WO2018159641A1 - Production method for fluorine-containing silane compound, and fluorine-containing silane compound - Google Patents
Production method for fluorine-containing silane compound, and fluorine-containing silane compound Download PDFInfo
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- WO2018159641A1 WO2018159641A1 PCT/JP2018/007364 JP2018007364W WO2018159641A1 WO 2018159641 A1 WO2018159641 A1 WO 2018159641A1 JP 2018007364 W JP2018007364 W JP 2018007364W WO 2018159641 A1 WO2018159641 A1 WO 2018159641A1
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- carbon atoms
- atom
- fluorine
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 126
- -1 silane compound Chemical class 0.000 title claims abstract description 68
- 239000011737 fluorine Substances 0.000 title claims abstract description 63
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 229910000077 silane Inorganic materials 0.000 title abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 204
- 238000005686 cross metathesis reaction Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 140
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 87
- 125000001153 fluoro group Chemical group F* 0.000 claims description 66
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 62
- 125000000962 organic group Chemical group 0.000 claims description 49
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 125000004428 fluoroalkoxy group Chemical group 0.000 claims description 20
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 16
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 14
- 125000006343 heptafluoro propyl group Chemical group 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 4
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 3
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims 3
- 238000005865 alkene metathesis reaction Methods 0.000 abstract description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 description 72
- 239000003054 catalyst Substances 0.000 description 62
- 238000006243 chemical reaction Methods 0.000 description 50
- 238000005481 NMR spectroscopy Methods 0.000 description 49
- XZDYFCGKKKSOEY-UHFFFAOYSA-N 1,3-bis[2,6-di(propan-2-yl)phenyl]-4,5-dihydro-2h-imidazol-1-ium-2-ide Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N1CCN(C=2C(=CC=CC=2C(C)C)C(C)C)[C]1 XZDYFCGKKKSOEY-UHFFFAOYSA-N 0.000 description 37
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 35
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 31
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 239000002904 solvent Substances 0.000 description 15
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- 239000010702 perfluoropolyether Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical group [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 8
- 229940126062 Compound A Drugs 0.000 description 7
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 7
- PDCBZHHORLHNCZ-UHFFFAOYSA-N 1,4-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(C(F)(F)F)C=C1 PDCBZHHORLHNCZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000012756 surface treatment agent Substances 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- LSMWOQFDLBIYPM-UHFFFAOYSA-N 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-2h-imidazol-1-ium-2-ide Chemical compound CC1=CC(C)=CC(C)=C1N1[C-]=[N+](C=2C(=CC(C)=CC=2C)C)CC1 LSMWOQFDLBIYPM-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 125000004104 aryloxy group Chemical group 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 0 C*(C)NNNOC(C)(C)N(C)*COCC=* Chemical compound C*(C)NNNOC(C)(C)N(C)*COCC=* 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- ZRPFJAPZDXQHSM-UHFFFAOYSA-L 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole;dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C ZRPFJAPZDXQHSM-UHFFFAOYSA-L 0.000 description 2
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- MQTZSGCSKOZKGU-UHFFFAOYSA-L benzylidene(dichloro)ruthenium;tricyclohexylphosphane Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 MQTZSGCSKOZKGU-UHFFFAOYSA-L 0.000 description 2
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011986 second-generation catalyst Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RUKVGXGTVPPWDD-UHFFFAOYSA-N 1,3-bis(2,4,6-trimethylphenyl)imidazolidine Chemical compound CC1=CC(C)=CC(C)=C1N1CN(C=2C(=CC(C)=CC=2C)C)CC1 RUKVGXGTVPPWDD-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- COAUHYBSXMIJDK-UHFFFAOYSA-N 3,3-dichloro-1,1,1,2,2-pentafluoropropane Chemical compound FC(F)(F)C(F)(F)C(Cl)Cl COAUHYBSXMIJDK-UHFFFAOYSA-N 0.000 description 1
- BYZZDOOPYQRYJO-UHFFFAOYSA-L C(C1=CC=CC=C1)=[Ru](Cl)Cl.C(C)(C)C1=C(C(=CC=C1)C(C)C)N1C(N(CC1)C1=C(C=CC=C1C(C)C)C(C)C)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1 Chemical compound C(C1=CC=CC=C1)=[Ru](Cl)Cl.C(C)(C)C1=C(C(=CC=C1)C(C)C)N1C(N(CC1)C1=C(C=CC=C1C(C)C)C(C)C)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1 BYZZDOOPYQRYJO-UHFFFAOYSA-L 0.000 description 1
- UBUPESSETMDPNX-UHFFFAOYSA-L C(C1=CC=CC=C1)=[Ru](Cl)Cl.C(C)(C)N1C(N(C=C1)C(C)C)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1 Chemical compound C(C1=CC=CC=C1)=[Ru](Cl)Cl.C(C)(C)N1C(N(C=C1)C(C)C)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1 UBUPESSETMDPNX-UHFFFAOYSA-L 0.000 description 1
- UXDVMGDBNDBMCE-UHFFFAOYSA-L C(C1=CC=CC=C1)=[Ru](Cl)Cl.C1(=C(C(=CC(=C1)C)C)N1C(N(CC1)C1=C(C=C(C=C1C)C)C)(C1=NC=CC=C1Br)C1=NC=CC=C1Br)C Chemical compound C(C1=CC=CC=C1)=[Ru](Cl)Cl.C1(=C(C(=CC(=C1)C)C)N1C(N(CC1)C1=C(C=C(C=C1C)C)C)(C1=NC=CC=C1Br)C1=NC=CC=C1Br)C UXDVMGDBNDBMCE-UHFFFAOYSA-L 0.000 description 1
- VWMKUZYJGUVNJX-UHFFFAOYSA-L C(C1=CC=CC=C1)=[Ru](Cl)Cl.C1(=C(C(=CC(=C1)C)C)N1C(N(CC1)C1=C(C=C(C=C1C)C)C)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1)C Chemical compound C(C1=CC=CC=C1)=[Ru](Cl)Cl.C1(=C(C(=CC(=C1)C)C)N1C(N(CC1)C1=C(C=C(C=C1C)C)C)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1)C VWMKUZYJGUVNJX-UHFFFAOYSA-L 0.000 description 1
- GUEOQRBYMGTBMD-UHFFFAOYSA-L C(C1=CC=CC=C1)=[Ru](Cl)Cl.C1(CCCCC1)N1C(N(C=C1)C1CCCCC1)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1 Chemical compound C(C1=CC=CC=C1)=[Ru](Cl)Cl.C1(CCCCC1)N1C(N(C=C1)C1CCCCC1)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1 GUEOQRBYMGTBMD-UHFFFAOYSA-L 0.000 description 1
- SMGHYXRAMHZLGM-UHFFFAOYSA-L C(C1=CC=CC=C1)=[Ru](Cl)Cl.C1(CCCCC1)N1C(N(CC1)C1CCCCC1)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1 Chemical compound C(C1=CC=CC=C1)=[Ru](Cl)Cl.C1(CCCCC1)N1C(N(CC1)C1CCCCC1)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1 SMGHYXRAMHZLGM-UHFFFAOYSA-L 0.000 description 1
- UZUNGPQZCKHZED-UHFFFAOYSA-L C(C1=CC=CC=C1)=[Ru](Cl)Cl.CC1=C(C=CC=C1)N1C(N(CC1)C1=C(C=CC=C1)C)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1 Chemical compound C(C1=CC=CC=C1)=[Ru](Cl)Cl.CC1=C(C=CC=C1)N1C(N(CC1)C1=C(C=CC=C1)C)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1 UZUNGPQZCKHZED-UHFFFAOYSA-L 0.000 description 1
- JIOSRMMISAZMJC-UHFFFAOYSA-N C=CCC(C(F)(F)F)C(F)(F)F Chemical compound C=CCC(C(F)(F)F)C(F)(F)F JIOSRMMISAZMJC-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 108010021119 Trichosanthin Proteins 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
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- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
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- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- PNPBGYBHLCEVMK-UHFFFAOYSA-L benzylidene(dichloro)ruthenium;tricyclohexylphosphane Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-L 0.000 description 1
- FNQDSOUHKJMXBK-UHFFFAOYSA-L benzylidene(dichloro)ruthenium;triphenylphosphane Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FNQDSOUHKJMXBK-UHFFFAOYSA-L 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001717 carbocyclic compounds Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 1
- LNZMEOLVTKHUAS-UHFFFAOYSA-N cyclohexane;dichloromethane Chemical compound ClCCl.C1CCCCC1 LNZMEOLVTKHUAS-UHFFFAOYSA-N 0.000 description 1
- 125000004431 deuterium atom Chemical group 0.000 description 1
- CSYMWOCQWBALLE-UHFFFAOYSA-L dichloro(ethoxymethylidene)ruthenium;tricyclohexylphosphane Chemical compound CCOC=[Ru](Cl)Cl.C1CCCCC1P(C1CCCCC1)C1CCCCC1 CSYMWOCQWBALLE-UHFFFAOYSA-L 0.000 description 1
- PAOXUKUJFRPEDY-UHFFFAOYSA-L dichloro(ethoxymethylidene)ruthenium;tricyclohexylphosphane Chemical compound CCOC=[Ru](Cl)Cl.C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 PAOXUKUJFRPEDY-UHFFFAOYSA-L 0.000 description 1
- INCDKKABOVOFIV-UHFFFAOYSA-L dichlororuthenium;2-methylbutane;tricyclohexylphosphane Chemical compound Cl[Ru]Cl.[CH][CH][C](C)C.C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 INCDKKABOVOFIV-UHFFFAOYSA-L 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000004407 fluoroaryl group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- FVIZARNDLVOMSU-UHFFFAOYSA-N ginsenoside K Natural products C1CC(C2(CCC3C(C)(C)C(O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC1OC(CO)C(O)C(O)C1O FVIZARNDLVOMSU-UHFFFAOYSA-N 0.000 description 1
- ZTQSADJAYQOCDD-UHFFFAOYSA-N ginsenoside-Rd2 Natural products C1CC(C2(CCC3C(C)(C)C(OC4C(C(O)C(O)C(CO)O4)O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC(C(C(O)C1O)O)OC1COC1OCC(O)C(O)C1O ZTQSADJAYQOCDD-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000003041 laboratory chemical Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002953 preparative HPLC Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
Definitions
- the present invention relates to a method for producing a fluorinated silane compound by a cross metathesis reaction and a fluorinated silane compound.
- a base material having an organic group containing a fluorine atom in its surface layer is industrially useful in applications where water repellency, oil repellency and antifouling properties are required, such as displays, glasses and touch panels.
- the organic group containing a fluorine atom exhibits high lubricity, water / oil repellency, etc., it is preferably used as a surface treatment agent for a substrate.
- the surface treatment agent imparts water and oil repellency to the surface of the base material, it becomes easy to wipe off the dirt on the surface of the base material, and the dirt removability is improved.
- Patent Document 1 discloses a surface treatment agent that uses a compound having two or more silicon atoms in the molecule as the fluorine-containing silane compound.
- olefin metathesis reaction which is a double bond recombination reaction using a metal catalyst
- metal metathesis which is a double bond recombination reaction using a metal catalyst
- the conventional surface treatment agent containing a fluorine-containing silane compound is feared to deteriorate in performance due to long-term use. For example, there is room for improvement such as insufficient friction durability.
- Non-Patent Document 1 describes that the reactivity of electron-deficient olefins is low. Furthermore, since olefins having halogen atoms such as fluorine atoms and chlorine atoms are also electron-deficient olefins, there are few reports used for olefin metathesis, and in Non-Patent Document 2, the expected products, namely ethylene and tetrafluoroethylene, are completely absent. It is stated that it was not obtained.
- the substrate surface is crosslinkable. It becomes possible to introduce a fluorine-containing alkyl group having a site, and it is possible to produce a substrate having a higher durability compared to existing methods.
- the present invention has been made in view of the above-described conventional circumstances, and is a production that can easily and efficiently produce a fluorine-containing silane compound having a reactive carbon-carbon double bond by mild process under olefin metathesis.
- the object is to provide a method and a novel fluorine-containing silane compound.
- the present inventor has found that the above-mentioned problems can be solved by cross-metathesis reaction between specific compounds, and has completed the present invention. That is, the present invention relates to the following ⁇ 1> to ⁇ 11>.
- ⁇ 1> A method for producing a compound represented by the following formula (3 ′), wherein a compound represented by the following formula (1 ′) and a compound represented by the following formula (2) are subjected to a cross metathesis reaction.
- X represents a chlorine atom or an alkoxy group having a carbon number of 1 ⁇ 6
- Z 1 -Z 4 each independently represents a hydrogen atom or a monovalent organic group
- Q is a h-valent organic group which contains a fluorine atom and may have a hetero atom
- R 4 has 4 to 4 carbon atoms.
- h represents a natural number of 2 or more
- a plurality of Z 1 and Z 2 may be the same or different
- R 4 and X are the same If there are multiple molecules in the molecule, they may be the same or different.
- a is 0 or 1
- b is 0 or 1
- c is 0, 1 or 2
- the sum of c and d is 3
- X is a chlorine atom or 1 to 6 carbon atoms.
- Y represents a single bond, an etheric oxygen atom or —CH 2 O—
- Z 1 to Z 4 each independently represents a hydrogen atom or a monovalent organic group
- R 1 represents a fluorine atom or Represents a monovalent fluorine-containing organic group
- R 2 represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group
- R 3 represents a fluorine atom or a monovalent fluorine-containing organic group
- any two selected from the group consisting of R 3 may be bonded to each other to form a ring
- R 4 represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms
- a is 0 or 1
- b is 0, c is 0,
- X represents a chlorine atom, a methoxy group or an ethoxy group,
- Y represents a single bond, an etheric oxygen atom or —CH 2 O
- R 1 represents a (per) fluoroalkyl group having 1 to 12 carbon atoms, a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, or 2 to 400 carbon atoms containing an etheric oxygen atom.
- R 2 represents a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom.
- R 3 represents a fluorine atom, a trifluoromethyl group or a C 2 -C 400 including an etheric oxygen atom, (per) fluoroalkyl group, the ⁇ The method according to>.
- Z 1 to Z 4 are each independently a hydrogen atom, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, propoxy group, phenyl group, phenyloxy group, trifluoromethyl group, pentafluoroethyl group, ⁇ 2 which represents heptafluoropropyl group, trifluoromethoxy group, pentafluoroethoxy group, heptafluoropropoxy group, perfluoro (methoxymethoxy) group, perfluoro (propoxypropoxy) group, pentafluorophenyl group or pentafluorophenyloxy group > Or ⁇ 3>.
- X represents a chlorine atom or an alkoxy group having 1 to 6 carbon atoms
- Q is An h-valent organic group which contains a fluorine atom and may have a hetero atom
- R 4 represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms
- h is 2 or more. And when there are a plurality of R 4 s and Xs, they may be the same or different.
- R 11 represents a monovalent fluorine-containing group.
- R 2 represents a hydrogen atom, a fluorine atom or a monovalent fluorinated organic group
- R 3 represents a fluorine atom or a monovalent fluorinated organic group
- R 11 , R 2 and R 3 Any two selected from the group consisting of may be bonded to each other to form a ring
- R 4 represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and a plurality of R 4 are present. They may be the same or different.
- Y represents a single bond, an etheric oxygen atom or —CH 2 O—
- R 11 represents a (per) fluoroalkyl group having 1 to 12 carbon atoms
- a carbon containing an etheric oxygen atom Represents a (per) fluoroalkyl group having 2 to 400 carbon atoms or a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom
- R 2 represents a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a hepta Represents a fluoropropyl group or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom
- R 3 is a fluorine atom, trifluoromethyl group or 2 to 400 carbon atoms containing an etheric oxygen atom
- Y represents a single bond, an etheric oxygen atom or —CH 2 O—;
- R 1 represents a fluorine atom or a monovalent fluorine-containing organic group,
- R 2 represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group, and
- R 3 represents a fluorine atom or a monovalent fluorine-containing organic group.
- R 1 , R 2 , and R 3 may be bonded to each other to form a ring, and R 4 represents an aryl group having 4 to 20 carbon atoms or 1 to 6 carbon atoms And when a plurality of R 4 are present, they may be the same or different.
- b is 0, c is 0, Y represents a single bond, an etheric oxygen atom or —CH 2 O—, R 1 represents a (per) fluoroalkyl group having 1 to 12 carbon atoms, ether Represents a (per) fluoroalkyl group having 2 to 400 carbon atoms containing a reactive oxygen atom or a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 2 represents a fluorine atom, a trifluoromethyl group, Represents a pentafluoroethyl group, a heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 3 is a carbon containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom
- R 1 represents a (per) fluoroalkyl group having 1
- R 1 represents a fluorine atom or a monovalent group.
- R 2 represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group
- R 3 represents a fluorine atom or a monovalent fluorine-containing organic group
- R 1 , R 2 and Any two selected from the group consisting of R 3 may be bonded to each other to form a ring
- R 4 represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms
- R 5 Represents an alkyl group having 1 to 6 carbon atoms, and when there are a plurality of R 4 and R 5 , they may be the same or different.
- Y represents a single bond, an etheric oxygen atom or —CH 2 O—
- R 1 is a (per) fluoroalkyl group having 1 to 12 carbon atoms, a carbon containing an etheric oxygen atom
- R 2 represents a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group
- a hepta represents a fluoropropyl group or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom
- R 3 is a fluorine atom, trifluoromethyl group or 2 to 400 carbon atoms containing an etheric oxygen atom
- a novel and useful fluorine-containing silane compound having a reactive carbon-carbon double bond can be easily and efficiently produced under mild conditions.
- the present invention relates to olefin metathesis by a metal catalyst, and description of general features common to the prior art may be omitted.
- the “compound represented by the formula (n)” may be simply referred to as “compound (n)”.
- the number of carbons means the total number of carbon atoms contained in an entire group, and when the group has no substituent, it represents the number of carbon atoms forming the skeleton of the group. In the case where the group has a substituent, the total number is obtained by adding the number of carbon atoms in the substituent to the number of carbon atoms forming the skeleton of the group.
- An etheric oxygen atom is an oxygen atom that forms an ether bond (—O—) between carbon-carbon atoms.
- An aryl group means a monovalent group corresponding to a residue obtained by removing one hydrogen atom bonded to any one of carbon atoms forming an aromatic ring in an aromatic compound, and a carbocyclic compound And a heteroaryl group derived from a heterocyclic compound.
- the term “(per) fluoroalkyl group” is used as a general term that combines a fluoroalkyl group and a perfluoroalkyl group. That is, the group is an alkyl group having one or more fluorine atoms. The same applies to a (per) fluoroalkoxy group, a (per) fluoroaryl group, and a (per) fluoroaryloxy group.
- One embodiment of the present invention is by subjecting a compound represented by the following formula (1) (compound (1)) and a compound represented by the following formula (2) (compound (2)) to a cross metathesis reaction.
- the present invention relates to a method for producing a compound represented by the following formula (3) (compound (3)).
- a is 0 or 1
- b is 0 or 1
- c is 0, 1 or 2
- the sum of c and d is 3
- X is a chlorine atom or 1 to 6 carbon atoms.
- Y represents a single bond, an etheric oxygen atom or —CH 2 O—
- Z 1 to Z 4 each independently represents a hydrogen atom or a monovalent organic group
- R 1 represents a fluorine atom or 1
- R 2 represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group
- R 3 represents a fluorine atom or a monovalent fluorine-containing organic group
- R 1 , R 2 and any two selected from the group consisting of R 3 may be bonded to each other to form a ring
- R 4 represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms; 4.
- a compound (compound (1 ′)) represented by the following formula (1 ′) and a compound (compound (2)) represented by the following formula (2) are cross-metathesized. It is related with the manufacturing method of the compound (compound (3 ')) represented by following formula (3') by making it react.
- b is 0 or 1
- c is 0, 1 or 2
- the sum of c and d is 3
- X represents a chlorine atom or an alkoxy group having 1 to 6 carbon atoms
- Z 1 to Z 4 each independently represents a hydrogen atom or a monovalent organic group
- Q is a h-valent organic group which contains a fluorine atom and may have a hetero atom
- R 4 has 4 to 20 carbon atoms.
- an alkyl group having 1 to 6 carbon atoms h represents a natural number of 2 or more
- a plurality of Z 1 and Z 2 may be the same or different
- R 4 and X are the same molecule And when there are a plurality of them, they may be the same or different.
- the left carbene part of the double bond in the formula (1 ′) (the part obtained by removing CZ 1 Z 2 from the compound (1 ′)) and the left carbene part of the double bond in the formula (3 ′) are
- the right carbene part of the double bond in the formula (2) (the part obtained by removing CZ 3 Z 4 from the compound (2)) and the right carbene part of the double bond in the formula (3 ′) are the same.
- a is 0 or 1, preferably 1.
- b is 0 or 1, preferably 0.
- c is 0, 1 or 2, preferably 0.
- the sum of c and d is 3. That is, d is 1, 2 or 3, preferably 3.
- X represents a chlorine atom or an alkoxy group having 1 to 6 carbon atoms, and when d is 2 or 3, a plurality of X present in the same molecule may be the same or different.
- the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group. Among these, a chlorine atom, a methoxy group, and an ethoxy group are preferable.
- Y represents a single bond, an etheric oxygen atom or —CH 2 O—, preferably a single bond or an etheric oxygen atom.
- Z 1 to Z 4 each independently represents a hydrogen atom or a monovalent organic group.
- the monovalent organic group include an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 5 to 20 carbon atoms, an aryloxy group having 5 to 20 carbon atoms, and 1 carbon atom.
- halogenated alkyl group having ⁇ 12 (per) halogenated alkoxy group having 1 to 12 carbon atoms, (per) halogenated aryl group having 5 to 20 carbon atoms and (per) halogenation having 5 to 20 carbon atoms And a group selected from the group consisting of aryloxy groups, the alkyl group, alkoxy group, aryl group, aryloxy group, (per) halogenated alkyl group, (per) halogenated alkoxy group, and (per) halogenated aryl.
- the group selected from the group consisting of a group and a (per) halogenated aryloxy group is selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. Atoms may contain at least one element.
- a hydrogen atom methyl group, ethyl group, propyl group, methoxy group, ethoxy group, propoxy group, phenyl group, phenyloxy group, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, A trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoropropoxy group, a perfluoro (methoxymethoxy) group, a perfluoro (propoxypropoxy) group, a pentafluorophenyl group, and a pentafluorophenyloxy group.
- R 1 represents a fluorine atom or a monovalent fluorine-containing organic group.
- the fluorine-containing organic group include (per) fluoroalkyl groups having 1 to 12 carbon atoms, (per) fluoroalkoxy groups having 1 to 12 carbon atoms, and (per) carbon atoms having 2 to 400 carbon atoms containing an etheric oxygen atom. Examples thereof include a fluoroalkyl group and a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom.
- a (per) fluoroalkyl group having 1 to 12 carbon atoms preferably, a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and 2 to 2 carbon atoms containing an etheric oxygen atom. 400 (per) fluoroalkoxy groups.
- R 2 represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group.
- the fluorine-containing organic group include (per) fluoroalkyl groups having 1 to 12 carbon atoms, (per) fluoroalkoxy groups having 1 to 12 carbon atoms, and (per) carbon atoms having 2 to 400 carbon atoms containing an etheric oxygen atom. Examples thereof include a fluoroalkyl group and a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom.
- a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a (per) fluoroalkyl group having 2 to 400 carbon atoms including an etheric oxygen atom are preferable.
- R 3 represents a fluorine atom or a monovalent fluorine-containing organic group, preferably a fluorine atom, a (per) fluoroalkyl group having 1 to 12 carbon atoms, or (per) carbon atoms having 2 to 400 carbon atoms including an etheric oxygen atom. It is a fluoroalkyl group, more preferably a (per) fluoroalkyl group having 2 to 400 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom.
- R 4 represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and when c is 2, two R 4 s may be the same or different.
- the aryl group having 4 to 20 carbon atoms include a phenyl group, a naphthyl group, and a biphenyl group.
- the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Among these, a phenyl group, a methyl group, and an ethyl group are preferable.
- the compound (1 ') and the compound (2) are subjected to a cross metathesis reaction.
- h represents a natural number of 2 or more
- Q is a h-valent organic group that contains a fluorine atom and may have a hetero atom.
- h is preferably a natural number of 2 to 5, and more preferably 2 or 3.
- Q is preferably a fluorine-containing organic group having 2 to 400 carbon atoms containing an oxygen atom, a fluorine-containing organic group having 2 to 400 carbon atoms containing an oxygen atom and a silicon atom, or the like.
- Z 1 and Z 2 in the compound (1 ') are each same as Z 1 and Z 2 of compound in the cross metathesis reaction with aforementioned the compound (1) and the compound (2) (1), preferred embodiments Is the same.
- a plurality of Z 1 and Z 2 may be the same or different.
- B to d, X, Z 3 , Z 4 and R 4 in the compound (2) are the same as b to d, X, Z of the compound (2) in the cross metathesis reaction between the compound (1) and the compound (2).
- 3 , Z 4 and R 4 are the same, and the preferred embodiments are also the same.
- compound (1) examples include the compounds shown below.
- the perfluoroalkylene group may be a block chain or a random chain.
- Compound (3) is produced by the cross metathesis of the present invention.
- the sum of a, b, c, c and d, X, Y, R 1 , R 2 , R 3 and R 4 are as defined above. Any two selected from the group consisting of R 1 , R 2 , and R 3 may be bonded to each other to form a ring.
- a is 0 or 1
- X is a chlorine atom, a methoxy group or an ethoxy group
- Y is a single bond, an etheric oxygen atom or —CH 2 O -
- R 1 is a (per) fluoroalkyl group having 1 to 12 carbon atoms, a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, or a carbon number of 2 to 400 containing an etheric oxygen atom
- R 2 is a fluorine atom, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom
- R 3 is A compound which is a fluorine atom, a trifluoromethyl group or a (per) fluorine
- Specific examples of the compound (3) include the following compounds.
- Compound (3 ′) is produced by the cross metathesis of the present invention.
- b, c, the sum of c and d, X, Q, R 4 and h are as defined above.
- Specific examples of the compound (3 ′) include the compounds shown below.
- the present invention relates to a method for producing a fluorine-containing silane compound by cross-metathesis, wherein “compound (1) and compound (2)” or “compound (1 ′) and compound (2)” is brought into contact with a catalyst.
- cross metathesis is performed to obtain an olefin (compound (3) or compound (3 ′)) different from the raw material.
- the geometric isomerism on the double bond of compound (1), compound (1 ′) and compound (2) is not particularly limited. From the viewpoint of improving the yield of the desired product, it is preferable to use degassed and dehydrated compounds (1), (1 ′) and (2). There is no particular limitation on the deaeration operation, but freeze deaeration and the like may be performed. Although there is no restriction
- the compound (1), the compound (1 ′) and the compound (2) may contain a trace amount of impurities (for example, hydrogen fluoride and peroxide), they may be purified in terms of improving the yield of the target product.
- impurities for example, hydrogen fluoride and peroxide
- the purification method it can be carried out according to the method described in the literature (Armarego, WLF et al., Purification of Laboratory Chemicals (Sixth Edition), 2009, Elsevier).
- Compound (1) or compound (1 ') and compound (2) may be added after mixing in the reaction vessel in advance or separately.
- the second olefin may be contacted with the mixture obtained by contacting the first olefin with the catalyst.
- the molar ratio of the compound (1) or the compound (1 ′) and the compound (2) is not particularly limited, but the other olefin is preferably used in an amount of 0.01 to 100 mol with respect to 1 mol of the standard olefin. Is used in an amount of 0.1 to 10 mol.
- the catalyst may be added as a reagent or generated in the system.
- a commercially available catalyst may be used as it is, or a non-commercial catalyst synthesized from a commercially available reagent by a known method may be used.
- a catalyst prepared from a metal complex as a precursor by a known method can be used in the present invention.
- Examples of the catalyst include metal-carbene complex compounds.
- ruthenium-carbene complex a compound in which the metal is ruthenium is generally called a ruthenium-carbene complex, and is described in, for example, Vougioukalakis, G., et al. C. et al. Chem. Rev. , 2010, 110, 1746-1787.
- the ruthenium-carbene complex described in 1) can be used.
- a ruthenium-carbene complex commercially available from Aldrich or Umicore can be used.
- ruthenium-carbene complex examples include, for example, bis (triphenylphosphine) benzylidene ruthenium dichloride, bis (tricyclohexylphosphine) benzylidene ruthenium dichloride, bis (tricyclohexylphosphine) -3-methyl-2-butenylidene ruthenium dichloride.
- the names beginning with “Umicore” are trade names of Umicore products.
- the ruthenium-carbene complex may be used alone or in combination of two or more. Further, if necessary, it may be supported on a carrier such as silica gel, alumina or polymer.
- molybdenum-carbene complexes compounds in which the metal is molybdenum or tungsten are generally called molybdenum-carbene complexes or tungsten-carbene complexes.
- the molybdenum-carbene complex or tungsten-carbene complex described in 1) can be used.
- a molybdenum-carbene complex or a tungsten-carbene complex commercially available from Aldrich or Strem can be used.
- molybdenum-carbene complex or tungsten-carbene complex may be used alone or in combination of two or more. Further, if necessary, it may be supported on a carrier such as silica gel, alumina or polymer.
- Me represents a methyl group
- i-Pr represents an isopropyl group
- t-Bu represents a tertiary butyl group
- Ph represents a phenyl group.
- tungsten-carbene complex examples include the following compounds.
- the amount of the catalyst is not particularly limited, but 0.0001 to 1 mol is usually used with respect to 1 mol of the standard olefin in the compound (1) or the compound (1 ′) and the compound (2). Is used in an amount of 0.001 to 0.2 mol.
- the catalyst is usually charged into the reaction vessel as a solid, but may be charged after dissolving or suspending in a solvent.
- the solvent used at this time is not particularly limited as long as it does not adversely affect the reaction, and an organic solvent, a fluorine-containing organic solvent, an ionic liquid, water or the like can be used alone or in combination.
- an organic solvent, a fluorine-containing organic solvent, an ionic liquid, water or the like can be used alone or in combination.
- some or all of the hydrogen atoms may be substituted with deuterium atoms.
- organic solvent examples include aromatic hydrocarbon solvents such as benzene, toluene, o-, m-, p-xylene and mesitylene; aliphatic hydrocarbon solvents such as hexane and cyclohexane; dichloromethane, chloroform, 1, 2 -Halogen solvents such as dichloroethane, chlorobenzene, o-dichlorobenzene; ether solvents such as tetrahydrofuran, dioxane, diethyl ether, glyme and diglyme can be used.
- aromatic hydrocarbon solvents such as benzene, toluene, o-, m-, p-xylene and mesitylene
- aliphatic hydrocarbon solvents such as hexane and cyclohexane
- dichloromethane, chloroform, 1, 2 -Halogen solvents such as dichloroethane, chlorobenzene, o-
- fluorine-containing organic solvent for example, hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, ⁇ , ⁇ , ⁇ -trifluoromethylbenzene, dichloropentafluoropropane is used. can do.
- ionic liquid for example, various pyridinium salts and various imidazolium salts can be used.
- benzene, toluene, o-, m-, p-xylene, mesitylene, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, diethyl ether, dioxane, THF (tetrahydrofuran) in terms of solubility of the catalyst Hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, ⁇ , ⁇ , ⁇ -trifluoromethylbenzene, and mixtures thereof are preferred.
- a degassed and dehydrated solvent for improving the yield of the target product.
- the deaeration operation freeze deaeration and the like may be performed.
- dehydration operation Usually, it is made to contact with a molecular sieve etc.
- the degassing and dehydration operations are usually performed before contacting with the catalyst.
- the atmosphere in which the compound (1) or the compound (1 ′) and the compound (2) are brought into contact with the catalyst is not particularly limited, but an inert gas atmosphere is preferable from the viewpoint of extending the life of the catalyst. Or an argon atmosphere is preferable. However, when using the olefin which becomes gas in reaction conditions as a raw material, it can carry out in these gas atmosphere.
- the phase in which the compound (1) or the compound (1 ') and the compound (2) are brought into contact with the catalyst is not particularly limited, but a liquid phase is usually used in terms of reaction rate.
- a liquid phase is usually used in terms of reaction rate.
- a solvent can be used in the case of carrying out in the liquid phase.
- the same solvents as those used for dissolving or suspending the catalyst can be used.
- the same solvents as those used for dissolving or suspending the catalyst can be used.
- at least one of the compound (1) or the compound (1 ') and the compound (2) is liquid under the reaction conditions, it may be carried out without a solvent.
- the container for bringing the compound (1) or the compound (1 ′) and the compound (2) into contact with the catalyst is not particularly limited as long as the reaction is not adversely affected.
- a metal container or a glass container is used. it can.
- the cross metathesis concerning this invention may handle the olefin in a gaseous state on reaction conditions, the pressure-resistant container in which high airtightness is possible is preferable.
- the temperature at which the compound (1) or the compound (1 ′) and the compound (2) are brought into contact with the catalyst is not particularly limited, but the reaction can usually be carried out in the range of ⁇ 100 to 200 ° C. And 0 to 150 ° C. is preferable. Note that the reaction does not start at low temperatures, and the complex may be rapidly decomposed at high temperatures. Therefore, it is necessary to appropriately set the lower limit and the upper limit of the temperature. Usually, it is carried out at a temperature below the boiling point of the solvent used.
- the time for bringing the compound (1) or the compound (1 ′) and the compound (2) into contact with the catalyst is not particularly limited, but is usually in the range of 1 minute to 48 hours.
- the pressure at which the compound (1) or the compound (1 ′) and the compound (2) are brought into contact with the catalyst is not particularly limited, but may be under pressure, normal pressure, or reduced pressure. Usually, it is about 0.001 to 10 MPa, preferably about 0.01 to 1 MPa.
- an inorganic salt, an organic compound, or a metal complex may be allowed to coexist in a range that does not adversely affect the reaction.
- the compound (1) or the compound (1 ′) and the mixture of the compound (2) and the catalyst may be stirred as long as the reaction is not adversely affected.
- a mechanical stirrer or a magnetic stirrer can be used as a stirring method.
- the target product After contacting compound (1) or compound (1 ′) and compound (2) with the catalyst, the target product is usually obtained as a mixture of a plurality of olefins, and therefore may be isolated by a known method. Examples of the isolation method include distillation, column chromatography, and recycle preparative HPLC, and these can be used alone or in combination as required.
- the compound (3) or compound (3 ′) obtained by this reaction can be identified by a known method similar to that for ordinary organic compounds. Examples thereof include 1 H-, 19 F-, 13 C-NMR, and GC-MS, and these can be used alone or in combination as required.
- This invention relates to the compound (compound (4)) represented by following formula (4).
- the compound (4) is an example of the compound (3), and the following compound (4-1) as the compound (1) and the following compound (4-2) as the compound (2) are catalyzed by the method described above. A cross-metathesis reaction can be performed and obtained by contacting with.
- R 11 represents a monovalent fluorine-containing organic group.
- the fluorine-containing organic group include (per) fluoroalkyl groups having 1 to 12 carbon atoms, (per) fluoroalkoxy groups having 1 to 12 carbon atoms, and (per) carbon atoms having 2 to 400 carbon atoms containing an etheric oxygen atom.
- examples thereof include a fluoroalkyl group and a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom.
- a (per) fluoroalkyl group having 1 to 12 carbon atoms preferably, a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and 2 to 2 carbon atoms containing an etheric oxygen atom. 400 (per) fluoroalkoxy groups.
- Z 1 to Z 4 , c, the sum of c and d, Y, R 2 , R 3 and R 4 are the same as defined in the compounds (1) to (3). Further, any two selected from the group consisting of R 11 , R 2 and R 3 may be bonded to each other to form a ring.
- Y is a single bond, etheric oxygen atom or —CH 2 O—
- R 11 is a (per) fluoroalkyl group having 1 to 12 carbon atoms, etheric oxygen (Per) fluoroalkyl group having 2 to 400 carbon atoms containing atom or (per) fluoroalkoxy group having 2 to 400 carbon atoms containing etheric oxygen atom
- R 2 is fluorine atom, trifluoromethyl group, pentafluoroethyl group , A heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom
- R 3 having 2 to 400 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom
- Compounds that are per) fluoroalkyl groups are preferred.
- Compound (5) Moreover, this invention relates to the compound (compound (5)) represented by following formula (5).
- Compound (5) is an example of compound (3), and the following compound (5-1) as compound (1) and the following compound (5-2) as compound (2) are catalyzed by the method described above. A cross metathesis reaction can be carried out by contacting with.
- Z 1 to Z 4 , b, c, the sum of c and d, Y, R 1 , R 2 , R 3 and R 4 are the same as defined in the compounds (1) to (3). Any two selected from the group consisting of R 1 , R 2 , and R 3 may be bonded to each other to form a ring.
- b is 0, c is 0, d is 3, Y is a single bond, etheric oxygen atom or —CH 2 O—, and R 1 is a (per) fluoroalkyl group having 1 to 12 carbon atoms.
- R 2 is a fluorine atom, a trifluoromethyl group
- R 3 having 2 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom
- Compounds with up to 400 (per) fluoroalkyl groups are preferred.
- This invention relates to the compound (compound (6)) represented by following formula (6).
- the compound (6) is an example of the compound (3), and the following compound (6-1) as the compound (1) and the following compound (6-2) as the compound (2) are catalyzed by the method described above. A cross metathesis reaction can be carried out by contacting with.
- R 5 represents an alkyl group having 1 to 6 carbon atoms, and when a plurality of R 5 are present in the same molecule, they may be the same or different.
- the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, and a propyl group. Among these, a methyl group and an ethyl group are preferable.
- Z 1 to Z 4 , c, the sum of c and d, Y, R 1 , R 2 , R 3 and R 4 are as defined in the compounds (1) to (3). Any two selected from the group consisting of R 1 , R 2 , and R 3 may be bonded to each other to form a ring.
- Y is a single bond, an etheric oxygen atom or —CH 2 O—
- R 1 is a (per) fluoroalkyl group having 1 to 12 carbon atoms, etheric oxygen (Per) fluoroalkyl group having 2 to 400 carbon atoms containing atom or (per) fluoroalkoxy group having 2 to 400 carbon atoms containing etheric oxygen atom
- R 2 is fluorine atom, trifluoromethyl group, pentafluoroethyl group , A heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom
- R 3 having 2 to 400 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom
- Compounds that are per) fluoroalkyl groups are preferred.
- the structure of the synthesized compound was identified by performing 1 H-NMR and 19 F-NMR measurements using a nuclear magnetic resonance apparatus “JNM-AL300” manufactured by JEOL Ltd.
- Example 15 Cross Metathesis of C 8 F 17 —CH 2 —CH ⁇ CH 2 and Trichlorovinylsilane with Umicore M73 SIPr Catalyst Same as Example 1 except that the solvent in Example 1 was changed to heavy benzene (C 6 D 6 ) The formation of Compound A is confirmed by a simple method.
- Example 16 Cross Metathesis of C 8 F 17 —CH 2 —CH ⁇ CH 2 and Trichlorovinylsilane with Grubbs Second Generation Catalyst
- the catalyst in Example 1 was changed to a Grubbs second generation catalyst (10 mol%, 0.006 mmol).
- the production of Compound A was confirmed by the same method as in Example 1 except that. A series of these reactions is shown below.
- the fluorine-containing silane compound according to the production method of the present invention can be used as a pharmaceutical / agrochemical intermediate, a fingerprint remover, an antifouling agent, and a moisture-proof coating agent.
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Abstract
The purpose of the present invention is to provide: a production method capable of easily and efficiently producing, by olefin metathesis, a fluorine-containing silane compound having a reactive carbon-carbon double bond under mild conditions; and a novel fluorine-containing silane compound. The present invention pertains to a production method for a compound represented by formula (3), the method comprising causing a compound represented by formula (1) and a compound represented by formula (2) to undergo cross metathesis. In the formulas, reference characters are as defined in the description.
Description
本発明は、クロスメタセシス反応により含フッ素シラン化合物を製造する方法及び含フッ素シラン化合物に関する。
The present invention relates to a method for producing a fluorinated silane compound by a cross metathesis reaction and a fluorinated silane compound.
フッ素原子を含む有機基を表面層に有する基材は、ディスプレイやメガネ、タッチパネルなど、撥水、撥油、防汚性が求められる用途において産業上有用である。ここで、フッ素原子を含む有機基は、高い潤滑性、撥水撥油性等を示すため、基材の表面処理剤に好適に用いられる。該表面処理剤によって基材の表面に撥水撥油性を付与すると、基材の表面の汚れを拭き取りやすくなり、汚れの除去性が向上する。
A base material having an organic group containing a fluorine atom in its surface layer is industrially useful in applications where water repellency, oil repellency and antifouling properties are required, such as displays, glasses and touch panels. Here, since the organic group containing a fluorine atom exhibits high lubricity, water / oil repellency, etc., it is preferably used as a surface treatment agent for a substrate. When the surface treatment agent imparts water and oil repellency to the surface of the base material, it becomes easy to wipe off the dirt on the surface of the base material, and the dirt removability is improved.
基材の表面に含フッ素化合物を導入する方法としては、含フッ素シラン化合物を含む表面処理剤を用いる方法などが知られている。
例えば、特許文献１には含フッ素シラン化合物として、分子内に２つ以上のケイ素原子を有する化合物を用いる表面処理剤が開示されている。 As a method for introducing a fluorine-containing compound into the surface of a substrate, a method using a surface treatment agent containing a fluorine-containing silane compound is known.
For example, Patent Document 1 discloses a surface treatment agent that uses a compound having two or more silicon atoms in the molecule as the fluorine-containing silane compound.
例えば、特許文献１には含フッ素シラン化合物として、分子内に２つ以上のケイ素原子を有する化合物を用いる表面処理剤が開示されている。 As a method for introducing a fluorine-containing compound into the surface of a substrate, a method using a surface treatment agent containing a fluorine-containing silane compound is known.
For example, Patent Document 1 discloses a surface treatment agent that uses a compound having two or more silicon atoms in the molecule as the fluorine-containing silane compound.
一方、金属触媒による二重結合組み換え反応であるオレフィンメタセシス反応（以下、単に、「オレフィンメタセシス」または「メタセシス」ということもある。）は、多彩な置換基を有するオレフィンの製造方法として広く利用されている。
例えば、非特許文献１では、種々の置換基を有するオレフィンの反応性が調べられており、非特許文献２では、ルテニウム錯体とフッ化ビニリデン（すなわち、１，１－ジフルオロエチレン）のオレフィンメタセシスが検討されている。 On the other hand, the olefin metathesis reaction (hereinafter sometimes simply referred to as “olefin metathesis” or “metathesis”), which is a double bond recombination reaction using a metal catalyst, is widely used as a method for producing olefins having various substituents. ing.
For example, in Non-Patent Document 1, the reactivity of olefins having various substituents has been investigated, and in Non-Patent Document 2, olefin metathesis of a ruthenium complex and vinylidene fluoride (that is, 1,1-difluoroethylene) is investigated. It is being considered.
例えば、非特許文献１では、種々の置換基を有するオレフィンの反応性が調べられており、非特許文献２では、ルテニウム錯体とフッ化ビニリデン（すなわち、１，１－ジフルオロエチレン）のオレフィンメタセシスが検討されている。 On the other hand, the olefin metathesis reaction (hereinafter sometimes simply referred to as “olefin metathesis” or “metathesis”), which is a double bond recombination reaction using a metal catalyst, is widely used as a method for producing olefins having various substituents. ing.
For example, in Non-Patent Document 1, the reactivity of olefins having various substituents has been investigated, and in Non-Patent Document 2, olefin metathesis of a ruthenium complex and vinylidene fluoride (that is, 1,1-difluoroethylene) is investigated. It is being considered.
しかしながら、従来の含フッ素シラン化合物を含む表面処理剤は長期の使用による性能の低下が懸念され、例えば、摩擦耐久性が充分でない等、改善の余地があった。
However, the conventional surface treatment agent containing a fluorine-containing silane compound is feared to deteriorate in performance due to long-term use. For example, there is room for improvement such as insufficient friction durability.
また、電子求引性置換基を有する電子不足オレフィンは反応性が低いため、オレフィンメタセシスに利用することは容易ではない。実際、非特許文献１では、電子不足オレフィンの反応性が低いと記載されている。
さらに、フッ素原子や塩素原子等、ハロゲン原子を有するオレフィンも電子不足オレフィンであるため、オレフィンメタセシスに用いた報告はほとんどなく、非特許文献２では、期待した生成物すなわちエチレン及びテトラフルオロエチレンは全く得られなかったと述べられている。 In addition, since an electron-deficient olefin having an electron-withdrawing substituent has low reactivity, it is not easy to use it for olefin metathesis. In fact, Non-Patent Document 1 describes that the reactivity of electron-deficient olefins is low.
Furthermore, since olefins having halogen atoms such as fluorine atoms and chlorine atoms are also electron-deficient olefins, there are few reports used for olefin metathesis, and in Non-Patent Document 2, the expected products, namely ethylene and tetrafluoroethylene, are completely absent. It is stated that it was not obtained.
さらに、フッ素原子や塩素原子等、ハロゲン原子を有するオレフィンも電子不足オレフィンであるため、オレフィンメタセシスに用いた報告はほとんどなく、非特許文献２では、期待した生成物すなわちエチレン及びテトラフルオロエチレンは全く得られなかったと述べられている。 In addition, since an electron-deficient olefin having an electron-withdrawing substituent has low reactivity, it is not easy to use it for olefin metathesis. In fact, Non-Patent Document 1 describes that the reactivity of electron-deficient olefins is low.
Furthermore, since olefins having halogen atoms such as fluorine atoms and chlorine atoms are also electron-deficient olefins, there are few reports used for olefin metathesis, and in Non-Patent Document 2, the expected products, namely ethylene and tetrafluoroethylene, are completely absent. It is stated that it was not obtained.
そのため、工業的に入手容易な含フッ素化合物を用いて、反応性炭素－炭素二重結合を有する含フッ素シラン化合物を、温和な条件下で簡便かつ効率的に製造できれば、基材表面に架橋性部位を有する含フッ素アルキル基を導入する事が可能となり、既存手法と比較して耐久性の高い基材を製造できる。
Therefore, if a fluorine-containing silane compound having a reactive carbon-carbon double bond can be easily and efficiently produced under mild conditions using an industrially available fluorine-containing compound, the substrate surface is crosslinkable. It becomes possible to introduce a fluorine-containing alkyl group having a site, and it is possible to produce a substrate having a higher durability compared to existing methods.
本発明は、上記従来の実情を鑑みてなされたものであって、オレフィンメタセシスにより、反応性炭素－炭素二重結合を有する含フッ素シラン化合物を温和な条件下で簡便かつ効率的に製造できる製造方法及び新規な含フッ素シラン化合物を提供することを目的とする。
The present invention has been made in view of the above-described conventional circumstances, and is a production that can easily and efficiently produce a fluorine-containing silane compound having a reactive carbon-carbon double bond by mild process under olefin metathesis. The object is to provide a method and a novel fluorine-containing silane compound.
本発明者は、鋭意検討を重ねた結果、特定の化合物同士をクロスメタセシス反応させることで上記課題を解決できることを見出し、本発明を完成するに至った。
すなわち、本発明は下記＜１＞～＜１１＞に関するものである。
＜１＞下記式（１’）で表される化合物と、下記式（２）で表される化合物とをクロスメタセシス反応させる、下記式（３’）で表される化合物の製造方法。 As a result of intensive studies, the present inventor has found that the above-mentioned problems can be solved by cross-metathesis reaction between specific compounds, and has completed the present invention.
That is, the present invention relates to the following <1> to <11>.
<1> A method for producing a compound represented by the following formula (3 ′), wherein a compound represented by the following formula (1 ′) and a compound represented by the following formula (2) are subjected to a cross metathesis reaction.
すなわち、本発明は下記＜１＞～＜１１＞に関するものである。
＜１＞下記式（１’）で表される化合物と、下記式（２）で表される化合物とをクロスメタセシス反応させる、下記式（３’）で表される化合物の製造方法。 As a result of intensive studies, the present inventor has found that the above-mentioned problems can be solved by cross-metathesis reaction between specific compounds, and has completed the present invention.
That is, the present invention relates to the following <1> to <11>.
<1> A method for producing a compound represented by the following formula (3 ′), wherein a compound represented by the following formula (1 ′) and a compound represented by the following formula (2) are subjected to a cross metathesis reaction.
（式中、ｂは０または１であり、ｃは０、１または２であり、ｃとｄの和は３であり、Ｘは塩素原子または炭素数１～６のアルコキシ基を表し、Ｚ１～Ｚ４はそれぞれ独立に水素原子または１価の有機基を表し、Ｑはフッ素原子を含み、かつヘテロ原子を有していてもよいｈ価の有機基であり、Ｒ４は炭素数４～２０のアリール基または炭素数１～６のアルキル基を表し、ｈは２以上の自然数を表し、複数存在するＺ１、Ｚ２はそれぞれ同一でも異なっていてもよく、Ｒ４、Ｘがそれぞれ同一分子内に複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。）
(Wherein, b is 0 or 1, c is 0, 1 or 2, the sum of c and d is 3, X represents a chlorine atom or an alkoxy group having a carbon number of 1 ~ 6, Z 1 -Z 4 each independently represents a hydrogen atom or a monovalent organic group, Q is a h-valent organic group which contains a fluorine atom and may have a hetero atom, and R 4 has 4 to 4 carbon atoms. 20 represents an aryl group or an alkyl group having 1 to 6 carbon atoms, h represents a natural number of 2 or more, a plurality of Z 1 and Z 2 may be the same or different, and R 4 and X are the same If there are multiple molecules in the molecule, they may be the same or different.)
＜２＞下記式（１）で表される化合物と、下記式（２）で表される化合物とをクロスメタセシス反応させる、下記式（３）で表される化合物の製造方法。
<2> A method for producing a compound represented by the following formula (3), wherein a compound represented by the following formula (1) and a compound represented by the following formula (2) are subjected to a cross metathesis reaction.
（式中、ａは０または１であり、ｂは０または１であり、ｃは０、１または２であり、ｃとｄの和は３であり、Ｘは塩素原子または炭素数１～６のアルコキシ基を表し、Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－を表し、Ｚ１～Ｚ４はそれぞれ独立に水素原子または１価の有機基を表し、Ｒ１はフッ素原子または１価の含フッ素有機基を表し、Ｒ２は水素原子、フッ素原子または１価の含フッ素有機基を表し、Ｒ３はフッ素原子または１価の含フッ素有機基を表し、Ｒ１、Ｒ２、およびＲ３からなる群から選ばれる任意の２つは互いに結合して環を形成してもよく、Ｒ４は炭素数４～２０のアリール基または炭素数１～６のアルキル基を表し、Ｒ４、Ｘがそれぞれ同一分子内に複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。）
(In the formula, a is 0 or 1, b is 0 or 1, c is 0, 1 or 2, the sum of c and d is 3, and X is a chlorine atom or 1 to 6 carbon atoms. Y represents a single bond, an etheric oxygen atom or —CH 2 O—, Z 1 to Z 4 each independently represents a hydrogen atom or a monovalent organic group, and R 1 represents a fluorine atom or Represents a monovalent fluorine-containing organic group, R 2 represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group, R 3 represents a fluorine atom or a monovalent fluorine-containing organic group, R 1 , R 2 And any two selected from the group consisting of R 3 may be bonded to each other to form a ring, and R 4 represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, When a plurality of R 4 and X are present in the same molecule, they are the same But it may be different.)
＜３＞ａは０または１であり、ｂは０であり、ｃは０であり、Ｘは塩素原子、メトキシ基またはエトキシ基を表し、Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－を表し、Ｒ１は炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基を表し、Ｒ２はフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表し、Ｒ３はフッ素原子、トリフルオロメチル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表す、前記＜２＞に記載の製造方法。
＜４＞Ｚ１～Ｚ４はそれぞれ独立に水素原子、メチル基、エチル基、プロピル基、メトキシ基、エトキシ基、プロポキシ基、フェニル基、フェニルオキシ基、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、トリフルオロメトキシ基、ペンタフルオロエトキシ基、ヘプタフルオロプロポキシ基、ペルフルオロ（メトキシメトキシ）基、ペルフルオロ（プロポキシプロポキシ）基、ペンタフルオロフェニル基またはペンタフルオロフェニルオキシ基を表す、前記＜２＞または＜３＞に記載の製造方法。
＜５＞下記式（３’）で表される化合物。 <3> a is 0 or 1, b is 0, c is 0, X represents a chlorine atom, a methoxy group or an ethoxy group, Y represents a single bond, an etheric oxygen atom or —CH 2 O R 1 represents a (per) fluoroalkyl group having 1 to 12 carbon atoms, a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, or 2 to 400 carbon atoms containing an etheric oxygen atom. Wherein R 2 represents a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom. the stands, R 3 represents a fluorine atom, a trifluoromethyl group or a C 2 -C 400 including an etheric oxygen atom, (per) fluoroalkyl group, the < The method according to>.
<4> Z 1 to Z 4 are each independently a hydrogen atom, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, propoxy group, phenyl group, phenyloxy group, trifluoromethyl group, pentafluoroethyl group, <2 which represents heptafluoropropyl group, trifluoromethoxy group, pentafluoroethoxy group, heptafluoropropoxy group, perfluoro (methoxymethoxy) group, perfluoro (propoxypropoxy) group, pentafluorophenyl group or pentafluorophenyloxy group > Or <3>.
<5> A compound represented by the following formula (3 ′).
＜４＞Ｚ１～Ｚ４はそれぞれ独立に水素原子、メチル基、エチル基、プロピル基、メトキシ基、エトキシ基、プロポキシ基、フェニル基、フェニルオキシ基、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、トリフルオロメトキシ基、ペンタフルオロエトキシ基、ヘプタフルオロプロポキシ基、ペルフルオロ（メトキシメトキシ）基、ペルフルオロ（プロポキシプロポキシ）基、ペンタフルオロフェニル基またはペンタフルオロフェニルオキシ基を表す、前記＜２＞または＜３＞に記載の製造方法。
＜５＞下記式（３’）で表される化合物。 <3> a is 0 or 1, b is 0, c is 0, X represents a chlorine atom, a methoxy group or an ethoxy group, Y represents a single bond, an etheric oxygen atom or —CH 2 O R 1 represents a (per) fluoroalkyl group having 1 to 12 carbon atoms, a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, or 2 to 400 carbon atoms containing an etheric oxygen atom. Wherein R 2 represents a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom. the stands, R 3 represents a fluorine atom, a trifluoromethyl group or a C 2 -C 400 including an etheric oxygen atom, (per) fluoroalkyl group, the < The method according to>.
<4> Z 1 to Z 4 are each independently a hydrogen atom, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, propoxy group, phenyl group, phenyloxy group, trifluoromethyl group, pentafluoroethyl group, <2 which represents heptafluoropropyl group, trifluoromethoxy group, pentafluoroethoxy group, heptafluoropropoxy group, perfluoro (methoxymethoxy) group, perfluoro (propoxypropoxy) group, pentafluorophenyl group or pentafluorophenyloxy group > Or <3>.
<5> A compound represented by the following formula (3 ′).
（式中、ｂは０または１であり、ｃは０、１または２であり、ｃとｄの和は３であり、Ｘは塩素原子または炭素数１～６のアルコキシ基を表し、Ｑはフッ素原子を含み、かつヘテロ原子を有していてもよいｈ価の有機基であり、Ｒ４は炭素数４～２０のアリール基または炭素数１～６のアルキル基を表し、ｈは２以上の自然数を表し、Ｒ４、Ｘがそれぞれ複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。）
(Wherein b is 0 or 1, c is 0, 1 or 2, the sum of c and d is 3, X represents a chlorine atom or an alkoxy group having 1 to 6 carbon atoms, Q is An h-valent organic group which contains a fluorine atom and may have a hetero atom, R 4 represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and h is 2 or more. And when there are a plurality of R 4 s and Xs, they may be the same or different.)
＜６＞下記式（４）で表される化合物。
<6> A compound represented by the following formula (4).
（式中、ｃは０、１または２であり、ｃとｄの和は３であり、Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－を表し、Ｒ１１は１価の含フッ素有機基を表し、Ｒ２は水素原子、フッ素原子または１価の含フッ素有機基を表し、Ｒ３はフッ素原子または１価の含フッ素有機基を表し、Ｒ１１、Ｒ２、およびＲ３からなる群から選ばれる任意の２つは互いに結合して環を形成してもよく、Ｒ４は炭素数４～２０のアリール基または炭素数１～６のアルキル基を表し、Ｒ４が複数存在する場合、それらは同一でも異なっていてもよい。）
(In the formula, c is 0, 1 or 2, the sum of c and d is 3, Y represents a single bond, an etheric oxygen atom or —CH 2 O—, and R 11 represents a monovalent fluorine-containing group. Represents an organic group, R 2 represents a hydrogen atom, a fluorine atom or a monovalent fluorinated organic group, R 3 represents a fluorine atom or a monovalent fluorinated organic group, and R 11 , R 2 and R 3 Any two selected from the group consisting of may be bonded to each other to form a ring, R 4 represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and a plurality of R 4 are present. They may be the same or different.)
＜７＞ｃは０であり、Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－を表し、Ｒ１１は炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基を表し、Ｒ２はフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表し、Ｒ３はフッ素原子、トリフルオロメチル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表す、前記＜６＞に記載の化合物。
＜８＞下記式（５）で表される化合物。 <7> c is 0, Y represents a single bond, an etheric oxygen atom or —CH 2 O—, R 11 represents a (per) fluoroalkyl group having 1 to 12 carbon atoms, a carbon containing an etheric oxygen atom Represents a (per) fluoroalkyl group having 2 to 400 carbon atoms or a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 2 represents a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a hepta Represents a fluoropropyl group or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 3 is a fluorine atom, trifluoromethyl group or 2 to 400 carbon atoms containing an etheric oxygen atom ( The compound according to <6>, which represents a per) fluoroalkyl group.
<8> A compound represented by the following formula (5).
＜８＞下記式（５）で表される化合物。 <7> c is 0, Y represents a single bond, an etheric oxygen atom or —CH 2 O—, R 11 represents a (per) fluoroalkyl group having 1 to 12 carbon atoms, a carbon containing an etheric oxygen atom Represents a (per) fluoroalkyl group having 2 to 400 carbon atoms or a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 2 represents a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a hepta Represents a fluoropropyl group or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 3 is a fluorine atom, trifluoromethyl group or 2 to 400 carbon atoms containing an etheric oxygen atom ( The compound according to <6>, which represents a per) fluoroalkyl group.
<8> A compound represented by the following formula (5).
（式中、ｂは０または１であり、ｃは０、１または２であり、ｃとｄの和は３であり、Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－を表し、Ｒ１はフッ素原子または１価の含フッ素有機基を表し、Ｒ２は水素原子、フッ素原子または１価の含フッ素有機基を表し、Ｒ３はフッ素原子または１価の含フッ素有機基を表し、Ｒ１、Ｒ２、およびＲ３からなる群から選ばれる任意の２つは互いに結合して環を形成してもよく、Ｒ４は炭素数４～２０のアリール基または炭素数１～６のアルキル基を表し、Ｒ４が複数存在する場合、それらは同一でも異なっていてもよい。）
(Wherein b is 0 or 1, c is 0, 1 or 2, the sum of c and d is 3, Y represents a single bond, an etheric oxygen atom or —CH 2 O—; R 1 represents a fluorine atom or a monovalent fluorine-containing organic group, R 2 represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group, and R 3 represents a fluorine atom or a monovalent fluorine-containing organic group. Any two selected from the group consisting of R 1 , R 2 , and R 3 may be bonded to each other to form a ring, and R 4 represents an aryl group having 4 to 20 carbon atoms or 1 to 6 carbon atoms And when a plurality of R 4 are present, they may be the same or different.)
＜９＞ｂは０であり、ｃは０であり、Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－を表し、Ｒ１は炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基を表し、Ｒ２はフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表し、Ｒ３はフッ素原子、トリフルオロメチル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表す、前記＜８＞に記載の化合物。
＜１０＞下記式（６）で表される化合物。 <9> b is 0, c is 0, Y represents a single bond, an etheric oxygen atom or —CH 2 O—, R 1 represents a (per) fluoroalkyl group having 1 to 12 carbon atoms, ether Represents a (per) fluoroalkyl group having 2 to 400 carbon atoms containing a reactive oxygen atom or a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 2 represents a fluorine atom, a trifluoromethyl group, Represents a pentafluoroethyl group, a heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 3 is a carbon containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom The compound according to <8>, which represents a (per) fluoroalkyl group having a number of 2 to 400.
<10> A compound represented by the following formula (6).
＜１０＞下記式（６）で表される化合物。 <9> b is 0, c is 0, Y represents a single bond, an etheric oxygen atom or —CH 2 O—, R 1 represents a (per) fluoroalkyl group having 1 to 12 carbon atoms, ether Represents a (per) fluoroalkyl group having 2 to 400 carbon atoms containing a reactive oxygen atom or a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 2 represents a fluorine atom, a trifluoromethyl group, Represents a pentafluoroethyl group, a heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 3 is a carbon containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom The compound according to <8>, which represents a (per) fluoroalkyl group having a number of 2 to 400.
<10> A compound represented by the following formula (6).
（式中、ｃは０、１または２であり、ｃとｄの和は３であり、Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－を表し、Ｒ１はフッ素原子または１価の含フッ素有機基を表し、Ｒ２は水素原子、フッ素原子または１価の含フッ素有機基を表し、Ｒ３はフッ素原子または１価の含フッ素有機基を表し、Ｒ１、Ｒ２、およびＲ３からなる群から選ばれる任意の２つは互いに結合して環を形成してもよく、Ｒ４は炭素数４～２０のアリール基または炭素数１～６のアルキル基を表し、Ｒ５は炭素数１～６のアルキル基を表し、Ｒ４、Ｒ５がそれぞれ複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。）
(In the formula, c is 0, 1 or 2, the sum of c and d is 3, Y represents a single bond, an etheric oxygen atom or —CH 2 O—, and R 1 represents a fluorine atom or a monovalent group. R 2 represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group, R 3 represents a fluorine atom or a monovalent fluorine-containing organic group, R 1 , R 2 , and Any two selected from the group consisting of R 3 may be bonded to each other to form a ring, R 4 represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and R 5 Represents an alkyl group having 1 to 6 carbon atoms, and when there are a plurality of R 4 and R 5 , they may be the same or different.
＜１１＞ｃは０であり、Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－を表し、Ｒ１は炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基を表し、Ｒ２はフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表し、Ｒ３はフッ素原子、トリフルオロメチル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表す、前記＜１０＞に記載の化合物。
<11> c is 0, Y represents a single bond, an etheric oxygen atom or —CH 2 O—, R 1 is a (per) fluoroalkyl group having 1 to 12 carbon atoms, a carbon containing an etheric oxygen atom Represents a (per) fluoroalkyl group having 2 to 400 carbon atoms or a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 2 represents a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a hepta Represents a fluoropropyl group or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 3 is a fluorine atom, trifluoromethyl group or 2 to 400 carbon atoms containing an etheric oxygen atom ( The compound according to <10>, which represents a per) fluoroalkyl group.
本発明によれば、新規で有用な反応性炭素－炭素二重結合を有する含フッ素シラン化合物を温和な条件下で簡便かつ効率的に製造できる。
According to the present invention, a novel and useful fluorine-containing silane compound having a reactive carbon-carbon double bond can be easily and efficiently produced under mild conditions.
以下、本発明を詳細に説明するが、本発明は以下の実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲において、任意に変形して実施することができる。また、本発明は金属触媒によるオレフィンメタセシスに関するものであり、従来技術と共通する一般的特徴については記載を省略することがある。
なお、本明細書において、「式（ｎ）で表される化合物」のことを、単に「化合物（ｎ）」と称する場合がある。 Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the gist of the present invention. In addition, the present invention relates to olefin metathesis by a metal catalyst, and description of general features common to the prior art may be omitted.
In the present specification, the “compound represented by the formula (n)” may be simply referred to as “compound (n)”.
なお、本明細書において、「式（ｎ）で表される化合物」のことを、単に「化合物（ｎ）」と称する場合がある。 Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the gist of the present invention. In addition, the present invention relates to olefin metathesis by a metal catalyst, and description of general features common to the prior art may be omitted.
In the present specification, the “compound represented by the formula (n)” may be simply referred to as “compound (n)”.
また、本明細書において、炭素数とは、ある基全体に含まれる炭素原子の総数を意味し、該基が置換基を有さない場合は当該基の骨格を形成する炭素原子の数を表し、該基が置換基を有する場合は当該基の骨格を形成する炭素原子の数に置換基中の炭素原子の数を加えた総数を表す。
In this specification, the number of carbons means the total number of carbon atoms contained in an entire group, and when the group has no substituent, it represents the number of carbon atoms forming the skeleton of the group. In the case where the group has a substituent, the total number is obtained by adding the number of carbon atoms in the substituent to the number of carbon atoms forming the skeleton of the group.
エーテル性酸素原子とは、炭素－炭素原子間においてエーテル結合（－Ｏ－）を形成する酸素原子である。
アリール基とは、芳香族化合物において芳香環を形成する炭素原子の内いずれか１つの炭素原子に結合した１つの水素原子を取り去った残基に相当する一価の基を意味し、炭素環化合物から誘導されるホモアリール基と、ヘテロ環化合物から誘導されるヘテロアリール基とを合わせた総称で用いる。
（ペル）フルオロアルキル基とは、フルオロアルキル基とペルフルオロアルキル基とを合わせた総称で用いる。すなわち該基は１個以上のフッ素原子を有するアルキル基である。（ペル）フルオロアルコキシ基、（ペル）フルオロアリール基、（ペル）フルオロアリールオキシ基についても同様である。 An etheric oxygen atom is an oxygen atom that forms an ether bond (—O—) between carbon-carbon atoms.
An aryl group means a monovalent group corresponding to a residue obtained by removing one hydrogen atom bonded to any one of carbon atoms forming an aromatic ring in an aromatic compound, and a carbocyclic compound And a heteroaryl group derived from a heterocyclic compound.
The term “(per) fluoroalkyl group” is used as a general term that combines a fluoroalkyl group and a perfluoroalkyl group. That is, the group is an alkyl group having one or more fluorine atoms. The same applies to a (per) fluoroalkoxy group, a (per) fluoroaryl group, and a (per) fluoroaryloxy group.
アリール基とは、芳香族化合物において芳香環を形成する炭素原子の内いずれか１つの炭素原子に結合した１つの水素原子を取り去った残基に相当する一価の基を意味し、炭素環化合物から誘導されるホモアリール基と、ヘテロ環化合物から誘導されるヘテロアリール基とを合わせた総称で用いる。
（ペル）フルオロアルキル基とは、フルオロアルキル基とペルフルオロアルキル基とを合わせた総称で用いる。すなわち該基は１個以上のフッ素原子を有するアルキル基である。（ペル）フルオロアルコキシ基、（ペル）フルオロアリール基、（ペル）フルオロアリールオキシ基についても同様である。 An etheric oxygen atom is an oxygen atom that forms an ether bond (—O—) between carbon-carbon atoms.
An aryl group means a monovalent group corresponding to a residue obtained by removing one hydrogen atom bonded to any one of carbon atoms forming an aromatic ring in an aromatic compound, and a carbocyclic compound And a heteroaryl group derived from a heterocyclic compound.
The term “(per) fluoroalkyl group” is used as a general term that combines a fluoroalkyl group and a perfluoroalkyl group. That is, the group is an alkyl group having one or more fluorine atoms. The same applies to a (per) fluoroalkoxy group, a (per) fluoroaryl group, and a (per) fluoroaryloxy group.
［クロスメタセシス反応］
本発明の一態様は、下記式（１）で表される化合物（化合物（１））と、下記式（２）で表される化合物（化合物（２））とをクロスメタセシス反応させることによる、下記式（３）で表される化合物（化合物（３））の製造方法に関するものである。 [Cross metathesis reaction]
One embodiment of the present invention is by subjecting a compound represented by the following formula (1) (compound (1)) and a compound represented by the following formula (2) (compound (2)) to a cross metathesis reaction. The present invention relates to a method for producing a compound represented by the following formula (3) (compound (3)).
本発明の一態様は、下記式（１）で表される化合物（化合物（１））と、下記式（２）で表される化合物（化合物（２））とをクロスメタセシス反応させることによる、下記式（３）で表される化合物（化合物（３））の製造方法に関するものである。 [Cross metathesis reaction]
One embodiment of the present invention is by subjecting a compound represented by the following formula (1) (compound (1)) and a compound represented by the following formula (2) (compound (2)) to a cross metathesis reaction. The present invention relates to a method for producing a compound represented by the following formula (3) (compound (3)).
式中、ａは０または１であり、ｂは０または１であり、ｃは０、１または２であり、ｃとｄの和は３であり、Ｘは塩素原子または炭素数１～６のアルコキシ基を表し、Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－を表し、Ｚ１～Ｚ４はそれぞれ独立に水素原子または１価の有機基を表し、Ｒ１はフッ素原子または１価の含フッ素有機基を表し、Ｒ２は水素原子、フッ素原子または１価の含フッ素有機基を表し、Ｒ３はフッ素原子または１価の含フッ素有機基を表し、Ｒ１、Ｒ２、およびＲ３からなる群から選ばれる任意の２つは互いに結合して環を形成してもよく、Ｒ４は炭素数４～２０のアリール基または炭素数１～６のアルキル基を表し、Ｒ４、Ｘがそれぞれ同一分子内に複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。
クロスメタセシス反応においては、式（１）における二重結合の左側カルベン部分（化合物（１）からＣＺ１Ｚ２を除いた部分）と式（３）における二重結合の左側カルベン部分は同一となり、式（２）における二重結合の右側カルベン部分（化合物（２）からＣＺ３Ｚ４を除いた部分）と式（３）における二重結合の右側カルベン部分は同一となる。 In the formula, a is 0 or 1, b is 0 or 1, c is 0, 1 or 2, the sum of c and d is 3, and X is a chlorine atom or 1 to 6 carbon atoms. Represents an alkoxy group, Y represents a single bond, an etheric oxygen atom or —CH 2 O—, Z 1 to Z 4 each independently represents a hydrogen atom or a monovalent organic group, and R 1 represents a fluorine atom or 1 R 2 represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group, R 3 represents a fluorine atom or a monovalent fluorine-containing organic group, R 1 , R 2 , And any two selected from the group consisting of R 3 may be bonded to each other to form a ring, R 4 represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms; 4. When multiple Xs exist in the same molecule, they are the same. May be different.
In the cross metathesis reaction, the left carbene part of the double bond in formula (1) (the part obtained by removing CZ 1 Z 2 from compound (1)) and the left carbene part of the double bond in formula (3) are the same, The right carbene part of the double bond in the formula (2) (the part obtained by removing CZ 3 Z 4 from the compound (2)) and the right carbene part of the double bond in the formula (3) are the same.
クロスメタセシス反応においては、式（１）における二重結合の左側カルベン部分（化合物（１）からＣＺ１Ｚ２を除いた部分）と式（３）における二重結合の左側カルベン部分は同一となり、式（２）における二重結合の右側カルベン部分（化合物（２）からＣＺ３Ｚ４を除いた部分）と式（３）における二重結合の右側カルベン部分は同一となる。 In the formula, a is 0 or 1, b is 0 or 1, c is 0, 1 or 2, the sum of c and d is 3, and X is a chlorine atom or 1 to 6 carbon atoms. Represents an alkoxy group, Y represents a single bond, an etheric oxygen atom or —CH 2 O—, Z 1 to Z 4 each independently represents a hydrogen atom or a monovalent organic group, and R 1 represents a fluorine atom or 1 R 2 represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group, R 3 represents a fluorine atom or a monovalent fluorine-containing organic group, R 1 , R 2 , And any two selected from the group consisting of R 3 may be bonded to each other to form a ring, R 4 represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms; 4. When multiple Xs exist in the same molecule, they are the same. May be different.
In the cross metathesis reaction, the left carbene part of the double bond in formula (1) (the part obtained by removing CZ 1 Z 2 from compound (1)) and the left carbene part of the double bond in formula (3) are the same, The right carbene part of the double bond in the formula (2) (the part obtained by removing CZ 3 Z 4 from the compound (2)) and the right carbene part of the double bond in the formula (3) are the same.
また、本発明の別の態様は、下記式（１’）で表される化合物（化合物（１’））と、下記式（２）で表される化合物（化合物（２））とをクロスメタセシス反応させることによる、下記式（３’）で表される化合物（化合物（３’））の製造方法に関するものである。
In another embodiment of the present invention, a compound (compound (1 ′)) represented by the following formula (1 ′) and a compound (compound (2)) represented by the following formula (2) are cross-metathesized. It is related with the manufacturing method of the compound (compound (3 ')) represented by following formula (3') by making it react.
式中、ｂは０または１であり、ｃは０、１または２であり、ｃとｄの和は３であり、Ｘは塩素原子または炭素数１～６のアルコキシ基を表し、Ｚ１～Ｚ４はそれぞれ独立に水素原子または１価の有機基を表し、Ｑはフッ素原子を含み、かつヘテロ原子を有していてもよいｈ価の有機基であり、Ｒ４は炭素数４～２０のアリール基または炭素数１～６のアルキル基を表し、ｈは２以上の自然数を表し、複数存在するＺ１、Ｚ２はそれぞれ同一でも異なっていてもよく、Ｒ４、Ｘがそれぞれ同一分子内に複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。
クロスメタセシス反応においては、式（１’）における二重結合の左側カルベン部分（化合物（１’）からＣＺ１Ｚ２を除いた部分）と式（３’）における二重結合の左側カルベン部分は同一となり、式（２）における二重結合の右側カルベン部分（化合物（２）からＣＺ３Ｚ４を除いた部分）と式（３’）における二重結合の右側カルベン部分は同一となる。 In the formula, b is 0 or 1, c is 0, 1 or 2, the sum of c and d is 3, X represents a chlorine atom or an alkoxy group having 1 to 6 carbon atoms, Z 1 to Z 4 each independently represents a hydrogen atom or a monovalent organic group, Q is a h-valent organic group which contains a fluorine atom and may have a hetero atom, and R 4 has 4 to 20 carbon atoms. Or an alkyl group having 1 to 6 carbon atoms, h represents a natural number of 2 or more, a plurality of Z 1 and Z 2 may be the same or different, and R 4 and X are the same molecule And when there are a plurality of them, they may be the same or different.
In the cross metathesis reaction, the left carbene part of the double bond in the formula (1 ′) (the part obtained by removing CZ 1 Z 2 from the compound (1 ′)) and the left carbene part of the double bond in the formula (3 ′) are The right carbene part of the double bond in the formula (2) (the part obtained by removing CZ 3 Z 4 from the compound (2)) and the right carbene part of the double bond in the formula (3 ′) are the same.
クロスメタセシス反応においては、式（１’）における二重結合の左側カルベン部分（化合物（１’）からＣＺ１Ｚ２を除いた部分）と式（３’）における二重結合の左側カルベン部分は同一となり、式（２）における二重結合の右側カルベン部分（化合物（２）からＣＺ３Ｚ４を除いた部分）と式（３’）における二重結合の右側カルベン部分は同一となる。 In the formula, b is 0 or 1, c is 0, 1 or 2, the sum of c and d is 3, X represents a chlorine atom or an alkoxy group having 1 to 6 carbon atoms, Z 1 to Z 4 each independently represents a hydrogen atom or a monovalent organic group, Q is a h-valent organic group which contains a fluorine atom and may have a hetero atom, and R 4 has 4 to 20 carbon atoms. Or an alkyl group having 1 to 6 carbon atoms, h represents a natural number of 2 or more, a plurality of Z 1 and Z 2 may be the same or different, and R 4 and X are the same molecule And when there are a plurality of them, they may be the same or different.
In the cross metathesis reaction, the left carbene part of the double bond in the formula (1 ′) (the part obtained by removing CZ 1 Z 2 from the compound (1 ′)) and the left carbene part of the double bond in the formula (3 ′) are The right carbene part of the double bond in the formula (2) (the part obtained by removing CZ 3 Z 4 from the compound (2)) and the right carbene part of the double bond in the formula (3 ′) are the same.
（原料化合物）
本発明においては、化合物（１）と化合物（２）をクロスメタセシス反応させる。 (Raw compound)
In the present invention, the compound (1) and the compound (2) are subjected to a cross metathesis reaction.
本発明においては、化合物（１）と化合物（２）をクロスメタセシス反応させる。 (Raw compound)
In the present invention, the compound (1) and the compound (2) are subjected to a cross metathesis reaction.
化合物（１）及び化合物（２）において、ａは０または１であり、好ましくは１である。
ｂは０または１であり、好ましくは０である。
ｃは０、１または２であり、好ましくは０である。
ｃとｄの和は３である。すなわち、ｄは１、２または３であり、好ましくは３である。 In compound (1) and compound (2), a is 0 or 1, preferably 1.
b is 0 or 1, preferably 0.
c is 0, 1 or 2, preferably 0.
The sum of c and d is 3. That is, d is 1, 2 or 3, preferably 3.
ｂは０または１であり、好ましくは０である。
ｃは０、１または２であり、好ましくは０である。
ｃとｄの和は３である。すなわち、ｄは１、２または３であり、好ましくは３である。 In compound (1) and compound (2), a is 0 or 1, preferably 1.
b is 0 or 1, preferably 0.
c is 0, 1 or 2, preferably 0.
The sum of c and d is 3. That is, d is 1, 2 or 3, preferably 3.
Ｘは塩素原子または炭素数１～６のアルコキシ基を表し、ｄが２または３である場合、同一分子内に複数存在するＸは同一でも異なっていてもよい。
炭素数１～６のアルコキシ基としては、例えば、メトキシ基、エトキシ基、またはプロポキシ基が挙げられる。
これらの中でも、好ましくは、塩素原子、メトキシ基、エトキシ基である。 X represents a chlorine atom or an alkoxy group having 1 to 6 carbon atoms, and when d is 2 or 3, a plurality of X present in the same molecule may be the same or different.
Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.
Among these, a chlorine atom, a methoxy group, and an ethoxy group are preferable.
炭素数１～６のアルコキシ基としては、例えば、メトキシ基、エトキシ基、またはプロポキシ基が挙げられる。
これらの中でも、好ましくは、塩素原子、メトキシ基、エトキシ基である。 X represents a chlorine atom or an alkoxy group having 1 to 6 carbon atoms, and when d is 2 or 3, a plurality of X present in the same molecule may be the same or different.
Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.
Among these, a chlorine atom, a methoxy group, and an ethoxy group are preferable.
Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－を表し、好ましくは、単結合、エーテル性酸素原子である。
Y represents a single bond, an etheric oxygen atom or —CH 2 O—, preferably a single bond or an etheric oxygen atom.
Ｚ１～Ｚ４はそれぞれ独立に水素原子または１価の有機基を表す。
１価の有機基としては、例えば、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、炭素数５～２０のアリール基、炭素数５～２０のアリールオキシ基、炭素数１～１２の（ペル）ハロゲン化アルキル基、炭素数１～１２の（ペル）ハロゲン化アルコキシ基、炭素数５～２０の（ペル）ハロゲン化アリール基及び炭素数５～２０の（ペル）ハロゲン化アリールオキシ基からなる群から選ばれる基が挙げられ、前記アルキル基、アルコキシ基、アリール基、アリールオキシ基、（ペル）ハロゲン化アルキル基、（ペル）ハロゲン化アルコキシ基、（ペル）ハロゲン化アリール基及び（ペル）ハロゲン化アリールオキシ基からなる群から選ばれる基は、酸素原子、窒素原子、イオウ原子、リン原子、及びケイ素原子からなる群から選ばれる原子を１以上含んでもよい。 Z 1 to Z 4 each independently represents a hydrogen atom or a monovalent organic group.
Examples of the monovalent organic group include an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 5 to 20 carbon atoms, an aryloxy group having 5 to 20 carbon atoms, and 1 carbon atom. (Per) halogenated alkyl group having ˜12, (per) halogenated alkoxy group having 1 to 12 carbon atoms, (per) halogenated aryl group having 5 to 20 carbon atoms and (per) halogenation having 5 to 20 carbon atoms And a group selected from the group consisting of aryloxy groups, the alkyl group, alkoxy group, aryl group, aryloxy group, (per) halogenated alkyl group, (per) halogenated alkoxy group, and (per) halogenated aryl. The group selected from the group consisting of a group and a (per) halogenated aryloxy group is selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. Atoms may contain at least one element.
１価の有機基としては、例えば、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、炭素数５～２０のアリール基、炭素数５～２０のアリールオキシ基、炭素数１～１２の（ペル）ハロゲン化アルキル基、炭素数１～１２の（ペル）ハロゲン化アルコキシ基、炭素数５～２０の（ペル）ハロゲン化アリール基及び炭素数５～２０の（ペル）ハロゲン化アリールオキシ基からなる群から選ばれる基が挙げられ、前記アルキル基、アルコキシ基、アリール基、アリールオキシ基、（ペル）ハロゲン化アルキル基、（ペル）ハロゲン化アルコキシ基、（ペル）ハロゲン化アリール基及び（ペル）ハロゲン化アリールオキシ基からなる群から選ばれる基は、酸素原子、窒素原子、イオウ原子、リン原子、及びケイ素原子からなる群から選ばれる原子を１以上含んでもよい。 Z 1 to Z 4 each independently represents a hydrogen atom or a monovalent organic group.
Examples of the monovalent organic group include an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 5 to 20 carbon atoms, an aryloxy group having 5 to 20 carbon atoms, and 1 carbon atom. (Per) halogenated alkyl group having ˜12, (per) halogenated alkoxy group having 1 to 12 carbon atoms, (per) halogenated aryl group having 5 to 20 carbon atoms and (per) halogenation having 5 to 20 carbon atoms And a group selected from the group consisting of aryloxy groups, the alkyl group, alkoxy group, aryl group, aryloxy group, (per) halogenated alkyl group, (per) halogenated alkoxy group, and (per) halogenated aryl. The group selected from the group consisting of a group and a (per) halogenated aryloxy group is selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. Atoms may contain at least one element.
これらの中でも、好ましくは、水素原子、メチル基、エチル基、プロピル基、メトキシ基、エトキシ基、プロポキシ基、フェニル基、フェニルオキシ基、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、トリフルオロメトキシ基、ペンタフルオロエトキシ基、ヘプタフルオロプロポキシ基、ペルフルオロ（メトキシメトキシ）基、ペルフルオロ（プロポキシプロポキシ）基、ペンタフルオロフェニル基、ペンタフルオロフェニルオキシ基である。
Among these, preferably a hydrogen atom, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, propoxy group, phenyl group, phenyloxy group, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, A trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoropropoxy group, a perfluoro (methoxymethoxy) group, a perfluoro (propoxypropoxy) group, a pentafluorophenyl group, and a pentafluorophenyloxy group.
Ｒ１はフッ素原子または１価の含フッ素有機基を表す。
含フッ素有機基としては、例えば、炭素数１～１２の（ペル）フルオロアルキル基、炭素数１～１２の（ペル）フルオロアルコキシ基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、及びエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基が挙げられる。
これらの中でも、好ましくは、炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、及びエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基である。 R 1 represents a fluorine atom or a monovalent fluorine-containing organic group.
Examples of the fluorine-containing organic group include (per) fluoroalkyl groups having 1 to 12 carbon atoms, (per) fluoroalkoxy groups having 1 to 12 carbon atoms, and (per) carbon atoms having 2 to 400 carbon atoms containing an etheric oxygen atom. Examples thereof include a fluoroalkyl group and a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom.
Among these, preferably, a (per) fluoroalkyl group having 1 to 12 carbon atoms, a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and 2 to 2 carbon atoms containing an etheric oxygen atom. 400 (per) fluoroalkoxy groups.
含フッ素有機基としては、例えば、炭素数１～１２の（ペル）フルオロアルキル基、炭素数１～１２の（ペル）フルオロアルコキシ基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、及びエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基が挙げられる。
これらの中でも、好ましくは、炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、及びエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基である。 R 1 represents a fluorine atom or a monovalent fluorine-containing organic group.
Examples of the fluorine-containing organic group include (per) fluoroalkyl groups having 1 to 12 carbon atoms, (per) fluoroalkoxy groups having 1 to 12 carbon atoms, and (per) carbon atoms having 2 to 400 carbon atoms containing an etheric oxygen atom. Examples thereof include a fluoroalkyl group and a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom.
Among these, preferably, a (per) fluoroalkyl group having 1 to 12 carbon atoms, a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and 2 to 2 carbon atoms containing an etheric oxygen atom. 400 (per) fluoroalkoxy groups.
Ｒ２は水素原子、フッ素原子または１価の含フッ素有機基を表す。
含フッ素有機基としては、例えば、炭素数１～１２の（ペル）フルオロアルキル基、炭素数１～１２の（ペル）フルオロアルコキシ基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、及びエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基が挙げられる。
これらの中でも、好ましくは、フッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基である。 R 2 represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group.
Examples of the fluorine-containing organic group include (per) fluoroalkyl groups having 1 to 12 carbon atoms, (per) fluoroalkoxy groups having 1 to 12 carbon atoms, and (per) carbon atoms having 2 to 400 carbon atoms containing an etheric oxygen atom. Examples thereof include a fluoroalkyl group and a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom.
Among these, a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a (per) fluoroalkyl group having 2 to 400 carbon atoms including an etheric oxygen atom are preferable.
含フッ素有機基としては、例えば、炭素数１～１２の（ペル）フルオロアルキル基、炭素数１～１２の（ペル）フルオロアルコキシ基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、及びエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基が挙げられる。
これらの中でも、好ましくは、フッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基である。 R 2 represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group.
Examples of the fluorine-containing organic group include (per) fluoroalkyl groups having 1 to 12 carbon atoms, (per) fluoroalkoxy groups having 1 to 12 carbon atoms, and (per) carbon atoms having 2 to 400 carbon atoms containing an etheric oxygen atom. Examples thereof include a fluoroalkyl group and a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom.
Among these, a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a (per) fluoroalkyl group having 2 to 400 carbon atoms including an etheric oxygen atom are preferable.
Ｒ３はフッ素原子または１価の含フッ素有機基を表し、好ましくは、フッ素原子、炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基であり、より好ましくはフッ素原子、トリフルオロメチル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基である。
R 3 represents a fluorine atom or a monovalent fluorine-containing organic group, preferably a fluorine atom, a (per) fluoroalkyl group having 1 to 12 carbon atoms, or (per) carbon atoms having 2 to 400 carbon atoms including an etheric oxygen atom. It is a fluoroalkyl group, more preferably a (per) fluoroalkyl group having 2 to 400 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom.
Ｒ４は炭素数４～２０のアリール基または炭素数１～６のアルキル基を表し、ｃが２である場合、２つ存在するＲ４は同一でも異なっていてもよい。
炭素数４～２０のアリール基としては、例えばフェニル基、ナフチル基、ビフェニル基が挙げられる。
炭素数１～６のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基が挙げられる。
これらの中でも、好ましくは、フェニル基、メチル基、エチル基である。 R 4 represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and when c is 2, two R 4 s may be the same or different.
Examples of the aryl group having 4 to 20 carbon atoms include a phenyl group, a naphthyl group, and a biphenyl group.
Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
Among these, a phenyl group, a methyl group, and an ethyl group are preferable.
炭素数４～２０のアリール基としては、例えばフェニル基、ナフチル基、ビフェニル基が挙げられる。
炭素数１～６のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基が挙げられる。
これらの中でも、好ましくは、フェニル基、メチル基、エチル基である。 R 4 represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and when c is 2, two R 4 s may be the same or different.
Examples of the aryl group having 4 to 20 carbon atoms include a phenyl group, a naphthyl group, and a biphenyl group.
Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
Among these, a phenyl group, a methyl group, and an ethyl group are preferable.
本発明の別の態様においては、化合物（１’）と化合物（２）をクロスメタセシス反応させる。
In another embodiment of the present invention, the compound (1 ') and the compound (2) are subjected to a cross metathesis reaction.
化合物（１’）におけるｈは２以上の自然数を表し、Ｑはフッ素原子を含み、かつヘテロ原子を有していてもよいｈ価の有機基である。
ｈは２～５の自然数が好ましく、２または３がより好ましい。
Ｑは酸素原子を含む炭素数２～４００の含フッ素有機基、酸素原子とケイ素原子を含む炭素数２～４００の含フッ素有機基等が好ましい。
なお、化合物（１’）におけるＺ１及びＺ２は、先述した化合物（１）と化合物（２）とのクロスメタセシス反応における化合物（１）のＺ１及びＺ２とそれぞれ同様であり、好ましい態様も同様である。また、複数存在するＺ１、Ｚ２はそれぞれ同一でも異なっていてもよい。 In the compound (1 ′), h represents a natural number of 2 or more, and Q is a h-valent organic group that contains a fluorine atom and may have a hetero atom.
h is preferably a natural number of 2 to 5, and more preferably 2 or 3.
Q is preferably a fluorine-containing organic group having 2 to 400 carbon atoms containing an oxygen atom, a fluorine-containing organic group having 2 to 400 carbon atoms containing an oxygen atom and a silicon atom, or the like.
Incidentally, Z 1 and Z 2 in the compound (1 ') are each same as Z 1 and Z 2 of compound in the cross metathesis reaction with aforementioned the compound (1) and the compound (2) (1), preferred embodiments Is the same. A plurality of Z 1 and Z 2 may be the same or different.
ｈは２～５の自然数が好ましく、２または３がより好ましい。
Ｑは酸素原子を含む炭素数２～４００の含フッ素有機基、酸素原子とケイ素原子を含む炭素数２～４００の含フッ素有機基等が好ましい。
なお、化合物（１’）におけるＺ１及びＺ２は、先述した化合物（１）と化合物（２）とのクロスメタセシス反応における化合物（１）のＺ１及びＺ２とそれぞれ同様であり、好ましい態様も同様である。また、複数存在するＺ１、Ｚ２はそれぞれ同一でも異なっていてもよい。 In the compound (1 ′), h represents a natural number of 2 or more, and Q is a h-valent organic group that contains a fluorine atom and may have a hetero atom.
h is preferably a natural number of 2 to 5, and more preferably 2 or 3.
Q is preferably a fluorine-containing organic group having 2 to 400 carbon atoms containing an oxygen atom, a fluorine-containing organic group having 2 to 400 carbon atoms containing an oxygen atom and a silicon atom, or the like.
Incidentally, Z 1 and Z 2 in the compound (1 ') are each same as Z 1 and Z 2 of compound in the cross metathesis reaction with aforementioned the compound (1) and the compound (2) (1), preferred embodiments Is the same. A plurality of Z 1 and Z 2 may be the same or different.
化合物（２）におけるｂ～ｄ、Ｘ、Ｚ３、Ｚ４及びＲ４は、先述した化合物（１）と化合物（２）とのクロスメタセシス反応における化合物（２）のｂ～ｄ、Ｘ、Ｚ３、Ｚ４及びＲ４とそれぞれ同様であり、好ましい態様も同様である。
B to d, X, Z 3 , Z 4 and R 4 in the compound (2) are the same as b to d, X, Z of the compound (2) in the cross metathesis reaction between the compound (1) and the compound (2). 3 , Z 4 and R 4 are the same, and the preferred embodiments are also the same.
化合物（１）の具体例としては、例えば、下記に示す化合物が挙げられる。なお、化学式中、複数種類のオキシペルフルオロアルキレン基が並んでいる場合（例えば［－Ｏ－ＣＦ２－］ｃ５－［－Ｏ－ＣＦ２－ＣＦ２－］ｃ６の場合）、当該複数種類のオキシペルフルオロアルキレン基はブロック鎖であってもランダム鎖であってもよい。
Specific examples of compound (1) include the compounds shown below. In the chemical formula, when multiple types of oxyperfluoroalkylene groups are arranged (for example, [—O—CF 2 —] c5 — [— O—CF 2 —CF 2 —] c6 ), The perfluoroalkylene group may be a block chain or a random chain.
これらの中でも、好ましくは、下記に示す化合物が挙げられる。
Among these, Preferably, the compounds shown below are mentioned.
化合物（１’）の具体例としては、例えば、下記に示す化合物が挙げられる。
Specific examples of the compound (1 ′) include the compounds shown below.
化合物（２）の具体例としては、例えば、下記に示す化合物が挙げられる。
Specific examples of the compound (2) include the compounds shown below.
これらの中でも、好ましくは、下記に示す化合物が挙げられる。
Among these, Preferably, the compounds shown below are mentioned.
（生成化合物）
本発明のクロスメタセシスにより化合物（３）が製造される。
化合物（３）中の、ａ、ｂ、ｃ、ｃとｄの和、Ｘ、Ｙ、Ｒ１、Ｒ２、Ｒ３及びＲ４は前記定義と同様である。また、Ｒ１、Ｒ２、およびＲ３からなる群から選ばれる任意の２つは互いに結合して環を形成してもよい。
化合物（３）としては、ａが０または１、ｂが０、ｃが０、ｄが３、Ｘが塩素原子、メトキシ基またはエトキシ基、Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－、Ｒ１が炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基、Ｒ２がフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、Ｒ３がフッ素原子、トリフルオロメチル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基である化合物が好ましい。 (Production compound)
Compound (3) is produced by the cross metathesis of the present invention.
In the compound (3), the sum of a, b, c, c and d, X, Y, R 1 , R 2 , R 3 and R 4 are as defined above. Any two selected from the group consisting of R 1 , R 2 , and R 3 may be bonded to each other to form a ring.
As the compound (3), a is 0 or 1, b is 0, c is 0, d is 3, X is a chlorine atom, a methoxy group or an ethoxy group, Y is a single bond, an etheric oxygen atom or —CH 2 O -, R 1 is a (per) fluoroalkyl group having 1 to 12 carbon atoms, a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, or a carbon number of 2 to 400 containing an etheric oxygen atom ( Per) fluoroalkoxy group, R 2 is a fluorine atom, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, R 3 is A compound which is a fluorine atom, a trifluoromethyl group or a (per) fluoroalkyl group having 2 to 400 carbon atoms and containing an etheric oxygen atom is preferred.
本発明のクロスメタセシスにより化合物（３）が製造される。
化合物（３）中の、ａ、ｂ、ｃ、ｃとｄの和、Ｘ、Ｙ、Ｒ１、Ｒ２、Ｒ３及びＲ４は前記定義と同様である。また、Ｒ１、Ｒ２、およびＲ３からなる群から選ばれる任意の２つは互いに結合して環を形成してもよい。
化合物（３）としては、ａが０または１、ｂが０、ｃが０、ｄが３、Ｘが塩素原子、メトキシ基またはエトキシ基、Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－、Ｒ１が炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基、Ｒ２がフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、Ｒ３がフッ素原子、トリフルオロメチル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基である化合物が好ましい。 (Production compound)
Compound (3) is produced by the cross metathesis of the present invention.
In the compound (3), the sum of a, b, c, c and d, X, Y, R 1 , R 2 , R 3 and R 4 are as defined above. Any two selected from the group consisting of R 1 , R 2 , and R 3 may be bonded to each other to form a ring.
As the compound (3), a is 0 or 1, b is 0, c is 0, d is 3, X is a chlorine atom, a methoxy group or an ethoxy group, Y is a single bond, an etheric oxygen atom or —CH 2 O -, R 1 is a (per) fluoroalkyl group having 1 to 12 carbon atoms, a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, or a carbon number of 2 to 400 containing an etheric oxygen atom ( Per) fluoroalkoxy group, R 2 is a fluorine atom, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, R 3 is A compound which is a fluorine atom, a trifluoromethyl group or a (per) fluoroalkyl group having 2 to 400 carbon atoms and containing an etheric oxygen atom is preferred.
化合物（３）の具体例としては、例えば、下記に示す化合物が挙げられる。
Specific examples of the compound (3) include the following compounds.
これらの中でも、好ましくは、下記に示す化合物が挙げられる。
Among these, Preferably, the compounds shown below are mentioned.
本発明のクロスメタセシスにより化合物（３’）が製造される。
化合物（３’）中の、ｂ、ｃ、ｃとｄの和、Ｘ、Ｑ、Ｒ４及びｈは前記定義と同様である。
化合物（３’）の具体例としては、例えば、下記に示す化合物が挙げられる。 Compound (3 ′) is produced by the cross metathesis of the present invention.
In the compound (3 ′), b, c, the sum of c and d, X, Q, R 4 and h are as defined above.
Specific examples of the compound (3 ′) include the compounds shown below.
化合物（３’）中の、ｂ、ｃ、ｃとｄの和、Ｘ、Ｑ、Ｒ４及びｈは前記定義と同様である。
化合物（３’）の具体例としては、例えば、下記に示す化合物が挙げられる。 Compound (3 ′) is produced by the cross metathesis of the present invention.
In the compound (3 ′), b, c, the sum of c and d, X, Q, R 4 and h are as defined above.
Specific examples of the compound (3 ′) include the compounds shown below.
（製造方法）
本発明はクロスメタセシスによる含フッ素シラン化合物の製造方法に関するものであり、「化合物（１）及び化合物（２）」と、または「化合物（１’）及び化合物（２）」と触媒とを接触させることによってクロスメタセシスを行い、原料とは異なるオレフィン（化合物（３）または化合物（３’））を得るものである。 (Production method)
The present invention relates to a method for producing a fluorine-containing silane compound by cross-metathesis, wherein “compound (1) and compound (2)” or “compound (1 ′) and compound (2)” is brought into contact with a catalyst. Thus, cross metathesis is performed to obtain an olefin (compound (3) or compound (3 ′)) different from the raw material.
本発明はクロスメタセシスによる含フッ素シラン化合物の製造方法に関するものであり、「化合物（１）及び化合物（２）」と、または「化合物（１’）及び化合物（２）」と触媒とを接触させることによってクロスメタセシスを行い、原料とは異なるオレフィン（化合物（３）または化合物（３’））を得るものである。 (Production method)
The present invention relates to a method for producing a fluorine-containing silane compound by cross-metathesis, wherein “compound (1) and compound (2)” or “compound (1 ′) and compound (2)” is brought into contact with a catalyst. Thus, cross metathesis is performed to obtain an olefin (compound (3) or compound (3 ′)) different from the raw material.
化合物（１）、化合物（１’）及び化合物（２）の、二重結合上の幾何異性は特に限定はない。
目的物収率向上の点で、化合物（１）、化合物（１’）及び化合物（２）は脱気及び脱水されたものを用いることが好ましい。脱気操作について、特に制限はないが、凍結脱気等を行うことがある。脱水操作について、特に制限はないが、通常モレキュラーシーブ等と接触させる。化合物（１）、化合物（１’）及び化合物（２）について、前記脱気及び脱水操作は通常触媒と接触させる前に行う。 The geometric isomerism on the double bond of compound (1), compound (1 ′) and compound (2) is not particularly limited.
From the viewpoint of improving the yield of the desired product, it is preferable to use degassed and dehydrated compounds (1), (1 ′) and (2). There is no particular limitation on the deaeration operation, but freeze deaeration and the like may be performed. Although there is no restriction | limiting in particular about dehydration operation, Usually, it is made to contact with a molecular sieve etc. For the compound (1), the compound (1 ′) and the compound (2), the degassing and dehydration operations are usually performed before contacting with the catalyst.
目的物収率向上の点で、化合物（１）、化合物（１’）及び化合物（２）は脱気及び脱水されたものを用いることが好ましい。脱気操作について、特に制限はないが、凍結脱気等を行うことがある。脱水操作について、特に制限はないが、通常モレキュラーシーブ等と接触させる。化合物（１）、化合物（１’）及び化合物（２）について、前記脱気及び脱水操作は通常触媒と接触させる前に行う。 The geometric isomerism on the double bond of compound (1), compound (1 ′) and compound (2) is not particularly limited.
From the viewpoint of improving the yield of the desired product, it is preferable to use degassed and dehydrated compounds (1), (1 ′) and (2). There is no particular limitation on the deaeration operation, but freeze deaeration and the like may be performed. Although there is no restriction | limiting in particular about dehydration operation, Usually, it is made to contact with a molecular sieve etc. For the compound (1), the compound (1 ′) and the compound (2), the degassing and dehydration operations are usually performed before contacting with the catalyst.
また化合物（１）、化合物（１’）及び化合物（２）は微量の不純物（例えばフッ化水素、過酸化物）を含むことがあるので、目的物収率向上の点で精製してもよい。精製方法については特に制限はない。例えば、文献（Ａｒｍａｒｅｇｏ，Ｗ．Ｌ．Ｆ．ｅｔ ａｌ．，Ｐｕｒｉｆｉｃａｔｉｏｎ ｏｆ Ｌａｂｏｒａｔｏｒｙ Ｃｈｅｍｉｃａｌｓ（Ｓｉｘｔｈ Ｅｄｉｔｉｏｎ），２００９，Ｅｌｓｅｖｉｅｒ）記載の方法に従って行うことができる。
Further, since the compound (1), the compound (1 ′) and the compound (2) may contain a trace amount of impurities (for example, hydrogen fluoride and peroxide), they may be purified in terms of improving the yield of the target product. . There is no particular limitation on the purification method. For example, it can be carried out according to the method described in the literature (Armarego, WLF et al., Purification of Laboratory Chemicals (Sixth Edition), 2009, Elsevier).
化合物（１）または化合物（１’）及び化合物（２）は、反応容器にあらかじめ混合してから投入しても、別々に投入しても構わない。第一のオレフィンを触媒と接触させて得られた混合物に、第二のオレフィンを接触させる場合もある。
Compound (1) or compound (1 ') and compound (2) may be added after mixing in the reaction vessel in advance or separately. The second olefin may be contacted with the mixture obtained by contacting the first olefin with the catalyst.
化合物（１）または化合物（１’）及び化合物（２）のモル比に特に限定はないが、通常基準となるオレフィン１モルに対して、もう一方のオレフィンを０．０１～１００モル用い、好ましくは、０．１～１０モル用いる。
The molar ratio of the compound (1) or the compound (1 ′) and the compound (2) is not particularly limited, but the other olefin is preferably used in an amount of 0.01 to 100 mol with respect to 1 mol of the standard olefin. Is used in an amount of 0.1 to 10 mol.
触媒は試薬として投入しても、系内で発生させてもよい。
試薬として投入する場合、市販の触媒をそのまま用いてもよく、あるいは市販試薬から公知の方法で合成した市販されていない触媒を用いてもよい。
系内で発生させる場合、公知の方法で前駆体となる金属錯体から調製した触媒を本発明に用いることができる。 The catalyst may be added as a reagent or generated in the system.
When charging as a reagent, a commercially available catalyst may be used as it is, or a non-commercial catalyst synthesized from a commercially available reagent by a known method may be used.
When generated in the system, a catalyst prepared from a metal complex as a precursor by a known method can be used in the present invention.
試薬として投入する場合、市販の触媒をそのまま用いてもよく、あるいは市販試薬から公知の方法で合成した市販されていない触媒を用いてもよい。
系内で発生させる場合、公知の方法で前駆体となる金属錯体から調製した触媒を本発明に用いることができる。 The catalyst may be added as a reagent or generated in the system.
When charging as a reagent, a commercially available catalyst may be used as it is, or a non-commercial catalyst synthesized from a commercially available reagent by a known method may be used.
When generated in the system, a catalyst prepared from a metal complex as a precursor by a known method can be used in the present invention.
触媒としては、例えば、金属－カルベン錯体化合物が挙げられる。
Examples of the catalyst include metal-carbene complex compounds.
金属－カルベン錯体化合物のうち金属がルテニウムである化合物は、一般的にルテニウム－カルベン錯体と称されるものであり、例えばＶｏｕｇｉｏｕｋａｌａｋｉｓ，Ｇ．Ｃ．ｅｔ ａｌ．Ｃｈｅｍ．Ｒｅｖ．，２０１０，１１０，１７４６－１７８７．に記載されているルテニウム－カルベン錯体を利用することができる。
また、例えばＡｌｄｒｉｃｈ社やＵｍｉｃｏｒｅ社から市販されているルテニウム－カルベン錯体を利用することができる。 Among the metal-carbene complex compounds, a compound in which the metal is ruthenium is generally called a ruthenium-carbene complex, and is described in, for example, Vougioukalakis, G., et al. C. et al. Chem. Rev. , 2010, 110, 1746-1787. The ruthenium-carbene complex described in 1) can be used.
Further, for example, a ruthenium-carbene complex commercially available from Aldrich or Umicore can be used.
また、例えばＡｌｄｒｉｃｈ社やＵｍｉｃｏｒｅ社から市販されているルテニウム－カルベン錯体を利用することができる。 Among the metal-carbene complex compounds, a compound in which the metal is ruthenium is generally called a ruthenium-carbene complex, and is described in, for example, Vougioukalakis, G., et al. C. et al. Chem. Rev. , 2010, 110, 1746-1787. The ruthenium-carbene complex described in 1) can be used.
Further, for example, a ruthenium-carbene complex commercially available from Aldrich or Umicore can be used.
ルテニウム－カルベン錯体の具体例としては、例えば、ビス（トリフェニルホスフィン）ベンジリデンルテニウムジクロリド、ビス（トリシクロヘキシルホスフィン）ベンジリデンルテニウムジクロリド、ビス（トリシクロヘキシルホスフィン）－３－メチル－２－ブテニリデンルテニウムジクロリド、（１，３－ジイソプロピルイミダゾール－２－イリデン）（トリシクロヘキシルホスフィン）ベンジリデンルテニウムジクロリド、（１，３－ジシクロヘキシルイミダゾール－２－イリデン）（トリシクロヘキシルホスフィン）ベンジリデンルテニウムジクロリド、（１，３－ジメシチルイミダゾール－２－イリデン）（トリシクロヘキシルホスフィン）ベンジリデンルテニウムジクロリド、（１，３－ジメシチル－４，５－ジヒドロイミダゾール－２－イリデン）（トリシクロヘキシルホスフィン）ベンジリデンルテニウムジクロリド、［１，３－ビス（２，６－ジイソプロピルフェニル）－４，５－ジヒドロイミダゾール－２－イリデン］（トリシクロヘキシルホスフィン）ベンジリデンルテニウムジクロリド、［１，３－ビス（２－メチルフェニル）－４，５－ジヒドロイミダゾール－２－イリデン］（トリシクロヘキシルホスフィン）ベンジリデンルテニウムジクロリド、［１，３－ジシクロヘキシル－４，５－ジヒドロイミダゾール－２－イリデン］（トリシクロヘキシルホスフィン）ベンジリデンルテニウムジクロリド、ビス（トリシクロヘキシルホスフィン）エトキシメチリデンルテニウムジクロリド、（１，３－ジメシチル－４，５－ジヒドロイミダゾール－２－イリデン）（トリシクロヘキシルホスフィン）エトキシメチリデンルテニウムジクロリド、（１，３－ジメシチル－４，５－ジヒドロイミダゾール－２－イリデン）［ビス（３－ブロモピリジン）］ベンジリデンルテニウムジクロリド、（１，３－ジメシチル－４，５－ジヒドロイミダゾール－２－イリデン）（２－イソプロポキシフェニルメチリデン）ルテニウムジクロリド、（１，３－ジメシチル－４，５－ジヒドロイミダゾール－２－イリデン）［（トリシクロヘキシルホスホラニル）メチリデン］ジクロロルテニウムテトラフルオロボラート、ＵｍｉｃｏｒｅＭ２、ＵｍｉｃｏｒｅＭ５１、ＵｍｉｃｏｒｅＭ５２、ＵｍｉｃｏｒｅＭ７１ＳＩＭｅｓ、ＵｍｉｃｏｒｅＭ７１ＳＩＰｒ、ＵｍｉｃｏｒｅＭ７３ＳＩＭｅｓ、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒが挙げられる。
Specific examples of the ruthenium-carbene complex include, for example, bis (triphenylphosphine) benzylidene ruthenium dichloride, bis (tricyclohexylphosphine) benzylidene ruthenium dichloride, bis (tricyclohexylphosphine) -3-methyl-2-butenylidene ruthenium dichloride. (1,3-diisopropylimidazole-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dicyclohexylimidazole-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dimesi Tilimidazol-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dimesityl-4,5-dihydroyl) Dazol-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, [1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene] (tricyclohexylphosphine) benzylideneruthenium dichloride, [1,3-bis (2-methylphenyl) -4,5-dihydroimidazol-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-dicyclohexyl-4,5-dihydroimidazol-2-ylidene ] (Tricyclohexylphosphine) benzylideneruthenium dichloride, bis (tricyclohexylphosphine) ethoxymethylideneruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazole) -Ylidene) (tricyclohexylphosphine) ethoxymethylidene ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) [bis (3-bromopyridine)] benzylidene ruthenium dichloride, (1,3- Dimesityl-4,5-dihydroimidazol-2-ylidene) (2-isopropoxyphenylmethylidene) ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) [(tricyclohexylphosphoranyl ) Methylidene] dichlororuthenium tetrafluoroborate, Umicore M2, Umicore M51, Umicore M52, Umicore M71 SIMes, Umicore M71 SIPr, Umicore M73 SIMes, Umico reM73 SIPr.
これらの中でも、（１，３－ジメシチル－４，５－ジヒドロイミダゾール－２－イリデン）（トリシクロヘキシルホスフィン）ベンジリデンルテニウムジクロリド、（１，３－ジメシチル－４，５－ジヒドロイミダゾール－２－イリデン）（２－イソプロポキシフェニルメチリデン）ルテニウムジクロリド、（１，３－ジメシチル－４，５－ジヒドロイミダゾール－２－イリデン）［（トリシクロヘキシルホスホラニル）メチリデン］ジクロロルテニウムテトラフルオロボラート、ＵｍｉｃｏｒｅＭ２、ＵｍｉｃｏｒｅＭ５１、ＵｍｉｃｏｒｅＭ５２、ＵｍｉｃｏｒｅＭ７１ＳＩＭｅｓ、ＵｍｉｃｏｒｅＭ７１ＳＩＰｒ、ＵｍｉｃｏｒｅＭ７３ＳＩＭｅｓ、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒが特に好ましい。
Among these, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) ( 2-isopropoxyphenylmethylidene) ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) [(tricyclohexylphosphoranyl) methylidene] dichlororuthenium tetrafluoroborate, Umicore M2, Umicore M51, Umicore M52, Umicore M71 SIMes, Umicore M71 SIPr, Umicore M73 SIMes, Umicore M73 SIPr are particularly preferable.
なお、上記錯体のうち、「Ｕｍｉｃｏｒｅ」で始まる名称は、Ｕｍｉｃｏｒｅ社の製品の商品名である。また、上記ルテニウム－カルベン錯体は、単独で用いてもよいし、２種類以上併用してもよい。さらに必要に応じてシリカゲルやアルミナ、ポリマー等の担体に担持して用いてもよい。
Of the above complexes, the names beginning with “Umicore” are trade names of Umicore products. Further, the ruthenium-carbene complex may be used alone or in combination of two or more. Further, if necessary, it may be supported on a carrier such as silica gel, alumina or polymer.
金属－カルベン錯体化合物のうち金属がモリブデンまたはタングステンである化合物は、一般的にモリブデン－カルベン錯体やタングステン－カルベン錯体と称されるものであり、例えばＧｒｅｌａ，Ｋ．（Ｅｄ）Ｏｌｅｆｉｎ Ｍｅｔａｔｈｅｓｉｓ：Ｔｈｅｏｒｙ ａｎｄ Ｐｒａｃｔｉｃｅ，Ｗｉｌｅｙ，２０１４．に記載されているモリブデン－カルベン錯体またはタングステン－カルベン錯体を利用することができる。
また、例えばＡｌｄｒｉｃｈ社やＳｔｒｅｍ社から市販されているモリブデン－カルベン錯体またはタングステン－カルベン錯体を利用することができる。 Among the metal-carbene complex compounds, compounds in which the metal is molybdenum or tungsten are generally called molybdenum-carbene complexes or tungsten-carbene complexes. For example, Grela, K. et al. (Ed) Olefin Metathesis: Theory and Practice, Wiley, 2014. The molybdenum-carbene complex or tungsten-carbene complex described in 1) can be used.
Further, for example, a molybdenum-carbene complex or a tungsten-carbene complex commercially available from Aldrich or Strem can be used.
また、例えばＡｌｄｒｉｃｈ社やＳｔｒｅｍ社から市販されているモリブデン－カルベン錯体またはタングステン－カルベン錯体を利用することができる。 Among the metal-carbene complex compounds, compounds in which the metal is molybdenum or tungsten are generally called molybdenum-carbene complexes or tungsten-carbene complexes. For example, Grela, K. et al. (Ed) Olefin Metathesis: Theory and Practice, Wiley, 2014. The molybdenum-carbene complex or tungsten-carbene complex described in 1) can be used.
Further, for example, a molybdenum-carbene complex or a tungsten-carbene complex commercially available from Aldrich or Strem can be used.
なお、上記モリブデン－カルベン錯体またはタングステン－カルベン錯体は、単独で用いてもよいし、２種類以上併用してもよい。さらに必要に応じてシリカゲルやアルミナ、ポリマー等の担体に担持して用いてもよい。
The above molybdenum-carbene complex or tungsten-carbene complex may be used alone or in combination of two or more. Further, if necessary, it may be supported on a carrier such as silica gel, alumina or polymer.
モリブデン－カルベン錯体の具体例を下記に示す。
なお、Ｍｅとはメチル基を、ｉ－Ｐｒとはイソプロピル基を、ｔ－Ｂｕとはターシャリーブチル基を、Ｐｈとはフェニル基を、それぞれ意味する。 Specific examples of the molybdenum-carbene complex are shown below.
Me represents a methyl group, i-Pr represents an isopropyl group, t-Bu represents a tertiary butyl group, and Ph represents a phenyl group.
なお、Ｍｅとはメチル基を、ｉ－Ｐｒとはイソプロピル基を、ｔ－Ｂｕとはターシャリーブチル基を、Ｐｈとはフェニル基を、それぞれ意味する。 Specific examples of the molybdenum-carbene complex are shown below.
Me represents a methyl group, i-Pr represents an isopropyl group, t-Bu represents a tertiary butyl group, and Ph represents a phenyl group.
タングステン－カルベン錯体の具体例としては、下記化合物が挙げられる。
Specific examples of the tungsten-carbene complex include the following compounds.
触媒の量としては、特に制限はないが、化合物（１）または化合物（１’）及び化合物（２）の内、基準となるオレフィン１モルに対して、通常０．０００１～１モル用い、好ましくは、０．００１～０．２モル用いる。
The amount of the catalyst is not particularly limited, but 0.0001 to 1 mol is usually used with respect to 1 mol of the standard olefin in the compound (1) or the compound (1 ′) and the compound (2). Is used in an amount of 0.001 to 0.2 mol.
触媒は、通常固体のまま反応容器に投入するが、溶媒に溶解または懸濁させて投入してもよい。
The catalyst is usually charged into the reaction vessel as a solid, but may be charged after dissolving or suspending in a solvent.
この時用いる溶媒としては、反応に悪影響を及ぼさない範囲で特に制限はなく、有機溶媒、含フッ素有機溶媒、イオン液体、水等を単独または混合して用いることができる。なお、これらの溶媒分子中、一部またはすべての水素原子が重水素原子で置換されていてもよい。
The solvent used at this time is not particularly limited as long as it does not adversely affect the reaction, and an organic solvent, a fluorine-containing organic solvent, an ionic liquid, water or the like can be used alone or in combination. In these solvent molecules, some or all of the hydrogen atoms may be substituted with deuterium atoms.
有機溶媒としては、例えば、ベンゼン、トルエン、ｏ－，ｍ－，ｐ－キシレン、メシチレン等の芳香族炭化水素系溶媒；ヘキサン、シクロヘキサン等の脂肪族炭化水素系溶媒；ジクロロメタン、クロロホルム、１，２－ジクロロエタン、クロロベンゼン、ｏ－ジクロロベンゼン等のハロゲン系溶媒；テトラヒドロフラン、ジオキサン、ジエチルエーテル、グライム、ジグライム等のエーテル系溶媒を使用することができる。
Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, toluene, o-, m-, p-xylene and mesitylene; aliphatic hydrocarbon solvents such as hexane and cyclohexane; dichloromethane, chloroform, 1, 2 -Halogen solvents such as dichloroethane, chlorobenzene, o-dichlorobenzene; ether solvents such as tetrahydrofuran, dioxane, diethyl ether, glyme and diglyme can be used.
含フッ素有機溶媒としては、例えば、ヘキサフルオロベンゼン、ｍ－ビス（トリフルオロメチル）ベンゼン、ｐ－ビス（トリフルオロメチル）ベンゼン、α，α，α－トリフルオロメチルベンゼン、ジクロロペンタフルオロプロパンを使用することができる。
As the fluorine-containing organic solvent, for example, hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, α, α, α-trifluoromethylbenzene, dichloropentafluoropropane is used. can do.
イオン液体としては、例えば、各種ピリジニウム塩、各種イミダゾリウム塩を用いることができる。
As the ionic liquid, for example, various pyridinium salts and various imidazolium salts can be used.
上記溶媒の中でも、触媒の溶解性等の点で、ベンゼン、トルエン、ｏ－，ｍ－，ｐ－キシレン、メシチレン、ジクロロメタン、クロロホルム、クロロベンゼン、ｏ－ジクロロベンゼン、ジエチルエーテル、ジオキサン、ＴＨＦ（テトラヒドロフラン）、ヘキサフルオロベンゼン、ｍ－ビス（トリフルオロメチル）ベンゼン、ｐ－ビス（トリフルオロメチル）ベンゼン、α，α，α－トリフルオロメチルベンゼン、及びこれらの混合物が好ましい。
Among the above solvents, benzene, toluene, o-, m-, p-xylene, mesitylene, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, diethyl ether, dioxane, THF (tetrahydrofuran) in terms of solubility of the catalyst Hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, α, α, α-trifluoromethylbenzene, and mixtures thereof are preferred.
なお、目的物収率向上の点で、前記溶媒は脱気及び脱水されたものを用いることが好ましい。脱気操作について、特に制限はないが、凍結脱気等を行うことがある。脱水操作について、特に制限はないが、通常モレキュラーシーブ等と接触させる。前記脱気及び脱水操作は通常触媒と接触させる前に行う。
In addition, it is preferable to use a degassed and dehydrated solvent for improving the yield of the target product. There is no particular limitation on the deaeration operation, but freeze deaeration and the like may be performed. Although there is no restriction | limiting in particular about dehydration operation, Usually, it is made to contact with a molecular sieve etc. The degassing and dehydration operations are usually performed before contacting with the catalyst.
化合物（１）または化合物（１’）及び化合物（２）と触媒とを接触させる雰囲気としては、特に限定はないが、触媒の長寿命化の点で、不活性気体雰囲気下が好ましく、中でも窒素またはアルゴン雰囲気下が好ましい。
ただし、反応条件において気体となるオレフィンを原料として用いる場合、これらの気体雰囲気下で行うことができる。 The atmosphere in which the compound (1) or the compound (1 ′) and the compound (2) are brought into contact with the catalyst is not particularly limited, but an inert gas atmosphere is preferable from the viewpoint of extending the life of the catalyst. Or an argon atmosphere is preferable.
However, when using the olefin which becomes gas in reaction conditions as a raw material, it can carry out in these gas atmosphere.
ただし、反応条件において気体となるオレフィンを原料として用いる場合、これらの気体雰囲気下で行うことができる。 The atmosphere in which the compound (1) or the compound (1 ′) and the compound (2) are brought into contact with the catalyst is not particularly limited, but an inert gas atmosphere is preferable from the viewpoint of extending the life of the catalyst. Or an argon atmosphere is preferable.
However, when using the olefin which becomes gas in reaction conditions as a raw material, it can carry out in these gas atmosphere.
化合物（１）または化合物（１’）及び化合物（２）と触媒を接触させる相としては、特に制限はないが、反応速度の点で、通常は液相が用いられる。化合物（１）または化合物（１’）及び化合物（２）のうち少なくとも一方が反応条件下で気体の場合、液相で実施するのが難しいため、気－液二相で実施することもできる。なお、液相で実施する場合には溶媒を用いることができる。
The phase in which the compound (1) or the compound (1 ') and the compound (2) are brought into contact with the catalyst is not particularly limited, but a liquid phase is usually used in terms of reaction rate. When at least one of the compound (1) or the compound (1 ') and the compound (2) is a gas under the reaction conditions, it is difficult to carry out in the liquid phase, and therefore it can be carried out in the gas-liquid two phase. In the case of carrying out in the liquid phase, a solvent can be used.
このとき用いる溶媒としては、上記、触媒の溶解または懸濁に用いた溶媒と同様のものを利用することができる。なお、化合物（１）または化合物（１’）及び化合物（２）のうち少なくとも一方が反応条件下で液体の場合、無溶媒で実施できることがある。
As the solvent used at this time, the same solvents as those used for dissolving or suspending the catalyst can be used. In addition, when at least one of the compound (1) or the compound (1 ') and the compound (2) is liquid under the reaction conditions, it may be carried out without a solvent.
化合物（１）または化合物（１’）及び化合物（２）と触媒とを接触させる容器としては、反応に悪影響を与えない範囲で特に制限はなく、例えば金属製容器またはガラス製容器を用いることができる。なお、本発明にかかるクロスメタセシスは反応条件下、気体状態のオレフィンを扱うことがあるので、高気密が可能な耐圧容器が好ましい。
The container for bringing the compound (1) or the compound (1 ′) and the compound (2) into contact with the catalyst is not particularly limited as long as the reaction is not adversely affected. For example, a metal container or a glass container is used. it can. In addition, since the cross metathesis concerning this invention may handle the olefin in a gaseous state on reaction conditions, the pressure-resistant container in which high airtightness is possible is preferable.
化合物（１）または化合物（１’）及び化合物（２）と触媒とを接触させる温度としては、特に制限はないが、通常－１００～２００℃の範囲で実施することができ、反応速度の点で、０～１５０℃が好ましい。なお、低温では反応が開始せず、高温では錯体の速やかな分解が生じることがあるので適宜温度の下限と上限を設定する必要がある。通常、用いる溶媒の沸点以下の温度で実施される。
The temperature at which the compound (1) or the compound (1 ′) and the compound (2) are brought into contact with the catalyst is not particularly limited, but the reaction can usually be carried out in the range of −100 to 200 ° C. And 0 to 150 ° C. is preferable. Note that the reaction does not start at low temperatures, and the complex may be rapidly decomposed at high temperatures. Therefore, it is necessary to appropriately set the lower limit and the upper limit of the temperature. Usually, it is carried out at a temperature below the boiling point of the solvent used.
化合物（１）または化合物（１’）及び化合物（２）と触媒とを接触させる時間としては、特に制限はないが、通常１分～４８時間の範囲で実施される。
化合物（１）または化合物（１’）及び化合物（２）と触媒とを接触させる圧力としては、特に制限はないが、加圧下でも、常圧下でもよいし、減圧下でもよい。通常０．００１～１０ＭＰａ程度、好ましくは、０．０１～１ＭＰａ程度である。 The time for bringing the compound (1) or the compound (1 ′) and the compound (2) into contact with the catalyst is not particularly limited, but is usually in the range of 1 minute to 48 hours.
The pressure at which the compound (1) or the compound (1 ′) and the compound (2) are brought into contact with the catalyst is not particularly limited, but may be under pressure, normal pressure, or reduced pressure. Usually, it is about 0.001 to 10 MPa, preferably about 0.01 to 1 MPa.
化合物（１）または化合物（１’）及び化合物（２）と触媒とを接触させる圧力としては、特に制限はないが、加圧下でも、常圧下でもよいし、減圧下でもよい。通常０．００１～１０ＭＰａ程度、好ましくは、０．０１～１ＭＰａ程度である。 The time for bringing the compound (1) or the compound (1 ′) and the compound (2) into contact with the catalyst is not particularly limited, but is usually in the range of 1 minute to 48 hours.
The pressure at which the compound (1) or the compound (1 ′) and the compound (2) are brought into contact with the catalyst is not particularly limited, but may be under pressure, normal pressure, or reduced pressure. Usually, it is about 0.001 to 10 MPa, preferably about 0.01 to 1 MPa.
化合物（１）または化合物（１’）及び化合物（２）と触媒とを接触させる際に、反応に悪影響を及ぼさない範囲で無機塩や有機化合物、金属錯体を共存させてもよい。
In contacting the compound (1) or the compound (1 ') and the compound (2) with the catalyst, an inorganic salt, an organic compound, or a metal complex may be allowed to coexist in a range that does not adversely affect the reaction.
また、反応に悪影響を及ぼさない範囲で、化合物（１）または化合物（１’）及び化合物（２）と触媒との混合物を攪拌してもよい。このとき、攪拌の方法としては、メカニカルスターラーやマグネティックスターラーを用いることができる。
In addition, the compound (1) or the compound (1 ′) and the mixture of the compound (2) and the catalyst may be stirred as long as the reaction is not adversely affected. At this time, a mechanical stirrer or a magnetic stirrer can be used as a stirring method.
化合物（１）または化合物（１’）及び化合物（２）と触媒とを接触させた後、目的物は通常複数のオレフィンの混合物として得られるため、公知の方法で単離してもよい。
単離方法としては、例えば蒸留、カラムクロマトグラフィー、リサイクル分取ＨＰＬＣが挙げられ、必要に応じてこれらを単独または複数組み合わせて用いることができる。 After contacting compound (1) or compound (1 ′) and compound (2) with the catalyst, the target product is usually obtained as a mixture of a plurality of olefins, and therefore may be isolated by a known method.
Examples of the isolation method include distillation, column chromatography, and recycle preparative HPLC, and these can be used alone or in combination as required.
単離方法としては、例えば蒸留、カラムクロマトグラフィー、リサイクル分取ＨＰＬＣが挙げられ、必要に応じてこれらを単独または複数組み合わせて用いることができる。 After contacting compound (1) or compound (1 ′) and compound (2) with the catalyst, the target product is usually obtained as a mixture of a plurality of olefins, and therefore may be isolated by a known method.
Examples of the isolation method include distillation, column chromatography, and recycle preparative HPLC, and these can be used alone or in combination as required.
本反応で得られた化合物（３）または化合物（３’）は、通常の有機化合物と同様の公知の方法で同定することができる。例えば、１Ｈ－，１９Ｆ－，１３Ｃ－ＮＭＲやＧＣ－ＭＳが挙げられ、必要に応じてこれらを単独または複数組み合わせて用いることができる。
The compound (3) or compound (3 ′) obtained by this reaction can be identified by a known method similar to that for ordinary organic compounds. Examples thereof include 1 H-, 19 F-, 13 C-NMR, and GC-MS, and these can be used alone or in combination as required.
［化合物（４）］
また、本発明は、下記式（４）で表される化合物（化合物（４））に関するものである。
化合物（４）は化合物（３）の一例であり、化合物（１）として下記の化合物（４－１）及び化合物（２）として下記の化合物（４－２）を上記に記載した方法にて触媒と接触させることによってクロスメタセシス反応を行い、得ることができる。 [Compound (4)]
Moreover, this invention relates to the compound (compound (4)) represented by following formula (4).
The compound (4) is an example of the compound (3), and the following compound (4-1) as the compound (1) and the following compound (4-2) as the compound (2) are catalyzed by the method described above. A cross-metathesis reaction can be performed and obtained by contacting with.
また、本発明は、下記式（４）で表される化合物（化合物（４））に関するものである。
化合物（４）は化合物（３）の一例であり、化合物（１）として下記の化合物（４－１）及び化合物（２）として下記の化合物（４－２）を上記に記載した方法にて触媒と接触させることによってクロスメタセシス反応を行い、得ることができる。 [Compound (4)]
Moreover, this invention relates to the compound (compound (4)) represented by following formula (4).
The compound (4) is an example of the compound (3), and the following compound (4-1) as the compound (1) and the following compound (4-2) as the compound (2) are catalyzed by the method described above. A cross-metathesis reaction can be performed and obtained by contacting with.
式中、Ｒ１１は１価の含フッ素有機基を表す。
含フッ素有機基としては、例えば、炭素数１～１２の（ペル）フルオロアルキル基、炭素数１～１２の（ペル）フルオロアルコキシ基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、及びエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基が挙げられる。
これらの中でも、好ましくは、炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、及びエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基である。 In the formula, R 11 represents a monovalent fluorine-containing organic group.
Examples of the fluorine-containing organic group include (per) fluoroalkyl groups having 1 to 12 carbon atoms, (per) fluoroalkoxy groups having 1 to 12 carbon atoms, and (per) carbon atoms having 2 to 400 carbon atoms containing an etheric oxygen atom. Examples thereof include a fluoroalkyl group and a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom.
Among these, preferably, a (per) fluoroalkyl group having 1 to 12 carbon atoms, a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and 2 to 2 carbon atoms containing an etheric oxygen atom. 400 (per) fluoroalkoxy groups.
含フッ素有機基としては、例えば、炭素数１～１２の（ペル）フルオロアルキル基、炭素数１～１２の（ペル）フルオロアルコキシ基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、及びエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基が挙げられる。
これらの中でも、好ましくは、炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、及びエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基である。 In the formula, R 11 represents a monovalent fluorine-containing organic group.
Examples of the fluorine-containing organic group include (per) fluoroalkyl groups having 1 to 12 carbon atoms, (per) fluoroalkoxy groups having 1 to 12 carbon atoms, and (per) carbon atoms having 2 to 400 carbon atoms containing an etheric oxygen atom. Examples thereof include a fluoroalkyl group and a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom.
Among these, preferably, a (per) fluoroalkyl group having 1 to 12 carbon atoms, a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and 2 to 2 carbon atoms containing an etheric oxygen atom. 400 (per) fluoroalkoxy groups.
Ｚ１～Ｚ４、ｃ、ｃとｄの和、Ｙ、Ｒ２、Ｒ３及びＲ４は前記化合物（１）～（３）における定義とそれぞれ同様である。
また、Ｒ１１、Ｒ２、およびＲ３からなる群から選ばれる任意の２つは互いに結合して環を形成してもよい。
化合物（４）としては、ｃが０、ｄが３、Ｙが単結合、エーテル性酸素原子または－ＣＨ２Ｏ－、Ｒ１１が炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基、Ｒ２がフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、Ｒ３がフッ素原子、トリフルオロメチル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基である化合物が好ましい。 Z 1 to Z 4 , c, the sum of c and d, Y, R 2 , R 3 and R 4 are the same as defined in the compounds (1) to (3).
Further, any two selected from the group consisting of R 11 , R 2 and R 3 may be bonded to each other to form a ring.
As the compound (4), c is 0, d is 3, Y is a single bond, etheric oxygen atom or —CH 2 O—, R 11 is a (per) fluoroalkyl group having 1 to 12 carbon atoms, etheric oxygen (Per) fluoroalkyl group having 2 to 400 carbon atoms containing atom or (per) fluoroalkoxy group having 2 to 400 carbon atoms containing etheric oxygen atom, R 2 is fluorine atom, trifluoromethyl group, pentafluoroethyl group , A heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 3 having 2 to 400 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom ( Compounds that are per) fluoroalkyl groups are preferred.
また、Ｒ１１、Ｒ２、およびＲ３からなる群から選ばれる任意の２つは互いに結合して環を形成してもよい。
化合物（４）としては、ｃが０、ｄが３、Ｙが単結合、エーテル性酸素原子または－ＣＨ２Ｏ－、Ｒ１１が炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基、Ｒ２がフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、Ｒ３がフッ素原子、トリフルオロメチル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基である化合物が好ましい。 Z 1 to Z 4 , c, the sum of c and d, Y, R 2 , R 3 and R 4 are the same as defined in the compounds (1) to (3).
Further, any two selected from the group consisting of R 11 , R 2 and R 3 may be bonded to each other to form a ring.
As the compound (4), c is 0, d is 3, Y is a single bond, etheric oxygen atom or —CH 2 O—, R 11 is a (per) fluoroalkyl group having 1 to 12 carbon atoms, etheric oxygen (Per) fluoroalkyl group having 2 to 400 carbon atoms containing atom or (per) fluoroalkoxy group having 2 to 400 carbon atoms containing etheric oxygen atom, R 2 is fluorine atom, trifluoromethyl group, pentafluoroethyl group , A heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 3 having 2 to 400 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom ( Compounds that are per) fluoroalkyl groups are preferred.
化合物（４）の具体例としては、下記に示す化合物が挙げられる。
Specific examples of the compound (4) include the compounds shown below.
これらの中でも、好ましくは、下記に示す化合物が挙げられる。
Among these, Preferably, the compounds shown below are mentioned.
［化合物（５）］
また、本発明は、下記式（５）で表される化合物（化合物（５））に関するものである。
化合物（５）は化合物（３）の一例であり、化合物（１）として下記の化合物（５－１）及び化合物（２）として下記の化合物（５－２）を上記に記載した方法にて触媒と接触させることによってクロスメタセシス反応を行い得ることができる。 [Compound (5)]
Moreover, this invention relates to the compound (compound (5)) represented by following formula (5).
Compound (5) is an example of compound (3), and the following compound (5-1) as compound (1) and the following compound (5-2) as compound (2) are catalyzed by the method described above. A cross metathesis reaction can be carried out by contacting with.
また、本発明は、下記式（５）で表される化合物（化合物（５））に関するものである。
化合物（５）は化合物（３）の一例であり、化合物（１）として下記の化合物（５－１）及び化合物（２）として下記の化合物（５－２）を上記に記載した方法にて触媒と接触させることによってクロスメタセシス反応を行い得ることができる。 [Compound (5)]
Moreover, this invention relates to the compound (compound (5)) represented by following formula (5).
Compound (5) is an example of compound (3), and the following compound (5-1) as compound (1) and the following compound (5-2) as compound (2) are catalyzed by the method described above. A cross metathesis reaction can be carried out by contacting with.
Ｚ１～Ｚ４、ｂ、ｃ、ｃとｄの和、Ｙ、Ｒ１、Ｒ２、Ｒ３及びＲ４は前記化合物（１）～（３）における定義とそれぞれ同様である。また、Ｒ１、Ｒ２、およびＲ３からなる群から選ばれる任意の２つは互いに結合して環を形成してもよい。
化合物（５）としては、ｂが０、ｃが０、ｄが３、Ｙが単結合、エーテル性酸素原子または－ＣＨ２Ｏ－、Ｒ１が炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基、Ｒ２がフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、Ｒ３がフッ素原子、トリフルオロメチル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基である化合物が好ましい。 Z 1 to Z 4 , b, c, the sum of c and d, Y, R 1 , R 2 , R 3 and R 4 are the same as defined in the compounds (1) to (3). Any two selected from the group consisting of R 1 , R 2 , and R 3 may be bonded to each other to form a ring.
As the compound (5), b is 0, c is 0, d is 3, Y is a single bond, etheric oxygen atom or —CH 2 O—, and R 1 is a (per) fluoroalkyl group having 1 to 12 carbon atoms. , A (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom or a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom, R 2 is a fluorine atom, a trifluoromethyl group, A pentafluoroethyl group, a heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 3 having 2 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom Compounds with up to 400 (per) fluoroalkyl groups are preferred.
化合物（５）としては、ｂが０、ｃが０、ｄが３、Ｙが単結合、エーテル性酸素原子または－ＣＨ２Ｏ－、Ｒ１が炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基、Ｒ２がフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、Ｒ３がフッ素原子、トリフルオロメチル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基である化合物が好ましい。 Z 1 to Z 4 , b, c, the sum of c and d, Y, R 1 , R 2 , R 3 and R 4 are the same as defined in the compounds (1) to (3). Any two selected from the group consisting of R 1 , R 2 , and R 3 may be bonded to each other to form a ring.
As the compound (5), b is 0, c is 0, d is 3, Y is a single bond, etheric oxygen atom or —CH 2 O—, and R 1 is a (per) fluoroalkyl group having 1 to 12 carbon atoms. , A (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom or a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom, R 2 is a fluorine atom, a trifluoromethyl group, A pentafluoroethyl group, a heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 3 having 2 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom Compounds with up to 400 (per) fluoroalkyl groups are preferred.
化合物（５）の具体例としては、例えば、下記に示す化合物が挙げられる。
Specific examples of the compound (5) include the compounds shown below.
これらの中でも、好ましくは、下記に示す化合物が挙げられる。
Among these, Preferably, the compounds shown below are mentioned.
［化合物（６）］
また、本発明は、下記式（６）で表される化合物（化合物（６））に関するものである。
化合物（６）は化合物（３）の一例であり、化合物（１）として下記の化合物（６－１）及び化合物（２）として下記の化合物（６－２）を上記に記載した方法にて触媒と接触させることによってクロスメタセシス反応を行い得ることができる。 [Compound (6)]
Moreover, this invention relates to the compound (compound (6)) represented by following formula (6).
The compound (6) is an example of the compound (3), and the following compound (6-1) as the compound (1) and the following compound (6-2) as the compound (2) are catalyzed by the method described above. A cross metathesis reaction can be carried out by contacting with.
また、本発明は、下記式（６）で表される化合物（化合物（６））に関するものである。
化合物（６）は化合物（３）の一例であり、化合物（１）として下記の化合物（６－１）及び化合物（２）として下記の化合物（６－２）を上記に記載した方法にて触媒と接触させることによってクロスメタセシス反応を行い得ることができる。 [Compound (6)]
Moreover, this invention relates to the compound (compound (6)) represented by following formula (6).
The compound (6) is an example of the compound (3), and the following compound (6-1) as the compound (1) and the following compound (6-2) as the compound (2) are catalyzed by the method described above. A cross metathesis reaction can be carried out by contacting with.
式中、Ｒ５は炭素数１～６のアルキル基を表し、Ｒ５が同一分子内に複数存在する場合、それらは同一でも異なっていてもよい。
炭素数１～６のアルキル基としては、メチル基、エチル基、またはプロピル基が挙げられる。これらの中でも、好ましくは、メチル基、エチル基である。
Ｚ１～Ｚ４、ｃ、ｃとｄの和、Ｙ、Ｒ１、Ｒ２、Ｒ３及びＲ４は前記化合物（１）～（３）における定義と同様である。また、Ｒ１、Ｒ２、およびＲ３からなる群から選ばれる任意の２つは互いに結合して環を形成してもよい。
化合物（６）としては、ｃが０、ｄが３、Ｙが単結合、エーテル性酸素原子または－ＣＨ２Ｏ－、Ｒ１が炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基、Ｒ２がフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、Ｒ３がフッ素原子、トリフルオロメチル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基である化合物が好ましい。 In the formula, R 5 represents an alkyl group having 1 to 6 carbon atoms, and when a plurality of R 5 are present in the same molecule, they may be the same or different.
Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, and a propyl group. Among these, a methyl group and an ethyl group are preferable.
Z 1 to Z 4 , c, the sum of c and d, Y, R 1 , R 2 , R 3 and R 4 are as defined in the compounds (1) to (3). Any two selected from the group consisting of R 1 , R 2 , and R 3 may be bonded to each other to form a ring.
As the compound (6), c is 0, d is 3, Y is a single bond, an etheric oxygen atom or —CH 2 O—, R 1 is a (per) fluoroalkyl group having 1 to 12 carbon atoms, etheric oxygen (Per) fluoroalkyl group having 2 to 400 carbon atoms containing atom or (per) fluoroalkoxy group having 2 to 400 carbon atoms containing etheric oxygen atom, R 2 is fluorine atom, trifluoromethyl group, pentafluoroethyl group , A heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 3 having 2 to 400 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom ( Compounds that are per) fluoroalkyl groups are preferred.
炭素数１～６のアルキル基としては、メチル基、エチル基、またはプロピル基が挙げられる。これらの中でも、好ましくは、メチル基、エチル基である。
Ｚ１～Ｚ４、ｃ、ｃとｄの和、Ｙ、Ｒ１、Ｒ２、Ｒ３及びＲ４は前記化合物（１）～（３）における定義と同様である。また、Ｒ１、Ｒ２、およびＲ３からなる群から選ばれる任意の２つは互いに結合して環を形成してもよい。
化合物（６）としては、ｃが０、ｄが３、Ｙが単結合、エーテル性酸素原子または－ＣＨ２Ｏ－、Ｒ１が炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基、Ｒ２がフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基、Ｒ３がフッ素原子、トリフルオロメチル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基である化合物が好ましい。 In the formula, R 5 represents an alkyl group having 1 to 6 carbon atoms, and when a plurality of R 5 are present in the same molecule, they may be the same or different.
Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, and a propyl group. Among these, a methyl group and an ethyl group are preferable.
Z 1 to Z 4 , c, the sum of c and d, Y, R 1 , R 2 , R 3 and R 4 are as defined in the compounds (1) to (3). Any two selected from the group consisting of R 1 , R 2 , and R 3 may be bonded to each other to form a ring.
As the compound (6), c is 0, d is 3, Y is a single bond, an etheric oxygen atom or —CH 2 O—, R 1 is a (per) fluoroalkyl group having 1 to 12 carbon atoms, etheric oxygen (Per) fluoroalkyl group having 2 to 400 carbon atoms containing atom or (per) fluoroalkoxy group having 2 to 400 carbon atoms containing etheric oxygen atom, R 2 is fluorine atom, trifluoromethyl group, pentafluoroethyl group , A heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 3 having 2 to 400 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom ( Compounds that are per) fluoroalkyl groups are preferred.
化合物（６）の具体例としては、例えば、下記に示す化合物が挙げられる。
Specific examples of the compound (6) include the compounds shown below.
これらの中でも、好ましくは、下記に示す化合物が挙げられる。
Among these, Preferably, the compounds shown below are mentioned.
以下に実施例を挙げ、本発明を具体的に説明するが、本発明は何らこれらに限定されるものではない。
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.
＜市販試薬＞
本実施例において、触媒は、特に記載しない場合においては、市販品をそのまま反応に用いた。
溶媒（クロロホルム－ｄ）は、Ｓｉｇｍａ－Ａｌｄｒｉｃｈ社製「クロロホルム－ｄ」をあらかじめ凍結脱気したあと、モレキュラーシーブ４Ａで乾燥してから反応に用いた。 <Commercially available reagents>
In this example, unless otherwise specified, a commercially available catalyst was used as it was for the reaction.
As the solvent (chloroform-d), “chloroform-d” manufactured by Sigma-Aldrich was freeze-degassed in advance and dried over molecular sieve 4A before use in the reaction.
本実施例において、触媒は、特に記載しない場合においては、市販品をそのまま反応に用いた。
溶媒（クロロホルム－ｄ）は、Ｓｉｇｍａ－Ａｌｄｒｉｃｈ社製「クロロホルム－ｄ」をあらかじめ凍結脱気したあと、モレキュラーシーブ４Ａで乾燥してから反応に用いた。 <Commercially available reagents>
In this example, unless otherwise specified, a commercially available catalyst was used as it was for the reaction.
As the solvent (chloroform-d), “chloroform-d” manufactured by Sigma-Aldrich was freeze-degassed in advance and dried over molecular sieve 4A before use in the reaction.
＜評価方法＞
本実施例において、合成した化合物の構造は日本電子株式会社製の核磁気共鳴装置「ＪＮＭ－ＡＬ３００」により１Ｈ－ＮＭＲ、１９Ｆ－ＮＭＲ測定を行うことで同定した。 <Evaluation method>
In this example, the structure of the synthesized compound was identified by performing 1 H-NMR and 19 F-NMR measurements using a nuclear magnetic resonance apparatus “JNM-AL300” manufactured by JEOL Ltd.
本実施例において、合成した化合物の構造は日本電子株式会社製の核磁気共鳴装置「ＪＮＭ－ＡＬ３００」により１Ｈ－ＮＭＲ、１９Ｆ－ＮＭＲ測定を行うことで同定した。 <Evaluation method>
In this example, the structure of the synthesized compound was identified by performing 1 H-NMR and 19 F-NMR measurements using a nuclear magnetic resonance apparatus “JNM-AL300” manufactured by JEOL Ltd.
＜実施例１＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒によるＣ８Ｆ１７－ＣＨ２－ＣＨ＝ＣＨ２とトリクロロビニルシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．２１７ｍｍｏｌ）、トリクロロビニルシラン（１０．９ｍｍｏｌ、１．７６ｇ、５モル当量）、Ｃ８Ｆ１７－ＣＨ２－ＣＨ＝ＣＨ２（２．１７ｍｍｏｌ、１．００ｇ、１モル当量）及びクロロホルム－ｄ（３．５ｍＬ）を１０ｍＬのフラスコの中に量り入れた。 Example 1 Cross Metathesis of C 8 F 17 —CH 2 —CH═CH 2 and Trichlorovinylsilane with Umicore M73 SIPr Catalyst Umicore M73 SIPr catalyst (10 mol%, 0.217 mmol), trichlorovinyl silane (10.9 mmol, 1. 76 g, 5 molar equivalents), C 8 F 17 —CH 2 —CH═CH 2 (2.17 mmol, 1.00 g, 1 molar equivalent) and chloroform-d (3.5 mL) were weighed into a 10 mL flask. It was.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．２１７ｍｍｏｌ）、トリクロロビニルシラン（１０．９ｍｍｏｌ、１．７６ｇ、５モル当量）、Ｃ８Ｆ１７－ＣＨ２－ＣＨ＝ＣＨ２（２．１７ｍｍｏｌ、１．００ｇ、１モル当量）及びクロロホルム－ｄ（３．５ｍＬ）を１０ｍＬのフラスコの中に量り入れた。 Example 1 Cross Metathesis of C 8 F 17 —CH 2 —CH═CH 2 and Trichlorovinylsilane with Umicore M73 SIPr Catalyst Umicore M73 SIPr catalyst (10 mol%, 0.217 mmol), trichlorovinyl silane (10.9 mmol, 1. 76 g, 5 molar equivalents), C 8 F 17 —CH 2 —CH═CH 2 (2.17 mmol, 1.00 g, 1 molar equivalent) and chloroform-d (3.5 mL) were weighed into a 10 mL flask. It was.
フラスコを６０℃で加熱し２時間反応させた。反応終了後、ＮＭＲを測定して下記式Ａで表される化合物Ａの生成を確認した。収率は７４％であった。また、減圧蒸留により化合物Ａを単離した。
これら一連の反応を以下に示す。 The flask was heated at 60 ° C. and reacted for 2 hours. After completion of the reaction, NMR was measured to confirm the formation of compound A represented by the following formula A. The yield was 74%. Further, Compound A was isolated by distillation under reduced pressure.
A series of these reactions is shown below.
これら一連の反応を以下に示す。 The flask was heated at 60 ° C. and reacted for 2 hours. After completion of the reaction, NMR was measured to confirm the formation of compound A represented by the following formula A. The yield was 74%. Further, Compound A was isolated by distillation under reduced pressure.
A series of these reactions is shown below.
得られた化合物Ａの評価結果を以下に示す。
Evaluation results of the obtained compound A are shown below.
（化合物Ａ）
１Ｈ－ＮＭＲ（ＣＤＣｌ３、３００ＭＨｚ、テトラメチルシラン基準）：δ（ｐｐｍ）３．０７（２Ｈ、ｄｔ、Ｊ＝６，１７Ｈｚ）、６．１４（１Ｈ、ｄ、Ｊ＝１８Ｈｚ）、６．６１（１Ｈ、ｄｔ、Ｊ＝６，１８Ｈｚ）．
１９Ｆ－ＮＭＲ（ＣＤＣｌ３、２８３ＭＨｚ、トリクロロフルオロメタン基準）：δ（ｐｐｍ）－８１．２（３Ｆ、ｔ、Ｊ＝１１Ｈｚ）、－１１２．８（２Ｆ、ｔ、Ｊ＝１７Ｈｚ）、－１２２．２－－１２２．４（６Ｆ、ｍ）、－１２３．２－－１２３．４（４Ｆ、ｍ）、－１２６．６（２Ｆ）． (Compound A)
1 H-NMR (CDCl 3 , 300 MHz, tetramethylsilane standard): δ (ppm) 3.07 (2H, dt, J = 6, 17 Hz), 6.14 (1H, d, J = 18 Hz), 6. 61 (1H, dt, J = 6, 18 Hz).
19 F-NMR (CDCl 3 , 283 MHz, trichlorofluoromethane standard): δ (ppm) −81.2 (3F, t, J = 11 Hz), −112.8 (2F, t, J = 17 Hz), −122 -2-122.4 (6F, m), -123.2--123.4 (4F, m), -126.6 (2F).
１Ｈ－ＮＭＲ（ＣＤＣｌ３、３００ＭＨｚ、テトラメチルシラン基準）：δ（ｐｐｍ）３．０７（２Ｈ、ｄｔ、Ｊ＝６，１７Ｈｚ）、６．１４（１Ｈ、ｄ、Ｊ＝１８Ｈｚ）、６．６１（１Ｈ、ｄｔ、Ｊ＝６，１８Ｈｚ）．
１９Ｆ－ＮＭＲ（ＣＤＣｌ３、２８３ＭＨｚ、トリクロロフルオロメタン基準）：δ（ｐｐｍ）－８１．２（３Ｆ、ｔ、Ｊ＝１１Ｈｚ）、－１１２．８（２Ｆ、ｔ、Ｊ＝１７Ｈｚ）、－１２２．２－－１２２．４（６Ｆ、ｍ）、－１２３．２－－１２３．４（４Ｆ、ｍ）、－１２６．６（２Ｆ）． (Compound A)
1 H-NMR (CDCl 3 , 300 MHz, tetramethylsilane standard): δ (ppm) 3.07 (2H, dt, J = 6, 17 Hz), 6.14 (1H, d, J = 18 Hz), 6. 61 (1H, dt, J = 6, 18 Hz).
19 F-NMR (CDCl 3 , 283 MHz, trichlorofluoromethane standard): δ (ppm) −81.2 (3F, t, J = 11 Hz), −112.8 (2F, t, J = 17 Hz), −122 -2-122.4 (6F, m), -123.2--123.4 (4F, m), -126.6 (2F).
＜実施例２＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒によるペルフルオロポリエーテル基含有オレフィン（１）とトリクロロビニルシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、ペルフルオロポリエーテル基含有オレフィン（１）（０．０６ｍｍｏｌ、ｌの平均値：２０、平均分子量：４０００、０．２４ｇ、１モル当量）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｂの生成を確認する。
これら一連の反応を以下に示す。 <Example 2> Cross metathesis of perfluoropolyether group-containing olefin (1) and trichlorovinylsilane using Umicore M73 SIPr catalyst Under nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents) ), Perfluoropolyether group-containing olefin (1) (0.06 mmol, average value of l: 20, average molecular weight: 4000, 0.24 g, 1 molar equivalent) and chloroform-d (0.56 mL) in an NMR measuring tube. Weigh in. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound B.
A series of these reactions is shown below.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、ペルフルオロポリエーテル基含有オレフィン（１）（０．０６ｍｍｏｌ、ｌの平均値：２０、平均分子量：４０００、０．２４ｇ、１モル当量）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｂの生成を確認する。
これら一連の反応を以下に示す。 <Example 2> Cross metathesis of perfluoropolyether group-containing olefin (1) and trichlorovinylsilane using Umicore M73 SIPr catalyst Under nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents) ), Perfluoropolyether group-containing olefin (1) (0.06 mmol, average value of l: 20, average molecular weight: 4000, 0.24 g, 1 molar equivalent) and chloroform-d (0.56 mL) in an NMR measuring tube. Weigh in. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound B.
A series of these reactions is shown below.
＜実施例３＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒によるペルフルオロポリエーテル基含有オレフィン（３）とトリクロロビニルシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００３ｍｍｏｌ）、トリクロロビニルシラン（０．１５ｍｍｏｌ、２５ｍｇ、５モル当量）、ペルフルオロポリエーテル基含有オレフィン（３）（０．０３ｍｍｏｌ、ｍの平均値：２１、ｎの平均値：２４、平均分子量：４８００、０．１５ｇ）及び１，４－ビス（トリフルオロメチル）ベンゼン（０．４４ｍＬ）、クロロホルム－ｄ（０．１１ｍＬ）をＮＭＲ測定管の中に量り入れた。ＮＭＲ管を６０℃で加熱し３時間反応させた。反応終了後、ＮＭＲを測定して化合物Ｄの生成を確認した。収率は５６％であった。
これら一連の反応を以下に示す。 <Example 3> Cross-metathesis of perfluoropolyether group-containing olefin (3) and trichlorovinylsilane using Umicore M73 SIPr catalyst Umicore M73 SIPr catalyst (10 mol%, 0.003 mmol), trichlorovinylsilane (0.15 mmol, 25 mg, 5 molar equivalents) in a nitrogen atmosphere ), Perfluoropolyether group-containing olefin (3) (0.03 mmol, m average value: 21, n average value: 24, average molecular weight: 4800, 0.15 g) and 1,4-bis (trifluoromethyl) Benzene (0.44 mL) and chloroform-d (0.11 mL) were weighed into an NMR measuring tube. The NMR tube was heated at 60 ° C. and reacted for 3 hours. After completion of the reaction, NMR was measured to confirm the formation of Compound D. The yield was 56%.
A series of these reactions is shown below.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００３ｍｍｏｌ）、トリクロロビニルシラン（０．１５ｍｍｏｌ、２５ｍｇ、５モル当量）、ペルフルオロポリエーテル基含有オレフィン（３）（０．０３ｍｍｏｌ、ｍの平均値：２１、ｎの平均値：２４、平均分子量：４８００、０．１５ｇ）及び１，４－ビス（トリフルオロメチル）ベンゼン（０．４４ｍＬ）、クロロホルム－ｄ（０．１１ｍＬ）をＮＭＲ測定管の中に量り入れた。ＮＭＲ管を６０℃で加熱し３時間反応させた。反応終了後、ＮＭＲを測定して化合物Ｄの生成を確認した。収率は５６％であった。
これら一連の反応を以下に示す。 <Example 3> Cross-metathesis of perfluoropolyether group-containing olefin (3) and trichlorovinylsilane using Umicore M73 SIPr catalyst Umicore M73 SIPr catalyst (10 mol%, 0.003 mmol), trichlorovinylsilane (0.15 mmol, 25 mg, 5 molar equivalents) in a nitrogen atmosphere ), Perfluoropolyether group-containing olefin (3) (0.03 mmol, m average value: 21, n average value: 24, average molecular weight: 4800, 0.15 g) and 1,4-bis (trifluoromethyl) Benzene (0.44 mL) and chloroform-d (0.11 mL) were weighed into an NMR measuring tube. The NMR tube was heated at 60 ° C. and reacted for 3 hours. After completion of the reaction, NMR was measured to confirm the formation of Compound D. The yield was 56%.
A series of these reactions is shown below.
＜実施例４＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒による含フッ素オレフィン（４）とトリクロロビニルシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（４）（０．０６ｍｍｏｌ、１１ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｅの生成を確認する。
これら一連の反応を以下に示す。 <Example 4> Cross-metathesis of fluorine-containing olefin (4) and trichlorovinylsilane by Umicore M73 SIPr catalyst Under nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents), Fluorine olefin (4) (0.06 mmol, 11 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound E.
A series of these reactions is shown below.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（４）（０．０６ｍｍｏｌ、１１ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｅの生成を確認する。
これら一連の反応を以下に示す。 <Example 4> Cross-metathesis of fluorine-containing olefin (4) and trichlorovinylsilane by Umicore M73 SIPr catalyst Under nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents), Fluorine olefin (4) (0.06 mmol, 11 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound E.
A series of these reactions is shown below.
＜実施例５＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒による含フッ素オレフィン（５）とトリクロロビニルシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（５）（０．０６ｍｍｏｌ、１５ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｆの生成を確認する。
これら一連の反応を以下に示す。 <Example 5> Cross-metathesis of fluorine-containing olefin (5) and trichlorovinylsilane using Umicore M73 SIPr catalyst In a nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents), Fluorine olefin (5) (0.06 mmol, 15 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound F.
A series of these reactions is shown below.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（５）（０．０６ｍｍｏｌ、１５ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｆの生成を確認する。
これら一連の反応を以下に示す。 <Example 5> Cross-metathesis of fluorine-containing olefin (5) and trichlorovinylsilane using Umicore M73 SIPr catalyst In a nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents), Fluorine olefin (5) (0.06 mmol, 15 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound F.
A series of these reactions is shown below.
＜実施例６＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒による含フッ素オレフィン（６）とトリクロロビニルシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（６）（０．０６ｍｍｏｌ、１９ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｇの生成を確認する。
これら一連の反応を以下に示す。 <Example 6> Cross-metathesis of fluorine-containing olefin (6) and trichlorovinylsilane using Umicore M73 SIPr catalyst In a nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents), Fluorine olefin (6) (0.06 mmol, 19 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound G.
A series of these reactions is shown below.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（６）（０．０６ｍｍｏｌ、１９ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｇの生成を確認する。
これら一連の反応を以下に示す。 <Example 6> Cross-metathesis of fluorine-containing olefin (6) and trichlorovinylsilane using Umicore M73 SIPr catalyst In a nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents), Fluorine olefin (6) (0.06 mmol, 19 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound G.
A series of these reactions is shown below.
＜実施例７＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒による含フッ素オレフィン（７）とトリクロロビニルシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（７）（０．０６ｍｍｏｌ、１２ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｈの生成を確認する。
これら一連の反応を以下に示す。 <Example 7> Cross-metathesis of fluorine-containing olefin (7) and trichlorovinylsilane using Umicore M73 SIPr catalyst Under nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents), Fluorine olefin (7) (0.06 mmol, 12 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound H.
A series of these reactions is shown below.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（７）（０．０６ｍｍｏｌ、１２ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｈの生成を確認する。
これら一連の反応を以下に示す。 <Example 7> Cross-metathesis of fluorine-containing olefin (7) and trichlorovinylsilane using Umicore M73 SIPr catalyst Under nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents), Fluorine olefin (7) (0.06 mmol, 12 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound H.
A series of these reactions is shown below.
＜実施例８＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒による含フッ素オレフィン（８）とトリクロロビニルシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（８）（０．０６ｍｍｏｌ、２２ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｉの生成を確認する。
これら一連の反応を以下に示す。 <Example 8> Cross-metathesis of fluorine-containing olefin (8) and trichlorovinylsilane using Umicore M73 SIPr catalyst In a nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents), Fluorine olefin (8) (0.06 mmol, 22 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound I.
A series of these reactions is shown below.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（８）（０．０６ｍｍｏｌ、２２ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｉの生成を確認する。
これら一連の反応を以下に示す。 <Example 8> Cross-metathesis of fluorine-containing olefin (8) and trichlorovinylsilane using Umicore M73 SIPr catalyst In a nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents), Fluorine olefin (8) (0.06 mmol, 22 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound I.
A series of these reactions is shown below.
＜実施例９＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒による含フッ素オレフィン（９）とトリクロロビニルシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（９）（０．０６ｍｍｏｌ、１７ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｊの生成を確認する。
これら一連の反応を以下に示す。 <Example 9> Cross-metathesis of fluorine-containing olefin (9) and trichlorovinylsilane using Umicore M73 SIPr catalyst In a nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents), Fluorine olefin (9) (0.06 mmol, 17 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound J.
A series of these reactions is shown below.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（９）（０．０６ｍｍｏｌ、１７ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｊの生成を確認する。
これら一連の反応を以下に示す。 <Example 9> Cross-metathesis of fluorine-containing olefin (9) and trichlorovinylsilane using Umicore M73 SIPr catalyst In a nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents), Fluorine olefin (9) (0.06 mmol, 17 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound J.
A series of these reactions is shown below.
＜実施例１０＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒による含フッ素オレフィン（１０）とトリクロロビニルシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（１０）（０．０６ｍｍｏｌ、１３ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｋの生成を確認する。
これら一連の反応を以下に示す。 <Example 10> Cross-metathesis of fluorine-containing olefin (10) and trichlorovinylsilane using Umicore M73 SIPr catalyst In a nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents), Fluorine olefin (10) (0.06 mmol, 13 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound K.
A series of these reactions is shown below.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（１０）（０．０６ｍｍｏｌ、１３ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｋの生成を確認する。
これら一連の反応を以下に示す。 <Example 10> Cross-metathesis of fluorine-containing olefin (10) and trichlorovinylsilane using Umicore M73 SIPr catalyst In a nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents), Fluorine olefin (10) (0.06 mmol, 13 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound K.
A series of these reactions is shown below.
＜実施例１１＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒による含フッ素オレフィン（１１）とトリクロロビニルシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（１１）（０．０６ｍｍｏｌ、１８ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｌの生成を確認する。
これら一連の反応を以下に示す。 <Example 11> Cross-metathesis of fluorine-containing olefin (11) and trichlorovinylsilane using Umicore M73 SIPr catalyst Under nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalent), Fluorine olefin (11) (0.06 mmol, 18 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound L.
A series of these reactions is shown below.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロビニルシラン（０．３０ｍｍｏｌ、４８ｍｇ、５モル当量）、含フッ素オレフィン（１１）（０．０６ｍｍｏｌ、１８ｍｇ）及びクロロホルム－ｄ（０．５６ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｌの生成を確認する。
これら一連の反応を以下に示す。 <Example 11> Cross-metathesis of fluorine-containing olefin (11) and trichlorovinylsilane using Umicore M73 SIPr catalyst Under nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalent), Fluorine olefin (11) (0.06 mmol, 18 mg) and chloroform-d (0.56 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound L.
A series of these reactions is shown below.
＜実施例１２＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒によるＣ８Ｆ１７－ＣＨ２－ＣＨ＝ＣＨ２とビニルトリメトキシシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、ビニルトリメトキシシラン（０．３０ｍｍｏｌ、４４ｍｇ、５モル当量）、Ｃ８Ｆ１７－ＣＨ２－ＣＨ＝ＣＨ２（０．０６ｍｍｏｌ、２８ｍｇ、１モル当量）及びクロロホルム－ｄ（０．５４ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｍの生成を確認する。
これら一連の反応を以下に示す。 Example 12 Cross Metathesis of C 8 F 17 —CH 2 —CH═CH 2 and Vinyl Trimethoxysilane with Umicore M73 SIPr Catalyst Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), vinyl trimethoxysilane (0. 30 mmol, 44 mg, 5 molar equivalents), C 8 F 17 —CH 2 —CH═CH 2 (0.06 mmol, 28 mg, 1 molar equivalent) and chloroform-d (0.54 mL) are weighed into an NMR measuring tube. . The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound M.
A series of these reactions is shown below.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、ビニルトリメトキシシラン（０．３０ｍｍｏｌ、４４ｍｇ、５モル当量）、Ｃ８Ｆ１７－ＣＨ２－ＣＨ＝ＣＨ２（０．０６ｍｍｏｌ、２８ｍｇ、１モル当量）及びクロロホルム－ｄ（０．５４ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｍの生成を確認する。
これら一連の反応を以下に示す。 Example 12 Cross Metathesis of C 8 F 17 —CH 2 —CH═CH 2 and Vinyl Trimethoxysilane with Umicore M73 SIPr Catalyst Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), vinyl trimethoxysilane (0. 30 mmol, 44 mg, 5 molar equivalents), C 8 F 17 —CH 2 —CH═CH 2 (0.06 mmol, 28 mg, 1 molar equivalent) and chloroform-d (0.54 mL) are weighed into an NMR measuring tube. . The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound M.
A series of these reactions is shown below.
＜実施例１３＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒によるＣ８Ｆ１７－ＣＨ２－ＣＨ＝ＣＨ２とトリクロロアリルシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロアリルシラン（０．３０ｍｍｏｌ、５２ｍｇ、５モル当量）、Ｃ８Ｆ１７－ＣＨ２－ＣＨ＝ＣＨ２（０．０６ｍｍｏｌ、２８ｍｇ、１モル当量）及びクロロホルム－ｄ（０．５４ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｎの生成を確認する。
これら一連の反応を以下に示す。 Example 13 Cross Metathesis of C 8 F 17 —CH 2 —CH═CH 2 and Trichloroallylsilane with Umicore M73 SIPr Catalyst Under a nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichloroallyl silane (0.30 mmol, 52 mg, 5 molar equivalents), C 8 F 17 —CH 2 —CH═CH 2 (0.06 mmol, 28 mg, 1 molar equivalent) and chloroform-d (0.54 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound N.
A series of these reactions is shown below.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）、トリクロロアリルシラン（０．３０ｍｍｏｌ、５２ｍｇ、５モル当量）、Ｃ８Ｆ１７－ＣＨ２－ＣＨ＝ＣＨ２（０．０６ｍｍｏｌ、２８ｍｇ、１モル当量）及びクロロホルム－ｄ（０．５４ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｎの生成を確認する。
これら一連の反応を以下に示す。 Example 13 Cross Metathesis of C 8 F 17 —CH 2 —CH═CH 2 and Trichloroallylsilane with Umicore M73 SIPr Catalyst Under a nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.006 mmol), trichloroallyl silane (0.30 mmol, 52 mg, 5 molar equivalents), C 8 F 17 —CH 2 —CH═CH 2 (0.06 mmol, 28 mg, 1 molar equivalent) and chloroform-d (0.54 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound N.
A series of these reactions is shown below.
＜実施例１４＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒によるＣ８Ｆ１７－ＣＨ２－ＣＨ＝ＣＨ２とトリクロロビニルシランのクロスメタセシス
実施例１におけるＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒の使用量を０．１ｍｏｌ％（０．００２１７ｍｍｏｌ）に変更した以外は実施例１と同様な方法により化合物Ａの生成を確認する。 Except for changing the amount of UmicoreM73SIPr catalyst in the cross-metathesis Example 1 of C 8 F 17 -CH 2 -CH = CH 2 and trichlorovinylsilane according <Example 14> UmicoreM73SIPr catalyst 0.1mol% (0.00217mmol) Production of Compound A is confirmed by the same method as in Example 1.
実施例１におけるＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒の使用量を０．１ｍｏｌ％（０．００２１７ｍｍｏｌ）に変更した以外は実施例１と同様な方法により化合物Ａの生成を確認する。 Except for changing the amount of UmicoreM73SIPr catalyst in the cross-metathesis Example 1 of C 8 F 17 -CH 2 -CH = CH 2 and trichlorovinylsilane according <Example 14> UmicoreM73SIPr catalyst 0.1mol% (0.00217mmol) Production of Compound A is confirmed by the same method as in Example 1.
＜実施例１５＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒によるＣ８Ｆ１７－ＣＨ２－ＣＨ＝ＣＨ２とトリクロロビニルシランのクロスメタセシス
実施例１における溶媒を重ベンゼン（Ｃ６Ｄ６）に変更した以外は実施例１と同様な方法により化合物Ａの生成を確認する。 Example 15 Cross Metathesis of C 8 F 17 —CH 2 —CH═CH 2 and Trichlorovinylsilane with Umicore M73 SIPr Catalyst Same as Example 1 except that the solvent in Example 1 was changed to heavy benzene (C 6 D 6 ) The formation of Compound A is confirmed by a simple method.
実施例１における溶媒を重ベンゼン（Ｃ６Ｄ６）に変更した以外は実施例１と同様な方法により化合物Ａの生成を確認する。 Example 15 Cross Metathesis of C 8 F 17 —CH 2 —CH═CH 2 and Trichlorovinylsilane with Umicore M73 SIPr Catalyst Same as Example 1 except that the solvent in Example 1 was changed to heavy benzene (C 6 D 6 ) The formation of Compound A is confirmed by a simple method.
＜実施例１６＞Ｇｒｕｂｂｓ第二世代触媒によるＣ８Ｆ１７－ＣＨ２－ＣＨ＝ＣＨ２とトリクロロビニルシランのクロスメタセシス
実施例１における触媒をＧｒｕｂｂｓ第二世代触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）に変更した以外は実施例１と同様な方法により化合物Ａの生成を確認する。
これら一連の反応を以下に示す。 Example 16 Cross Metathesis of C 8 F 17 —CH 2 —CH═CH 2 and Trichlorovinylsilane with Grubbs Second Generation Catalyst The catalyst in Example 1 was changed to a Grubbs second generation catalyst (10 mol%, 0.006 mmol). The production of Compound A was confirmed by the same method as in Example 1 except that.
A series of these reactions is shown below.
実施例１における触媒をＧｒｕｂｂｓ第二世代触媒（１０ｍｏｌ％、０．００６ｍｍｏｌ）に変更した以外は実施例１と同様な方法により化合物Ａの生成を確認する。
これら一連の反応を以下に示す。 Example 16 Cross Metathesis of C 8 F 17 —CH 2 —CH═CH 2 and Trichlorovinylsilane with Grubbs Second Generation Catalyst The catalyst in Example 1 was changed to a Grubbs second generation catalyst (10 mol%, 0.006 mmol). The production of Compound A was confirmed by the same method as in Example 1 except that.
A series of these reactions is shown below.
＜実施例１７＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒によるペルフルオロポリエーテル基含有オレフィン（１２）とトリクロロビニルシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００３ｍｍｏｌ）、トリクロロビニルシラン（０．１５ｍｍｏｌ、２４ｍｇ、５モル当量）、ペルフルオロポリエーテル基含有オレフィン（１２）（０．０３ｍｍｏｌ、０．１１ｇ）及び１，４－ビス（トリフルオロメチル）ベンゼン（０．４４ｍＬ）、クロロホルム－ｄ（０．１１ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｏの生成を確認する。
これら一連の反応を以下に示す。 <Example 17> Cross metathesis of perfluoropolyether group-containing olefin (12) and trichlorovinylsilane using Umicore M73 SIPr catalyst Umicore M73 SIPr catalyst (10 mol%, 0.003 mmol), trichlorovinylsilane (0.15 mmol, 24 mg, 5 molar equivalents) in a nitrogen atmosphere ), Perfluoropolyether group-containing olefin (12) (0.03 mmol, 0.11 g), 1,4-bis (trifluoromethyl) benzene (0.44 mL), and chloroform-d (0.11 mL) in an NMR measuring tube Measure in. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound O.
A series of these reactions is shown below.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００３ｍｍｏｌ）、トリクロロビニルシラン（０．１５ｍｍｏｌ、２４ｍｇ、５モル当量）、ペルフルオロポリエーテル基含有オレフィン（１２）（０．０３ｍｍｏｌ、０．１１ｇ）及び１，４－ビス（トリフルオロメチル）ベンゼン（０．４４ｍＬ）、クロロホルム－ｄ（０．１１ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｏの生成を確認する。
これら一連の反応を以下に示す。 <Example 17> Cross metathesis of perfluoropolyether group-containing olefin (12) and trichlorovinylsilane using Umicore M73 SIPr catalyst Umicore M73 SIPr catalyst (10 mol%, 0.003 mmol), trichlorovinylsilane (0.15 mmol, 24 mg, 5 molar equivalents) in a nitrogen atmosphere ), Perfluoropolyether group-containing olefin (12) (0.03 mmol, 0.11 g), 1,4-bis (trifluoromethyl) benzene (0.44 mL), and chloroform-d (0.11 mL) in an NMR measuring tube Measure in. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound O.
A series of these reactions is shown below.
＜実施例１８＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒によるペルフルオロポリエーテル基含有オレフィン（１３）とトリクロロビニルシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００３ｍｍｏｌ）、トリクロロビニルシラン（０．１５ｍｍｏｌ、２４ｍｇ、５モル当量）、ペルフルオロポリエーテル基含有オレフィン（１３）（０．０３ｍｍｏｌ、５５ｍｇ）及び１，４－ビス（トリフルオロメチル）ベンゼン（０．４４ｍＬ）、クロロホルム－ｄ（０．１１ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｐの生成を確認する。
これら一連の反応を以下に示す。 <Example 18> Cross-metathesis of perfluoropolyether group-containing olefin (13) and trichlorovinylsilane using Umicore M73 SIPr catalyst Under nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.003 mmol), trichlorovinylsilane (0.15 mmol, 24 mg, 5 molar equivalents) ), Perfluoropolyether group-containing olefin (13) (0.03 mmol, 55 mg), 1,4-bis (trifluoromethyl) benzene (0.44 mL) and chloroform-d (0.11 mL) in an NMR measuring tube. Weigh in. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of compound P.
A series of these reactions is shown below.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（１０ｍｏｌ％、０．００３ｍｍｏｌ）、トリクロロビニルシラン（０．１５ｍｍｏｌ、２４ｍｇ、５モル当量）、ペルフルオロポリエーテル基含有オレフィン（１３）（０．０３ｍｍｏｌ、５５ｍｇ）及び１，４－ビス（トリフルオロメチル）ベンゼン（０．４４ｍＬ）、クロロホルム－ｄ（０．１１ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｐの生成を確認する。
これら一連の反応を以下に示す。 <Example 18> Cross-metathesis of perfluoropolyether group-containing olefin (13) and trichlorovinylsilane using Umicore M73 SIPr catalyst Under nitrogen atmosphere, Umicore M73 SIPr catalyst (10 mol%, 0.003 mmol), trichlorovinylsilane (0.15 mmol, 24 mg, 5 molar equivalents) ), Perfluoropolyether group-containing olefin (13) (0.03 mmol, 55 mg), 1,4-bis (trifluoromethyl) benzene (0.44 mL) and chloroform-d (0.11 mL) in an NMR measuring tube. Weigh in. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of compound P.
A series of these reactions is shown below.
＜実施例１９＞ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒によるペルフルオロポリエーテル基含有オレフィン（１４）とトリクロロビニルシランのクロスメタセシス
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（０．００３ｍｍｏｌ）、トリクロロビニルシラン（０．１５ｍｍｏｌ、２４ｍｇ）、ペルフルオロポリエーテル基含有オレフィン（１３）（０．１３ｇ）及び１，４－ビス（トリフルオロメチル）ベンゼン（０．４４ｍＬ）、クロロホルム－ｄ（０．１１ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｑの生成を確認する。
これら一連の反応を以下に示す。 <Example 19> Cross-metathesis of perfluoropolyether group-containing olefin (14) and trichlorovinylsilane with Umicore M73 SIPr catalyst Umicore M73 SIPr catalyst (0.003 mmol), trichlorovinylsilane (0.15 mmol, 24 mg), perfluoropolyether group containing under nitrogen atmosphere Olefin (13) (0.13 g), 1,4-bis (trifluoromethyl) benzene (0.44 mL) and chloroform-d (0.11 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound Q.
A series of these reactions is shown below.
窒素雰囲気下、ＵｍｉｃｏｒｅＭ７３ＳＩＰｒ触媒（０．００３ｍｍｏｌ）、トリクロロビニルシラン（０．１５ｍｍｏｌ、２４ｍｇ）、ペルフルオロポリエーテル基含有オレフィン（１３）（０．１３ｇ）及び１，４－ビス（トリフルオロメチル）ベンゼン（０．４４ｍＬ）、クロロホルム－ｄ（０．１１ｍＬ）をＮＭＲ測定管の中に量り入れる。ＮＭＲ管を６０℃で加熱し２時間反応させる。反応終了後、ＮＭＲを測定して化合物Ｑの生成を確認する。
これら一連の反応を以下に示す。 <Example 19> Cross-metathesis of perfluoropolyether group-containing olefin (14) and trichlorovinylsilane with Umicore M73 SIPr catalyst Umicore M73 SIPr catalyst (0.003 mmol), trichlorovinylsilane (0.15 mmol, 24 mg), perfluoropolyether group containing under nitrogen atmosphere Olefin (13) (0.13 g), 1,4-bis (trifluoromethyl) benzene (0.44 mL) and chloroform-d (0.11 mL) are weighed into an NMR measuring tube. The NMR tube is heated at 60 ° C. and allowed to react for 2 hours. After completion of the reaction, NMR is measured to confirm the formation of Compound Q.
A series of these reactions is shown below.
本発明を詳細に、また特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は２０１７年３月２日出願の日本特許出願（特願２０１７－０３９８９４）に基づくものであり、その内容はここに参照として取り込まれる。
Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on March 2, 2017 (Japanese Patent Application No. 2017-039894), the contents of which are incorporated herein by reference.
本発明の製造方法に係る含フッ素シラン化合物は、医農薬中間体、指紋除去剤、防汚剤、防湿コーティング剤として利用可能である。
The fluorine-containing silane compound according to the production method of the present invention can be used as a pharmaceutical / agrochemical intermediate, a fingerprint remover, an antifouling agent, and a moisture-proof coating agent.
Claims (11)
- 下記式（１’）で表される化合物と、下記式（２）で表される化合物とをクロスメタセシス反応させる、下記式（３’）で表される化合物の製造方法。
- 下記式（１）で表される化合物と、下記式（２）で表される化合物とをクロスメタセシス反応させる、下記式（３）で表される化合物の製造方法。
- ａは０または１であり、ｂは０であり、ｃは０であり、Ｘは塩素原子、メトキシ基またはエトキシ基を表し、Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－を表し、Ｒ１は炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基を表し、Ｒ２はフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表し、Ｒ３はフッ素原子、トリフルオロメチル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表す、請求項２に記載の製造方法。 a is 0 or 1, b is 0, c is 0, X represents a chlorine atom, a methoxy group or an ethoxy group, Y represents a single bond, an etheric oxygen atom or —CH 2 O—. , R 1 is a (per) fluoroalkyl group having 1 to 12 carbon atoms, a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, or a (per) fluorocarbon group having 2 to 400 carbon atoms containing an etheric oxygen atom (per ) Represents a fluoroalkoxy group, R 2 represents a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, R 3 represents a fluorine atom, a trifluoromethyl group or an etheric oxygen atom carbon number of 2 to 400 containing (per) fluoroalkyl group, according to claim 2 Manufacturing method.
- Ｚ１～Ｚ４はそれぞれ独立に水素原子、メチル基、エチル基、プロピル基、メトキシ基、エトキシ基、プロポキシ基、フェニル基、フェニルオキシ基、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、トリフルオロメトキシ基、ペンタフルオロエトキシ基、ヘプタフルオロプロポキシ基、ペルフルオロ（メトキシメトキシ）基、ペルフルオロ（プロポキシプロポキシ）基、ペンタフルオロフェニル基またはペンタフルオロフェニルオキシ基を表す、請求項２または３に記載の製造方法。 Z 1 to Z 4 are each independently a hydrogen atom, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, propoxy group, phenyl group, phenyloxy group, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl 4 represents a group, trifluoromethoxy group, pentafluoroethoxy group, heptafluoropropoxy group, perfluoro (methoxymethoxy) group, perfluoro (propoxypropoxy) group, pentafluorophenyl group or pentafluorophenyloxy group. The manufacturing method as described.
- 下記式（３’）で表される化合物。
- 下記式（４）で表される化合物。
- ｃは０であり、Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－を表し、Ｒ１１は炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基を表し、Ｒ２はフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表し、Ｒ３はフッ素原子、トリフルオロメチル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表す、請求項６に記載の化合物。 c is 0, Y represents a single bond, an etheric oxygen atom or —CH 2 O—, R 11 represents a (per) fluoroalkyl group having 1 to 12 carbon atoms, and 2 to 2 carbon atoms including an etheric oxygen atom. Represents a 400 (per) fluoroalkyl group or a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 2 represents a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group. Or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 3 is a (per) fluorocarbon having 2 to 400 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom 7. A compound according to claim 6, which represents an alkyl group.
- 下記式（５）で表される化合物。
- ｂは０であり、ｃは０であり、Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－を表し、Ｒ１は炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基を表し、Ｒ２はフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表し、Ｒ３はフッ素原子、トリフルオロメチル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表す、請求項８に記載の化合物。 b is 0, c is 0, Y represents a single bond, an etheric oxygen atom or —CH 2 O—, R 1 represents a (per) fluoroalkyl group having 1 to 12 carbon atoms, an etheric oxygen atom Represents a (per) fluoroalkyl group having 2 to 400 carbon atoms containing or a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 2 represents a fluorine atom, a trifluoromethyl group, pentafluoroethyl Represents a group, a heptafluoropropyl group, or a (per) fluoroalkyl group containing 2 to 400 carbon atoms containing an etheric oxygen atom, and R 3 represents a fluorine atom, a trifluoromethyl group or an etheric oxygen atom containing 2 to 2 carbon atoms 9. A compound according to claim 8, which represents 400 (per) fluoroalkyl groups.
- 下記式（６）で表される化合物。
- ｃは０であり、Ｙは単結合、エーテル性酸素原子または－ＣＨ２Ｏ－を表し、Ｒ１は炭素数１～１２の（ペル）フルオロアルキル基、エーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルコキシ基を表し、Ｒ２はフッ素原子、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表し、Ｒ３はフッ素原子、トリフルオロメチル基またはエーテル性酸素原子を含む炭素数２～４００の（ペル）フルオロアルキル基を表す、請求項１０に記載の化合物。
c is 0, Y represents a single bond, an etheric oxygen atom or —CH 2 O—, R 1 represents a (per) fluoroalkyl group having 1 to 12 carbon atoms, and 2 to 2 carbon atoms containing an etheric oxygen atom. Represents a 400 (per) fluoroalkyl group or a (per) fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 2 represents a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group. Or a (per) fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R 3 is a (per) fluorocarbon having 2 to 400 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom 11. A compound according to claim 10, which represents an alkyl group.
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