WO2000055164A1 - Phosphabenzolverbindungen und ihre verwendung als liganden für hydroformylierungskatalysatoren - Google Patents
Phosphabenzolverbindungen und ihre verwendung als liganden für hydroformylierungskatalysatoren Download PDFInfo
- Publication number
- WO2000055164A1 WO2000055164A1 PCT/EP2000/002288 EP0002288W WO0055164A1 WO 2000055164 A1 WO2000055164 A1 WO 2000055164A1 EP 0002288 W EP0002288 W EP 0002288W WO 0055164 A1 WO0055164 A1 WO 0055164A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- radicals
- hydrogen
- alkyl
- phosphabenzene
- mmol
- Prior art date
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- UNQNIRQQBJCMQR-UHFFFAOYSA-N phosphorine Chemical class C1=CC=PC=C1 UNQNIRQQBJCMQR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 title claims abstract description 16
- 239000003446 ligand Substances 0.000 title description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 229910052783 alkali metal Chemical group 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 3
- 150000001450 anions Chemical group 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000002904 solvent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical class C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000003085 diluting agent Substances 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 150000002390 heteroarenes Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 abstract 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 1
- 229910003202 NH4 Inorganic materials 0.000 abstract 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000007787 solid Substances 0.000 description 21
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 20
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 18
- 230000015556 catabolic process Effects 0.000 description 17
- 238000006731 degradation reaction Methods 0.000 description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 14
- -1 aralkyl radicals Chemical class 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 14
- 150000003254 radicals Chemical class 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 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 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- JRPPVSMCCSLJPL-UHFFFAOYSA-N 7-methyloctanal Chemical compound CC(C)CCCCCC=O JRPPVSMCCSLJPL-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- 229910052703 rhodium Inorganic materials 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- YRKKPRNXRCQRIS-UHFFFAOYSA-N 2,6-bis(2,4-dimethylphenyl)-4-phenylphosphinine Chemical compound CC1=CC(C)=CC=C1C1=CC(C=2C=CC=CC=2)=CC(C=2C(=CC(C)=CC=2)C)=P1 YRKKPRNXRCQRIS-UHFFFAOYSA-N 0.000 description 4
- KNWXVLAZJFVIFF-UHFFFAOYSA-N 2,6-bis(2-methylphenyl)-4-phenylphosphinine Chemical compound CC1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=CC(C=2C(=CC=CC=2)C)=P1 KNWXVLAZJFVIFF-UHFFFAOYSA-N 0.000 description 4
- ZKPFRIDJMMOODR-UHFFFAOYSA-N 2-Methyloctanal Chemical compound CCCCCCC(C)C=O ZKPFRIDJMMOODR-UHFFFAOYSA-N 0.000 description 4
- QJIQXCMZLHPMPE-UHFFFAOYSA-N 4-phenyl-2,6-bis(2,4,5-trimethylphenyl)phosphinine Chemical compound C1=C(C)C(C)=CC(C)=C1C1=CC(C=2C=CC=CC=2)=CC(C=2C(=CC(C)=C(C)C=2)C)=P1 QJIQXCMZLHPMPE-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QDCBISZSSFKOHB-UHFFFAOYSA-N 2,3,4,5,6-pentakis-phenylphosphinine Chemical compound C1=CC=CC=C1C(C(=C1C=2C=CC=CC=2)C=2C=CC=CC=2)=PC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 QDCBISZSSFKOHB-UHFFFAOYSA-N 0.000 description 3
- CNEIITMFCADFIS-UHFFFAOYSA-N 2,3,5,6-tetraphenylphosphinine Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)P=C1C1=CC=CC=C1 CNEIITMFCADFIS-UHFFFAOYSA-N 0.000 description 3
- SPVWSVYJPGRPFL-UHFFFAOYSA-N 2,4,6-triphenylphosphinine Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=PC(C=2C=CC=CC=2)=C1 SPVWSVYJPGRPFL-UHFFFAOYSA-N 0.000 description 3
- IRTFWEZZZITMFI-UHFFFAOYSA-N 2,6-dinaphthalen-2-yl-4-phenylphosphinine Chemical compound C1=CC=CC=C1C1=CC(C=2C=C3C=CC=CC3=CC=2)=PC(C=2C=C3C=CC=CC3=CC=2)=C1 IRTFWEZZZITMFI-UHFFFAOYSA-N 0.000 description 3
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000012812 general test Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001145 hydrido group Chemical group *[H] 0.000 description 2
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 2
- LIINGNMKNRSOGW-UHFFFAOYSA-N oct-7-enal Chemical compound C=CCCCCCC=O LIINGNMKNRSOGW-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- ZOLLIQAKMYWTBR-MOLCZBCNSA-N (1z,5z,9z)-cyclododeca-1,5,9-triene Chemical compound C\1C\C=C/CC\C=C/CC\C=C/1 ZOLLIQAKMYWTBR-MOLCZBCNSA-N 0.000 description 1
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- HSDSKVWQTONQBJ-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C)C=C1C HSDSKVWQTONQBJ-UHFFFAOYSA-N 0.000 description 1
- VTMSSJKVUVVWNJ-UHFFFAOYSA-N 1-ethenyl-4-(2-methylpropyl)benzene Chemical compound CC(C)CC1=CC=C(C=C)C=C1 VTMSSJKVUVVWNJ-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- SHCSFZHSNSGTOP-UHFFFAOYSA-N Methyl 4-pentenoate Chemical compound COC(=O)CCC=C SHCSFZHSNSGTOP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical class CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical class OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- KJALUUCEMMPKAC-ONEGZZNKSA-N methyl (e)-pent-3-enoate Chemical compound COC(=O)C\C=C\C KJALUUCEMMPKAC-ONEGZZNKSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000000754 repressing effect Effects 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 150000008648 triflates Chemical class 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
- B01J31/2466—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring comprising aliphatic or saturated rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
- C07F15/008—Rhodium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
Definitions
- the present invention relates to phosphabenzene compounds and their use in complexes of transition metals of subgroup VIII of the Periodic Table of the Elements in the production of aldehydes by hydroformylation of oiefs with CO / H 2 at temperatures up to 200 ° C. and pressures up to 700 bar.
- Hydroformylation is a well-known, industrial process for the production of aldehydes from Oiefmen, carbon monoxide and hydrogen.
- phosphabenzenes are active cocatalysts for the hydroformylation of oiefmen.
- a process for the preparation of aldehydes by hydroformylation of oiefmen with CO / H 2 in the presence of complexes which contain phosphabenzene compounds as ligands is described.
- phosphabenzene compounds used such as 2,4,6-triphenylphosphabenzene and 2,6-bis (2-naphthyl) -4-phenylphosphabenzene, but also phospassizenes such as 2,3,5,6-tetraphenylphospazazene or 2,3,4,5,6-pentaphenylphosphabenzene have the disadvantage, however, that they can be degraded under hydroformylation conditions by partial or complete hydrogenation of the phosphabenzene system and by subsequent addition reactions (see Examples 11-14). This produces, among other things, secondary and tertiary phosphines, which strongly slow down the hydroformylation activity of the catalyst system. Similar phosphabenzene compounds are described in DE-A-19 621 967 and DE-A-16 68 416.
- the object of the present invention is to provide phosphabenzene ligands which avoid the disadvantages of the known ligands.
- alkyl, aryl, alkaryl and aralkyl radicals with the radicals mentioned above can be substituted and two or more of the radicals can be linked to form aliphatic or fused rings, at least one of the radicals R 4 and R 8 and at least one of the radicals R 9 and R 13 being different from hydrogen.
- At least one of the radicals R and R and at least one of the radicals R and R independently of one another are Ci- ⁇ -alkyl, C 6 -i 2 -aryl, C . ⁇ - aralkyl or C -i 2 -alkaryl, or R 4 and R 3 and / or R 1j and R 1 form a C 2- alkylene radical.
- At least one of the radicals R 4 and R 8 and at least one of the radicals R 9 and R 13 is -6- alkyl, or (R 4 and R 3 ) and (R 13 and R 1 ) each form a C 2- 3 alkylene radical.
- R " is a phenyl radical which may be substituted by 1 to 5, preferably 1 to 3, in particular 1 or 2 C ⁇ -6 alkyl.
- the radicals R 1 and R 3 are particularly preferably hydrogen, and in each case a maximum of three of the radicals R to R and R to R 13 are different from hydrogen.
- the radicals R 4 to R 8 and R 9 to R lj each have a particularly preferred maximum of 6, in particular a maximum of 3, carbon atoms.
- the phosphabenzene compounds of the general formula (I) have, apart from the one phosphorus atom, no atoms other than carbon or hydrogen.
- alkyl radicals in the compounds of the general formula (I) is preferably 0 in the case of purely cyclic structures, otherwise preferably 2 to 7, in particular 2 to 6.
- the alkyl radicals can be linear or branched alkyl radicals. Preferably there are only linear alkyl radicals. The same applies accordingly to bridging alkylene groups.
- pyrylium salts It is preferably carried out by reacting appropriate pyrylium salts with PH 3 in the presence or absence of a catalytic amount of acid or base and in the presence or absence of a solvent or diluent.
- the pyrylium salts are preferably brought together with PH 3 at a temperature above 0 ° C. and reacted at a temperature from 0 ° C. to 200 ° C. and a pressure above 1 bar.
- phosphabenzene compounds of the above general formula can be obtained with PH 3 by reacting the corresponding pyrylium salts, ie compounds in which O + instead of phosphorus is present in the general formula with a corresponding counterion, if certain process conditions are observed.
- the pyrylium salts are technically available or can be easily manufactured.
- PH 3 is technically available.
- the reaction is preferably carried out at a PH partial pressure in the range from 0J to 100 bar, particularly preferably from 5 to 35 bar, in particular 20 to 30 bar.
- the total pressure in the system depends on the particular solvent.
- the total pressure can be increased by injecting PH 3 or inert gas.
- PH 3 is preferably introduced into the reaction mixture during the reaction in order to keep the PHs partial pressure essentially constant. This procedure allows a particularly economical and quick conversion to the desired phosphabenzene compounds. High product purities and sales are achieved.
- the method according to the invention can be used reliably for a large number of products. It can be operated continuously or batchwise, preferably batchwise.
- the pyrylium salts are brought together with PH 3 at ambient temperature, and the mixture obtained in this way is heated to a temperature in the range from 60 to 140 ° C., preferably 80 to 130 ° C.
- the temperature during the reaction is particularly preferably 100 to 120.degree.
- the reaction is preferably carried out in an autoclave.
- an inert gas can also be used to set the desired total pressure. However, preferably only PH 3 is used.
- the reaction can be carried out in the presence or absence of a solvent or diluent. It is preferably carried out in the presence of a solvent or diluent.
- Suitable solvents or diluents are, for example, lower aliphatic alcohols, such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, tert-butanol or pentanol isomers, preferably ethanol, propanol or butanols, especially n-butanol.
- the reaction can be carried out in the presence of an acid catalyst.
- Suitable acid catalysts are mineral acids, such as HI, HC1, HBr.
- hydrogen bromide in acetic acid or acetic anhydride is used as an acid catalyst. It is preferable to work without an acid catalyst.
- the reaction mixture is preferably let down and, if appropriate, flushed with an inert gas, the gases emerging from the reaction mixture being cooled in liquid form to remove unreacted PH 3 and passed through a separator, and the separated PH 3 being returned to the reaction.
- a method in which PH 3 is introduced into a reactor, the reaction is carried out, and the gas stream is passed via a further line through a cooler of any design in which the PH 3 is condensed out is particularly economical and ecologically harmless.
- the PH 3 is then separated off and returned to the reaction, for example with the aid of a pump.
- the use of a second cooler and separator connected downstream is advantageous.
- a flushing line should be provided for flushing with an inert gas such as nitrogen.
- the purge gas should be passed through the combination of cooler and separator.
- the time required for the reaction depends on the type of the pyrylium salt. Depending on the pyrylium salt, the reaction is preferably carried out for a period of 1 to 4 hours.
- the amount of acid catalyst used is, based on the pyrylium salts, preferably 0.01 to 1%, particularly preferably 0.03 to 0J%.
- pyrylium salts can be used in the process according to the invention.
- the method is generally not restricted to certain classes of compounds.
- the organic radical of the pyrylium salts used according to the invention is described in more detail below with reference to the phosphabenzene compounds prepared therefrom.
- the compounds according to the invention can be used for the preparation of complexes with metals from subgroup VIII of the Periodic Table of the Elements.
- Such complexes can be used as (co) catalysts in hydroformylations of Oiefmen with CO / H 2 .
- Suitable reaction conditions are described in DE-A-196 21 967 and WO 97/02757.
- the effective catalysts are those of the formula M (L) n (CO) m , in which M has at least one central atom of an element of subgroup VIII.
- L at least one ligand of the formula I, n and m in each case at least 1 to 3 and the sum of n + m are 2 to 5 and further residues such as hydrido or alkyl or acyl residues may be present as ligands.
- the active carbonyl complex is usually in situ, i. H. in the hydroformylation reactor, formed from a salt or a compound of metal M, the ligand and carbon monoxide; but it can also be manufactured separately and used as such.
- the complex catalysts preferably consist of a central atom M, selected from the transition metals cobalt, ruthenium, rhodium, palladium or platinum, but in particular cobalt and rhodium, complexed with carbonyl and hydrido, alkyl or acyl radicals and, as ligands, the mono- or multidentate preferred phosphabenzenes. If the complex catalysts are generated in situ, simple precursor complexes such as rhodium biscarbonylacetylacetonate or rhodium acetate are exposed to the reaction conditions in the presence of the corresponding ligands, or precursor complexes are mixed with activating additives such as Bronsted or Lewis acids and Lewis bases.
- activating additives such as Bronsted or Lewis acids and Lewis bases.
- the ligand is used in a molar ratio (calculated as equivalent phosphorus) to rhodium of 1: 1 to 1000: 1 and an inert solvent is additionally used.
- Particularly preferred solvents are the aldehydes which are formed by the reaction of the respective olefin, and the synthesis-specific high boilers which are formed by subsequent reactions of the respective aldehyde in the hydroformylation process.
- water, alcohols or other polar solvents are preferably used.
- the composition of the synthesis gas CO / H 2 used in the hydroformylation process according to the invention can be varied within wide limits.
- synthesis gas can with CO / H 2 molar ratios of 5: 95 to 70: 30 are inserted successful synthesis gas is preferably with CO / H 2 - ratios of 40: 60 to 60: 40, particularly preferably a CO / H 2 - Ratio of about 1: 1 applied.
- the hydroformylation reaction with CO and HT in the presence of the catalyst is carried out at a temperature of 0 to 200 ° C., preferably at a temperature between 20 and 180 ° C., in particular 50 to 150 ° C.
- an optimal temperature is expediently determined experimentally for each catalyst system.
- the reaction pressure can vary depending on the (co) catalyst, i.e. H. Ligand, and substrate in a range of normal pressure, i.e. Atmospheric pressure, up to 700 bar, preferably up to 300 bar, fluctuate, reactions in a range up to about 30 bar are usually referred to as low pressure, in a range up to about 100 bar as medium pressure and over 100 bar as high pressure reactions.
- the catalyst used is homogeneously dissolved in the reaction medium and is separated from the discharge from the hydroformylation reaction and returned to the hydroformylation stage.
- Suitable olefins to be hydroformylated according to the invention are ⁇ -olefins or internal olefins or internal, branched olefins.
- Examples include the following olefins: ethylene, propene, 1-butene, 1-octene, C 5-2 o- ⁇ -olefins, linear C 5-20 internal olefins, butene-2; branched, internal octene mixtures; branched, internal non-mixtures; branched, internal dodecene mixtures, cyclohexene, ⁇ -pinene, styrene, 4-isobutylstyrene, 3-pentenoic acid methyl ester, 4-pentenoic acid methyl ester, oleic acid methyl ester, 3-pentenenitrile, 4-pentenenitrile, 2.7- Octadienol-1, 7-octenal, acrylic acid methyl ester, meth
- suitable substrates are di- or polyenes with isolated or conjugated double bonds.
- suitable substrates are 1,3-butadiene, 1,5-hexadiene, vinylcyclohexene, dicyclopentadiene, 1,5,9-cyclooctatriene, butadiene homo- and copolymers, polyisobutene.
- the rhodium precursor, ligand and solvent were mixed under nitrogen inert gas in a Schlenk tube.
- the solution obtained was transferred to a 100 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 5 bar CO / H 2 (1: 1) were pressed in cold. With vigorous stirring with a gas stirrer, this was Reaction mixture heated to the desired temperature within 30 min.
- the olefin used was then pressed into the autoclave with CO / H2 overpressure via a lock.
- the desired reaction pressure was then immediately set using CO / H2 (1: 1). During the reaction, the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time, the autoclave was cooled, decompressed and emptied.
- the reaction mixture was analyzed by GC with an internal standard and correction factor.
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT00910839T ATE227298T1 (de) | 1999-03-17 | 2000-03-15 | Phosphabenzolverbindungen und ihre verwendung als liganden für hydroformylierungskatalysatoren |
JP2000605593A JP2002539216A (ja) | 1999-03-17 | 2000-03-15 | ホスファベンゾール化合物および該化合物のヒドロホルミル化触媒のための配位子としての使用 |
KR1020017011769A KR20010112339A (ko) | 1999-03-17 | 2000-03-15 | 포스파벤젠 화합물 및 히드로포밀화 촉매를 위한리간드로서 그의 용도 |
DE50000730T DE50000730D1 (de) | 1999-03-17 | 2000-03-15 | Phosphabenzolverbindungen und ihre verwendung als liganden für hydroformylierungskatalysatoren |
US09/936,346 US6509505B1 (en) | 1999-03-17 | 2000-03-15 | Phosphabenzene compounds and their use in hydroformylation |
EP00910839A EP1161437B1 (de) | 1999-03-17 | 2000-03-15 | Phosphabenzolverbindungen und ihre verwendung als liganden für hydroformylierungskatalysatoren |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19911920.1 | 1999-03-17 | ||
DE19911920A DE19911920A1 (de) | 1999-03-17 | 1999-03-17 | Phosphabenzolverbindungen und ihre Verwendung in der Hydroformylierung |
Publications (1)
Publication Number | Publication Date |
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WO2000055164A1 true WO2000055164A1 (de) | 2000-09-21 |
Family
ID=7901325
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2000/002288 WO2000055164A1 (de) | 1999-03-17 | 2000-03-15 | Phosphabenzolverbindungen und ihre verwendung als liganden für hydroformylierungskatalysatoren |
Country Status (9)
Country | Link |
---|---|
US (1) | US6509505B1 (de) |
EP (1) | EP1161437B1 (de) |
JP (1) | JP2002539216A (de) |
KR (1) | KR20010112339A (de) |
CN (1) | CN1223599C (de) |
AT (1) | ATE227298T1 (de) |
DE (2) | DE19911920A1 (de) |
ES (1) | ES2186636T3 (de) |
WO (1) | WO2000055164A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002000669A2 (de) * | 2000-06-26 | 2002-01-03 | Basf Aktiengesellschaft | Phosphacyclohexane und ihre verwendung in der hydroformylierung von olefinen |
US7317130B2 (en) | 2002-08-31 | 2008-01-08 | Oxeno Olefinchemie Gmbh | Method for the hydroformylation of olefinically unsaturated compounds, especially olefins, in the presence of cyclic carbonic acid esters |
WO2010057099A1 (en) | 2008-11-14 | 2010-05-20 | University Of Kansas | Polymer-supported transition metal catalyst complexes and methods of use |
WO2017150337A1 (ja) | 2016-03-01 | 2017-09-08 | 株式会社クラレ | ジアルデヒド化合物の製造方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105384773A (zh) * | 2015-12-06 | 2016-03-09 | 杨秀娟 | 一种含磷杂芳环化合物的催化合成方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1618668A1 (de) * | 1967-03-18 | 1971-02-25 | Gottfried Prof Dr Maerkl | Verfahren zur Herstellung von Phosphabenzolen |
DE1668416A1 (de) * | 1967-10-18 | 1971-08-05 | Gottfried Prof Dr Maerkl | Phosphabenzole und Verfahren zu ihrer Herstellung |
WO1997046507A1 (de) * | 1996-05-31 | 1997-12-11 | Basf Aktiengesellschaft | Verfahren zur hydroformylierung und dafür geeignete katalysatoren, die phosphorverbindungen als liganden enthalten |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19743197A1 (de) * | 1997-09-30 | 1999-04-01 | Basf Ag | Verfahren zur Herstellung von Phosphabenzolverbindungen |
DE19911922A1 (de) * | 1999-03-17 | 2000-09-21 | Basf Ag | Verfahren zur Herstellung von Phosphabenzolverbindungen |
-
1999
- 1999-03-17 DE DE19911920A patent/DE19911920A1/de not_active Withdrawn
-
2000
- 2000-03-15 CN CNB008050511A patent/CN1223599C/zh not_active Expired - Fee Related
- 2000-03-15 US US09/936,346 patent/US6509505B1/en not_active Expired - Fee Related
- 2000-03-15 KR KR1020017011769A patent/KR20010112339A/ko not_active Application Discontinuation
- 2000-03-15 EP EP00910839A patent/EP1161437B1/de not_active Expired - Lifetime
- 2000-03-15 JP JP2000605593A patent/JP2002539216A/ja not_active Withdrawn
- 2000-03-15 DE DE50000730T patent/DE50000730D1/de not_active Expired - Lifetime
- 2000-03-15 AT AT00910839T patent/ATE227298T1/de not_active IP Right Cessation
- 2000-03-15 WO PCT/EP2000/002288 patent/WO2000055164A1/de not_active Application Discontinuation
- 2000-03-15 ES ES00910839T patent/ES2186636T3/es not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1618668A1 (de) * | 1967-03-18 | 1971-02-25 | Gottfried Prof Dr Maerkl | Verfahren zur Herstellung von Phosphabenzolen |
DE1668416A1 (de) * | 1967-10-18 | 1971-08-05 | Gottfried Prof Dr Maerkl | Phosphabenzole und Verfahren zu ihrer Herstellung |
WO1997046507A1 (de) * | 1996-05-31 | 1997-12-11 | Basf Aktiengesellschaft | Verfahren zur hydroformylierung und dafür geeignete katalysatoren, die phosphorverbindungen als liganden enthalten |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002000669A2 (de) * | 2000-06-26 | 2002-01-03 | Basf Aktiengesellschaft | Phosphacyclohexane und ihre verwendung in der hydroformylierung von olefinen |
WO2002000669A3 (de) * | 2000-06-26 | 2002-06-20 | Basf Ag | Phosphacyclohexane und ihre verwendung in der hydroformylierung von olefinen |
US7317130B2 (en) | 2002-08-31 | 2008-01-08 | Oxeno Olefinchemie Gmbh | Method for the hydroformylation of olefinically unsaturated compounds, especially olefins, in the presence of cyclic carbonic acid esters |
WO2010057099A1 (en) | 2008-11-14 | 2010-05-20 | University Of Kansas | Polymer-supported transition metal catalyst complexes and methods of use |
WO2017150337A1 (ja) | 2016-03-01 | 2017-09-08 | 株式会社クラレ | ジアルデヒド化合物の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1161437A1 (de) | 2001-12-12 |
DE50000730D1 (de) | 2002-12-12 |
ES2186636T3 (es) | 2003-05-16 |
JP2002539216A (ja) | 2002-11-19 |
CN1343211A (zh) | 2002-04-03 |
US6509505B1 (en) | 2003-01-21 |
CN1223599C (zh) | 2005-10-19 |
EP1161437B1 (de) | 2002-11-06 |
KR20010112339A (ko) | 2001-12-20 |
DE19911920A1 (de) | 2000-09-21 |
ATE227298T1 (de) | 2002-11-15 |
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