JP4951754B2 - フルオロビス(アリールスルホニル)メタンおよびその製造法 - Google Patents
フルオロビス(アリールスルホニル)メタンおよびその製造法 Download PDFInfo
- Publication number
- JP4951754B2 JP4951754B2 JP2006057330A JP2006057330A JP4951754B2 JP 4951754 B2 JP4951754 B2 JP 4951754B2 JP 2006057330 A JP2006057330 A JP 2006057330A JP 2006057330 A JP2006057330 A JP 2006057330A JP 4951754 B2 JP4951754 B2 JP 4951754B2
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- Japan
- Prior art keywords
- bis
- group
- methane
- mmol
- fluoro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 51
- 125000004391 aryl sulfonyl group Chemical group 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 7
- -1 2,4,6-trimethylphenyl group Chemical group 0.000 claims description 22
- TUZGMBZILYZZRU-UHFFFAOYSA-N [benzenesulfonyl(fluoro)methyl]sulfonylbenzene Chemical compound C=1C=CC=CC=1S(=O)(=O)C(F)S(=O)(=O)C1=CC=CC=C1 TUZGMBZILYZZRU-UHFFFAOYSA-N 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 claims description 2
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 claims description 2
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 claims description 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 2
- 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 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 53
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 45
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 235000019270 ammonium chloride Nutrition 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 229920006395 saturated elastomer Polymers 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000007069 methylation reaction Methods 0.000 description 8
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 8
- QBMBQMKZGFOAHR-DARPEHSRSA-N 1-[(e)-4,4-bis(benzenesulfonyl)-4-fluoro-3-[4-(2-methylpropyl)phenyl]but-1-enyl]-4-(2-methylpropyl)benzene Chemical compound C1=CC(CC(C)C)=CC=C1\C=C\C(C(F)(S(=O)(=O)C=1C=CC=CC=1)S(=O)(=O)C=1C=CC=CC=1)C1=CC=C(CC(C)C)C=C1 QBMBQMKZGFOAHR-DARPEHSRSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- OUQSAXROROGQEE-JOCHJYFZSA-N (s)-ipr-phox Chemical compound CC(C)[C@H]1COC(C=2C(=CC=CC=2)P(C=2C=CC=CC=2)C=2C=CC=CC=2)=N1 OUQSAXROROGQEE-JOCHJYFZSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000005688 desulfonylation reaction Methods 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001728 carbonyl compounds Chemical class 0.000 description 3
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 2
- GJYSYQQXHBPJRD-UHFFFAOYSA-N 1-(2-methylpropyl)-4-prop-1-enylbenzene Chemical compound CC=CC1=CC=C(CC(C)C)C=C1 GJYSYQQXHBPJRD-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- PHQQLRUNFPCGQC-UHFFFAOYSA-N 3,3-bis(benzenesulfonyl)-3-fluoro-2-[4-(2-methylpropyl)phenyl]propan-1-ol Chemical compound C1=CC(CC(C)C)=CC=C1C(CO)C(F)(S(=O)(=O)C=1C=CC=CC=1)S(=O)(=O)C1=CC=CC=C1 PHQQLRUNFPCGQC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QCHNSJNRFSOCLJ-UHFFFAOYSA-N benzenesulfonylmethylsulfonylbenzene Chemical compound C=1C=CC=CC=1S(=O)(=O)CS(=O)(=O)C1=CC=CC=C1 QCHNSJNRFSOCLJ-UHFFFAOYSA-N 0.000 description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].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 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 2
- KMPWYEUPVWOPIM-KODHJQJWSA-N cinchonidine Chemical compound C1=CC=C2C([C@H]([C@H]3[N@]4CC[C@H]([C@H](C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-KODHJQJWSA-N 0.000 description 2
- KMPWYEUPVWOPIM-UHFFFAOYSA-N cinchonidine Natural products C1=CC=C2C(C(C3N4CCC(C(C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-UHFFFAOYSA-N 0.000 description 2
- CHDFNIZLAAFFPX-UHFFFAOYSA-N ethoxyethane;oxolane Chemical compound CCOCC.C1CCOC1 CHDFNIZLAAFFPX-UHFFFAOYSA-N 0.000 description 2
- QWLICVXJMVMDDQ-UHFFFAOYSA-N fluoro acetate Chemical compound CC(=O)OF QWLICVXJMVMDDQ-UHFFFAOYSA-N 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000007344 nucleophilic reaction Methods 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical class [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 2
- XHFXMNZYIKFCPN-UHFFFAOYSA-N perchloryl fluoride Chemical compound FCl(=O)(=O)=O XHFXMNZYIKFCPN-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- LOUPRKONTZGTKE-LHHVKLHASA-N quinidine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@H]2[C@@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-LHHVKLHASA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- SMBZJSVIKJMSFP-UHFFFAOYSA-N trifluoromethyl hypofluorite Chemical compound FOC(F)(F)F SMBZJSVIKJMSFP-UHFFFAOYSA-N 0.000 description 2
- QKZWXPLBVCKXNQ-UHFFFAOYSA-N (2-methoxyphenyl)-[2-[(2-methoxyphenyl)-phenylphosphanyl]ethyl]-phenylphosphane Chemical compound COC1=CC=CC=C1P(C=1C=CC=CC=1)CCP(C=1C(=CC=CC=1)OC)C1=CC=CC=C1 QKZWXPLBVCKXNQ-UHFFFAOYSA-N 0.000 description 1
- CQYMOICHLLQQAH-UHFFFAOYSA-N (r)-binaphane Chemical compound C1C2=CC=C3C=CC=CC3=C2C(C2=CC=CC=C2C=C2)=C2CP1C1=CC=CC=C1P(C1)CC2=CC=C(C=CC=C3)C3=C2C2=C1C=CC1=CC=CC=C21 CQYMOICHLLQQAH-UHFFFAOYSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- SHJGEWDYIYRFSP-UHFFFAOYSA-N 1,3,5-tri(propan-2-yl)-2-[[2,4,6-tri(propan-2-yl)phenyl]sulfonylmethylsulfonyl]benzene Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1S(=O)(=O)CS(=O)(=O)C1=C(C(C)C)C=C(C(C)C)C=C1C(C)C SHJGEWDYIYRFSP-UHFFFAOYSA-N 0.000 description 1
- HZASUHYGVVTQEP-UHFFFAOYSA-N 1,3,5-trimethyl-2-[(2,4,6-trimethylphenyl)sulfonylmethylsulfonyl]benzene Chemical compound CC1=CC(C)=CC(C)=C1S(=O)(=O)CS(=O)(=O)C1=C(C)C=C(C)C=C1C HZASUHYGVVTQEP-UHFFFAOYSA-N 0.000 description 1
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 1
- JOCCGEZBHLDSQO-UHFFFAOYSA-N 1,3-bis[4-(2-methylpropyl)phenyl]prop-1-enyl acetate Chemical compound C1=CC(CC(C)C)=CC=C1CC=C(OC(C)=O)C1=CC=C(CC(C)C)C=C1 JOCCGEZBHLDSQO-UHFFFAOYSA-N 0.000 description 1
- OEDGFUGQLGKHEI-UHFFFAOYSA-N 1,3-ditert-butyl-5-[(3,5-ditert-butyl-4-methoxyphenyl)sulfonylmethylsulfonyl]-2-methoxybenzene Chemical compound C1=C(C(C)(C)C)C(OC)=C(C(C)(C)C)C=C1S(=O)(=O)CS(=O)(=O)C1=CC(C(C)(C)C)=C(OC)C(C(C)(C)C)=C1 OEDGFUGQLGKHEI-UHFFFAOYSA-N 0.000 description 1
- BUXRLPFUABMDCB-UHFFFAOYSA-N 1-[4-(2-methylpropyl)phenyl]propan-1-ol Chemical compound CCC(O)C1=CC=C(CC(C)C)C=C1 BUXRLPFUABMDCB-UHFFFAOYSA-N 0.000 description 1
- WEASZDNVBVZIJR-UHFFFAOYSA-N 1-bromo-2-[(2-bromophenyl)sulfonylmethylsulfonyl]benzene Chemical compound BrC1=CC=CC=C1S(=O)(=O)CS(=O)(=O)C1=CC=CC=C1Br WEASZDNVBVZIJR-UHFFFAOYSA-N 0.000 description 1
- GJTGIDYYCVVXRG-UHFFFAOYSA-N 1-bromo-3-[(3-bromophenyl)sulfonylmethylsulfonyl]benzene Chemical compound BrC1=CC=CC(S(=O)(=O)CS(=O)(=O)C=2C=C(Br)C=CC=2)=C1 GJTGIDYYCVVXRG-UHFFFAOYSA-N 0.000 description 1
- GNLWRDUYIDEDLG-UHFFFAOYSA-N 1-bromo-4-[(4-bromophenyl)sulfonylmethylsulfonyl]benzene Chemical compound C1=CC(Br)=CC=C1S(=O)(=O)CS(=O)(=O)C1=CC=C(Br)C=C1 GNLWRDUYIDEDLG-UHFFFAOYSA-N 0.000 description 1
- ATFJHZXDDVVTJJ-UHFFFAOYSA-N 1-butyl-4-prop-1-enylbenzene Chemical compound CCCCC1=CC=C(C=CC)C=C1 ATFJHZXDDVVTJJ-UHFFFAOYSA-N 0.000 description 1
- AWOQZDGIHNOBLG-UHFFFAOYSA-N 1-chloro-2-[(2-chlorophenyl)sulfonylmethylsulfonyl]benzene Chemical compound ClC1=CC=CC=C1S(=O)(=O)CS(=O)(=O)C1=CC=CC=C1Cl AWOQZDGIHNOBLG-UHFFFAOYSA-N 0.000 description 1
- UQLKRAFFXYZVBU-UHFFFAOYSA-N 1-chloro-4-[(4-chlorophenyl)sulfonylmethylsulfonyl]benzene Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)CS(=O)(=O)C1=CC=C(Cl)C=C1 UQLKRAFFXYZVBU-UHFFFAOYSA-N 0.000 description 1
- YKRHNBVOPORYLN-UHFFFAOYSA-N 1-ethyl-2-[(2-ethylphenyl)sulfonylmethylsulfonyl]benzene Chemical compound CCC1=CC=CC=C1S(=O)(=O)CS(=O)(=O)C1=CC=CC=C1CC YKRHNBVOPORYLN-UHFFFAOYSA-N 0.000 description 1
- UFHYXWKNIQRCES-UHFFFAOYSA-N 1-ethyl-3-[(3-ethylphenyl)sulfonylmethylsulfonyl]benzene Chemical compound CCC1=CC=CC(S(=O)(=O)CS(=O)(=O)C=2C=C(CC)C=CC=2)=C1 UFHYXWKNIQRCES-UHFFFAOYSA-N 0.000 description 1
- SDYJGSMJUIHMKT-UHFFFAOYSA-N 1-ethyl-4-[(4-ethylphenyl)sulfonylmethylsulfonyl]benzene Chemical compound C1=CC(CC)=CC=C1S(=O)(=O)CS(=O)(=O)C1=CC=C(CC)C=C1 SDYJGSMJUIHMKT-UHFFFAOYSA-N 0.000 description 1
- LWZRPYZXABAHFJ-UHFFFAOYSA-N 1-fluoro-4,6-bis(trifluoromethyl)pyridin-1-ium-2-sulfonate Chemical compound [O-]S(=O)(=O)C1=CC(C(F)(F)F)=CC(C(F)(F)F)=[N+]1F LWZRPYZXABAHFJ-UHFFFAOYSA-N 0.000 description 1
- PCUDTDNTOMIWJB-UHFFFAOYSA-N 1-fluoro-4,6-dimethylpyridin-1-ium-2-sulfonate Chemical compound CC1=CC(C)=[N+](F)C(S([O-])(=O)=O)=C1 PCUDTDNTOMIWJB-UHFFFAOYSA-N 0.000 description 1
- CZLMNRIAOUVXNU-UHFFFAOYSA-N 1-fluoro-4-methylpyridin-1-ium-2-sulfonate Chemical compound CC1=CC=[N+](F)C(S([O-])(=O)=O)=C1 CZLMNRIAOUVXNU-UHFFFAOYSA-N 0.000 description 1
- MEYCMYZKEHOPIF-UHFFFAOYSA-N 1-fluoro-5-(trifluoromethyl)pyridin-1-ium-2-sulfonate Chemical compound [O-]S(=O)(=O)C1=CC=C(C(F)(F)F)C=[N+]1F MEYCMYZKEHOPIF-UHFFFAOYSA-N 0.000 description 1
- AZKUIBOAKSSQTO-UHFFFAOYSA-N 1-methoxy-2-[(2-methoxyphenyl)sulfonylmethylsulfonyl]benzene Chemical compound COC1=CC=CC=C1S(=O)(=O)CS(=O)(=O)C1=CC=CC=C1OC AZKUIBOAKSSQTO-UHFFFAOYSA-N 0.000 description 1
- BVCFGPCNPFVMTP-UHFFFAOYSA-N 1-methoxy-3-[(3-methoxyphenyl)sulfonylmethylsulfonyl]benzene Chemical compound COC1=CC=CC(S(=O)(=O)CS(=O)(=O)C=2C=C(OC)C=CC=2)=C1 BVCFGPCNPFVMTP-UHFFFAOYSA-N 0.000 description 1
- QBTQTYZIRALXPA-UHFFFAOYSA-N 1-methoxy-4-[(4-methoxyphenyl)sulfonylmethylsulfonyl]benzene Chemical compound C1=CC(OC)=CC=C1S(=O)(=O)CS(=O)(=O)C1=CC=C(OC)C=C1 QBTQTYZIRALXPA-UHFFFAOYSA-N 0.000 description 1
- DFNFBOZIKZXFRN-UHFFFAOYSA-N 1-methyl-2-[(2-methylphenyl)sulfonylmethylsulfonyl]benzene Chemical compound CC1=CC=CC=C1S(=O)(=O)CS(=O)(=O)C1=CC=CC=C1C DFNFBOZIKZXFRN-UHFFFAOYSA-N 0.000 description 1
- IVCKPVXMLYBDOM-UHFFFAOYSA-N 1-methyl-3-[(3-methylphenyl)sulfonylmethylsulfonyl]benzene Chemical compound CC1=CC=CC(S(=O)(=O)CS(=O)(=O)C=2C=C(C)C=CC=2)=C1 IVCKPVXMLYBDOM-UHFFFAOYSA-N 0.000 description 1
- XLOXYWLRAKCDQL-UHFFFAOYSA-N 1-methyl-4-[(4-methylphenyl)sulfonylmethylsulfonyl]benzene Chemical compound C1=CC(C)=CC=C1S(=O)(=O)CS(=O)(=O)C1=CC=C(C)C=C1 XLOXYWLRAKCDQL-UHFFFAOYSA-N 0.000 description 1
- LSMSSYSRCUNIFX-UHFFFAOYSA-N 1-methyl-4-prop-1-enylbenzene Chemical compound CC=CC1=CC=C(C)C=C1 LSMSSYSRCUNIFX-UHFFFAOYSA-N 0.000 description 1
- HIFFIDIWEOBZII-UHFFFAOYSA-N 1-prop-1-enyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=CC)C=C1 HIFFIDIWEOBZII-UHFFFAOYSA-N 0.000 description 1
- SWOGZDBSWSFUIE-UHFFFAOYSA-N 1-tert-butyl-4-[(4-tert-butylphenyl)sulfonylmethylsulfonyl]benzene Chemical compound C1=CC(C(C)(C)C)=CC=C1S(=O)(=O)CS(=O)(=O)C1=CC=C(C(C)(C)C)C=C1 SWOGZDBSWSFUIE-UHFFFAOYSA-N 0.000 description 1
- BOMOHWDVLAJWEI-UHFFFAOYSA-N 2,4-dimethyl-1-prop-1-enylbenzene Chemical compound CC=CC1=CC=C(C)C=C1C BOMOHWDVLAJWEI-UHFFFAOYSA-N 0.000 description 1
- FYNXDGNCEBQLGC-KYJUHHDHSA-N 2,4-ditert-butyl-6-[[(1S,2S)-2-[(3,5-ditert-butyl-2-hydroxyphenyl)methylideneamino]cyclohexyl]iminomethyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C=N[C@@H]2[C@H](CCCC2)N=CC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O FYNXDGNCEBQLGC-KYJUHHDHSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- VTBGENTZANWBTA-UHFFFAOYSA-N 2-prop-1-enylnaphthalene Chemical compound C1=CC=CC2=CC(C=CC)=CC=C21 VTBGENTZANWBTA-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- PZVVUAIULJGRJE-UHFFFAOYSA-N 3-phenylprop-1-enyl acetate Chemical compound CC(=O)OC=CCC1=CC=CC=C1 PZVVUAIULJGRJE-UHFFFAOYSA-N 0.000 description 1
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BNMZNFDZDSXYHM-UHFFFAOYSA-N CCCCCCCCC1=CC=C(C=CC)C=C1 Chemical compound CCCCCCCCC1=CC=C(C=CC)C=C1 BNMZNFDZDSXYHM-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 235000001258 Cinchona calisaya Nutrition 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- RAIPGNPEEVDMSP-QURGRASLSA-N [(e)-4,4-bis(benzenesulfonyl)-4-fluoro-3-phenylbut-1-enyl]benzene Chemical compound C=1C=CC=CC=1S(=O)(=O)C(S(=O)(=O)C=1C=CC=CC=1)(F)C(C=1C=CC=CC=1)\C=C\C1=CC=CC=C1 RAIPGNPEEVDMSP-QURGRASLSA-N 0.000 description 1
- RZZDRSHFIVOQAF-UHFFFAOYSA-N [4-(5-diphenylphosphanyl-1,3-benzodioxol-4-yl)-1,3-benzodioxol-5-yl]-diphenylphosphane Chemical compound C=12OCOC2=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C1=C2OCOC2=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RZZDRSHFIVOQAF-UHFFFAOYSA-N 0.000 description 1
- JQBNSDVAZKYNOW-UHFFFAOYSA-M [F-].[Cs+].OS(O)(=O)=O Chemical compound [F-].[Cs+].OS(O)(=O)=O JQBNSDVAZKYNOW-UHFFFAOYSA-M 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical group C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- RRSCGNXXNRAXJC-UHFFFAOYSA-N bis(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1PC1=CC=C(C)C=C1 RRSCGNXXNRAXJC-UHFFFAOYSA-N 0.000 description 1
- QKLWAMMQKBOTCD-UHFFFAOYSA-N butane;diphenylphosphane Chemical compound CCCC.C=1C=CC=CC=1PC1=CC=CC=C1 QKLWAMMQKBOTCD-UHFFFAOYSA-N 0.000 description 1
- FWXAUDSWDBGCMN-ZEQRLZLVSA-N chiraphos Chemical compound C=1C=CC=CC=1P([C@@H](C)[C@H](C)P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 FWXAUDSWDBGCMN-ZEQRLZLVSA-N 0.000 description 1
- AVPBPSOSZLWRDN-UHFFFAOYSA-M chloropalladium(1+);methanidylbenzene;triphenylphosphane Chemical compound [Pd+]Cl.[CH2-]C1=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 AVPBPSOSZLWRDN-UHFFFAOYSA-M 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000006104 desulfonylation Effects 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- OKUTYUNUKKPYJS-VWLOTQADSA-N diphenyl-[2-[(4r)-4-phenyl-4,5-dihydro-1,3-oxazol-2-yl]phenyl]phosphane Chemical compound C1([C@H]2N=C(OC2)C=2C(=CC=CC=2)P(C=2C=CC=CC=2)C=2C=CC=CC=2)=CC=CC=C1 OKUTYUNUKKPYJS-VWLOTQADSA-N 0.000 description 1
- TWWJJVNUZQLCPD-UHFFFAOYSA-N diphenylphosphane;methane Chemical compound C.C=1C=CC=CC=1PC1=CC=CC=C1 TWWJJVNUZQLCPD-UHFFFAOYSA-N 0.000 description 1
- ONDPGJBEBGWAKI-UHFFFAOYSA-N diphenylphosphane;propane Chemical compound CCC.C=1C=CC=CC=1PC1=CC=CC=C1 ONDPGJBEBGWAKI-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- WDNMAVMEDYSCBN-UHFFFAOYSA-N hex-4-en-3-yl acetate Chemical compound CC(=O)OC(CC)C=CC WDNMAVMEDYSCBN-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 1
- RLKHFSNWQCZBDC-UHFFFAOYSA-N n-(benzenesulfonyl)-n-fluorobenzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)N(F)S(=O)(=O)C1=CC=CC=C1 RLKHFSNWQCZBDC-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- PENAXHPKEVTBLF-UHFFFAOYSA-L palladium(2+);prop-1-ene;dichloride Chemical compound [Pd+]Cl.[Pd+]Cl.[CH2-]C=C.[CH2-]C=C PENAXHPKEVTBLF-UHFFFAOYSA-L 0.000 description 1
- ULYNIEUXPCUIEL-UHFFFAOYSA-L palladium(2+);triethylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CCP(CC)CC.CCP(CC)CC ULYNIEUXPCUIEL-UHFFFAOYSA-L 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- XDASSWBZWFFNPX-UHFFFAOYSA-N palladium(ii) cyanide Chemical compound [Pd+2].N#[C-].N#[C-] XDASSWBZWFFNPX-UHFFFAOYSA-N 0.000 description 1
- QJPQVXSHYBGQGM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].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 QJPQVXSHYBGQGM-UHFFFAOYSA-N 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 229960001404 quinidine Drugs 0.000 description 1
- 229960000948 quinine Drugs 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012363 selectfluor Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
すなわち、本発明は、下記式(1)で表されるビス(アリールスルホニル)メタンを
(ArSO2)2CH2(1)
(Arは置換または無置換フェニル基、ナフチル基を表す)
塩基と処理し、ついで、フッ素化試薬を加えることによる下記式(2)で表されるフルオロビス(アリールスルホニル)メタンの製造法
(ArSO2)2CHF(2)
(Arは前に同じ)
および、モノフルオロメチル方を製造するのに極めて有用な新規化合物である下記式(2)で表されるフルオロビス(アリールスルホニル)メタン(2)からなる。
(ArSO 2 ) 2 CHF(2)
(Arはフェニル基、2−メチルフェニル基、3−メチルフェニル基、4−メチルフェニル基、2,4,6−トリメチルフェニル基、2−エチルフェニル基、3−エチルフェニル基、4−エチルフェニル基、2,4,6−トリ−iso−プロピルフェニル基、4−t−ブチルフェニル基、2−メトキシフェニル基、3−メトキシフェニル基、4−メトキシフェニル基、3,5−ジ−t−ブチル−4−メトキシフェニル基、2−クロロフェニル基、3−クロロフェニル基、4−クロロフェニル基、2−ブロモフェニル基、3−ブロモフェニル基、4−ブロモフェニル基を表す)
60% 油分散された水素化ナトリウム (205.3 mg, 0.833 mmol, 1.0 eq)のテトラヒドロフラン溶液40 mlを0 ℃に冷却した後に,ビス(フェニルスルホニル)メタン(241 mg, 0.813 mmol, 1.0 eq)を加え,室温で1時間攪拌する。得られた懸濁液を0 ℃でSelectfluor (N-フルオロ-N'-クロロメチルトリエチレンジアミン ビス(テトラフルオロボラート) (33.3 mg, 0.833 mmol, 1.0 eq)のアセトニトリル溶液50 mlに加え,室温で1 時間攪拌する。飽和塩化アンモニウム水溶液を加え,水層を塩化メチレンで抽出し,無水硫酸ナトリウムで乾燥させ,減圧下で溶媒を留去した後,カラムクロマトグラフィー (へキサン:塩化メチレン=2:8) で精製し,(2)を白色固体195 mg (57%)として得た。
1H NMR (200 MHz; CDCl3) δ 5.70 (1H, d, J = 45.8 Hz, CH), 7.55-7.65 (4H, m, Ar), 7.70-7.80 (2H, m, Ar), 7.95-8.05 (4H, d, Ar)
19F NMR (188 MHz; CDCl3)δ167.2 (d, J = 14.8 Hz)
MS (ESI-TOF) 314 (M+), 173 (M+ -SO2Ph), 141 (M+ -PhSO2CHF)
(4S)-2-(2-ジフェニルホスフィノフェニル)-4-イソプロピル-1,3-オキサゾリン (2.5 mg, 0.0067mmol, 5 mol%)と[Pd(C3H5)Cl]2 (1.2 mg, 0.0033 mmol, 2.5 mol%)と酢酸(2E)-1,3-ビス(4-イソブチルフェニル)-2-プロペニル (99.1 mg, 0.272 mmol, 2.0 eq)を塩化メチレン中,室温で15分間撹拌した。0 ℃に冷却した後に,1-フルオロ-1,1-ビス(フェニルスルホニル)メタン (42.6 mg, 0.136 mmol, 1.0 eq)とCs2CO3(87.8 mg, 0.270 mmol, 2.0 eq)を加え,0 ℃で60 時間攪拌した。飽和塩化アンモニウム水溶液を加え,水層を塩化メチレンで抽出し,無水硫酸ナトリウムで乾燥させ,減圧下で溶媒を留去した後,カラムクロマトグラフィー (へキサン:酢酸エチル=8:2) で精製し, (E)-4-フルオロ-1,3-ビス(4-イソブチルフェニル)-4,4-ビス(フェニルスルホニル)ブト-1-エンを黄色固体(77 mg 、91%, 98% ee)として得た。
HPLC (CHIRALCEL AD-H, Hexane/iPrOH=80:20, 1.0 ml/min, 10.0 min and 15.2 min)
1H NMR (200 MHz; CDCl3) δ 0.88 (12H, t, J = 5.8 Hz, CH3), 1.71-1.92 (2H, m, CH), 2.38 (2H, d, J = 7.2 Hz, CH2), 2.45 (2H, d, J = 7.0 Hz, CH2), 4.70 (1H, dd, J = 9.6, 14.5 Hz, CH=CH-CH), 6.46 (1H, d, J = 15.8 Hz, CH=CH-CH), 6.98-7.90 (19H, m, CH=CH-CH, Ar)
13C NMR (50 MHz; CDCl3)δ127.8 (d, J = 14.5 Hz) 14.3, 21.1, 30.1, 30.3, 45.0, 45.2. 51.1, 51.4, 60.3, 116.4, 119.0, 121.6, 121.7, 126.3, 128.1, 128.3, 128.5, 129.0, 130.0, 130.7, 132.4, 134.0, 134.4, 135.5, 136.0, 136.7, 141.0, 141.2
19F NMR (188 MHz; CDCl3)δ127.8 (d, J = 14.5 Hz)
(4S)-2-(2-ジフェニルホスフィノフェニル)-4-イソプロピル-1,3-オキサゾリン(2.5 mg, 0.0067 mmol, 5 mol%)と[Pd(C3H5)Cl]2 (1.3 mg, 0.0036 mmol, 2.5 mol%)と酢酸(2E)-1,3-ビス(4-イソブチルフェニル)-2-プロペニル(50.2 mg, 0.138 mmol, 1.0 eq)をトリフルオロメチルベンゼン中,室温で15分間撹拌した。0 ℃に冷却した後に,1-フルオロ-1,1-ビス(フェニルスルホニル)メタン(47.9 mg, 0.152 mmol, 1.1 eq)とCs2CO3(49.3 mg, 0.151 mmol, 1.1 eq)を加え,0 ℃で10 時間攪拌した。飽和塩化アンモニウム水溶液を加え,水層を塩化メチレンで抽出し,無水硫酸ナトリウムで乾燥させ,減圧下で溶媒を留去した後,カラムクロマトグラフィー (へキサン:酢酸エチル=8:2) で精製し,(E)-4-フルオロ-1,3-ビス(4-イソブチルフェニル)-4,4-ビス(フェニルスルホニル)ブト-1-エンを黄色固体(12.0mg, 14%, 97% ee)として得た。
(4S)-2-(2-ジフェニルホスフィノフェニル)-4-イソプロピル-1,3-オキサゾリン (2.6 mg, 0.0070 mmol, 5 mol%)と[Pd(C3H5)Cl]2 (1.4 mg, 0.0038 mmol, 2.5 mol%)と酢酸(2E)-1,3-ビス(4-イソブチルフェニル)-2-プロペニル(50.8 mg, 0.139 mmol, 1.0 eq)をクロロホルム中,室温で15分間撹拌した。0 ℃に冷却した後に,1-フルオロ-1,1-ビス(フェニルスルホニル)メタン(47.4 mg, 0.151 mmol, 1.1 eq)とCs2CO3(49.5 mg, 0.152 mmol, 1.1 eq)を加え,0 ℃で24 時間攪拌した。飽和塩化アンモニウム水溶液を加え,水層を塩化メチレンで抽出し,無水硫酸ナトリウムで乾燥させ,減圧下で溶媒を留去した後,カラムクロマトグラフィー (へキサン:酢酸エチル=8:2) で精製し,(E)-4-フルオロ-1,3-ビス(4-イソブチルフェニル)-4,4-ビス(フェニルスルホニル)ブト-1-エンを黄色固体(5.8mg, 8%, 97% ee)として得た。
(4S)-2-(2-ジフェニルホスフィノフェニル)-4-イソプロピル-1,3-オキサゾリン (2.7 mg, 0.0072 mmol, 5 mol%)と[Pd(C3H5)Cl]2 (1.5 mg, 0.0041 mmol, 2.5 mol%)と酢酸(2E)-1,3-ビス(4-イソブチルフェニル)-2-プロペニル(81.9 mg, 0.225 mmol, 1.5 eq)をTHF中,室温で15分間撹拌した。0 ℃に冷却した後に,1-フルオロ-1,1-ビス(フェニルスルホニル)メタン(47.0 mg, 0.150 mmol, 1.0 eq)とNaH(9.2 mg, 0.230 mmol, 1.5 eq)のTHF溶液を滴下し,0 ℃で24 時間攪拌した。飽和塩化アンモニウム水溶液を加え,水層を塩化メチレンで抽出し,無水硫酸ナトリウムで乾燥させ,減圧下で溶媒を留去した後,カラムクロマトグラフィー (へキサン:酢酸エチル=8:2) で精製し,(E)-4-フルオロ-1,3-ビス(4-イソブチルフェニル)-4,4-ビス(フェニルスルホニル)ブト-1-エンを黄色固体(19.9mg, 21%, 95%ee)として得た。
2,2’-ビス(ジフェニルホスフィノ)-1,1’-ビナフチル (4.8 mg, 0.0077 mmol, 5 mol%)と[Pd(C3H5)Cl]2(1.6 mg, 0.0044 mmol, 2.5 mol%)と酢酸(2E)-1,3-ビス(4-イソブチルフェニル)-2-プロペニル(109.6 mg, 0.301 mmol, 2.0 eq)を塩化メチレン中,室温で15分間撹拌した。0 ℃に冷却した後に,1-フルオロ-1,1-ビス(フェニルスルホニル)メタン( 46.9 mg, 0.149 mmol, 1.0 eq)とCs2CO3 (98.4 mg, 0.302 mmol, 2.0 eq)を加え,0 ℃で48 時間攪拌した。飽和塩化アンモニウム水溶液を加え,水層を塩化メチレンで抽出し,無水硫酸ナトリウムで乾燥させ,減圧下で溶媒を留去した後,カラムクロマトグラフィー (へキサン:酢酸エチル=8:2) で精製し,(E)-4-フルオロ-1,3-ビス(4-イソブチルフェニル)-4,4-ビス(フェニルスルホニル)ブト-1-エンを黄色固体(80.3mg, 87%, 88% ee)として得た。
(4S)-2-(2-ジフェニルホスフィノフェニル)-4-イソプロピル-1,3-オキサゾリン(3.6 mg, 0.0096 mmol, 5 mol%)と[Pd(C3H5)Cl]2 (1.8 mg, 0.0049 mmol, 2.5 mol%)と酢酸(2E)-1,3-ビス(4-イソブチルフェニル)-2-プロペニル(74.5 mg, 0.204 mmol, 1.0 eq)を塩化メチレン中,室温で15分間撹拌した。0 ℃に冷却した後に,1-フルオロ-1,1-ビス(フェニルスルホニル)メタン (70.6 mg, 0.225 mmol, 1.1 eq)とK2CO3(30.8 mg, 0.223 mmol, 1.1 eq)を加え,0 ℃で14 時間攪拌した。飽和塩化アンモニウム水溶液を加え,水層を塩化メチレンで抽出し,無水硫酸ナトリウムで乾燥させ,減圧下で溶媒を留去した後,カラムクロマトグラフィー (へキサン:酢酸エチル=8:2) で精製し,(E)-4-フルオロ-1,3-ビス(4-イソブチルフェニル)-4,4-ビス(フェニルスルホニル)ブト-1-エンを黄色固体(40 mg, 31%, 94% ee)として得た。
(4S)-2-(2-ジフェニルホスフィノフェニル)-4-イソプロピル-1,3-オキサゾリン(2.3 mg, 0.0062 mmol, 5 mol%)と[Pd(C3H5)Cl]2 (1.3 mg, 0.0036 mmol, 2.5 mol%)と酢酸(2E)-1,3-ビス(4-イソブチルフェニル)-2-プロペニル (50.6 mg, 0.139 mmol, 1.0 eq)をトルエン中,室温で15分間撹拌した。0 ℃に冷却した後に,1-フルオロ-1,1-ビス(フェニルスルホニル)メタン ( 48.2 mg, 0.153 mmol, 1.1 eq)とCs2CO3(49.8 mg, 0.153 mmol, 1.1 eq)を加え,0 ℃で8 時間攪拌した。飽和塩化アンモニウム水溶液を加え,水層を塩化メチレンで抽出し,無水硫酸ナトリウムで乾燥させ,減圧下で溶媒を留去した後,カラムクロマトグラフィー (へキサン:酢酸エチル=8:2) で精製し,(E)-4-フルオロ-1,3-ビス(4-イソブチルフェニル)-4,4-ビス(フェニルスルホニル)ブト-1-エンを黄色固体(8.8 mg, 10%, 96% ee)として得た。
(E)-4-フルオロ-1,3-ジフェニル-4,4-ビス(フェニルスルホニル)ブト-1-エンの合成
(4S)-2-(2-ジフェニルホスフィノフェニル)-4-イソプロピル-1,3-オキサゾリン(3.5 mg, 0.00937 mmol, 5 mol%)と[Pd(C3H5)Cl]2 (1.8 mg, 0.0049 mmol, 2.5 mol%)と酢酸(E)-1,3-ジフェニルアリル (50.5 mg, 0.200 mmol, 1.0 eq)を1,2-ジクロロエタン中,室温で15分間撹拌した。0 ℃に冷却した後に,1-フルオロ-1,1-ビス(フェニルスルホニル)メタン (68.6 mg, 0.218 mmol, 1.1 eq)とCs2CO3(71.2 mg, 0.219 mmol, 1.1 eq)を加え,0 ℃で2 時間攪拌した。飽和塩化アンモニウム水溶液を加え,水層を塩化メチレンで抽出し,無水硫酸ナトリウムで乾燥させ,減圧下で溶媒を留去した後,カラムクロマトグラフィー (へキサン:塩化メチレン=3:7) で精製し,(E)-4-フルオロ-1,3-ジフェニル-4,4-ビス(フェニルスルホニル)ブト-1-エン(33.4mg, 33%, 91% ee)を白色固体として得た。
1H NMR (200 MHz; CDCl3) δ4.72 (1H, dd, J = 9.2, 14.5 Hz, CH=CH-CH), 6.49 (1H, d, J = 15.8 Hz, CH=CH-CH), 7.00-7.90 (21H, m, CH=CH-CH, Ar)
19F NMR (188 MHz; CDCl3)δ128.5 (d, J = 14.5 Hz)
(E)-4-フルオロ-1,3-ビス(4-イソブチルフェニル)-4,4-ビス(フェニルスルホニル)ブト-1-エン (5a, 506 mg, 0.818 mmol, 1.0 eq)のMeOH 20 ml, CH2Cl2 7 ml溶液を-78 ℃に冷却し,そこにオゾン発生装置で発生させたオゾンガスを30 min導入した後,5分間O2を導入し,過剰のオゾンを除いた。続いてNaBH4(93.1 mg, 2.49 mmol, 3.0 eq)を加え,2 hかけて室温まで昇温した。飽和塩化アンモニウム水溶液を加え,水層を塩化メチレンで抽出し,無水硫酸ナトリウムで乾燥させ,減圧下で溶媒を留去した後,カラムクロマトグラフィー (へキサン:酢酸エチル=6:4) で精製し,3-フルオロ-2-(4-イソブチルフェニル)-3,3-ビス(フェニルスルホニル)プロパン-1-オールを白色固体(393 mg, 98%)として得た。
1H NMR (200 MHz; CDCl3) δ 0.88 (6H, d, J= 6.6 Hz, CH3), 1.70-1.90 (1H, m, CH), 2.19 (1H, t, J = 6.2 Hz, OH), 2.39 (2H, d, J = 7.2 Hz, CH2), 3.95-4.10 (1H, m, CH), 4.42-4.60 (1H, m, CHH), 4.68-4.84 (1H, m, CHH), 6.90-7.10 (4H, m, Ar), 7.40-7.60 (4H, m, Ar), 7.60-7.80 (6H, m, Ar)
19F NMR (188 MHz; CDCl3)δ129.7 (d, J = 9.2 Hz)
マグネシウムリボン (707 mg, 29.1 mmol, 45.0 eq)のMeOH 5 ml溶液にCH2Br2を1滴,続いてTMSClを1滴加える。0℃に冷却した後,3-フルオロ-2-(4-イソブチルフェニル)-3,3-ビス(フェニルスルホニル)プロパン-1-オール (317 mg, 0.646 mmol, 1.0 eq)のMeOH 5 ml溶液を滴下する。0 ℃で2時間攪拌したのち,水を加えて反応を停止させ,1M HClで水溶液を酸性にする。水層を塩化メチレンで抽出し,無水硫酸ナトリウムで乾燥させ,減圧下で溶媒を留去した後,カラムクロマトグラフィー (へキサン:酢酸エチル=7:3) で精製し,3-フルオロ-2-(4-イソブチルフェニル)プロパン-1-オール(119 mg, 87%)を得た。
1H NMR (200 MHz; CDCl3) δ 0.90 (6H, d, J = 6.6 Hz, CH3), 1.55 (1H, br, OH), 1.74-1.95 (1H, m, CH), 2.44 (2H, d, J = 7.2 Hz, CH2), 3.05-3.30 (1H, dm, J= 19.8 Hz, CHCH2F), 4.69 (2H, dd, J = 5.6, 47.2 Hz, CH2F), 7.00-7.20 (4H, m, Ar)
19F NMR (188 MHz; CDCl3)δ 8.15 (dt, J = 19.8, 47.2 Hz)
MS (ESI-TOF) 210 (M+), 179 (M+ -CH2OH), 160 (M+-CH2OH, F)
Claims (3)
- 下記式(1)で表されるビス(アリールスルホニル)メタンを
(ArSO2) 2 CH2(1)
(Arは置換または無置換フェニル基、ナフチル基を表す)
塩基と処理し、ついで、フッ素化試薬を加えることによる下記式(2)で表されるフルオロビス(アリールスルホニル)メタンの製造法。
(ArSO2) 2 CHF(2)
(Arは前に同じ) - 下記式(2)で表されるフルオロビス(アリールスルホニル)メタン。
(ArSO 2 ) 2 CHF(2)
(Arはフェニル基、2−メチルフェニル基、3−メチルフェニル基、4−メチルフェニル基、2,4,6−トリメチルフェニル基、2−エチルフェニル基、3−エチルフェニル基、4−エチルフェニル基、2,4,6−トリ−iso−プロピルフェニル基、4−t−ブチルフェニル基、2−メトキシフェニル基、3−メトキシフェニル基、4−メトキシフェニル基、3,5−ジ−t−ブチル−4−メトキシフェニル基、2−クロロフェニル基、3−クロロフェニル基、4−クロロフェニル基、2−ブロモフェニル基、3−ブロモフェニル基、4−ブロモフェニル基を表す) - Arがフェニル基である請求項2に記載の式(2)で表されるフルオロビス(フェニルスルホニル)メタン。
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PCT/JP2007/053997 WO2007100074A1 (ja) | 2006-03-03 | 2007-03-02 | 1-フルオロ-1,1-ビス(フェニルスルホニル)メタンおよびその製造法 |
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