JP7210552B2 - リガンド、それを含むオリゴマー化触媒、およびそれを用いたエチレンオリゴマーの製造方法 - Google Patents
リガンド、それを含むオリゴマー化触媒、およびそれを用いたエチレンオリゴマーの製造方法 Download PDFInfo
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- JP7210552B2 JP7210552B2 JP2020512872A JP2020512872A JP7210552B2 JP 7210552 B2 JP7210552 B2 JP 7210552B2 JP 2020512872 A JP2020512872 A JP 2020512872A JP 2020512872 A JP2020512872 A JP 2020512872A JP 7210552 B2 JP7210552 B2 JP 7210552B2
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- Prior art keywords
- ethylene
- ligand
- chemical formula
- catalyst
- producing
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- 239000003446 ligand Substances 0.000 title claims description 108
- 239000003054 catalyst Substances 0.000 title claims description 102
- 238000006384 oligomerization reaction Methods 0.000 title claims description 101
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 79
- 239000005977 Ethylene Substances 0.000 title claims description 79
- 238000004519 manufacturing process Methods 0.000 title claims description 54
- 239000000126 substance Substances 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 45
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 40
- LIKMAJRDDDTEIG-UHFFFAOYSA-N n-hexene Natural products CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 33
- 229910052723 transition metal Inorganic materials 0.000 claims description 33
- 150000003624 transition metals Chemical class 0.000 claims description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 29
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 23
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 19
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052804 chromium Inorganic materials 0.000 claims description 15
- 239000011651 chromium Substances 0.000 claims description 15
- 239000003426 co-catalyst Substances 0.000 claims description 13
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 12
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 11
- -1 aluminum compound Chemical class 0.000 claims description 11
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 10
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 10
- WGECXQBGLLYSFP-UHFFFAOYSA-N 2,3-dimethylpentane Chemical compound CCC(C)C(C)C WGECXQBGLLYSFP-UHFFFAOYSA-N 0.000 claims description 9
- BZHMBWZPUJHVEE-UHFFFAOYSA-N 2,3-dimethylpentane Natural products CC(C)CC(C)C BZHMBWZPUJHVEE-UHFFFAOYSA-N 0.000 claims description 9
- QRMPKOFEUHIBNM-UHFFFAOYSA-N p-dimethylcyclohexane Natural products CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 claims description 9
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 8
- VCJPCEVERINRSG-UHFFFAOYSA-N 1,2,4-trimethylcyclohexane Chemical compound CC1CCC(C)C(C)C1 VCJPCEVERINRSG-UHFFFAOYSA-N 0.000 claims description 6
- FLTJDUOFAQWHDF-UHFFFAOYSA-N 2,2-dimethylhexane Chemical compound CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 claims description 6
- CXOWYJMDMMMMJO-UHFFFAOYSA-N 2,2-dimethylpentane Chemical compound CCCC(C)(C)C CXOWYJMDMMMMJO-UHFFFAOYSA-N 0.000 claims description 6
- HDGQICNBXPAKLR-UHFFFAOYSA-N 2,4-dimethylhexane Chemical compound CCC(C)CC(C)C HDGQICNBXPAKLR-UHFFFAOYSA-N 0.000 claims description 6
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical compound CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 6
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 6
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 6
- RNTWWGNZUXGTAX-UHFFFAOYSA-N 3,4-dimethylhexane Chemical compound CCC(C)C(C)CC RNTWWGNZUXGTAX-UHFFFAOYSA-N 0.000 claims description 6
- VLJXXKKOSFGPHI-UHFFFAOYSA-N 3-methylhexane Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 claims description 6
- CHBAWFGIXDBEBT-UHFFFAOYSA-N 4-methylheptane Chemical compound CCCC(C)CCC CHBAWFGIXDBEBT-UHFFFAOYSA-N 0.000 claims description 6
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Chemical compound CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 6
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 6
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 6
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 6
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 claims description 4
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 claims description 4
- AEXMKKGTQYQZCS-UHFFFAOYSA-N 3,3-dimethylpentane Chemical compound CCC(C)(C)CC AEXMKKGTQYQZCS-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- HYZXMVILOKSUKA-UHFFFAOYSA-K chloro(dimethyl)alumane;dichloro(methyl)alumane Chemical compound C[Al](C)Cl.C[Al](Cl)Cl HYZXMVILOKSUKA-UHFFFAOYSA-K 0.000 claims description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 4
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 4
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- RLPGDEORIPLBNF-UHFFFAOYSA-N 2,3,4-trimethylpentane Chemical compound CC(C)C(C)C(C)C RLPGDEORIPLBNF-UHFFFAOYSA-N 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 claims 1
- 150000001639 boron compounds Chemical class 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 238000005481 NMR spectroscopy Methods 0.000 description 54
- 238000002360 preparation method Methods 0.000 description 31
- 150000001875 compounds Chemical class 0.000 description 27
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 230000003197 catalytic effect Effects 0.000 description 19
- 238000004252 FT/ICR mass spectrometry Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 15
- 238000009826 distribution Methods 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- 239000007858 starting material Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000005829 trimerization reaction Methods 0.000 description 8
- USCSRAJGJYMJFZ-UHFFFAOYSA-N 3-methyl-1-butyne Chemical compound CC(C)C#C USCSRAJGJYMJFZ-UHFFFAOYSA-N 0.000 description 7
- 229910052736 halogen Chemical group 0.000 description 7
- 150000002367 halogens Chemical group 0.000 description 7
- 125000005842 heteroatom Chemical group 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 125000004437 phosphorous atom Chemical group 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 6
- 239000003039 volatile agent Substances 0.000 description 6
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 5
- DLKBXVJWUKIOIH-UHFFFAOYSA-N 3,3-dimethylbut-1-ynyl-(2-fluorophenyl)-phenylphosphane Chemical compound CC(C#CP(C1=CC=CC=C1)C1=C(C=CC=C1)F)(C)C DLKBXVJWUKIOIH-UHFFFAOYSA-N 0.000 description 5
- TUXMHQUNNPZXFF-UHFFFAOYSA-N 3-methylbut-1-ynyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C#CC(C)C)C1=CC=CC=C1 TUXMHQUNNPZXFF-UHFFFAOYSA-N 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- GEGLBMPXRFOXTK-UHFFFAOYSA-N 1-diphenylphosphanylethenyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(=C)P(C=1C=CC=CC=1)C1=CC=CC=C1 GEGLBMPXRFOXTK-UHFFFAOYSA-N 0.000 description 4
- PPWNCLVNXGCGAF-UHFFFAOYSA-N 3,3-dimethylbut-1-yne Chemical compound CC(C)(C)C#C PPWNCLVNXGCGAF-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical compound C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- GHAKVYIBHNIGBD-UHFFFAOYSA-N chloro-(2-fluorophenyl)-phenylphosphane Chemical compound FC1=CC=CC=C1P(Cl)C1=CC=CC=C1 GHAKVYIBHNIGBD-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- JGWSLZVKNREDQJ-UHFFFAOYSA-N (2-fluorophenyl)-phenyl-(2-phenylethynyl)phosphane Chemical compound FC1=C(C=CC=C1)P(C#CC1=CC=CC=C1)C1=CC=CC=C1 JGWSLZVKNREDQJ-UHFFFAOYSA-N 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 3
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 3
- 125000005865 C2-C10alkynyl group Chemical group 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 125000003282 alkyl amino group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- YVQFNLHYHUESPN-UHFFFAOYSA-N (2-fluorophenyl)-hex-1-ynyl-phenylphosphane Chemical compound FC1=C(C=CC=C1)P(C1=CC=CC=C1)C#CCCCC YVQFNLHYHUESPN-UHFFFAOYSA-N 0.000 description 2
- ZURBOVRAOKXJOW-UHFFFAOYSA-N (2-fluorophenyl)-phenylphosphane Chemical compound FC1=CC=CC=C1PC1=CC=CC=C1 ZURBOVRAOKXJOW-UHFFFAOYSA-N 0.000 description 2
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CGHIBGNXEGJPQZ-UHFFFAOYSA-N 1-hexyne Chemical compound CCCCC#C CGHIBGNXEGJPQZ-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- 229910010082 LiAlH Inorganic materials 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000005091 alkenylcarbonylamino group Chemical group 0.000 description 2
- 125000005193 alkenylcarbonyloxy group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000003806 alkyl carbonyl amino group Chemical group 0.000 description 2
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 2
- 125000005103 alkyl silyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 125000005088 alkynylcarbonylamino group Chemical group 0.000 description 2
- 125000005198 alkynylcarbonyloxy group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- CYOMBOLDXZUMBU-UHFFFAOYSA-K chromium(3+);oxolane;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1.C1CCOC1.C1CCOC1 CYOMBOLDXZUMBU-UHFFFAOYSA-K 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- SVDKUDWYQQFRAZ-UHFFFAOYSA-N hex-1-ynyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C#CCCCC)C1=CC=CC=C1 SVDKUDWYQQFRAZ-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
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- WBKDDMYJLXVBNI-UHFFFAOYSA-K chromium(3+);2-ethylhexanoate Chemical compound [Cr+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O WBKDDMYJLXVBNI-UHFFFAOYSA-K 0.000 description 1
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- 238000007865 diluting Methods 0.000 description 1
- PPFOMDCEYDBUAE-UHFFFAOYSA-N diphenyl(2-phenylethynyl)phosphane Chemical compound C1=CC=CC=C1C#CP(C=1C=CC=CC=1)C1=CC=CC=C1 PPFOMDCEYDBUAE-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- ALSOCDGAZNNNME-UHFFFAOYSA-N ethene;hex-1-ene Chemical compound C=C.CCCCC=C ALSOCDGAZNNNME-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
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- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
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- 125000004438 haloalkoxy group Chemical group 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- DYFFAVRFJWYYQO-UHFFFAOYSA-O methyl(diphenyl)azanium Chemical compound C=1C=CC=CC=1[NH+](C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-O 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ITMSSZATZARZCA-UHFFFAOYSA-N n-ethyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CC)C1=CC=CC=C1 ITMSSZATZARZCA-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 125000004001 thioalkyl group Chemical group 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- UKHQRARQNZOXRL-UHFFFAOYSA-N trimethyltin Chemical compound C[SnH](C)C UKHQRARQNZOXRL-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
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-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
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
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- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
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- C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
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- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
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Description
R1はヒドロカルビルであり;
R2およびR3は、それぞれ独立して、ヒドロカルビルであり;
pおよびqは、それぞれ独立して、0~5の整数であり;
mおよびnは、それぞれ独立して、0~5の整数であって、1≦m+n≦10である。
R1は、置換されているかまたは置換されていないヒドロカルビルであり;
R2およびR3は、それぞれ独立して、ヒドロカルビルであり;
pおよびqは、それぞれ独立して、0~5の整数であり;
mおよびnは、それぞれ独立して、0~5の整数であって、1≦m+n≦10である。
R44およびR45は、それぞれ独立して、水素、ヒドロカルビル、置換されたヒドロカルビル、ヘテロヒドロカルビル、または置換されたヘテロヒドロカルビルである。
N,N-ジエチルアミノクロロ(フェニル)ホスフィンは、公知の文献(M.Oliana et.al.,J.Org.Chem.,2006,p.2472-2479)を参考して製造した。
1H NMR (500 MHz, C6D6) δ 7.74 (m, 2H, aromatics), 7.10 (m, 2H, aromatics), 7.03 (m, 1H, aromatics), 2.85 (m, 4H, -CH2-), 0.79 (m, 6H, -CH3).
窒素雰囲気下で乾燥されたフラスコに、1-ブロモ-2-フルオロベンゼン(7.0g、40mmol)を無水THF(30mL)に希釈させた後、-78℃に温度を下げ、1.6Mのn-ブチルリチウム(25.0mL、40mmol、アルドリッチ製)をゆっくりと添加した。低温を維持させながら混合物を1時間以上反応させた後、上記で得たN,N-ジエチルアミノクロロ(フェニル)ホスフィン(8.195g、38mmol)をゆっくりと添加した後、2時間以上反応させた。混合物の反応温度を常温に上げ、揮発性物質を減圧除去した後、ヘキサン:ジクロロメタン(1:1v/v)溶液で希釈してからシリカ濾過することで、無色透明の液体として標題の化合物を得た(8.967g、85.7%)。
1H NMR (500 MHz, C6D6) δ 7.45 (m, 2H, aromatics), 7.34 (m, 1H, aromatics), 7.14 (m, 3H, aromatics), 6.94 (m, 3H, aromatics), 3.00 (m, 4H, -CH2N), 0.83 (t, 6H, -CH3); 13C NMR (600 MHz, CDCl3) δ 164.3, 138.8, 132.6, 131.2, 130.3, 128.0, 123.9, 115.0, 44.6, 14.4; 19F NMR (500 MHz, C6D6) δ -103.7; 31P NMR (500 MHz, C6D6) δ 49.7.
窒素雰囲気下で乾燥されたフラスコに、上記で得たN,N-ジエチル-1-(2-フルオロフェニル)-1-フェニルホスフィンアミン(8.967g、32.6mmol)を無水ジエチルエテール(70mL)に希釈させた後、1Mの塩化水素/ジエチルエテール(68.4mL)をゆっくりと添加した。混合物を1時間以上反応させた後、活性アルミナで濾過することで、無色透明の液体として標題の化合物を得た(7.377g、94.9%)。
1H NMR (500 MHz, C6D6) δ 7.51 (m, 3H, aromatics), 6.97 (m, 3H, aromatics), 6.80 (m, 1H, aromatics), 6.73 (m, 1H, aromatics), 6.58 (m, 1H, aromatics); 13C NMR (600 MHz, CDCl3) δ 164.4, 137.3, 132.5-128.9, 124.6, 115.4; 19F NMR (500 MHz, C6D6) δ -104.8; 31P NMR (500 MHz, C6D6) δ 71.4.
1H NMR (500 MHz, C6D6) δ 7.37 (m, 2H, aromatics), 7.11 (m, 1H, aromatics), 6.97 (m, 3H, aromatics), 6.80 (m, 1H, aromatics), 6.68 (m, 1H, aromatics), 5.51-5.07 (d, 1H, -P).
窒素雰囲気下で乾燥されたフラスコに、3,3-ジメチル-1-ブチン(0.2875g、3.5mmol、アルドリッチ製)を無水THF(6mL)に希釈させた後、-78℃に温度を下げ、1.6Mのn-ブチルリチウム(1.75mL、2.8mmol、アルドリッチ製)をゆっくりと添加した。低温を維持させながら混合物を1時間以上反応させた後、前記製造例Aで得たクロロ(2-フルオロフェニル)フェニルホスフィン(0.5345g、2.24mmol)をゆっくりと添加した後、2時間以上反応させた。混合物の反応温度を常温に上げ、揮発性物質を減圧除去した後、ヘキサン溶液で希釈し、セライト濾過してから乾燥することで、黄色の固体として標題の化合物を得た(0.6214g、97.6%)。
1H NMR (500 MHz, CDCl3) δ 7.68 (m, 3H, aromatics), 7.27 (m, 4H, aromatics), 7.13 (m, 1H, aromatics), 6.96 (m, 1H, aromatics); 13C NMR (600 MHz, CDCl3) δ 165.1, 135.6, 133.1, 132.4, 130.9, 128.4, 124.4, 119.5, 115.2, 72.3, 30.8, 28.8; 19F NMR (500 MHz, CDCl3) δ -105.5; 31P NMR (500 MHz, CDCl3) δ -47.0; FT-ICR MS: m/z [M+H]+ calcd for C18H19FP+: 285.1208; found: 285.1206.
窒素雰囲気下で乾燥されたフラスコに、上記で製造された(3,3-ジメチル-1-ブチニル)(2-フルオロフェニル)フェニルホスフィン(0.1422g、0.5mmol)、ヨウ化第一銅(0.0048g、5mol%)、炭酸セシウム(0.0163g、10mol%)をジメチルホルムアミド(1mL)に希釈させた後、ジフェニルホスフィン(0.1117g、0.6mmol)をゆっくりと添加し、温度を90℃に昇温させて3時間反応させた。混合物をn-ヘキサン:酢酸エチル(9:1v/v)の溶液でシリカカラム精製することで、無色透明なオイルとしてリガンド(1)を得た(0.2236g、95.1%)。
1H NMR (500 MHz, CDCl3) δ 7.70 (m, 1H, aromatics), 7.65 (m, 1H, aromatics), 7.46 (m, 4H, aromatics), 7.29 (m, 4H, aromatics), 7.21 (m, 4H, aromatics), 7.21-6.99 (m, 4H, aromatics), 6.85 (m, 1H, aromatics), 1.28 (s, 9H, -CH3); 13C NMR (600 MHz, CDCl3) δ 165.2, 163.1, 138.9, 135.8, 134.1, 133.0, 128.6, 126.2, 123.8, 119.6, 115.2; 31P NMR (500 MHz, CDCl3) δ -11.0, -39.0; FT-ICR MS: m/z [M・]+ calcd for C30H29FP2: 470.1729; found: 470.1718.
出発物質として、3,3-ジメチル-1-ブチンの代わりに3-メチル-1-ブチンを使用したことを除き、リガンド(1)の製造方法と同様に反応を行い、標題の化合物を得た(80.93%)。
1H NMR (500 MHz, CDCl3) δ 7.62 (m, 3H, aromatics), 7.28 (m, 4H, aromatics), 7.09 (m, 1H, aromatics), 6.93 (m, 1H, aromatics), 2.77 (q, 1H, -CH-), 1.26 (d, 2H, -CH3); 13C NMR (600 MHz, CDCl3) δ 165.1, 135.4, 133.2, 131.1, 128.9, 124.3, 116.8, 115.2, 73.2, 22.7, 22.0; 19F NMR (500 MHz, CDCl3) δ -105.5; 31P NMR (500 MHz, CDCl3) δ -46.5; FT-ICR MS: m/z [M+H]+ calcd for C17H17FP+: 271.1052; found: 271.1049.
出発物質として、(3,3-ジメチル-1-ブチニル)(2-フルオロフェニル)フェニルホスフィンの代わりに上記で得た(2-フルオロフェニル)(3-メチル-1-ブチン)(フェニル)ホスフィンを使用したことを除き、リガンド(1)の製造方法と同様に反応を行い、リガンド(2)を得た(90.54%)。
1H NMR (500 MHz, CDCl3) δ 7.30 (m, 18H, aromatics), 7.05 (m, 1H, aromatics), 6.98 (m, 1H, =CH-), 2.50 (m, 1H, -CH-), 0.88 (t, 6H, -CH3); 13C NMR (600 MHz, CDCl3) δ 165.3, 162.2, 138.9, 136.3, 134.8, 133.6, 132.2, 130.7, 128.4, 127.8, 126.3, 124.1, 115.6, 33.5, 24.1; 19F NMR (500 MHz, CDCl3) δ -102.6; 31P NMR (500 MHz, CDCl3) δ -4.9, -35.3; FT-ICR MS: m/z [M・]+ calcd for C29H27FP2: 456.1572; found: 456.1567.
窒素雰囲気下で乾燥されたフラスコに、3-メチル-1-ブチン(3.406g、50mmol)を無水ジエチルエテール(40mL)に希釈させた後、-78℃に温度を下げ、1.6Mのn-ブチルリチウム(26.5mL、42.5mmol、アルドリッチ製)をゆっくりと添加した。低温を維持させながら混合物を1時間以上反応させた後、クロロジフェニルホスフィン(8.44g、38.2mmol)をゆっくりと添加し、2時間以上反応させた。混合物の反応温度を常温に上げ、揮発性物質を減圧除去した後、ヘキサン溶液で希釈し、セライト濾過してから乾燥することで、無色液体の標題の化合物を得た(8.9g、92.23%)。
1H NMR (500 MHz, CDCl3) δ 7.59 (m, 4H, aromatics), 7.30 (m, 6H, aromatics), 2.77 (m, 1H, -CH-), 1.26 (d, 6H, -CH3); 13C NMR (600 MHz, CDCl3) δ 137.1, 132.3, 128.6, 115.6, 74.7, 22.7, 21.9; 31P NMR (500 MHz, CDCl3) δ -33.8; FT-ICR MS: m/z [M+H]+ calcd for C17H18P+: 253.1146; found: 253.1143.
窒素雰囲気下で乾燥されたフラスコに、上記で製造された(3-メチル-1-ブチニル)ジフェニルホスフィン(0.1261g、0.5mmol)、ヨウ化第一銅(0.0048g、5mol%)、炭酸セシウム(0.0163g、10mol%)をジメチルホルムアミド(1mL)に希釈させた後、前記製造例Bで製造された(2-フルオロフェニル)(フェニル)ホスフィン(0.1225g、0.6mmol)をゆっくりと添加し、温度を90℃に昇温させて3時間反応させた。混合物をn-ヘキサン:酢酸エチル(9:1v/v)の溶液でシリカカラム精製することで、無色透明なオイルとしてリガンド(3)を得た(0.2282g、100.0%)。
1H NMR (500 MHz, CDCl3) δ 7.24 (m, 17H, aromatics), 7.05 (m, 2H, aromatics), 6.95 (s, 1H, =CH-), 2.45 (s, 1H, -CH-), 0.99 (t, 3H, -CH3), 0.83 (t, 3H, -CH3); 13C NMR (600 MHz, CDCl3) δ 165.3, 161.6, 139.5, 134.3, 133.4, 132.8, 130.5, 128.3, 124.0, 115.2, 33.8, 24.1, 23.6; 19F NMR (500 MHz, CDCl3) δ -101.6; 31P NMR (500 MHz, CDCl3) δ -16.4, -26.9; FT-ICR MS: m/z [M・]+ calcd for C29H27FP2: 456.1572; found: 456.1570.
1H NMR (500 MHz, CDCl3) δ 7.30-6.99 (m, 15H, aromatics), 7.10 (m, 3H, aromatics), 6.99 (s, 1H, =CH-), 2.47 (s, 1H, -CH-), 1.02 (t, 3H, -CH3), 0.86 (t, 3H, -CH3); 13C NMR (600 MHz, CDCl3) δ 165.3, 163.4, 161.5, 138.6, 134.8, 133.5, 132.2, 130.8, 128.5, 125.8, 115.3, 33.9, 24.1; 19F NMR (500 MHz, CDCl3) δ -101.6, -102.6; 31P NMR (500 MHz, CDCl3) δ -17.0, -36.0; FT-ICR MS: m/z [M・]+ calcd for C29H26F2P2: 474.1478; found: 474.1471.
出発物質として、3,3-ジメチル-1-ブチンの代わりに1-ヘキシンを使用したことを除き、リガンド(1)の製造方法と同様に反応を行い、標題の化合物を得た(79.45%)。
1H NMR (500 MHz, CDCl3) δ 7.69-7.62 (m, 3H, aromatics), 7.32 (m, 4H, aromatics), 7.15 (t, 1H, aromatics), 6.97 (m, 1H, aromatics), 2.43 (t, 2H, -CH2-), 1.62 (q, 2H, -CH2-), 1.45 (q, 2H, -CH2-), 0.93 (t, 3H, -CH3); 13C NMR (600 MHz, CDCl3) δ 165.1, 135.4, 133.3, 132.5, 131.1, 129.0, 124.1, 115.1, 111.6, 74.1, 30.5, 21.9, 20.0, 13.5; 19F NMR (500 MHz, CDCl3) δ -105.5; 31P NMR (500 MHz, CDCl3) δ -45.7; FT-ICR MS: m/z [M+H]+ calcd for C18H19FP+: 285.1208; found: 285.1206.
出発物質として、(3,3-ジメチル-1-ブチニル)(2-フルオロフェニル)フェニルホスフィンの代わりに(2-フルオロフェニル)(1-ヘキシニル)(フェニル)ホスフィンを使用したことを除き、リガンド(1)の製造方法と同様に反応を行い、リガンド(5)を得た(51.01%)。
1H NMR (500 MHz, CDCl3) δ 7.29-7.18 (m, 16H, aromatics), 7.10 (s, 1H, =CH-), 7.02 (m, 1H, aromatics), 6.95 (m, 1H, aromatics), 2.12 (t, 2H, -CH2-), 1.24 (m, 2H, -CH2-), 1.10 (m, 2H, -CH2-), 0.69 (t, 3H, -CH3); 13C NMR (600 MHz, CDCl3) δ 163.5, 156.5, 138.5, 136.3, 134.6, 133.2, 132.1, 130.6, 128.5, 127.9, 125.9, 115.5, 36.5, 30.9, 22.3, 13.7; 19F NMR (500 MHz, CDCl3) δ -102.5; 31P NMR (500 MHz, CDCl3) δ -7.9, -35.1; FT-ICR MS: m/z [M・]+ calcd for C30H29FP2: 470.1729; found: 470.1729.
出発物質として、3-メチル-1-ブチンの代わりに1-ヘキシンを使用したことを除き、リガンド(3)の製造方法と同様に反応を行い、標題の化合物を得た(8.6g、84.42%)。
1H NMR (500 MHz, CDCl3) δ 7.60 (t, 4H, aromatics), 7.30 (m, 6H, aromatics), 2.44 (t, 2H, -CH2-), 1.60 (q, 2H, -CH2-), 1.46 (m, 2H, -CH2-), 0.90 (t, 3H, -CH3); 13C NMR (600 MHz, CDCl3) δ 137.0, 132.2, 128.4, 110.4, 75.6, 30.5, 21.9, 20.0, 13.5; 31P NMR (500 MHz, CDCl3) δ -33.0; FT-ICR MS: m/z [M+H]+ calcd for C18H20P+: 267.1303; found: 267.1300.
出発物質として、(3-メチル-1-ブチニル)ジフェニルホスフィンの代わりに上記で製造された1-ヘキシニルジフェニルホスフィンを使用したことを除き、リガンド(3)の製造方法と同様に反応を行い、リガンド(6)を得た(0.1469g、62.43%)。
1H NMR (500 MHz, CDCl3) δ 7.25 (m, 16H, aromatics), 6.99 (m, 4H, aromatics, =CH-), 2.13 (m, 2H, -CH2-), 1.26 (m, 2H, -CH2-), 1.10 (m, 2H, -CH2-), 0.70 (t, 3H, -CH3); 13C NMR (600 MHz, CDCl3) δ 165.2, 155.5, 140.1, 139.3, 134.9, 134.0, 133.3, 130.5, 128.2, 124.0, 115.3, 37.0, 30.9, 22.4, 13.7; 19F NMR (500 MHz, CDCl3) δ -102.3; 31P NMR (500 MHz, CDCl3) δ -19.2, -26.2; FT-ICR MS: m/z [M・]+ calcd for C30H29FP2: 470.1729; found: 470.1721.
出発物質として、3,3-ジメチル-1-ブチンの代わりにエチニルベンゼンを使用したことを除き、リガンド(1)の製造方法と同様に反応を行い、標題の化合物を得た(70.95%)。
1H NMR (500 MHz, CDCl3) δ 7.72 (m, 3H, aromatics), 7.54 (m, 2H, aromatic), 7.36 (m, 7H, aromatics), 7.17 (m, 1H, aromatics), 7.00 (m, 1H, aromatics); 13C NMR (600 MHz, CDCl3) δ 165.1, 134.6, 132.8, 131.8, 129.2, 128.2, 124.5, 122.5, 115.4, 108.6, 84.2; 19F NMR (500 MHz, CDCl3) δ -105.1; 31P NMR (500 MHz, CDCl3) δ -45.9; FT-ICR MS: m/z [M+H]+ calcd for C20H15FP+: 305.0895; found: 305.0894.
出発物質として、(3,3-ジメチル-1-ブチニル)(2-フルオロフェニル)フェニルホスフィンの代わりに(2-フルオロフェニル)(フェニル)(フェニルエチニル)ホスフィンを使用したことを除き、リガンド(1)の製造方法と同様に反応を行い、リガンド(7)を得た(97.13%)。
1H NMR (500 MHz, CDCl3) δ 7.40-6.90 (m, 25H, aromatics, =CH-); 13C NMR (600 MHz, CDCl3) δ 165.2, 155.7, 145.9, 142.3, 139.1, 135.8, 133.3, 128.3, 126.8, 115.6; 19F NMR (500 MHz, CDCl3) δ -102.3; 31P NMR (500 MHz, CDCl3) δ -4.9, -25.9; FT-ICR MS: m/z [M・]+ calcd for C32H25FP2: 490.1416; found: 490.1418.
出発物質として、3-メチル-1-ブチンの代わりにエチニルベンゼンを使用したことを除き、リガンド(3)の製造方法と同様に反応を行い、標題の化合物を得た(7.865g、92.29%)。
1H NMR (500 MHz, CDCl3) δ 7.68 (m, 4H, aromatics), 7.54 (m, 2H, aromatic), 7.35 (m, 9H, aromatics); 13C NMR (600 MHz, CDCl3) δ 136.3, 132.6, 131.8, 128.9, 128.5, 122.7, 107.7, 85.8; 31P NMR (500 MHz, CDCl3) δ -33.4; FT-ICR MS: m/z [M+H]+ calcd for C20H16P+: 287.0990; found: 287.0987.
出発物質として、(3-メチル-1-ブチニル)ジフェニルホスフィンの代わりに上記で製造されたジフェニル(フェニルエチニル)ホスフィンを使用したことを除き、リガンド(3)の製造方法と同様に反応を行い、リガンド(8)を得た(0.2113g、86.16%)。
1H NMR (500 MHz, CDCl3) δ 7.40-6.79 (m, 25H, aromatics, =CH-); 13C NMR (600 MHz, CDCl3) δ 165.3, 154.8, 145.3, 142.1, 138.5, 133.4, 132.5, 128.3, 123.8, 114.9; 19F NMR (500 MHz, CDCl3) δ -102.2; 31P NMR (500 MHz, CDCl3) δ -25.9; FT-ICR MS: m/z [M・]+ calcd for C32H25FP2: 490.1416; found: 490.1415.
1H NMR (500 MHz, CDCl3) δ 7.42-6.77 (m, 24H, aromatics); 13C NMR (600 MHz, CDCl3) δ 165.4, 154.9, 143.9, 142.1, 137.9, 133.5, 132.5, 130.5, 128.5, 127.9, 125.1, 124.2, 115.7, 124.2, 115.7, 114.8; 19F NMR (500 MHz, CDCl3) δ -102.2; 31P NMR (500 MHz, CDCl3) δ -16.8, -35.0; FT-ICR MS: m/z [M・]+ calcd for C32H24F2P2: 508.1321; found: 508.1322.
[実施例1]
三塩化クロムトリステトラヒドロフラン(CrCl3(THF)3)(237mg、0.63μmol)をジクロロメタン(2.0mL)に溶かした後、リガンド(1)(製造例1)(298mg、0.63μmol)をジクロロメタン(1.0mL)に溶かして徐々に加えた。反応物を1時間さらに撹拌した後、0.45μmのシリンジフィルター(syringe filter)を用いて濾過した。濾過された液体から揮発物を真空で除去することで、乾燥された青色の固体(390mg、97.9%)を得た。これを、オリゴマー化触媒Iと命名した。
リガンド(1)の代わりにリガンド(2)を使用し、前記実施例1と同様の方法により触媒IIを製造した後、前記実施例1と同様の方法によりオリゴマー化反応を行った。本実施例の生成物の分布を下記表1にまとめた。
リガンド(1)の代わりにリガンド(3)を使用し、前記実施例1と同様の方法により触媒IIIを製造した後、前記実施例1と同様の方法によりオリゴマー化反応を行った。本実施例の生成物の分布を下記表1にまとめた。
リガンド(1)の代わりにリガンド(4)を使用し、前記実施例1と同様の方法により触媒IVを製造した後、前記実施例1と同様の方法によりオリゴマー化反応を行った。本実施例の生成物の分布を下記表1にまとめた。
リガンド(1)の代わりにリガンド(5)を使用し、前記実施例1と同様の方法により触媒Vを製造した後、前記実施例1と同様の方法によりオリゴマー化反応を行った。本実施例の生成物の分布を下記表1にまとめた。
リガンド(1)の代わりにリガンド(6)を使用し、前記実施例1と同様の方法により触媒VIを製造した後、前記実施例1と同様の方法によりオリゴマー化反応を行った。本実施例の生成物の分布を下記表1にまとめた。
リガンド(1)の代わりにリガンド(7)を使用し、前記実施例1と同様の方法により触媒VIIを製造した後、前記実施例1と同様の方法によりオリゴマー化反応を行った。本実施例の生成物の分布を下記表1にまとめた。
リガンド(1)の代わりにリガンド(8)を使用し、前記実施例1と同様の方法により触媒VIIIを製造した後、前記実施例1と同様の方法によりオリゴマー化反応を行った。本実施例の生成物の分布を下記表1にまとめた。
リガンド(1)の代わりにリガンド(9)を使用し、前記実施例1と同様の方法により触媒IXを製造した後、前記実施例1と同様の方法によりオリゴマー化反応を行った。本実施例の生成物の分布を下記表1にまとめた。
リガンド(1)の代わりに下記構造のリガンド(A)を使用し、前記実施例1と同様の方法により触媒Aを製造した後、前記実施例1と同様の方法によりオリゴマー化反応を行った。本比較例の生成物の分布を下記表1にまとめた。
リガンド(1)の代わりに下記構造のリガンド(B)を使用し、前記実施例1と同様の方法により触媒Bを製造した後、前記実施例1と同様の方法によりオリゴマー化反応を行った。本比較例の生成物の分布を下記表1にまとめた。
リガンド(1)の代わりに下記構造のリガンド(C)を使用し、前記実施例1と同様の方法により触媒Cを製造した後、前記実施例1と同様の方法によりオリゴマー化反応を行った。本比較例の生成物の分布を下記表1にまとめた。
リガンド(1)の代わりに下記構造のリガンド(D)を使用し、前記実施例1と同様の方法により触媒Dを製造した後、前記実施例1と同様の方法によりオリゴマー化反応を行った。本比較例の生成物の分布を下記表1にまとめた。
Claims (16)
- 前記R1は、C1-C7アルキルまたはC6-C12アリールである、請求項3に記載のリガンド。
- 請求項1から4の何れか一項に記載のリガンドと、
遷移金属と、
を含む、エチレンオリゴマー化触媒。 - 単核または二核性である、請求項5に記載のエチレンオリゴマー化触媒。
- 前記遷移金属は、4族、5族、または6族の遷移金属である、請求項5に記載のエチレンオリゴマー化触媒。
- 前記遷移金属は、クロム、モリブデン、タングステン、チタン、タンタル、バナジウム、またはジルコニウムである、請求項7に記載のエチレンオリゴマー化触媒。
- 前記遷移金属はクロムである、請求項8に記載のエチレンオリゴマー化触媒。
- 請求項5に記載のエチレンオリゴマー化触媒を含む触媒組成物と、エチレンとを接触させるステップを含む、エチレンオリゴマーの製造方法。
- 前記触媒組成物は、助触媒をさらに含む、請求項10に記載のエチレンオリゴマーの製造方法。
- 前記助触媒は、有機アルミニウム化合物、有機アルミノキサン、有機ホウ素化合物、有機塩、またはこれらの混合物である、請求項11に記載のエチレンオリゴマーの製造方法。
- 前記助触媒は、メチルアルミノキサン(MAO)、変性メチルアルミノキサン(mMAO)、エチルアルミノキサン(EAO)、テトライソブチルアルミノキサン(TIBAO)、イソブチルアルミノキサン(IBAO)、トリメチルアルミニウム(TMA)、トリエチルアルミニウム(TEA)、トリイソブチルアルミニウム(TIBA)、トリ-n-オクチルアルミニウム、メチルアルミニウムジクロリド、エチルアルミニウムジクロリド、ジメチルアルミニウムクロリド、ジエチルアルミニウムクロリド、アルミニウムイソプロポキシド、エチルアルミニウムセスキクロリド、およびメチルアルミニウムセスキクロリドからなる群から選択される1つまたは2つ以上の混合物である、請求項12に記載のエチレンオリゴマーの製造方法。
- 前記エチレンオリゴマーは、1-ヘキセンまたは1-オクテンである、請求項13に記載のエチレンオリゴマーの製造方法。
- 脂肪族炭化水素を反応溶媒として用いる、請求項10に記載のエチレンオリゴマーの製造方法。
- 前記脂肪族炭化水素は、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、テトラデカン、2,2-ジメチルペンタン、2,3-ジメチルペンタン、2,4-ジメチルペンタン、3,3-ジメチルペンタン、2,2,4-トリメチルペンタン、2,3,4-トリメチルペンタン、2-メチルヘキサン、3-メチルヘキサン、2,2-ジメチルヘキサン、2,4-ジメチルヘキサン、2,5-ジメチルヘキサン、3,4-ジメチルヘキサン、2-メチルヘプタン、4-メチルヘプタン、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、イソプロピルシクロヘキサン、1,4-ジメチルシクロヘキサン、および1,2,4-トリメチルシクロヘキサンから選択される1種以上である、請求項15に記載のエチレンオリゴマーの製造方法。
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