a usual organic synthesis treatment method (recrystallization, distillation, column chromatography, etc.).
- a compound having a bis (trifluoromethanesulfonyl) ethyl group represented by the formulas [1] to [3] can be obtained by ordinary means.
- the compound can be easily obtained. Since the target product can be supplied with high purity and high yield, it is a very excellent method for producing the target product on an industrial scale.
- distillation When distillation is performed, normal pressure (0.1 MPa) may be used, but it is preferable to use reduced pressure conditions.
- reduced pressure There are no restrictions on the material of the distillation tower, glass, stainless steel, tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass lined inside, etc. Can be used.
- a filler can also be packed in the distillation column. Distillation is preferred because it can be achieved at a relatively low temperature when performed under reduced pressure.
- Boiling point 92-98 ° C. (15 mmHg). Higher purity samples can be obtained by recrystallization from chlorobenzene. Melting point: 51-53 ° C., elemental analysis: C 7 H 4 F 6 O 8 S 4 , calculated value: 14.7% C, 39.8% F, 0.7% H, analytical value: 15.0% C 39.6% F, 0.9% H
- Example 4 The procedure and conditions were the same as in Example 3, except that 2,4-dimethylphenol (33.6 mg, 0.275 mmol) was used instead of 2,6-xylenol. As a result, 2- (2,2-bis (trifluoromethylsulfonyl) ethyl) -4,6-dimethylphenol ( 1e ) was obtained in a yield of 86% (88.7 mg, 0.21 mmol). Further, recrystallization from hexane gave colorless crystals.
- Example 5 The procedure and conditions were the same as in Example 3, except that 2-bromo-4-methylphenol (33.2 ⁇ L, 0.275 mmol) was used instead of 2,6-xylenol and the reaction was performed at 100 ° C. for 10 hours. .
- 2- (2,2-bis (trifluoromethylsulfonyl) ethyl) -6-bromo-4-methylphenol ( 1f ) was obtained in 91% yield (109.1 mg, 0.23 mmol).
- Example 6 Operation and conditions were the same as in Example 3 except that methyl 2-hydroxy-5-methylbenzoate (45.7 mg, 0.275 mmol) was used instead of 2,6-xylenol and the reaction was performed at 100 ° C. for 24 hours. It was. As a result, methyl 3- (2,2-bis (trifluoromethylsulfonyl) ethyl) -2-hydroxy-5-methylbenzoate ( 1 g ) was obtained in 79% yield (90.6 mg, 0.20 mmol). Further, recrystallization from hexane gave colorless crystals.
- Example 7 The procedure and conditions were the same as in Example 3, except that 0.50 mL of tert-butylphenol (49.6 mg, 0.33 mmol) and acetonitrile were used instead of 2,6-xylenol and the reaction was performed at 80 ° C. for 10 hours. .
- 2,6-bis (2,2-bis (trifluoromethylsulfonyl) ethyl) -4-tert-butylphenol ( 1h ) was obtained in 88% yield (207.3 mg, 0.28 mmol). Further, recrystallization from hexane gave colorless crystals.
- Example 8 The procedure and conditions were the same as in Example 3, except that 1-methoxy-4-methylbenzene (34.2 mg, 0.28 mmol) was used instead of 2,6-xylenol and the reaction was performed at room temperature for 5 hours. As a result, 2- (2,2-bis (trifluoromethylsulfonyl) ethyl) -1-methoxy-4-methylbenzene ( 1i ) was obtained in 90% yield (93.6 mg, 0.23 mmol). Further, recrystallization from hexane gave colorless crystals.
- Example 9 Example 3 except that 1- (benzyloxy) -4-methylbenzene (54.5 mg, 0.275 mmol) was used instead of 2,6-xylenol, and the reaction was carried out at 80 ° C. for 6 hours with methylene chloride (50 ⁇ L). The operation and conditions were the same. As a result, 1- (benzyloxy) -2- (2,2-bis (trifluoromethylsulfonyl) ethyl) -4-methylbenzene ( 1j ) was obtained in a yield of 70% (86.0 mg, 0.18 mmol). Further, recrystallization from hexane gave colorless crystals.
- Example 10 Except for using 1,4-dimethoxybenzene (34.5 mg, 0.25 mmol) instead of 2,6-xylenol and reacting with acetonitrile (0.50 mL) at room temperature for 5 hours, both the operation and conditions were the same as in Example 3. The same was done. As a result, 2- (2,2-bis (trifluoromethylsulfonyl) ethyl) -1,4-dimethoxybenzene ( 1k ) was obtained in 88% yield (94.5 mg, 0.22 mmol). Further, recrystallization from benzene gave colorless crystals.
- Example 11 The procedure and conditions were the same as in Example 3, except that 1,2-dimethoxybenzene (34.5 mg, 0.25 mmol) was used instead of 2,6-xylenol, and 0.50 mL of acetonitrile was used. As a result, 4- (2,2-bis (trifluoromethylsulfonyl) ethyl) -1,2-dimethoxybenzene ( 1l ) was obtained in 86% yield (92.5 mg, 0.215 mmol). Further, recrystallization from benzene gave colorless crystals.
- Example 12 To a solution of 2-naphthol (79.0 mg, 0.55 mmol) in acetonitrile (0.5 ml) was added 1,1,3,3-tetrakis (trifluoromethylsulfonyl) propane ( 4 ) (285.8 mg, 0.50 mmol). Was added at room temperature. After stirring for 1 hour, recrystallization from chloroform gave colorless crystals of 1- (2,2-bis (trifluoromethylsulfonyl) ethyl) naphthalen-2-ol ( 1m ) in a yield of 70% (152 .7 mg, 0.35 mmol).
- Example 15 To a solution of 4-t-butylphenol (43.6 mg, 0.29 mmol) in acetonitrile (0.25 ml) was added 1,1,3,3-tetrakis (trifluoromethylsulfonyl) propane ( 4 ) (148.8 mg,. 264 mmol) was added at room temperature. After stirring for 1 hour, the reaction solution was concentrated under reduced pressure. The obtained residue was purified by Kugelrohr distillation (190-210 ° C./5 mmHg), and 2- (2,2-bis (trifluoromethylsulfonyl) ethyl-4-tert-butylphenol ( 1o ) was obtained in an almost quantitative manner. (97.0 mg, 0.24, mmol).
- Example 16 To a solution of 5-methylbiphenyl-2-ol (40.0 mg, 0.22 mmol) in acetonitrile (0.20 ml), 1,1,3,3-tetrakis (trifluoromethylsulfonyl) propane ( 4 ) (113.0 mg , 0.20 mmol) and stirred at 80 ° C. for 2 hours.
- the reaction solution was purified by Kugelrohr distillation (195-210 ° C./3 mmHg), and 3- (2,2-bis (trifluoromethylsulfonyl) ethyl) -5-methylbiphenyl-2-ol ( 1p ) was obtained in a yield of 51 % (48.4 mg, 0.10 mmol).
- Example 17 To a solution of p-cresol (21.1 mg, 0.19 mmol) in acetonitrile (0.20 ml), 1,1,3,3-tetrakis (trifluoromethylsulfonyl) propane ( 4 ) (330.4 mg, 0.58 mmol) And stirred at 80 ° C. for 10 hours.
- the reaction solution was purified by Kugelrohr distillation (210-230 ° C./3 mmHg), and 2,6-bis (2,2-bis (trifluoromethylsulfonyl) ethyl) -4-methylphenol ( 1q ) was obtained in a yield of 74%. (97.0 mg, 0.14 mmol).
- Example 18 To a solution of 1,3-dimethoxybenzene (18) (34.5 mg, 0.25 mmol) in acetonitrile (0.50 ml), 1,1,3,3-tetrakis (trifluoromethylsulfonyl) propane ( 4 ) (172. 5 mg, 0.30 mmol) was added at room temperature. After stirring for 2 hours, the reaction solution was purified by Kugelrohr distillation (180-190 ° C./3 mmHg) and 1- (2,2-bis (trifluoromethylsulfonyl) ethyl) -2,4-dimethoxybenzene ( 1r ). In 80% yield (86.3 mg, 0.201 mmol). Further, recrystallization from benzene gave colorless crystals.
- Example 19 To a solution of benzene-1,3,5-triol (126 mg, 1.0 mmol) in acetonitrile (1.0 ml) was added 1,1,3,3-tetrakis (trifluoromethylsulfonyl) propane ( 4 ) (1.89 g, 3.3 mmol) was added at room temperature. After stirring for 7 hours, the precipitate separated by filtration was washed with chloroform (about 5 ml). Drying under reduced pressure gave 2,4,6-tris (2,2-bis (trifluoromethylsulfonyl) ethyl) benzene-1,3,5-triol ( 1s ) in a yield of 64% (838 mg, 0.64 mmol). Further, recrystallization from diethyl ether gave colorless crystals.
- Example 21 to [Example 26] 4- (2,2-bis (trifluoromethylsulfonyl) ethyl-2,6-dimethylphenol ( 1d ), 2- (2,2-bis (trifluoromethylsulfonyl) ethyl-4-methylphenol ( 1c ),
- the same procedure as in Example 20 was performed, except that various equivalents were changed using 2,6-bis (2,2-bis (trifluoromethylsulfonyl) ethyl) -4-tert-butylphenol ( 1h ) ( note that In Examples 21 and 26, in addition to changing various equivalents, the reaction time was 3 to 5 hours).
- Example 29 ⁇ Examples of 2- (2,2-bis (trifluoromethylsulfonyl) ethyl-4-methylphenol ( 1c ) production and acid catalyst recovery>
- p-cresol 108.1 mg, 1.00 mmol
- acetonitrile 1.0 ml
- Propane ( 4 ) (574.4 mg, 1.00 mmol) was added at room temperature. After stirring for 3 hours, the reaction solution was concentrated under reduced pressure.
- the compound having a bis (trifluoromethanesulfonyl) ethyl group as a reference in the present invention can be used as an acid catalyst in various organic synthesis reactions.
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Abstract
Description
下記式[1]、[2]、又は[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。
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。
下記式[1]、[2]、又は[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からなる酸触媒。
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。
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。
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。
ール系の求核種と反応することにより得られたものと推測される。
<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。
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)。
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)。
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。
18.Anal.Calcd for C12H12F6O5S2:C,34.78;H,2.92.Found:C,35.18;H,3.07.
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)
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)
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)
459.0007;Found, 459.0003.
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)
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)
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)
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)
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)
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)。
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。
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)。
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)。
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)。
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)。
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。
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。
<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.
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 (8)
- 下記式[1]、[2]、又は[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。
- 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、請求項1に記載の化合物。
- 下記式[1]、[2]、又は[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からなる酸触媒。
- 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、請求項3に記載の酸触媒。
- 請求項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。
- 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。
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GB1312783.2A GB2500551A (en) | 2010-12-17 | 2011-12-08 | Bis(trifluoromethanesulfonyl)ethyl-bearing compound and acid catalyst, and method for preparing same |
US13/994,520 US9314782B2 (en) | 2010-12-17 | 2011-12-08 | Bis(trifluoromethanesulfonyl)ethyl-bearing compound and acid catalyst, and method for preparing same |
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 |
DE112011103786T DE112011103786T5 (de) | 2010-12-17 | 2011-12-08 | Bis(Trifluormethansulfonyl)ethyl tragende Verbindung und Säurekatalysator und Verfahren zum Herstellen derselben |
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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 |
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JP (1) | JP5696465B2 (ja) |
CN (2) | CN103261154B (ja) |
DE (1) | DE112011103786T5 (ja) |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2014050814A1 (ja) * | 2012-09-25 | 2014-04-03 | 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 |
WO2023136005A1 (ja) * | 2022-01-14 | 2023-07-20 | 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 |
Families Citing this family (2)
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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 |
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- 2011-12-08 CN CN201180060777.1A patent/CN103261154B/zh not_active Expired - Fee Related
- 2011-12-08 GB GB1312783.2A patent/GB2500551A/en not_active Withdrawn
- 2011-12-08 WO PCT/JP2011/078409 patent/WO2012081488A1/ja active Application Filing
- 2011-12-08 CN CN201410320540.8A patent/CN104151215B/zh not_active Expired - Fee Related
- 2011-12-08 DE DE112011103786T patent/DE112011103786T5/de not_active Withdrawn
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WO2014050814A1 (ja) * | 2012-09-25 | 2014-04-03 | 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 |
JP2014111569A (ja) * | 2012-09-25 | 2014-06-19 | Central Glass Co Ltd | 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 |
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Also Published As
Publication number | Publication date |
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CN103261154A (zh) | 2013-08-21 |
JP5696465B2 (ja) | 2015-04-08 |
US9314782B2 (en) | 2016-04-19 |
DE112011103786T5 (de) | 2013-09-12 |
CN104151215A (zh) | 2014-11-19 |
GB2500551A (en) | 2013-09-25 |
JP2012126688A (ja) | 2012-07-05 |
US20140066659A1 (en) | 2014-03-06 |
CN104151215B (zh) | 2016-06-29 |
CN103261154B (zh) | 2015-12-16 |
GB201312783D0 (en) | 2013-08-28 |
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