JP4491667B2 - Process for producing substituted indenyl compounds - Google Patents
Process for producing substituted indenyl compounds Download PDFInfo
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- JP4491667B2 JP4491667B2 JP2004055360A JP2004055360A JP4491667B2 JP 4491667 B2 JP4491667 B2 JP 4491667B2 JP 2004055360 A JP2004055360 A JP 2004055360A JP 2004055360 A JP2004055360 A JP 2004055360A JP 4491667 B2 JP4491667 B2 JP 4491667B2
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- 238000000034 method Methods 0.000 title claims description 11
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 title description 3
- -1 indenyl compound Chemical class 0.000 claims description 56
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000012038 nucleophile Substances 0.000 claims description 22
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 15
- 239000012190 activator Substances 0.000 claims description 15
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000005104 aryl silyl group Chemical group 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 150000002902 organometallic compounds Chemical class 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 150000003623 transition metal compounds Chemical class 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 239000002841 Lewis acid Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 31
- 239000010936 titanium Substances 0.000 description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 229910052719 titanium Inorganic materials 0.000 description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 16
- VMRZYTKLQVKYKQ-UHFFFAOYSA-N lithium;1,9-dihydrofluoren-1-ide Chemical compound [Li+].C1=C[C-]=C2CC3=CC=CC=C3C2=C1 VMRZYTKLQVKYKQ-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 11
- 230000004913 activation Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012434 nucleophilic reagent Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 description 3
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 3
- LVKCSZQWLOVUGB-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].C[CH-]C LVKCSZQWLOVUGB-UHFFFAOYSA-M 0.000 description 3
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BULLHRADHZGONG-UHFFFAOYSA-N [cyclopenta-2,4-dien-1-ylidene(phenyl)methyl]benzene Chemical compound C1=CC=CC1=C(C=1C=CC=CC=1)C1=CC=CC=C1 BULLHRADHZGONG-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 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
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004915 dibutylamino group Chemical group C(CCC)N(CCCC)* 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 2
- 125000004914 dipropylamino group Chemical group C(CC)N(CCC)* 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 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 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- DWWZPYPYUFXZTL-UHFFFAOYSA-N lithium;2h-inden-2-ide Chemical compound [Li+].C1=CC=C2[CH-]C=CC2=C1 DWWZPYPYUFXZTL-UHFFFAOYSA-N 0.000 description 2
- DBKDYYFPDRPMPE-UHFFFAOYSA-N lithium;cyclopenta-1,3-diene Chemical compound [Li+].C=1C=C[CH-]C=1 DBKDYYFPDRPMPE-UHFFFAOYSA-N 0.000 description 2
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HANWWAAUFXCNBS-UHFFFAOYSA-N 2,6,6-tris(2-methylpropyl)oxaluminane Chemical compound CC(C)C[Al]1CCCC(CC(C)C)(CC(C)C)O1 HANWWAAUFXCNBS-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- GRWPYGBKJYICOO-UHFFFAOYSA-N 2-methylpropan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] GRWPYGBKJYICOO-UHFFFAOYSA-N 0.000 description 1
- JLLYLQLDYORLBB-UHFFFAOYSA-N 5-bromo-n-methylthiophene-2-sulfonamide Chemical compound CNS(=O)(=O)C1=CC=C(Br)S1 JLLYLQLDYORLBB-UHFFFAOYSA-N 0.000 description 1
- AMKGKYQBASDDJB-UHFFFAOYSA-N 9$l^{2}-borabicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1[B]2 AMKGKYQBASDDJB-UHFFFAOYSA-N 0.000 description 1
- FEJUGLKDZJDVFY-UHFFFAOYSA-N 9-borabicyclo[3.3.1]nonane Substances C1CCC2CCCC1B2 FEJUGLKDZJDVFY-UHFFFAOYSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DPSOUODMTOWXTB-UHFFFAOYSA-N CC1=C(C)C(C)([Ti])C(C)=C1C Chemical compound CC1=C(C)C(C)([Ti])C(C)=C1C DPSOUODMTOWXTB-UHFFFAOYSA-N 0.000 description 1
- FLAKGKCBSLMHQU-UHFFFAOYSA-N CC[Mg] Chemical compound CC[Mg] FLAKGKCBSLMHQU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 0 Cc1c(*)c(*)c(*)c(*)c1* Chemical compound Cc1c(*)c(*)c(*)c(*)c1* 0.000 description 1
- YJTIDPYXOKIQOA-KHAVMBNRSA-N ClC1=CCCC2=C1CC=C2C(C1c2ccccc2C/C=C\C=C/C1)(c1ccccc1)c1ccccc1 Chemical compound ClC1=CCCC2=C1CC=C2C(C1c2ccccc2C/C=C\C=C/C1)(c1ccccc1)c1ccccc1 YJTIDPYXOKIQOA-KHAVMBNRSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 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
- 125000006267 biphenyl group Chemical group 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- OEMXOWUECXMNKI-UHFFFAOYSA-M dimethylazanide;titanium(4+);chloride Chemical compound [Cl-].CN(C)[Ti+](N(C)C)N(C)C OEMXOWUECXMNKI-UHFFFAOYSA-M 0.000 description 1
- BYXDUORQHWFHKS-UHFFFAOYSA-L dimethylazanide;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].CN(C)[Ti+2]N(C)C BYXDUORQHWFHKS-UHFFFAOYSA-L 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 125000003250 fulvenyl group Chemical group C1(=CC=CC1=C)* 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052735 hafnium Chemical group 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- UKZCGMDMXDLAGZ-UHFFFAOYSA-M magnesium;2-methylpropane;bromide Chemical compound [Mg+2].[Br-].C[C-](C)C UKZCGMDMXDLAGZ-UHFFFAOYSA-M 0.000 description 1
- CQRPUKWAZPZXTO-UHFFFAOYSA-M magnesium;2-methylpropane;chloride Chemical compound [Mg+2].[Cl-].C[C-](C)C CQRPUKWAZPZXTO-UHFFFAOYSA-M 0.000 description 1
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 1
- LWLPYZUDBNFNAH-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CCC[CH2-] LWLPYZUDBNFNAH-UHFFFAOYSA-M 0.000 description 1
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- DQEUYIQDSMINEY-UHFFFAOYSA-M magnesium;prop-1-ene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C=C DQEUYIQDSMINEY-UHFFFAOYSA-M 0.000 description 1
- CYSFUFRXDOAOMP-UHFFFAOYSA-M magnesium;prop-1-ene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C=C CYSFUFRXDOAOMP-UHFFFAOYSA-M 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
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 125000000286 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
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- MQFGFMVFKVUOOF-UHFFFAOYSA-N potassium;1,9-dihydrofluoren-1-ide Chemical compound [K+].C1=C[C-]=C2CC3=CC=CC=C3C2=C1 MQFGFMVFKVUOOF-UHFFFAOYSA-N 0.000 description 1
- UOKNXAWCFOSJMN-UHFFFAOYSA-N potassium;1h-inden-1-ide Chemical compound [K+].C1=CC=C2[CH-]C=CC2=C1 UOKNXAWCFOSJMN-UHFFFAOYSA-N 0.000 description 1
- IZWIPIIVPHXLTN-UHFFFAOYSA-N potassium;cyclopenta-1,3-diene Chemical compound [K+].C1C=CC=[C-]1 IZWIPIIVPHXLTN-UHFFFAOYSA-N 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- DOAKMWHAYCOJJN-UHFFFAOYSA-N sodium;1,9-dihydrofluoren-1-ide Chemical compound [Na+].C1=C[C-]=C2CC3=CC=CC=C3C2=C1 DOAKMWHAYCOJJN-UHFFFAOYSA-N 0.000 description 1
- UDBORWKCIDLNIG-UHFFFAOYSA-N sodium;1h-inden-1-ide Chemical compound [Na+].C1=CC=C2[CH-]C=CC2=C1 UDBORWKCIDLNIG-UHFFFAOYSA-N 0.000 description 1
- OHUVHDUNQKJDKW-UHFFFAOYSA-N sodium;cyclopenta-1,3-diene Chemical compound [Na+].C=1C=C[CH-]C=1 OHUVHDUNQKJDKW-UHFFFAOYSA-N 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 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
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- DPNUIZVZBWBCPB-UHFFFAOYSA-J titanium(4+);tetraphenoxide Chemical compound [Ti+4].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 DPNUIZVZBWBCPB-UHFFFAOYSA-J 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- BPKXQSLAVGBZEM-UHFFFAOYSA-N tris[3,5-bis(trifluoromethyl)phenyl]borane Chemical compound FC(F)(F)C1=CC(C(F)(F)F)=CC(B(C=2C=C(C=C(C=2)C(F)(F)F)C(F)(F)F)C=2C=C(C=C(C=2)C(F)(F)F)C(F)(F)F)=C1 BPKXQSLAVGBZEM-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、求核試薬に対して反応不活性なジフェニルフルベンに、特定の活性化剤を加えて活性化させ、ジフェニルベンゾフルベンと求核試薬とを反応させることで、遷移金属錯体の配位子として有用な置換インデニル化合物を製造する方法に関する。 The present invention relates to coordination of a transition metal complex by reacting diphenylbenzofulvene with a nucleophile by adding a specific activator to diphenylfulvene which is inactive to the nucleophile and activating it. The present invention relates to a method for producing a substituted indenyl compound useful as a child.
フルベン化合物にアルキルリチウムなどの求核試薬を反応させると、求核試薬がフルベンの６位に攻撃して、フルベンと求核試薬の付加化合物が得られる［式（１）］（例えば、特許文献１、非特許文献１参照）。 When a nucleophilic reagent such as alkyllithium is reacted with a fulvene compound, the nucleophilic reagent attacks the 6-position of the fulvene to obtain an addition compound of the fulvene and the nucleophilic reagent [formula (1)] (for example, patent document) 1 and non-patent document 1).
フルベン化合物の代わりにベンゾフルベン化合物を用いた場合、例えば、求核試薬としてフルオレニルリチウムを用いると、８，８−ジメチルベンゾフルベンや８−メチル−８−フェニルベンゾフルベンとフルオレニルリチウムとの反応は進行し、対応する付加化合物が生成するが、８，８−ジフェニルベンゾフルベンとフルオレニルリチウムとの反応は進行しないことが知られている［式（２）〜（４）］（例えば、非特許文献２参照）。 When a benzofulvene compound is used instead of a fulvene compound, for example, when fluorenyl lithium is used as a nucleophile, 8,8-dimethylbenzofulvene, 8-methyl-8-phenylbenzofulvene, fluorenyllithium, It is known that the reaction of (1) proceeds and the corresponding addition compound is produced, but the reaction of 8,8-diphenylbenzofulvene and fluorenyllithium does not proceed [formulas (2) to (4)] ( For example, refer nonpatent literature 2).
ところがこの方法は、ジフェニルベンゾフルベンとクロムヘキサカルボニルを反応させるのに、高い温度と長い反応時間が必要であるため、工業的に用いることは困難である。そのため、ジフェニルベンゾフルベンとフルオレニルリチウムなどの求核試薬を工業的に使用可能な条件下で、反応させることが可能な新規な製造方法が求められている。 However, since this method requires a high temperature and a long reaction time to react diphenylbenzofulvene with chromium hexacarbonyl, it is difficult to use it industrially. Therefore, there is a demand for a novel production method capable of reacting nucleophiles such as diphenylbenzofulvene and fluorenyllithium under industrially usable conditions.
本発明は、工業的に利用可能な条件下で、ジフェニルベンゾフルベンと求核試薬との反応を進行させ、遷移金属錯体の配位子として有用な置換インデニル化合物を製造する方法を提供するものである。 The present invention provides a method for producing a substituted indenyl compound useful as a ligand of a transition metal complex by advancing the reaction between diphenylbenzofulvene and a nucleophile under industrially available conditions. is there.
本発明者らは、上記課題を達成するため鋭意検討の結果、ジフェニルベンゾフルベンに活性化剤を加えた後、求核試薬を反応させることで、置換インデニル化合物の製造が可能であることを見出し、本発明を完成するに到った。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a substituted indenyl compound can be produced by reacting a nucleophile after adding an activator to diphenylbenzofulvene. The present invention has been completed.
以下に本発明を詳細に説明する。 The present invention is described in detail below.
本発明は、ジフェニルベンゾフルベンまたはその誘導体に活性化剤を加えて活性化させた後、活性化したジフェニルベンゾフルベンと求核試薬とを反応させて、置換インデニル化合物を製造する方法である。 The present invention is a method for producing a substituted indenyl compound by reacting an activated diphenylbenzofulvene with a nucleophile after activating the diphenylbenzofulvene or a derivative thereof by adding an activator.
本発明で用いるジフェニルベンゾフルベンまたはその誘導体とは、下記一般式（５）で表すことが可能な化合物である。 Diphenylbenzofulvene or a derivative thereof used in the present invention is a compound that can be represented by the following general formula (5).
一般式（５）中のＰｈは、一般式（６）で表すことが可能な置換基を示す。 Ph in the general formula (5) represents a substituent that can be represented by the general formula (6).
一般式（５）中のＰｈの具体例として、フェニル基、メチルフェニル基、ジメチルフェニル基、トリメチルフェニル基、テトラメチルフェニル基、ペンタメチルフェニル基、２，６−ジメチルフェニル基、２，６−ジイソプロピルフェニル基、２，６−ジｔｅｒｔ−ブチルフェニル基、２，６−ジｔｅｒｔ−ブチル−４−メチルフェニル基、ビフェニル基、トリメチルシリルフェニル基、ジメチルアミノフェニル基、メトキシフェニル基、フェノキシフェニル基、フルオロフェニル基、ニトロフェニル基などを挙げることができる。 Specific examples of Ph in the general formula (5) include phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, tetramethylphenyl group, pentamethylphenyl group, 2,6-dimethylphenyl group, 2,6- Diisopropylphenyl group, 2,6-ditert-butylphenyl group, 2,6-ditert-butyl-4-methylphenyl group, biphenyl group, trimethylsilylphenyl group, dimethylaminophenyl group, methoxyphenyl group, phenoxyphenyl group, Examples thereof include a fluorophenyl group and a nitrophenyl group.
一般式（５）で表されるジフェニルベンゾフルベンまたはその誘導体の具体的な化合物としては、次の化合物を挙げることができるが、これらに限定されるものではない。 Specific examples of the diphenylbenzofulvene represented by the general formula (5) or a derivative thereof include, but are not limited to, the following compounds.
ジフェニルベンゾフルベンまたはその誘導体の活性化剤として用いる化合物の具体的な例としては、ジメチル亜鉛、ジエチル亜鉛、塩化アルミニウム、トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム、クロロジエチルアルミニウム、ジクロロエチルアルミニウム、メチルアルミノキサン、エチルアルミノキサン，トリイソブチルアルミノキサン、トリス（ペンタフルオロフェニル）ボラン、トリス［３，５−ジ（トリフルオロメチル）フェニル］ボラン、トリフルオロボランジエチルエーテル錯体、トリフェニルボラン、ジボラン、９−ＢＢＮ、臭化ニッケル、塩化ニッケル、塩化パラジウム、塩化鉄、四塩化チタン、チタンテトライソプロポキシド、チタンテトラメトキシド、チタンテトラエトキシド、チタンテトライソブトキシド、チタンテトラｔｅｒｔ−ブトキシド、チタンテトラブトキシド、チタンテトラプロポキシド、チタンテトラオクタデシルオキシド、チタンジイソプロポキシジクロリド、チタンジメトキシジクロリド、チタンジエトキシジクロリド、チタンジイソブトキシジクロリド、チタンジブトキシジクロリド、チタンジプロポキシジクロリド、チタンジオクタデシルオキシジクロリド、チタントリイソプロポキシクロリド、チタントリメトキシクロリド、チタントリエトキシクロリド、チタントリイソブトキシクロリド、チタントリブトキシクロリド、チタントリプロポキシクロリド、チタントリオクタデシルオキシクロリド、チタンテトラフェノキシド、チタンテトラ（２，６−ジｔｅｒｔ−ブチルフェノキシド）、チタンテトラ（ジメチルアミド）、チタンテトラ（エチルアミド）、チタントリ（ジメチルアミド）クロリド、チタンジ（ジメチルアミド）ジクロリド、チタノセンジクロリド、チタノセンジメトキシド、チタノセンジエトキシド、チタノセンジｔｅｒｔ−ブトキシド、チタノセンジフェノキシド、シクロペンタジエニルチタントリクロイド、シクロペンタジエニルチタンジクロロジメトキシド、シクロペンタジエニルチタンクロロジメトキシド、シクロペンタジエニルチタントリ（ジメチルアミド）、シクロペンタジエニルチタンジ（ジメチルアミド）クロリド、ペンタメチルシクロペンタジエニルチタントリクロイド、ペンタメチルシクロペンタジエニルチタンジクロロメトキシド、ペンタメチルシクロペンタジエニルチタンジクロロ（ジメチルアミド）、または上記チタン原子をジルコニウム原子もしくはハフニウム原子に代えた化合物を挙げることができる。 Specific examples of compounds used as activators of diphenylbenzofulvene or its derivatives include dimethylzinc, diethylzinc, aluminum chloride, trimethylaluminum, triethylaluminum, triisobutylaluminum, chlorodiethylaluminum, dichloroethylaluminum, methylaluminoxane , Ethylaluminoxane, triisobutylaluminoxane, tris (pentafluorophenyl) borane, tris [3,5-di (trifluoromethyl) phenyl] borane, trifluoroborane diethyl ether complex, triphenylborane, diborane, 9-BBN, odor Nickel chloride, nickel chloride, palladium chloride, iron chloride, titanium tetrachloride, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetraethoxide, Tan tetraisobutoxide, titanium tetra tert-butoxide, titanium tetrabutoxide, titanium tetrapropoxide, titanium tetraoctadecyl oxide, titanium diisopropoxy dichloride, titanium dimethoxy dichloride, titanium diethoxy dichloride, titanium diisobutoxy dichloride, titanium dibutoxy dichloride, titanium Dipropoxy dichloride, Titanium dioctadecyloxy dichloride, Titanium triisopropoxy chloride, Titanium trimethoxy chloride, Titanium triethoxy chloride, Titanium triisobutoxy chloride, Titanium tributoxy chloride, Titanium tripropoxycyclochloride, Titanium trioctadecyl oxychloride, Titanium tetra Phenoxide, titanium tetra (2,6-ditert-butylphenoxide), Tetra (dimethylamide), titanium tetra (ethylamide), titanium tri (dimethylamide) chloride, titanium di (dimethylamide) dichloride, titanocene dichloride, titanocene dimethoxide, titanocene diethoxide, titanocene di tert-butoxide, titanocene diphenoxide, cyclopentadiene Enyl titanium tricloid, cyclopentadienyl titanium dichlorodimethoxide, cyclopentadienyl titanium chlorodimethoxide, cyclopentadienyl titanium tri (dimethylamide), cyclopentadienyl titanium di (dimethylamide) chloride, pentamethylcyclopenta Dienyl titanium tricloid, pentamethylcyclopentadienyl titanium dichloromethoxide, pentamethylcyclopentadienyl titanium dichloro Tilamide), or a compound in which the titanium atom is replaced with a zirconium atom or a hafnium atom.
本発明において、ルイス酸性化合物と同時に用いる有機金属化合物は、ルイス酸性化合物と反応または相互作用することで、ジフェニルベンゾフルベンの活性化を高める化合物であれば特に制限はないが、アルキルリチウムやアルキルマグネシウム化合物であることが好ましい。 In the present invention, the organometallic compound used simultaneously with the Lewis acidic compound is not particularly limited as long as it is a compound that reacts with or interacts with the Lewis acidic compound to enhance the activation of diphenylbenzofulvene. A compound is preferred.
本発明で用いる有機金属化合物の具体的な例としては、メチルリチウム、ｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム、ｔｅｒｔ−ブチルリチウム、フェニルリチウム、メチルマグネシウムクロリド、メチルマグネシウムブロミド、エチルマグネシウムクロリド、エチルマグネシウムブロミド、イソプロピルマグネシウムクロリド、イソプロピルマグネシウムブロミド、ブチルマグネシウムクロリド、ブチルマグネシウムブロミド、ｔｅｒｔ−ブチルマグネシウムクロリド、ｔｅｒｔ−ブチルマグネシウムブロミド、フェニルマグネシウムクロリド、フェニルマグネシウムブロミド、アリルマグネシウムクロリド、アリルマグネシウムブロミドなどを挙げることができる。 Specific examples of the organometallic compound used in the present invention include methyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, phenyl lithium, methyl magnesium chloride, methyl magnesium bromide, ethyl magnesium chloride, ethyl magnesium. Examples include bromide, isopropylmagnesium chloride, isopropylmagnesium bromide, butylmagnesium chloride, butylmagnesium bromide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, allylmagnesium chloride, and allylmagnesium bromide. it can.
本発明において、ジフェニルベンゾフルベンとの反応を行なう求核試薬とは、求核試薬としての性質を有するものであれば特に制限はないが、金属化されたシクロペンタジエニル化合物、インデニル化合物、フルオレニル化合物、またはその化合物に置換基を有するものであることが好ましい。 In the present invention, the nucleophilic reagent that reacts with diphenylbenzofulvene is not particularly limited as long as it has properties as a nucleophilic reagent, but is metallized cyclopentadienyl compound, indenyl compound, fluorenyl. It is preferable that it is a compound or that which has a substituent in the compound.
本発明において、求核試薬として用いることが可能な化合物の具体例として、シクロペンタジエニルリチウム、シクロペンタジエニルナトリウム、シクロペンタジエニルカリウム、インデニルリチウム、インデニルナトリウム、インデニルカリウム、フルオレニルリチウム、フルオレニルナトリウム、フルオレニルカリウムなどを挙げることができるが、これらに限定されるものではない。 In the present invention, specific examples of compounds that can be used as nucleophiles include cyclopentadienyl lithium, cyclopentadienyl sodium, cyclopentadienyl potassium, indenyl lithium, indenyl sodium, indenyl potassium, Examples include, but are not limited to, oleenyl lithium, fluorenyl sodium, and fluorenyl potassium.
本発明で用いるジフェニルベンゾフルベンまたはその誘導体と活性化剤の比に制限はなく、ジフェニルベンゾフルベンまたはその誘導体を活性化するのに必要な量を用いればよいが、ジフェニルベンゾフルベンまたはその誘導体と活性化剤の比が１：０．０１〜１：１００の間で用いられることが好ましい。活性化剤と有機金属化合物の比に関しても特に制限はないが、活性化剤：有機金属化合物の比が１：１〜１：１００の間で用いられることが好ましい。 There is no limitation on the ratio of diphenylbenzofulvene or a derivative thereof to an activating agent used in the present invention, and an amount necessary to activate diphenylbenzofulvene or a derivative thereof may be used. It is preferable that the ratio of the agent is used between 1: 0.01 and 1: 100. The ratio of the activator to the organometallic compound is not particularly limited, but it is preferable that the activator: organometallic compound ratio is 1: 1 to 1: 100.
活性化したジフェニルベンゾフルベンまたはその誘導体と求核試薬との反応を行なう際の、活性化したジフェニルベンゾフルベンまたはその誘導体と求核試薬の比についても特に制限はないが、活性化したジフェニルベンゾフルベンまたはその誘導体と求核試薬の比が１：０．０１〜１：１００の間であることが好ましい。 There is no particular limitation on the ratio of the activated diphenylbenzofulvene or derivative thereof to the nucleophile in the reaction of the activated diphenylbenzofulvene or derivative thereof with the nucleophile, but the activated diphenylbenzofulvene is not limited. Alternatively, the ratio of the derivative to the nucleophile is preferably between 1: 0.01 and 1: 100.
ジフェニルベンゾフルベンまたはその誘導体と活性化剤を反応させる方法に関して、ジフェニルベンゾフルベンまたはその誘導体が活性化される反応条件であるならば特に制限はなく、ジフェニルベンゾフルベンまたはその誘導体に活性化剤を加えてもよいし、活性化剤にジフェニルベンゾフルベンまたはその誘導体を加えてもよい。 The method for reacting diphenylbenzofulvene or a derivative thereof with an activator is not particularly limited as long as the reaction conditions are such that diphenylbenzofulvene or a derivative thereof is activated, and an activator is added to diphenylbenzofulvene or a derivative thereof. Alternatively, diphenylbenzofulvene or a derivative thereof may be added to the activator.
活性化反応は、不活性ガス雰囲気下で行なうことが好ましい。 The activation reaction is preferably performed in an inert gas atmosphere.
活性化に用いる溶媒は、活性化剤を失活させる溶媒でなければ特に制限はなく、好ましくは、脱水テトラヒドロフラン、脱水ジエチルエーテル、脱水ヘキサン、脱水ヘプタン、脱水トルエンなどを挙げることができる。 The solvent used for the activation is not particularly limited as long as it does not deactivate the activator, and preferable examples include dehydrated tetrahydrofuran, dehydrated diethyl ether, dehydrated hexane, dehydrated heptane, and dehydrated toluene.
活性化させる温度、時間、圧力に関しても特に制限はなく、一般的な有機合成反応で用いられている条件の範囲内で活性化を行なうことが可能であるが、特に活性化時の具体的な条件として、活性化温度は−１００〜２００℃の間が好ましく、活性化時間は１秒〜１週間の間であることが好ましい。活性化圧力は、減圧下でも加圧下でも可能である。 There are no particular restrictions on the temperature, time, and pressure for activation, and activation can be performed within the range of conditions used in general organic synthesis reactions. As conditions, the activation temperature is preferably between −100 and 200 ° C., and the activation time is preferably between 1 second and 1 week. The activation pressure can be reduced or increased.
ジフェニルベンゾフルベンまたはその誘導体の活性化時に、複数の種類の活性化剤を同時に使用することも可能である。 When activating diphenylbenzofulvene or a derivative thereof, a plurality of types of activators can be used simultaneously.
活性化したジフェニルベンゾフルベンまたはその誘導体と求核試薬との反応方法については特に制限はなく、ジフェニルベンゾフルベンまたはその誘導体と活性化剤とを反応させて、活性化したジフェニルベンゾフルベンまたはその誘導体を単離精製した後、求核試薬との反応に用いてもよいし、ジフェニルベンゾフルベンまたはその誘導体と活性化剤とを反応させた後、そのまま求核試薬との反応を行ってもよい。 There is no particular limitation on the reaction method between the activated diphenylbenzofulvene or its derivative and the nucleophile. The activated diphenylbenzofulvene or its derivative is reacted with diphenylbenzofulvene or its derivative and an activator. After isolation and purification, it may be used for a reaction with a nucleophile, or after reacting diphenylbenzofulvene or a derivative thereof with an activating agent, a reaction with a nucleophile may be performed as it is.
本発明の反応方法を用いて得られる置換インデニル化合物は、一般式（５）で表されるジフェニルベンゾフルベンまたはその誘導体と求核試薬とが反応することで得られる化合物であるならば特に制限はない。 The substituted indenyl compound obtained by using the reaction method of the present invention is not particularly limited as long as it is a compound obtained by reacting diphenylbenzofulvene represented by the general formula (5) or a derivative thereof with a nucleophile. Absent.
置換インデニル化合物は、本反応により得られる化合物中に、インデニル環に相当する環構造が構築されていれば、求核試薬が一般式（５）中のいずれの位置で反応した化合物であってもかまわないが、求核試薬が一般式（５）で表されるジフェニルベンゾフルベンまたはその誘導体中の１位、２位、７位、８位の炭素と反応した化合物であることが好ましい。また、ジフェニルフルベンまたはその誘導体と求核試薬が反応した後は、反応系中に存在する他の反応試剤とさらなる反応が進行してもかまわない。 The substituted indenyl compound is a compound obtained by reacting the nucleophile at any position in the general formula (5) as long as the ring structure corresponding to the indenyl ring is constructed in the compound obtained by this reaction. However, it is preferable that the nucleophile is a compound that has reacted with the 1-position, 2-position, 7-position, and 8-position carbon in the diphenylbenzofulvene represented by the general formula (5) or a derivative thereof. Further, after the reaction of diphenylfulvene or a derivative thereof with a nucleophile, further reaction may proceed with other reaction reagents present in the reaction system.
本発明で得られる置換インデニル化合物の具体的な例として、以下の化合物を挙げることができる。 Specific examples of the substituted indenyl compound obtained in the present invention include the following compounds.
得られる生成物は、一般的な有機合成反応で用いられる方法で単離精製することが可能であり、具体的には、反応生成物が溶ける溶媒で抽出した後、溶媒を留去することで生成物の単離が可能であり、カラムクロマトグラフィー、再結晶、蒸留、昇華などの方法により生成物の精製をすることが可能である。 The resulting product can be isolated and purified by a method used in a general organic synthesis reaction. Specifically, after extraction with a solvent in which the reaction product is soluble, the solvent is distilled off. The product can be isolated, and the product can be purified by methods such as column chromatography, recrystallization, distillation, and sublimation.
本発明の方法を用いることにより、通常の条件では反応が進行しないジフェニルベンゾフルベンと求核試薬との反応を、工業的に利用可能な条件で進行させることが可能となる。 By using the method of the present invention, the reaction between diphenylbenzofulvene and a nucleophile, which does not proceed under normal conditions, can be allowed to proceed under industrially available conditions.
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれら実施例に限定されるものではない。反応はすべて不活性ガス雰囲気下で行った。また、反応に用いた溶媒は、すべて予め公知の方法で精製、乾燥、脱酸素を行ったものを用いた。１Ｈ−ＮＭＲは、日本電子製 ＧＳＸ−２７０を用いた。ＨＰＬＣ測定は、東ソー製 ＳＣ−８０１０装置を用い、カラムにＴＳＫ−ＧＥｌ Ｓｉｌｉｃａ−６０を用いた。溶離液としてヘキサン：塩化メチレン＝５：１を用い、１．０ｍＬ／分の流量で測定を行った。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. All reactions were carried out under an inert gas atmosphere. Moreover, the solvent used for reaction used the thing which refine | purified, dried and deoxygenated by the well-known method previously. 1 H-NMR used GSX-270 manufactured by JEOL. For HPLC measurement, SC-8010 manufactured by Tosoh Corporation was used, and TSK-GEl Silica-60 was used for the column. Measurement was performed at a flow rate of 1.0 mL / min using hexane: methylene chloride = 5: 1 as an eluent.
実施例１
１００ｍＬのシュレンク管中、３−クロロジフェニルベンゾフルベン（２．００ｇ，６．３５ｍｍｏｌ）のＴＨＦ溶液（４０ｍＬ）に、Ｔｉ（Ｏ（ｉ−Ｐｒ））４（５．６７ｍＬ，１９．５ｍｍｏｌ）を加え、室温で１時間撹拌した後、−７８℃に冷却して、フルオレニルリチウム（６．３５ｍｍｏｌ）のＴＨＦ溶液（４０ｍＬ）をゆっくり加えた。終夜撹拌しながら室温まで昇温した後、さらに２４時間反応を行った。水を加えて反応を停止させた後、１Ｎ塩酸を加え、塩化メチレンで抽出した。溶媒を留去した後、得られた残さをシリカゲルカラムで精製した。ヘキサンで未反応の３−クロロジフェニルベンゾフルベンを除いた後、ヘキサン：塩化メチレン＝１：１の混合溶媒から淡黄色の固体（０．２ｇ）を得た。この淡黄色固体のＨＰＬＣ測定を行ったところ、８．８分に保持時間を持つ化合物と１３．９分に保持時間を持つ化合物の混合物であることがわかった。
Example 1
In a 100 mL Schlenk tube, Ti (O (i-Pr)) 4 (5.67 mL, 19.5 mmol) was added to a THF solution (40 mL) of 3-chlorodiphenylbenzofulvene (2.00 g, 6.35 mmol). The mixture was stirred at room temperature for 1 hour, cooled to −78 ° C., and a THF solution (40 mL) of fluorenyl lithium (6.35 mmol) was slowly added. After raising the temperature to room temperature with stirring overnight, the reaction was further carried out for 24 hours. Water was added to stop the reaction, 1N hydrochloric acid was added, and the mixture was extracted with methylene chloride. After the solvent was distilled off, the obtained residue was purified with a silica gel column. After removing unreacted 3-chlorodiphenylbenzofulvene with hexane, a pale yellow solid (0.2 g) was obtained from a mixed solvent of hexane: methylene chloride = 1: 1. When this light yellow solid was subjected to HPLC measurement, it was found to be a mixture of a compound having a retention time of 8.8 minutes and a compound having a retention time of 13.9 minutes.
実施例２
１００ｍＬのシュレンク管中、３−クロロジフェニルベンゾフルベン（０．９４ｇ，３．０ｍｍｏｌ）のＴＨＦ溶液（２０ｍＬ）に、Ｔｉ（Ｏ（ｉ−Ｐｒ））４（０．８９ｍＬ，３．０ｍｍｏｌ）を加え、−７８℃に冷却した後、ｉ−ＰｒＭｇＢｒのＴＨＦ溶液（１Ｍ，６．０ｍＬ，６．０ｍｍｏｌ）をゆっくり加えた。−５０℃に昇温して３０分間撹拌した後、再度、−７８℃に冷却し、フルオレニルリチウム（３．０ｍｍｏｌ）のＴＨＦ溶液（２０ｍＬ）をゆっくり加えた。終夜撹拌しながら室温まで昇温した後、さらに２４時間反応を行った。水を加えて反応を停止させた後、１Ｎ塩酸を加え、塩化メチレンで抽出した。溶媒を留去した後、得られた残さをシリカゲルカラムで精製した。ヘキサンで未反応の３−クロロジフェニルベンゾフルベンを流出させた後、ヘキサン：塩化メチレン＝５：１の混合溶媒により淡黄色の固体（０．４１ｇ）と無色の固体（０．１０ｇ）を得た。それぞれの化合物のＨＰＬＣ測定を行ったところ、淡黄色固体の保持時間は１３．９分、無色固体の保持時間は８．８分で、実施例１で得られた化合物の保持時間と一致した。
Example 2
In a 100 mL Schlenk tube, Ti (O (i-Pr)) 4 (0.89 mL, 3.0 mmol) was added to a THF solution (20 mL) of 3-chlorodiphenylbenzofulvene (0.94 g, 3.0 mmol). After cooling to −78 ° C., a THF solution of i-PrMgBr (1M, 6.0 mL, 6.0 mmol) was slowly added. After raising the temperature to −50 ° C. and stirring for 30 minutes, the mixture was again cooled to −78 ° C., and a THF solution (20 mL) of fluorenyl lithium (3.0 mmol) was slowly added. After raising the temperature to room temperature with stirring overnight, the reaction was further carried out for 24 hours. Water was added to stop the reaction, 1N hydrochloric acid was added, and the mixture was extracted with methylene chloride. After the solvent was distilled off, the obtained residue was purified with a silica gel column. After flowing out unreacted 3-chlorodiphenylbenzofulvene with hexane, a light yellow solid (0.41 g) and a colorless solid (0.10 g) were obtained with a mixed solvent of hexane: methylene chloride = 5: 1. . When the HPLC measurement of each compound was performed, the retention time of the pale yellow solid was 13.9 minutes, and the retention time of the colorless solid was 8.8 minutes, which was consistent with the retention time of the compound obtained in Example 1.
淡黄色の固体
１Ｈ−ＮＭＲ（ＣＤＣｌ３，２７０ＭＨｚ）：δ＝７．８９（ｄ），７．７２（ｄ），７．４５（ｔ），６．９−７．３（ｍ），６．７９（ｔ），６．６４（ｄ），６．５４（ｄ），６．３−６．４（ｍ），５．１６（ｓ），５．１１（ｓ），４．４９（ｓ），３．２９（ｓ），３．１７（ｄ），２．９５（ｄ）．
この化合物の構造を決めるために、単結晶を作製し（ヘキサン：塩化メチレン＝１０：１）、Ｘ線結晶構造解析を行った結果、得られた化合物は、フルオレンが３−クロロジフェニルベンゾフルベンの２位で結合し、１位でもう一つの３−クロロジフェニルベンゾフルベンが結合した以下の構造を持つ置換インデニル化合物であった。
Pale yellow solid
1 H-NMR (CDCl 3 , 270 MHz): δ = 7.89 (d), 7.72 (d), 7.45 (t), 6.9-7.3 (m), 6.79 (t ), 6.64 (d), 6.54 (d), 6.3-6.4 (m), 5.16 (s), 5.11 (s), 4.49 (s), 3. 29 (s), 3.17 (d), 2.95 (d).
In order to determine the structure of this compound, a single crystal was prepared (hexane: methylene chloride = 10: 1), and X-ray crystal structure analysis was performed. As a result, the obtained compound was fluorene of 3-chlorodiphenylbenzofulvene. It was a substituted indenyl compound having the following structure bonded at the 2-position and bonded with another 3-chlorodiphenylbenzofulvene at the 1-position.
ＥＩ−Ｍａｓｓ（７０ｅＶ） ｍ／ｚ ４７９
１Ｈ−ＮＭＲ（ＣＤＣｌ３，２７０ＭＨｚ）：δ＝６．６−７．５（ｍ），５．５（ｂｒｓ），３．７（ｂｒｓ）．
この化合物は、フルオレンが３−クロロジフェニルベンゾフルベンの８位で結合した以下の構造を持つ置換インデニル化合物であった。
1 H-NMR (CDCl 3 , 270 MHz): δ = 6.6-7.5 (m), 5.5 (brs), 3.7 (brs).
This compound was a substituted indenyl compound having the following structure in which fluorene was bonded at the 8-position of 3-chlorodiphenylbenzofulvene.
実施例３
実施例２で用いたＴｉ（Ｏ（ｉ−Ｐｒ））４の代わりに、Ｔｉ（ＯＭｅ）４を用いた以外は同様の方法で反応を行ったところ、実施例２と同様の化合物が得られた（ＨＰＬＣ分析により決定）。
Example 3
When the reaction was carried out in the same manner except that Ti (OMe) 4 was used instead of Ti (O (i-Pr)) 4 used in Example 2, the same compound as Example 2 was obtained. (Determined by HPLC analysis).
実施例４
実施例２で用いたＴｉ（Ｏ（ｉ−Ｐｒ））４の代わりに、Ｔｉ（ＯＢｕ）４を用いた以外は同様の方法で反応を行ったところ、実施例２と同様の化合物が得られた（ＨＰＬＣ分析により決定）。
Example 4
When the reaction was carried out in the same manner except that Ti (OBu) 4 was used instead of Ti (O (i-Pr)) 4 used in Example 2, the same compound as Example 2 was obtained. (Determined by HPLC analysis).
実施例５
実施例２で用いた３−クロロジフェニルベンゾフルベンの代わりに、ジフェニルベンゾフルベンを用いた以外は同様の方法で、ジフェニルベンゾフルベンとフルオレニルリチウムの反応を行ったところ、実施例２と類似の２種類の化合物が得られた。
Example 5
The reaction of diphenylbenzofulvene and fluorenyllithium was carried out in the same manner except that diphenylbenzofulvene was used instead of 3-chlorodiphenylbenzofulvene used in Example 2, and similar to that of Example 2. Two types of compounds were obtained.
比較例１
実施例１で用いたＴｉ（Ｏ（ｉ−Ｐｒ））４を用いなかった以外は同様の方法で、３−クロロジフェニルベンゾフルベンとフルオレニルリチウムの反応を行ったが、反応は進行しなかった。
Comparative Example 1
The reaction of 3-chlorodiphenylbenzofulvene and fluorenyllithium was carried out in the same manner except that Ti (O (i-Pr)) 4 used in Example 1 was not used, but the reaction did not proceed. It was.
比較例２
実施例２で用いたＴｉ（Ｏ（ｉ−Ｐｒ））４とｉ−ＰｒＭｇＢｒを用いなかった以外は同様の方法で、３−クロロジフェニルベンゾフルベンとフルオレニルリチウムの反応を行ったが、反応は進行しなかった。
Comparative Example 2
The reaction of 3-chlorodiphenylbenzofulvene and fluorenyllithium was carried out in the same manner except that Ti (O (i-Pr)) 4 and i-PrMgBr used in Example 2 were not used. Did not progress.
Claims (3)
一般式（５）中のＰｈは、一般式（６）で表すことが可能な置換基を示す。
Ph in the general formula (5) represents a substituent that can be represented by the general formula (6).
一般式（５）中のＰｈは、一般式（６）で表すことが可能な置換基を示す。
Ph in the general formula (5) represents a substituent that can be represented by the general formula (6).
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