JP2007508131A - 燐を含む触媒組成物及びそれを利用したヒドロホルミル化の方法 - Google Patents
燐を含む触媒組成物及びそれを利用したヒドロホルミル化の方法 Download PDFInfo
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- JP2007508131A JP2007508131A JP2006532069A JP2006532069A JP2007508131A JP 2007508131 A JP2007508131 A JP 2007508131A JP 2006532069 A JP2006532069 A JP 2006532069A JP 2006532069 A JP2006532069 A JP 2006532069A JP 2007508131 A JP2007508131 A JP 2007508131A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 9
- 239000011574 phosphorus Substances 0.000 title claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 239000003446 ligand Substances 0.000 claims abstract description 72
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 23
- 150000003624 transition metals Chemical class 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- -1 phosphorus compound Chemical class 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 48
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 38
- 239000010948 rhodium Substances 0.000 claims description 32
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 18
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 229910052703 rhodium Inorganic materials 0.000 claims description 15
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 125000001246 bromo group Chemical group Br* 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000005129 aryl carbonyl group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims description 4
- 150000001925 cycloalkenes Chemical class 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000002560 nitrile group Chemical group 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 125000005106 triarylsilyl group Chemical group 0.000 claims description 4
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 125000004665 trialkylsilyl group Chemical group 0.000 claims description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- HDSUWQLDQNJISD-UHFFFAOYSA-N iridium;triphenylphosphane Chemical compound [Ir].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HDSUWQLDQNJISD-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 claims 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims 1
- FXESDMUBDCACQJ-UHFFFAOYSA-N C1=CNC(=C1)OP(N)O Chemical compound C1=CNC(=C1)OP(N)O FXESDMUBDCACQJ-UHFFFAOYSA-N 0.000 claims 1
- JPENYKGUOGPWBI-UHFFFAOYSA-N bis(oxomethylidene)iridium Chemical compound O=C=[Ir]=C=O JPENYKGUOGPWBI-UHFFFAOYSA-N 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 23
- 150000001299 aldehydes Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000008300 phosphoramidites Chemical class 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- GPMUMMNTAZMBEC-UHFFFAOYSA-N bis(oxomethylidene)rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-] GPMUMMNTAZMBEC-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 0 CC*(CC(C*)OC)N Chemical compound CC*(CC(C*)OC)N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ULUNQYODBKLBOE-UHFFFAOYSA-N 2-(1h-pyrrol-2-yl)-1h-pyrrole Chemical compound C1=CNC(C=2NC=CC=2)=C1 ULUNQYODBKLBOE-UHFFFAOYSA-N 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- HSKNRVWCHUCANG-UHFFFAOYSA-N pyrrol-1-ylphosphane Chemical compound PN1C=CC=C1 HSKNRVWCHUCANG-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
- B01J31/186—Mono- or diamide derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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Abstract
遷移金属触媒にリガンドとして単座及び二座の燐化合物を組合わせた触媒組成物及び触媒組成物をオレフィン系化合物、一酸化炭素及び水素の混合気体と共に攪拌しつつ、加温、加圧してアルデヒドを製造するオレフィン系化合物のヒドロホルミル化の方法である。これにより、二座配位子を単独で使用した場合の、イソ−アルデヒドに対するノルマル−アルデヒドの選択性(N/I選択性)を維持しつつ、触媒活性を向上させて触媒系を安定化させうる。
Description
硫黄(S)である。
R8、R9、R10、及びR11は、それぞれ、水素、炭素原子数1ないし20のアルキル基、炭素原子数6ないし20のアリール基、トリアリールシリル基、トリアルキルシリル基、カルボアルコキシ基、カルボアリールオキシ基、アリールオキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アミド基、ハロゲン原子、ニトリル基であり、この時、カルボアルコキシ基、−CO2RのRは、炭素原子数1ないし20のアルキル基、または炭素原子数6ないし20のアリール基であり、
R8は、メチル、メトキシ、またはt−ブチル基、R9は、水素、R10は、メチル、メトキシ、またはt−ブチル、及びR11は、メチルまたは水素であることが好ましい。
R12、R13、R14、R15、R16、及びR17は、それぞれ、水素、炭素原子数1ないし20のアルキル基、炭素原子数6ないし20のアリール基、トリアリールシリル基、トリアルキルシリル基、カルボアルコキシ基、カルボアリールオキシ基、アリールオキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アミド基、ハロゲン原子、ニトリル基であり、この時、カルボアルコキシ基、−CO2RのRは、炭素原子数1ないし20のアルキル基、炭素原子数6ないし20のアリール基である。
以下、下記の実施例により本発明を更に詳細に説明するが、本発明の範囲が実施例に限定されるものではない。
触媒であるRh(AcAc)(CO)2 10.0mg(37.8mmol)、GC分析の内標物質であるヘキサデカン 0.2mL及び下記表1に記載されたロジウムに対するモル比により、二座配位子であるBPO−P(Pyl)2及び単座配位子であるTPPOをトルエンに溶解させて、全体溶液を100mLにした後に、Auto Clave社製のハイスループットスクリーン(HTS)の反応器に添加した。前記反応器に、プロペン:CO:H2のモル比が1:1:1である反応気体を注入して、反応器内の圧力を6barに維持した後、85℃で攪拌しつつ2.5時間反応させた。
前記反応に用いた触媒及びリガンドの種類、触媒に対するリガンドのモル比、反応温度、N/I選択性及び触媒活性を表1に詳細に記載した。
触媒活性は、前記反応で生成されたノルマルアルデヒドとイソアルデヒドと総量を、ブチルアルデヒドの分子量、使用した触媒の濃度、そして反応時間で割った値である。この時、触媒活性の単位は、mol(BAL)/mol(Rh)/hである。
リガンドとしてTTPを単独で使用し、リガンド対ロジウムのモル比が100であることを除いては、実施例1と同じ方法で触媒活性実験を行い、その結果を表2に示した。
リガンドとしてTPPの代わりにP(Pyl)3を使用し、ロジウムに対するリガンドのモル比が50であることを除いては、比較例1と同じ方法で触媒活性実験を行い、その結果を表2に示した。
リガンドとしてTPPの代わりにBPO−P(Pyl)2を使用し、リガンド対ロジウムのモル比が1、3または5であることを除いては、比較例1と同じ方法で触媒活性実験を行い、その結果を表2に示した。
触媒としてRh(AcAc)(CO)2の代わりにRh(AcAc)(CO)(TPP)を使用したことを除いては、比較例4と同じ方法で触媒活性実験を行い、その結果を表2に示した。
単座配位子としてRhに対する結合力が弱いと知られているTPPOを適用すれば、実施例1ないし実施例4から分かるように、二座配位子である1,1’−ビフェニル−2,2’−ジイル−ビス(ジピロリルホスホルアミダイト)(BPO−P(Pyl)2)が触媒の1モル比ほど存在し、単座配位子であるTPPOを追加的に添加する場合、N/I選択性には大きい変化がなく、触媒活性は、15ないし20%が向上することが分かる。また、二座配位子が3モル比以上存在する実施例5ないし実施例12の場合、TPPOを各モル比で添加すれば、前記触媒系の活性及びN/I選択性はそのまま維持しつつ、安価なリガンドの添加により、触媒系の安全性を向上させうるという効果が得られる。以上のように、Rh触媒とBPO−P(Pyl)2とが共存する触媒系にTPPOを過剰量添加しても、高い触媒活性が維持されるか、または多少増加し、N/I選択性は高い値を維持できる。
Claims (12)
- (a)下記化学式1で表示される二座配位子;
(b)下記化学式2で表示される単座配位子;
(c)下記化学式3で表示される遷移金属触媒を含む触媒組成物。
R1及びR2は、それぞれ炭素原子数1ないし20の置換または非置換のアルキル基;炭素原子数1ないし20の置換または非置換のアルコキシ基;炭素原子数5ないし20の置換または非置換のシクロアルカンまたはシクロアルケン;炭素原子数6ないし36の置換または非置換のアリール基;炭素原子数1ないし20の置換または非置換のヘテロアルキル基;炭素原子数4ないし36の置換または非置換のヘテロアリール基;または炭素原子数4ないし36の置換または非置換の複素環基であり、
Ar1−Ar2は、ビスアリール系化合物であり、
Xは、酸素(O)または硫黄(S)である。)
R3、R4、及びR5は、それぞれ炭素原子数1ないし20の置換または非置換のアルキル基;炭素原子数1ないし20の置換または非置換のアルコキシ基;炭素原子数5ないし20の置換または非置換のシクロアルカンまたはシクロアルケン;炭素原子数6ないし36の置換または非置換のアリール基;炭素原子数1ないし20の置換または非置換のヘテロアルキル基;炭素原子数4ないし36の置換または非置換のヘテロアリール基;または炭素原子数4ないし36の置換または非置換の複素環基であり、この時置換基R3、R4、およびR5は、それぞれ、任意選択で、ニトロ(−NO2)、フッ素(F)、塩素(Cl)、ブロム(Br)、炭素原子数1ないし4のアルキル基で置換されていてもよく、
Yは、酸素(O)または硫黄(S)である。)
Mは、遷移金属であり、
L1、L2及びL3は、それぞれ水素、CO、アセチルアセトナート、シクロオキタジエン、ノルボルネン、塩素、またはトリフェニルホスフィンであり、
l、m、及びnは、それぞれ0ないし5の値を有し、但し、l、m及びnが同時に0である場合は除外される)。 - 前記式1で表示される二座配位子のR1及びR2が、それぞれピロール、フェニル、またはインドールであり、この時、燐が窒素原子と直接連結されたことを特徴とする請求項1に記載の触媒組成物。
- 前記式1で表示される二座配位子のビスアリール系化合物Ar1−Ar2が下記式5または式6であることを特徴とする請求項1に記載の触媒組成物。
R8、R9、R10、及びR11は、それぞれ水素、炭素原子数1ないし20のアルキル基、炭素原子数6ないし20のアリール基、トリアリールシリル基、トリアルキルシリル基、カルボアルコキシ基、カルボアリールオキシ、アリールオキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アミド基、ハロゲン原子、ニトリル基であり、この時カルボアルコキシ基、−CO2RのRは、炭素原子数1ないし20のアルキル基、または炭素原子数6ないし20のアリール基である。)
R12、R13、R14、R15、R16、及びR17、は、それぞれ水素、炭素原子数1ないし20のアルキル基、炭素原子数6ないし20のアリール基、トリアリールシリル基、トリアルキルシリル基、カルボアルコキシ基、カルボアリールオキシ、アリールオキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アミド基、ハロゲン原子、ニトリル基であり、この時カルボアルコキシ基、−CO2RのRは、炭素原子数1ないし20のアルキル基、または炭素原子数6ないし20のアリール基である。) - 前記式5の置換基のうち、R8は、メチル、メトキシ、またはt−ブチル基であり、R9は、水素であり、R10は、メチル、メトキシ、またはt−ブチルであり、R11は、メチルまたは水素であることを特徴とする請求項3に記載の触媒組成物。
- 前記式2で表示される単座配位子のYは、酸素(O)であり、R3、R4、及びR5が、それぞれフェニル基、フェニルオキシ基、シクロヘキシル基、またはt−ブチル基であることを特徴とする請求項1に記載の触媒組成物。
- 前記式3の遷移金属Mは、コバルト(Co)、ロジウム(Rh)、またはイリジウム(Ir)であることを特徴とする請求項1に記載の触媒組成物。
- 前記遷移金属触媒は、アセチルアセトナートジカルボニルロジウム(Rh(AcAc)(CO)2)、アセチルアセトナートカルボニルトリフェニルホスフィンロジウム(Rh(AcAc)(CO)(TPP))、ヒドリドカルボニルトリ(トリフェニルホスフィン)ロジウム(HRh(CO)(TPP)3)、アセチルアセトナートジカルボニルイリジウム(Ir(AcAc)(CO)2)、またはヒドリドカルボニルトリ(トリフェニルホスフィン)イリジウム(HIr(CO)(TPP)3)であることを特徴とする請求項1に記載の触媒組成物。
- 前記遷移金属の含量は、触媒組成物の量を基準に50ないし500ppmであり、遷移金属1モルを基準に前記二座配位子の含量は、0.5ないし20モルであり、前記単座配位子の含量は、0.1ないし200モルであることを特徴とする請求項1に記載の触媒組成物。
- 前記遷移金属触媒は、アセチルアセトナートジカルボニルロジウム(Rh(AcAc)(CO)2)であり、前記二座配位子が、1,1’−ビフェニル−2,2’−ジイル−ビス(ジピロリルホスホルアミダイト)(BPO−P(Pyl)2)であり、前記単座配位子がトリフェニルホスフィンオキシド(TPPO)であることを特徴とする請求項1に記載の触媒組成物。
- 請求項1ないし請求項9のうち、何れか1項に記載の触媒組成物を、オレフィン系化合物、一酸化炭素及び水素の混合気体と共に攪拌しつつ、加温、加圧してアルデヒドを製造するオレフィン系化合物のヒドロホルミル化の方法。
- 前記オレフィン系化合物は、エテン、プロペン、1−ブテン、1−ペンテン、1−ヘキセン、1−オクテン、及びスチレンからなる群から選択された化合物であることを特徴とする請求項10に記載のヒドロホルミル化の方法。
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US8710276B2 (en) | 2012-05-24 | 2014-04-29 | Lg Chem, Ltd. | Catalyst compositions for hydroformylation reaction and hydroformylation process using the same |
EP2855016A1 (en) | 2012-06-04 | 2015-04-08 | Dow Technology Investments LLC | Hydroformylation process |
CN112547128B (zh) * | 2019-09-26 | 2023-07-21 | 中国石油化工股份有限公司 | 一种催化剂组合物及高碳醛制备方法 |
CN114315895B (zh) * | 2022-01-11 | 2023-10-20 | 万华化学集团股份有限公司 | 一种配体及其制备方法和应用,一种制备线性二元醛的方法 |
CN115739184B (zh) * | 2022-09-27 | 2024-06-21 | 成都欣华源科技有限责任公司 | 二聚异丁烯氢甲酰化催化剂组合物及其应用 |
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- 2004-07-03 US US10/576,219 patent/US7550406B2/en not_active Expired - Lifetime
- 2004-07-03 JP JP2006532069A patent/JP4571141B2/ja not_active Expired - Lifetime
- 2004-07-03 CN CNB2004800298617A patent/CN100404132C/zh not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
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EP1755781A1 (en) | 2007-02-28 |
KR100547587B1 (ko) | 2006-01-31 |
WO2005120704A1 (en) | 2005-12-22 |
JP4571141B2 (ja) | 2010-10-27 |
EP1755781B1 (en) | 2012-08-29 |
CN100404132C (zh) | 2008-07-23 |
US20070093680A1 (en) | 2007-04-26 |
CN1867403A (zh) | 2006-11-22 |
KR20050118024A (ko) | 2005-12-15 |
US7550406B2 (en) | 2009-06-23 |
EP1755781A4 (en) | 2009-05-13 |
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