JP4789108B2 - 光学活性なα−トリフルオロメチルケトン化合物の製造方法 - Google Patents
光学活性なα−トリフルオロメチルケトン化合物の製造方法 Download PDFInfo
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- JP4789108B2 JP4789108B2 JP2005341454A JP2005341454A JP4789108B2 JP 4789108 B2 JP4789108 B2 JP 4789108B2 JP 2005341454 A JP2005341454 A JP 2005341454A JP 2005341454 A JP2005341454 A JP 2005341454A JP 4789108 B2 JP4789108 B2 JP 4789108B2
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- carbon
- titanium
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- 238000000034 method Methods 0.000 title claims description 24
- -1 Ketone compound Chemical class 0.000 claims description 46
- 229910052719 titanium Inorganic materials 0.000 claims description 28
- 239000010936 titanium Substances 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 150000002642 lithium compounds Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 150000003609 titanium compounds Chemical class 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 150000001721 carbon Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000005389 trialkylsiloxy group Chemical group 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical class [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 2
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- VBFKOAUPUOAIFJ-UHFFFAOYSA-N fluoroform;hydroiodide Chemical compound I.FC(F)F VBFKOAUPUOAIFJ-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 0 *C(*)(*)C(OI(*)(CN)(N)O)=C(*)* Chemical compound *C(*)(*)C(OI(*)(CN)(N)O)=C(*)* 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000000010 aprotic solvent Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- PECWKWDUAWCDTL-DAIOKFOQSA-N tert-butyl-[(Z,1R)-1-cyclohexyl-2-trimethylsilyloxybut-2-enoxy]-dimethylsilane Chemical compound C/C=C(/[C@@H](C1CCCCC1)O[Si](C)(C)C(C)(C)C)\O[Si](C)(C)C PECWKWDUAWCDTL-DAIOKFOQSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- KPCQMUGOTUXNTL-OAHLLOKOSA-N (1r)-1-[tert-butyl(dimethyl)silyl]oxy-1-cyclohexylbutan-2-one Chemical compound CC(C)(C)[Si](C)(C)O[C@@H](C(=O)CC)C1CCCCC1 KPCQMUGOTUXNTL-OAHLLOKOSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940043279 diisopropylamine Drugs 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DOKLGKGSDGWTMY-LBPRGKRZSA-N (4S)-4-[tert-butyl(dimethyl)silyl]oxyheptan-3-one Chemical compound CCC[C@@H](C(=O)CC)O[Si](C)(C)C(C)(C)C DOKLGKGSDGWTMY-LBPRGKRZSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UAXIGXVZSSTAPU-UHFFFAOYSA-M [I-].FC(F)(F)[Zn+] Chemical compound [I-].FC(F)(F)[Zn+] UAXIGXVZSSTAPU-UHFFFAOYSA-M 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 230000026045 iodination Effects 0.000 description 2
- 238000006192 iodination reaction Methods 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WNTFIKNDFAWRLE-HNNXBMFYSA-N tert-butyl-dimethyl-[(4S)-3-trimethylsilyloxyhept-2-en-4-yl]oxysilane Chemical compound CCC[C@@H](C(=CC)O[Si](C)(C)C)O[Si](C)(C)C(C)(C)C WNTFIKNDFAWRLE-HNNXBMFYSA-N 0.000 description 2
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RRLAPWHWYCNMOI-OAHLLOKOSA-N (1R)-1-[tert-butyl(dimethyl)silyl]oxy-1-phenylbutan-2-one Chemical compound CC(C)(C)[Si](C)(C)O[C@@H](C(=O)CC)C1=CC=CC=C1 RRLAPWHWYCNMOI-OAHLLOKOSA-N 0.000 description 1
- RRLAPWHWYCNMOI-HNNXBMFYSA-N (1S)-1-[tert-butyl(dimethyl)silyl]oxy-1-phenylbutan-2-one Chemical compound O([Si](C)(C)C(C)(C)C)[C@H](C(CC)=O)C1=CC=CC=C1 RRLAPWHWYCNMOI-HNNXBMFYSA-N 0.000 description 1
- KPCQMUGOTUXNTL-HNNXBMFYSA-N (1s)-1-[tert-butyl(dimethyl)silyl]oxy-1-cyclohexylbutan-2-one Chemical compound CC(C)(C)[Si](C)(C)O[C@H](C(=O)CC)C1CCCCC1 KPCQMUGOTUXNTL-HNNXBMFYSA-N 0.000 description 1
- LFSAPCRASZRSKS-ZCFIWIBFSA-N (2r)-2-methylcyclohexan-1-one Chemical compound C[C@@H]1CCCCC1=O LFSAPCRASZRSKS-ZCFIWIBFSA-N 0.000 description 1
- JRHWHSJDIILJAT-BYPYZUCNSA-N (2s)-2-hydroxypentanoic acid Chemical compound CCC[C@H](O)C(O)=O JRHWHSJDIILJAT-BYPYZUCNSA-N 0.000 description 1
- LFSAPCRASZRSKS-LURJTMIESA-N (2s)-2-methylcyclohexan-1-one Chemical compound C[C@H]1CCCCC1=O LFSAPCRASZRSKS-LURJTMIESA-N 0.000 description 1
- USFRKEWRSPLQSX-SNVBAGLBSA-N (4R)-4-[(2-methylpropan-2-yl)oxy]heptan-3-one Chemical compound CCC[C@H](C(=O)CC)OC(C)(C)C USFRKEWRSPLQSX-SNVBAGLBSA-N 0.000 description 1
- DOKLGKGSDGWTMY-GFCCVEGCSA-N (4R)-4-[tert-butyl(dimethyl)silyl]oxyheptan-3-one Chemical compound CCC[C@H](C(=O)CC)O[Si](C)(C)C(C)(C)C DOKLGKGSDGWTMY-GFCCVEGCSA-N 0.000 description 1
- ULPMRIXXHGUZFA-ZCFIWIBFSA-N (4R)-4-methylhexan-3-one Chemical compound CC[C@@H](C)C(=O)CC ULPMRIXXHGUZFA-ZCFIWIBFSA-N 0.000 description 1
- USFRKEWRSPLQSX-JTQLQIEISA-N (4S)-4-[(2-methylpropan-2-yl)oxy]heptan-3-one Chemical compound CCC[C@@H](C(=O)CC)OC(C)(C)C USFRKEWRSPLQSX-JTQLQIEISA-N 0.000 description 1
- MVLRILUUXLBENA-SSDOTTSWSA-N (4r)-4-methylheptan-3-one Chemical compound CCC[C@@H](C)C(=O)CC MVLRILUUXLBENA-SSDOTTSWSA-N 0.000 description 1
- ULPMRIXXHGUZFA-LURJTMIESA-N (4s)-4-methylhexan-3-one Chemical compound CC[C@H](C)C(=O)CC ULPMRIXXHGUZFA-LURJTMIESA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- KJCOVWBLDCWPKQ-WPZCJLIBSA-N CC(C(=O)[C@@H](C1CCCCC1)O[Si](C)(C)O[SiH2]C(C)(C)C)C(F)(F)F Chemical compound CC(C(=O)[C@@H](C1CCCCC1)O[Si](C)(C)O[SiH2]C(C)(C)C)C(F)(F)F KJCOVWBLDCWPKQ-WPZCJLIBSA-N 0.000 description 1
- WZROPJFOKKDPLT-RRKGBCIJSA-N CCC[C@H](C(=O)C(C)C(F)(F)F)O[Si](C)(C)O[SiH2]C(C)(C)C Chemical compound CCC[C@H](C(=O)C(C)C(F)(F)F)O[Si](C)(C)O[SiH2]C(C)(C)C WZROPJFOKKDPLT-RRKGBCIJSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- WZKSXHQDXQKIQJ-UHFFFAOYSA-N F[C](F)F Chemical compound F[C](F)F WZKSXHQDXQKIQJ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical compound [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- VJDVOZLYDLHLSM-UHFFFAOYSA-N diethylazanide;titanium(4+) Chemical compound [Ti+4].CC[N-]CC.CC[N-]CC.CC[N-]CC.CC[N-]CC VJDVOZLYDLHLSM-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
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- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- PECWKWDUAWCDTL-GOSISDBHSA-N tert-butyl-[(1R)-1-cyclohexyl-2-trimethylsilyloxybut-2-enoxy]-dimethylsilane Chemical compound CC=C([C@@H](C1CCCCC1)O[Si](C)(C)C(C)(C)C)O[Si](C)(C)C PECWKWDUAWCDTL-GOSISDBHSA-N 0.000 description 1
- PECWKWDUAWCDTL-SFHVURJKSA-N tert-butyl-[(1S)-1-cyclohexyl-2-trimethylsilyloxybut-2-enoxy]-dimethylsilane Chemical compound CC=C([C@H](C1CCCCC1)O[Si](C)(C)C(C)(C)C)O[Si](C)(C)C PECWKWDUAWCDTL-SFHVURJKSA-N 0.000 description 1
- HTVOROXLHZKLCO-GOSISDBHSA-N tert-butyl-dimethyl-[(1R)-1-phenyl-2-trimethylsilyloxybut-2-enoxy]silane Chemical compound CC=C([C@@H](C1=CC=CC=C1)O[Si](C)(C)C(C)(C)C)O[Si](C)(C)C HTVOROXLHZKLCO-GOSISDBHSA-N 0.000 description 1
- HTVOROXLHZKLCO-SFHVURJKSA-N tert-butyl-dimethyl-[(1S)-1-phenyl-2-trimethylsilyloxybut-2-enoxy]silane Chemical compound CC=C([C@H](C1=CC=CC=C1)O[Si](C)(C)C(C)(C)C)O[Si](C)(C)C HTVOROXLHZKLCO-SFHVURJKSA-N 0.000 description 1
- WNTFIKNDFAWRLE-OAHLLOKOSA-N tert-butyl-dimethyl-[(4R)-3-trimethylsilyloxyhept-2-en-4-yl]oxysilane Chemical compound CCC[C@H](C(=CC)O[Si](C)(C)C)O[Si](C)(C)C(C)(C)C WNTFIKNDFAWRLE-OAHLLOKOSA-N 0.000 description 1
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical compound CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- YRIFRPRVGIEKHO-CYBMUJFWSA-N trimethyl-[(4R)-4-[(2-methylpropan-2-yl)oxy]hept-2-en-3-yl]oxysilane Chemical compound CCC[C@H](C(=CC)O[Si](C)(C)C)OC(C)(C)C YRIFRPRVGIEKHO-CYBMUJFWSA-N 0.000 description 1
- YQMSNSDLEWTJNX-SNVBAGLBSA-N trimethyl-[(4R)-4-methylhept-2-en-3-yl]oxysilane Chemical compound CCC[C@@H](C)C(=CC)O[Si](C)(C)C YQMSNSDLEWTJNX-SNVBAGLBSA-N 0.000 description 1
- VECLFZFOXCZQDH-SECBINFHSA-N trimethyl-[(4R)-4-methylhex-2-en-3-yl]oxysilane Chemical compound CC[C@@H](C)C(=CC)O[Si](C)(C)C VECLFZFOXCZQDH-SECBINFHSA-N 0.000 description 1
- YRIFRPRVGIEKHO-ZDUSSCGKSA-N trimethyl-[(4S)-4-[(2-methylpropan-2-yl)oxy]hept-2-en-3-yl]oxysilane Chemical compound CCC[C@@H](C(=CC)O[Si](C)(C)C)OC(C)(C)C YRIFRPRVGIEKHO-ZDUSSCGKSA-N 0.000 description 1
- YQMSNSDLEWTJNX-JTQLQIEISA-N trimethyl-[(4S)-4-methylhept-2-en-3-yl]oxysilane Chemical compound CCC[C@H](C)C(=CC)O[Si](C)(C)C YQMSNSDLEWTJNX-JTQLQIEISA-N 0.000 description 1
- VECLFZFOXCZQDH-VIFPVBQESA-N trimethyl-[(4S)-4-methylhex-2-en-3-yl]oxysilane Chemical compound CC[C@H](C)C(=CC)O[Si](C)(C)C VECLFZFOXCZQDH-VIFPVBQESA-N 0.000 description 1
- IERTVMWHAUJPFI-SECBINFHSA-N trimethyl-[(6R)-6-methylcyclohexen-1-yl]oxysilane Chemical compound C[C@@H]1CCCC=C1O[Si](C)(C)C IERTVMWHAUJPFI-SECBINFHSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
J. Am. Chem. Soc., 115, 2156 (1993) J. Org. Chem., 59, 5692 (1994) Bull. Chem. Soc. Jpn., 64, 1542 (1991) Tetrahedron Letters, 31, 6391 (1990) J. Chem. Soc., Perkin Trans. 1, 1365 (1977) J. Am. Chem. Soc., 107, 5186 (1985)
で表されるチタンアートエノラート化合物を、ラジカル開始剤の存在下にヨウ化トリフルオロメタンと反応させ、一般式(4)
で表される光学活性なα−トリフルオロメチルケトンを製造する方法。
のケトン化合物及び/または一般式(2)
のシリルエノールエーテルとリチウム化合物及びチタン化合物を反応させることによって生成させる。
実施例
以下に実施例を用いて本発明を詳細に説明するが、本発明はこの実施例によって限定されるものではない。
50ml 2口フラスコにテトラヒドロフラン 10ml、ジイソプロピルアミン 0.224ml(1.6mmol)を入れ−78に冷却した。1.58mol/L n−ブチルリチウム ヘキサン溶液 0.76ml(1.2mmol)を添加し、0℃で30分攪拌した。再び−78℃に冷却し、(1R)−1−(t−ブチルジメチルシロキシ)−1−シクロヘキシルブタン−2−オン(J. Am. Chem. Soc., 103, 1566(1981)の方法に従い合成) 284mg(1.0mmol)を添加し、60分攪拌した。次いで、トリメチルシリルクロリド 0.202ml(1.6mmol)を添加し、室温で6.5時間攪拌した。反応混合物を冷炭酸水素ナトリウム水に注ぎ、ヘキサンで抽出した。抽出液を飽和食塩水で洗浄し、硫酸ナトリウムで乾燥後、溶媒を減圧下で留去した。得られた粗生成物をカラム精製し、[(2Z)−(1R)−1−(t−ブチルジメチルシロキシ)−2−トリメチルシロキシ−2−ブテニル]―シクロヘキサン 163mg(収率 46%)を得た。
13C NMR(75MHz,CDCl3)δ―5.0,−4.2,0.9,10.3,18.2,26.0,26.4,26.7,26.8,30.5,41.0,78.5,102.8,151.2
(1R)−1−(t−ブチルジメチルシロキシ)−1−シクロヘキシルブタン−2−オン 284mg(1.0mmol)を(4s)−4−t−ブチルジメチルシロキシヘプタン−3−オン((2S)−2−ヒドロキシペンタン酸を出発とし、J. Am. Chem. Soc., 103, 1566(1981)の方法に従い合成)242mg(1.0mmol)とした以外は参考例1と同様の操作を行い、[(4s)−4−t−ブチルジメチルシロキシ]−3−トリメチルシロキシ−2−ヘプテンを得た。
13C NMR(75MHz,CDCl3)δ−5.0,−4.7,11.5,11.5,18.2,25.8,26.1,26.2,27.6,29.2,29.7,41.1,44.0(q,JC-F=26.3Hz)、83.2,125.2(q,JC-F=278.7Hz),205.6
19F NMR(376Hz,CDCl3)δ―68.5(d,JH−F=8.3Hz),
[−68.9(d,JH−F=7.9Hz)副ジアステレオマー]
13C NMR(75MHz,CDCl3)δ−4.9,11.5,13.9,17.9,18.0,25.7,36.2,43.2(q,JC-F=26.3Hz)、78.5,125.2(q,JC-F=278.3Hz),206.7
19F NMR(376Hz,CDCl3)δ―68.8(d,JH−F=7.9Hz),
[−69.1(d,JH−F=8.2Hz)副ジアステレオマー]
Claims (4)
- 一般式(3)
で表されるチタンアートエノラート化合物を、ラジカル開始剤の存在下にヨウ化トリフルオロメタンと反応させ、一般式(4)
で表される光学活性なα−トリフルオロメチルケトン化合物の製造方法。 - ラジカル開始剤がトリアルキルボラン化合物及び分子状酸素であることを特徴とする請求項1に記載の光学活性なα−トリフルオロメチルケトン化合物の製造方法。
- リチウム化合物がアルキルリチウム化合物及び/またはリチウムアミド化合物であり、チタン化合物がチタンテトラアルコキサイドであることを特徴とする請求項3に記載の光学活性なα−トリフルオロメチルケトン化合物の製造方法。
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