HRP20040904A2 - Bisphosphines as bidentate ligands - Google Patents
Bisphosphines as bidentate ligandsInfo
- Publication number
- HRP20040904A2 HRP20040904A2 HRP20040904A HRP20040904A2 HR P20040904 A2 HRP20040904 A2 HR P20040904A2 HR P20040904 A HRP20040904 A HR P20040904A HR P20040904 A2 HRP20040904 A2 HR P20040904A2
- Authority
- HR
- Croatia
- Prior art keywords
- alkyl
- cycloalkyl
- aryl
- ligands
- aralkyl
- Prior art date
Links
- 239000003446 ligand Substances 0.000 title claims abstract description 87
- 229920000642 polymer Polymers 0.000 claims abstract description 56
- 125000003118 aryl group Chemical group 0.000 claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 14
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- 239000010948 rhodium Substances 0.000 claims abstract description 9
- 150000003624 transition metals Chemical class 0.000 claims abstract description 9
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims abstract description 8
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 5
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 49
- 239000003054 catalyst Substances 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 33
- -1 polysiloxane Polymers 0.000 claims description 33
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 31
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 26
- 125000005647 linker group Chemical group 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 238000009901 transfer hydrogenation reaction Methods 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 238000007037 hydroformylation reaction Methods 0.000 claims description 4
- 125000002524 organometallic group Chemical group 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- YTLYLLTVENPWFT-UHFFFAOYSA-N 3-aminoprop-2-enoic acid Chemical class NC=CC(O)=O YTLYLLTVENPWFT-UHFFFAOYSA-N 0.000 claims description 2
- 238000007341 Heck reaction Methods 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 238000006579 Tsuji-Trost allylation reaction Methods 0.000 claims description 2
- 238000005575 aldol reaction Methods 0.000 claims description 2
- 238000005888 cyclopropanation reaction Methods 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000007871 hydride transfer reaction Methods 0.000 claims description 2
- 238000006197 hydroboration reaction Methods 0.000 claims description 2
- 238000005669 hydrocyanation reaction Methods 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- 229920000765 poly(2-oxazolines) Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- QNLQKURWPIJSJS-UHFFFAOYSA-N trimethylsilylphosphane Chemical class C[Si](C)(C)P QNLQKURWPIJSJS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 9
- 125000001072 heteroaryl group Chemical group 0.000 abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 150000001805 chlorine compounds Chemical class 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 230000006698 induction Effects 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- GWLJTAJEHRYMCA-UHFFFAOYSA-N phospholane Chemical compound C1CCPC1 GWLJTAJEHRYMCA-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HBIZLNPVVDMPLQ-UHFFFAOYSA-N [SiH3]P1CCCC1 Chemical compound [SiH3]P1CCCC1 HBIZLNPVVDMPLQ-UHFFFAOYSA-N 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 241000349731 Afzelia bipindensis Species 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- CBULBTPNRQBYJE-RKDXNWHRSA-N [(2r,5r)-2,5-dimethylphospholan-1-yl]-trimethylsilane Chemical compound C[C@@H]1CC[C@@H](C)P1[Si](C)(C)C CBULBTPNRQBYJE-RKDXNWHRSA-N 0.000 description 3
- 150000001576 beta-amino acids Chemical class 0.000 description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 3
- 238000009295 crossflow filtration Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LYXHWHHENVLYCN-QMDOQEJBSA-N (1z,5z)-cycloocta-1,5-diene;rhodium;tetrafluoroborate Chemical compound [Rh].F[B-](F)(F)F.C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 LYXHWHHENVLYCN-QMDOQEJBSA-N 0.000 description 2
- GAEIPHYVQAKDSM-GHMZBOCLSA-N (2r,5r)-2,5-dimethyl-1-phenylphospholane Chemical compound C[C@@H]1CC[C@@H](C)P1C1=CC=CC=C1 GAEIPHYVQAKDSM-GHMZBOCLSA-N 0.000 description 2
- PNNFEYPWPCDLOC-UPHRSURJSA-N (z)-2,3-dichlorobut-2-enedioic acid Chemical class OC(=O)C(\Cl)=C(\Cl)C(O)=O PNNFEYPWPCDLOC-UPHRSURJSA-N 0.000 description 2
- AGULWIQIYWWFBJ-UHFFFAOYSA-N 3,4-dichlorofuran-2,5-dione Chemical compound ClC1=C(Cl)C(=O)OC1=O AGULWIQIYWWFBJ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 2
- 150000004850 phospholanes Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 2
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 1
- YTLYLLTVENPWFT-UPHRSURJSA-N (Z)-3-aminoacrylic acid Chemical class N\C=C/C(O)=O YTLYLLTVENPWFT-UPHRSURJSA-N 0.000 description 1
- YTLYLLTVENPWFT-OWOJBTEDSA-N (e)-3-aminoprop-2-enoic acid Chemical class N\C=C\C(O)=O YTLYLLTVENPWFT-OWOJBTEDSA-N 0.000 description 1
- 125000003088 (fluoren-9-ylmethoxy)carbonyl group Chemical group 0.000 description 1
- FVNZXCCNRZWMER-UPHRSURJSA-N (z)-2,3-dichlorobut-2-enediamide Chemical class NC(=O)C(\Cl)=C(\Cl)C(N)=O FVNZXCCNRZWMER-UPHRSURJSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- BHKKSKOHRFHHIN-MRVPVSSYSA-N 1-[[2-[(1R)-1-aminoethyl]-4-chlorophenyl]methyl]-2-sulfanylidene-5H-pyrrolo[3,2-d]pyrimidin-4-one Chemical compound N[C@H](C)C1=C(CN2C(NC(C3=C2C=CN3)=O)=S)C=CC(=C1)Cl BHKKSKOHRFHHIN-MRVPVSSYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OQHMFJKKVZGWDC-DDHJBXDOSA-N 3,4-bis[(2r,5r)-2,5-dimethylphospholan-1-yl]furan-2,5-dione Chemical compound C[C@@H]1CC[C@@H](C)P1C(C(OC1=O)=O)=C1P1[C@H](C)CC[C@H]1C OQHMFJKKVZGWDC-DDHJBXDOSA-N 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000004575 3-pyrrolidinyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001397 3-pyrrolyl group Chemical group [H]N1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical class NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- NJQFCQXFOHVYQJ-PMACEKPBSA-N BF 4 Chemical compound C1([C@@H]2CC(=O)C=3C(O)=C(C)C4=C(C=3O2)[C@H](C(C)C)C2=C(O4)C(C)=C(C(C2=O)(C)C)OC)=CC=CC=C1 NJQFCQXFOHVYQJ-PMACEKPBSA-N 0.000 description 1
- 229910015892 BF 4 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
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- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910021115 PF 6 Inorganic materials 0.000 description 1
- 229910021605 Palladium(II) bromide Inorganic materials 0.000 description 1
- 229910021606 Palladium(II) iodide Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-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
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- TWKVUTXHANJYGH-UHFFFAOYSA-L allyl palladium chloride Chemical class Cl[Pd]CC=C.Cl[Pd]CC=C TWKVUTXHANJYGH-UHFFFAOYSA-L 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- OKDHIPXOBPPHTG-UHFFFAOYSA-L benzonitrile;dibromopalladium Chemical compound Br[Pd]Br.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 OKDHIPXOBPPHTG-UHFFFAOYSA-L 0.000 description 1
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- ZXTRXJXCZHMBPZ-UHFFFAOYSA-N bis(trimethylsilyl)phosphane;lithium Chemical compound [Li].C[Si](C)(C)P[Si](C)(C)C ZXTRXJXCZHMBPZ-UHFFFAOYSA-N 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 description 1
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- ZOLLIQAKMYWTBR-RYMQXAEESA-N cyclododecatriene Chemical compound C/1C\C=C\CC\C=C/CC\C=C\1 ZOLLIQAKMYWTBR-RYMQXAEESA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical group C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000005610 enamide group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004475 heteroaralkyl group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 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
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 125000001145 hydrido group Chemical group *[H] 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000006140 methanolysis reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 238000007344 nucleophilic reaction Methods 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- FJOUSQLMIDWVAY-UHFFFAOYSA-L palladium(2+);n,n,n',n'-tetramethylethane-1,2-diamine;dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CN(C)CCN(C)C FJOUSQLMIDWVAY-UHFFFAOYSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- HNNUTDROYPGBMR-UHFFFAOYSA-L palladium(ii) iodide Chemical compound [Pd+2].[I-].[I-] HNNUTDROYPGBMR-UHFFFAOYSA-L 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 238000006368 phosphinylation reaction Methods 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001557 phthalyl group Chemical group C(=O)(O)C1=C(C(=O)*)C=CC=C1 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004943 pyrimidin-6-yl group Chemical group N1=CN=CC=C1* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000008648 triflates Chemical class 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OUMZKMRZMVDEOF-UHFFFAOYSA-N tris(trimethylsilyl)phosphane Chemical compound C[Si](C)(C)P([Si](C)(C)C)[Si](C)(C)C OUMZKMRZMVDEOF-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
- B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
-
- 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
-
- 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
- B01J31/2428—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 with more than one complexing phosphine-P atom
- B01J31/2433—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 with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
-
- 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
- B01J31/2471—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 with more than one complexing phosphine-P atom
- B01J31/2476—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 with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/16—Preparation of optical isomers
- C07C231/18—Preparation of optical isomers by stereospecific synthesis
-
- 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
- C07C45/505—Asymmetric hydroformylation
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5027—Polyphosphines
-
- 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
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/5537—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom the heteroring containing the structure -C(=O)-N-C(=O)- (both carbon atoms belong to the heteroring)
-
- 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
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6503—Five-membered rings
- C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
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Description
Predmetni izum se odnosi na bisfosfine kao bidentatne ligande, postupak za njihovu proizvodnju kao i njihovu uporabu. Predmetni se izum posebice odnosi na bisfosfine opće strukture (I).
Kiralni ligandi obogaćeni enantiomerima koriste se za asimetričnu sintezu ili asimetričnu katalizu. Vrlo je važno da elektronska i stereokemijska svojstva liganda budu optimalno prilagođena za određenu katalitičku reakciju. Značajan aspekt uspješnosti ovih skupina spojeva kao katalizatora pripisuje se stvaranju izražene asimetrije oko metalnog središta putem ovih sustava liganda. Kako bi se spomenuta asimetrija upotrijebila za učinkovit prijenos kiralnosti, korisno je kontrolirati fleksi-bilnost sustava liganda kao bitnog ograničenja asimetrične indukcije.
[image]
U okviru skupine liganda koji sadrže fosfor, ciklički fosfini, posebice fosfolani, imaju poseban značaj. Bidentatni, kiralni fosfolani su, na primjer, DuPhos i BPE ligandi koji se rabe u asimetričnoj katalizi. Idealno je stoga koristiti kiralni ligand s osnovnim skeletom sposobnim za mnogostruke modifikacije, koji se može mijenjati unutar širokog opsega s obzirom na svoje steričke i eletronske osobine.
Predmet izuma je stoga omogućiti ligandni skelet analogan onom kod postojećih fosfolanskih liganda, no koji se dodatno može mijenjati i koristiti unutar širokog opsega, te posjeduje relativno dobra katalitička svojstva. Posebice su predmet izuma novi, asimetrični, bidentatni i kiralni fosfinski ligandni sustavi za potrebe katalize, koji se mogu dobiti lako i u visokoj enantiomeričkoj čistoći.
Ti i drugi problemi koji nisu drugačije naznačeni, ali proizilaze iz prethodnog stanja tehnike, mogu se riješiti uporabom skupine kiralnih bidentatnih liganda bisfosfinskih spojeva opće formule (I), a spojevi sukladno predmetnom izumu imaju dva kiralna fosfinska radikala spojena nezasićenom vezom.
Pripravom enantiomerima obogaćenih bidentantih organofosfornih liganda, formule (I),
[image]
pri čemu
R1, R2, R3, R4, svaki za sebe predstavljaju, (C1C8)-alkil, (C2C8)-alkoksialkil, (C6C18)-aril, (C7C19)-aralkil, (C3C18)-heteroaril, (C4C19)-heteroaralkil, (C1C8)-alkil-(C6C18)-aril, (C1C8)-alkil(C3C18)-heteroaril, (C3C8)-cikloalkil, (C1C8)-alkil(C3C8)-cikloalkil, (C3C8)-cikloalkil(C1C8)alkil,
ili R1 i R2 i/ili R3 i R4 predstavljaju (C3-C5)-alkilenski most mono-ili polisupstituiran sa (C1C8)alkil, HO-(C1-C8)-alkil, (C1C8)alkoksi, (C2C8)alkoksialkil, (C6C18)aril, (C7C19)aralkil,(C1C8)alkil(C6C18)aril, (C3C8)cikloalkil,
(C1C8)alkil(C3C8)cikloalkil, (C3C8)cikloalkil(C1C8)alkil, koji su po izboru vezani na polimer,
a A označava jednu od sljedećih struktura
[image]
u kojima
R označava H, (C1C8)alkil, (C6C18)aril, (C7C19)aralkil, (C1C8)alkil(C6C18)aril, (C3C8)cikloalkil, (C1C8)alkil(C3C8)cikloalkil, (C3C8)cikloalkil(C1C8)alkil, ili vezu s polimerom,
Q = O, NH, NR, dobivaju se prethodno nepoznati spojevi, koji se mogu uspješno rabiti u asimetričnoj katalizi za proizvodnju organskih spojeva. Prema tome, pomoću liganda koji se dobivaju sukladno predmetnom izumu, mogu se proizvesti kompleksi ili katalizatori za uspješnu hidrogenaciju mješavine aciliranih E- i Z-β-aminoakrilnih kiselina ili njihovih derivata. Do danas je samo nekoliko kompleksa bilo uspješno testirano na mješavine ovih skupina spojeva, pa je do danas bilo nužno pročišćavati, često na vrlo kompliciran način, E/Z mješavine prije hidrogenacije, kako bi mogli reagirati s aciliranim E-β-aminoakrilnim kiselinama i derivatima, koji se jedino mogu hidrogenizirati s velikim enantiomerskimm viškovima, odvojeno od Z-komponenata.
Ligandi sukladno predmetnom izumu prvenstveno odgovaraju strukturama opće formule (II),
[image]
u kojima A ima prethodno određeno značenje,
R5 do R12, svaki za sebe, predstavljaju (C1C8)alkil, HO-(C1-C8)-alkil, (C1C8)alkoksi, (C2C8)alkoksialkil, (C6C18)aril, (C7C19)aralkil, (C1C8)alkil(C6C18)aril, (C3C8)cikloalkil, (C1C8)alkil(C3C8)cikloalkil, (C3C8)cikloalkil(C1C8)alkil,
ili vezu sa polimernim lancem.
Sustavi liganda sukladno predmetnom izumu mogu se stoga vezati za polimerni lanac. Ligandi ili kompleksi/katalizatori koji se od njih dobivaju, mogu se lako odvojiti od spojeva male molekulske mase, primjerice filtracijom, zahvaljujući vezi s polimernim lancem, a zbog toga se mogu rabiti za ponovljeni ciklus sukladno predmetnom izumu, koji je izuzetno jednostavan, ali uprkos tomu koristan. Ligandi/kompleksi mogu povećati svoju molekulsku težinu vezanjem za lanac polimera, a po izboru se na taj način mogu i heterogenizirati. Stoga se enantioselektivna hidrogenacija s kompleksima ili katalizatorima kojima se na taj način povećala molekulska težina može se nastaviti i u homogenoj i u heterogenoj fazi.
Polimerni lanac:
Veličina polimerskog lanca može se slobodno mijenjati u okviru predmetnog izuma. S jedne strane, ona je ograničena aspektima praktičnosti i troškova, a s druge strane uobičajenim tehničkim uvjetima (retencijski kapacitet, topljivost, itd.). Neki od polimernih lanaca koji se koriste za katalizatore poznati su iz prethodnog stanja tehnike (Reetz et al., Angew. Chem. 1997, 109, 1559f.; Seebach et al., Helv. Chim Acta 1996, 79, 1710f.; Kragl et al., Angew. Chem. 1996, 108, 684f.; Schurig et al., Chem. Ber./Recueil 1997, 130, 879f.; Bolm et al., Angew. Chem. 1997, 109, 773f.; Bolm et al. Eur. J. Org. Chem. 1998, 21f.; Baystone et al., u Speciality Chemicals 224f.; Salvadori et al., Tetrahedron: Asymmetry 1998, 9, 1479; Wandrey et al., Tetrahedron: Asymmetry 1997, 8, 1529f.; ibid. 1997, 8, 1975f.; Togni et al. J. Am. Chem. Soc. 1998, 120, 10274f., Salvadori et al., Tetrahedron Lett. 1996, 37, 3375f; WO 98/22415; posebice DE 19910691.6; Janda et al., J. Am. Chem. Soc. 1998, 120, 9481f.; Andersson et al., Chem. Commun. 1996, 1135f.; Janda et al., Soluble Polymers 1999, 1, 1; Janda et al., Chem. Rev. 1997, 97, 489; Geckler et al., Adv. Polym. Sci. 1995, 121, 31; White et al., u "The Chemistry of Organic Silicon Compounds" Wiley, Chichester, 1989, 1289; Schuberth et al., Macromol. Rapid Commun. 1998, 19, 309; Sharma et al., Synthesis 1997, 1217; "Functional Polymers" Ed.: R. Arshady, ASC, Washington, 1996; "Praktikum der Makromolekularen Stoffe", D. Braun et al., VCH-Wiley, Weinheim 1999).
Također je poželjno da se polimerni lanac tvori od poliakrilata, poliakrilamida, polivinilpirolidinona, polisiloksana, polibutadiena, poliizopropena, polialkana, poli-stirena, polioksazolina ili polietera, ili mješavine spomenutih skupina spojeva. U jednom posebice poželjnom utjelovljenju, polistireni se rabe za konstruiranje polimerskog lanca.
Linkeri:
Izmedju liganda i polimerskog lanca inkorporira se linker. Linkerom se postiže razmak izmedju liganda i polimera kako bi se smanjile ili uklonile medjusobne interakcije koje nisu korisne za reakciju.
U principu, linkere može slobodno odabrati stručnjak u predmetnom području. S jedne strane, oni se trebaju odabrati prema tome kako dobro se spajaju s polimerom/monomerom, s jedne strane, i s ligandom, s druge strane. Prikladni linkeri mogu se naći u ranije spomenutim referencama iz literature pod nazivom "Polimerni lanac".
U okviru predmetnog izuma, te se djelatne jedinice formule (I) do (IV) mogu vezati direktno za polimerni lanac, ili poželjno preko linkera koja je odabran iz skupine
a) -Si(R2)-
b) -(SiR2-O)n- n=1-10000
c) -(CHR-CHR-O)n- n=1-10000
d) -(X)n- n=1-20
e) Z-(X)n- n=0-20
f) -(X)n-W n=0-20
g) Z-(X)n-W n=0-20
gdje
R označava H, (C1-C8)-alkil, (C6-C18)-aril, (C7-C19)-aralkil, ((C1-C8)-alkil)13-(C6-C18)-aril, X označava (C6-C18)-arilen, (C1-C8)-alkilen, (C1-C8)-alkenilen, ((C1-C8)-alkil)13-(C6-C18)-arilen, (C7-C19)-aralkilen,
Z, W označavaju svaki za sebe, -C(=O)O-, -C(=O)NH-, -C(=O)-, NR, O, CHR, CH2, C=S, S, PR.
Drugi poželjni spojevi koji se mogu rabiti kao linkeri prikazani su na sljedećem dijagramu:
[image]
Medjutim, linkeri poput, primjerice, 1,4’-bifenil, 1,2-etilen, 1,3-propilen, PEG-(2-10), α,ω-siloksanilen ili 1,4-fenilen, kao i α,ω-bisetilenbenzen ili linkeri koji se mogu dobiti iz siloksana opće formule IV posebice su poželjni.
[image]
Oni se lako mogu vezati na bilo koju od dvostrukih veza u polimerima i na bilo koju od funkcijskih skupina iz aktivnih središta u uvjetima hidrosililacije (pregled reakcije hidrosililacije od Ojime, u “The Chemistry of Organic Silicon Compounds“, 1989 John Wiley & Sons Ltd., 1480-1526).
Poželjno je izračunati veličinu polimerskog lanca tako da se konkretni katalizator (koji se dobiva od liganda koji se po izboru vezuje za lanac i prijelaznog metala) rastapa u otapalu koje se koristi, kako bi reakcija mogla izvoditi u homogenoj fazi. Korišteni katalizator/kompleks koji se vezuju na polimerni lanac poželjno se otapaju u homogenoj fazi. Kao rezultat toga, mogu se izbjeći negativni učinci do kojih dolazi kao posljedica izmjene supstrata tijekom faze i proizvoda, koji su nužni za upotrebu heterogenog katalizatora. Ligandi koji se vezuju za polimerni lanac imaju prosječnu molekulsku masu u opsegu od 1.000-1.000.000, poželjno od 5.000-500.000, a najpoželjnije u opsegu od 5.000-300.000 g/mol.
U osnovi je predmetnog izuma da se gore spomenute komponente za katalizatore (I) do (IV), koji se vezuju za polimerni lanac (polimer, linker, ligand) mogu kombinirati po želji sukladno iskustvu stručnjaka kako bi se postigli najbolji uvjeti reakcije.
Kombinacija polimerskog lanca s linkerom/ ligandom:
U principu postoje dva načina na koji se linkeri/ligandi mogu vezati za polimerni lanac:
aktivna jedinica koja uzrokuje kiralnu indukciju (ligand) vezuje se na spojeni linker ili direktno na monomer, te dolazi do kompolimerizcije s ostalim nepromijenjenim monomerima, ili aktivna jedinica koja uzrokuje kiralnu indukciju (ligand) vezuje se za linker ili direktno za dovršeni polimer.
Polimeri prema a) ili b) mogu se po izboru pripraviti i podvrgnuti blok-kopolimerizacijom s ostalim polimerima, koji također posjeduju aktivnu jedinicu koja uzrokuje kiralnu indukciju (ligand) ili koji ih ne posjeduju.
U principu je također točno za veliki broj linkera/ liganda po monomeru u polimeru da je potrebno ubaciti što je moguće veći broj ovih katalitički aktivnih jedinica (liganda) u polimer, tako da kao posljedica toga dolazi do povećanja konverzije po polimerskom lancu. Medjutim, s druge strane, ligandi trebaju biti dovoljno udaljeni jedan od drugog tako da se umanji ili potpuno izbjegne recipročni negativni efekat na reaktivnost (TOF, selektivnost). Stoga je poželjno da razmak izmedju linkera/liganda u polimeru bude u opsegu od 1-200 monomernih jedinica ili, još poželjnije, od 5-25 monomernih jedinica.
U jednom poželjnom utjelovljenju izuma, oni položaji u polimeru ili monomeru koji se trebaju polimerizirati kako bi mogli postati funkcionalni, ili oni koji zadržavaju postojeću funkcionalnost radi vezivanja, koriste se za spajanje linkera/ liganda. Heteroatomi ili nezasićeni atomi ugljika posebice su poželjni za formiranje veze.
U slučaju stirena/polistirena kao dijela polimerskog lanca, postojeći aromatični spojevi mogu se koristiti kao točke vezanja za linkere/ligande. Funkcionalne skupine se lako mogu spajati na ove aromatične spojeva, poželjno u položajima 3-, 4- ili 5-, a posebice poželjno u položaju 4-, primjenom standarda kemije aromatičnih spojeva. Medjutim, također je korisno pomiješati već funkcionalizirani monomer s mješavinom koja se treba polimerizirati, te spojiti linker/ligand na funkcionalne skupine koje su prisutne u polistirenskom lancu nakon polimerizacije. Za tu su svrhu posebice korisni, primjerice, para-hidroksi, para-klorometil- ili para-aminostirenski derivati.
U slučaju poliakrilata, kiselinska skupina ili esterska skupina prisutna je u monomeru u svakom slučaju, za koju se linker ili aktivna jedinica spaja prije ili poslije polimeri-zacije, poželjno preko esterske ili amidne veze.
Polisiloksani kao dijelovi polimerskog lanca poželjno se tvore na takav način da su, osim dimetilsilanskih jedinica, također prisutne i hidrometilsilanske jedinice. Linkeri/ ligandi se također mogu vezati na ove položaje hidrosililacijom. Oni se poželjno vezuju na funkcionalne skupine u uvjetima hidrosililacije u polimerskom lancu (pregled reakcije hidrosililacije od Ojime, u “The Chemistry of Organic Silicon Compounds”, 1989 John Wiley & Sons Ltd., 1480-1526).
Prikladni polisiloksani koji se modificiraju na ovaj način poznati su u literaturi ("Siloxane polymers and copolymers" White et al., u Ed. S. Patai, "The Chemistry of Organic Silicon Compounds" Wiley, Chichester, 1989, 46, 2954; C. Wandrey et al. TH: Asymmetry 1997, 8, 1975).
Kombinacija linkera sa aktivnom jedinicom:
Ono što se odnosi na spajanje polimera na linker/ ligand, na isti način je primjenjivo i na vezanje liganda (aktivna jedinica) na linker.
Tako se vezanje linkera na aktivne jedinice poželjno vrši preko heteroatoma ili izvjesnih funkcijskalnih skupina, poput C= O, CH2, O, N, S, P, Si ili B, poželjno se vezuju veza eter, tioeter, amino veza ili amidna veza, ili se vrše esterifikacija, alkilacija, sililacija i adicija na dvostruku vezu.
Ti su postupci vezivanja monomernih aktivnih jedinica na polimerni lanac već ranije opisani u prethodnom stanju tehnike i posebice su poželjni (WO98/35927; Chem. Commun. 1999, 1917; Angew. Chem. 1997, 16, 1835; J. Am. Chem. Soc. 1996, 118, 7632; Tetrahedron Lett. 1997, 38, 1527; Eur. J. Org. Chem. 1998, 21; Angew. Chem. 1997, 109, 773; Chem. Commun. 1997, 2353; Tetrahedron: Asymmetry 1995, 6, 2687; ibid 1993, 4, 2351; Tetrahedron Lett. 1995, 36, 1549; Synlett 1999, 8, 1181; Tetrahedron: Asymmetry 1996, 7, 645; Tetrahedron Lett. 1992, 33, 5453; ibid 1994, 35, 6559; Tetrahedron 1994, 50, 11321; Chirality 1999, 11, 745; Tetrahedron Lett. 1991, 32, 5175; Tetrahedron Lett. 1990, 31, 3003; Chem. Commun. 1998, 2435; Tetrahedron Lett. 1997, 38, 2577).
Proizvodnja sustava liganda ili katalizatora koji se vezuju na polimerni lanac također se za svrhu predmetnog izuma može, u prinicipu, izvoditi prema opisu njemačke patentne prijave DE10029600.
Ligandi opće formule (III) ili (IV)
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u kojima
A i Q imaju značenje kao u patentnom zahtjevu 1, R’ = H ili R, i gdje R, u svakom slučaju neovisno jedan od drugog, označava (C1C8)alkil, HO-(C1-C8)-alkil, (C2C8)alkoksialkil, (C6C18)aril, (C7C19)aralkil, (C1C8)alkil(C6C18)aril, (C3C8)cikloalkil, (C1C8)alkil(C3C8)cikloalkil ili (C3C8)cikloalkil(C1C8)alkil. Ligandi iz gornjih formula (III) i (IV), u kojima je R metil, etil, propil, izo-propil, terc.-butil ili fenil, izuzetno su poželjni. Formule u kojima je Q kisik ili NR’, gdje je R’ (C1-C8)-alkil, (C6C18)aril ili benzil, kao i onima u kojima je Q kisik ili NR’, gdje je R’ metil, etil, propil, izo-propil, terc.-butil, fenil, naftil, fluorenil ili benzil, također su izuzetno poželjni.
Ako je moguće, ligandi sukladno predmetnom izumu trebaju imati visok stupanj enantiomeričke čistoće. Spojevi formule (I) do (IV) poželjno trebaju imati enantiomeričko obogaćenje od >90 %, još poželjnije > 98%.
Sljedeći se aspekt predmetnog izuma odnosi na komplekse koji sadrže ligande s najmanje jednim prijelaznim metalom. Paladij, platina, rodij, rutenij, osmij, iridij, kobalt, nikal ili bakar, u bilo kojem relevantnom oksidacijskom stanju tijekom katalize, pogodni su kao tranzicijski metali. Ti se kompleksni spojevi dobivaju u otopini jednostavnim dodatkom liganda sukladno predmetnom izumu prekusorima metalnog kompleksa, koji su poznati stručnjacima u predmetnom području.
U drugom svom obliku, predmetni se izum također odnosi na proces proizvodnje liganda sukladno izumu, u kojima se odgovarajući fosfini dobivaju reakcijom LiP(SiMe3)2 sa odgovarajućim ko-reaktantima koji posjeduju nukleofugalne odlazeće skupine u prisutnosti organometalne baze. Alkili koji sadrže metal, poput primjerice, n-, sec, terc.-BuLi, MeLi, ili slično, mogu se koristiti kao organometalne baze.
Tako dobiveni trimetilsililfosfini poželjno reagiraju s odgovarajućim dihalogenskim derivatom iz skupine A, koja je gore prikazana, a svaki od atoma halogena zauzima položaj u strukturi sa slobodnim valencama.
Jedan postupak za proizvodnju skupine sukladno predmetnom izumu bit će opisan dolje pomoću primjera. Radi jasnoće, derivati anhidrida maleinske kiseline odabrani su iz primjera, a da pri tom ne predstavljaju ikakva ograničenja za A. Općenito, postupak se sastoji u reakciji enantiomera bogatog sulfatom s fosfinom u prisutnosti jake baze kako bi se dobio monofosfolan. U još jednoj fazi reakcije, veza fosfor-ugljik se cijepa pomoću alkalijskog metala i prevodi u silil fosfolan dodatkom silil spojeva sa halogenom. U sljedećoj fazi reakcije, silil fosfolan reagira s 2,3-anhidridom dikloromaleinske kiseline ili s derivatom 2,3-dikloromaleamida kako bi se dobio bisfosfolan.
Diol se prevodi u dimezilat u prisutnosti dušične baze i potom u fosfolan u prisutnosti Li2PPh2-THF (Tetrahedron Asymmetry 1991, 2, 569-592).
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Fosfolan se također može dobiti reakcijom cikličkog sulfata s H2PPh u prisutnosti hidrida alkalijskih metala (J. Am. Chem. Soc. 1999, 121, 9899-9900).
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Još jedna alternativna priprava fosfolana se vrši reakcijom cikličkog sulfata s fenilfosfinom u prisutnosti butillitija.
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Nakon cijepanja veze Ph-P s elementarnim litijem, dobiva se P-sililirani spoj dodavanjem trimetilsilil klorida.
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Alternativni put sinteze obuhvaća reakciju cikličkog sulfata s litij bis(trimetilsilil)fosfinom (Organometallics 2000, 19, 250). Umjesto metanolize veza fosfor-silicij, koje su opisane u Burk i dr., pokazalo se korisnim u sintezi liganda sukladno predmetnom izumu izvršiti zatvaranje prstena dodatkom metillitija, pri čemu se dobiva fosfolan supstituiran s trimetilsililom.
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U obje reakcijske rute, uočena je tvorba fosfolana supstituiranog trimetilsililom u mezo-obliku kao sporedna reakcija.
U sljedećem koraku, reakcija silil fosfolana s derivatom 2,3-dikloromaleinske kiseline odigrava se analogno reakciji sparivanja od Fenske i dr. i Kinting i dr. (Chem. Ber. 1974, 107, 117; J. Organomet. Chem. 1986, 302, 259).
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Prečišćavanje liganda se odvija tvorbom metalnog kompleksa. Začudo, ovdje je otkriveno kako se kompleks dobiva u optički čistom obliku iz dijastereomeričke mješavine spojeva ligand-metal.
Spojevi opće formule (I) – (IV) mogu se koristiti kao ligandi za kompleksne spojeve u asimetričnim reakcijama, reakcijama koje su katalizirane metalom (kao što su, primjerice, hidrogenacija, hidroformilacija, premještanje (skupina), alilna alkilacija, ciklopropanacija, hidrosililacija, hidridni transferi, hidroboracije, hidrocijanacije, hidrokarboksilacije, aldolne reakcije ili Heckova reakcija). Oni su posebice pogodni za asimetrične reakcije.
Prikladni kompleksi, posebice oni opće formule (V), sadrže ligande sukladno predmetnom izumu formule (I) – (IV),
[MxPyLzSq]Ar (V)
pri čemu, u općoj formuli (V), M označava metalno središte, poželjno središte koje sadrži prijelazni metal, L označava iste ili različite, koordinirane, organske ili neorganske ligande, a P označava bidentatne organofosforne ligande formule (I) – (IV) sukladno predmetnom izumu, S predstavlja koordinacijske molekule otapala, a A predstavlja ekvivalente nekoordiniranih aniona, gdje x i y predstavljaju cijele brojeve veće od ili jednake 1, a z, q i r predstavljaju cijele brojeve veće od ili jednake 0.
Zbroj y + z + q ima gornju granicu odredjenu koordinacijskim središtima koja su dostupna u metalnom središtu, a pri tome nije nužno da sva koordinacijska mjesta budu zauzeta. Poželjni su kompleksni spojevi s oktaedarskim, pseudo-oktaedarskim, teteraedarskim, pseudo-teteraedarskim ili kvadratno-planarnim koordinacijskim sferama, koje, u svakom od slučajeva, također mogu biti deformirane oko središta prijelaznog metala. Zbroj y + z + q u tim je kompleksnim spojevima manji od ili jednak 6.
Kompleksni spojevi sukladno predmetnom izumu sadrže najmanje jedan metalni atom ili ion, koji je poželjno atom prijelaznog metala ili ion, najčešće paladij, platina, rodij, rutenij, osmij, iridij, kobalt, nikal ili bakar u bilo kojem relevantnom oksidacijskom stanju kod katalize.
Poželjni su kompleksni spojevi s manje od četiri metalna središta, dok su ona s jednim ili dva metalna središta posebice poželjna. Metalna središta mogu biti popunjena s različitim atomima metala i/ ili ionima.
Poželjni ligandi L tih kompleksnih spojeva su halidi, posebice Cl, Br i I, dien, posebice ciklooktadien, norbornadien, olefin, posebice etilen i ciklookten, acetato, trifluoro-acetato, acetilacetonato, alil, metalil, alkil, posebice metil i etil, nitril, posebice acetonitril i benzonitril, te također karbonil i hidrido ligandi.
Poželjna otapala za koordinacijske spojeve S su amini, posebice trietilamin, alkoholi, posebice metanol i aromatični spojevi, posebice benzen i kumol (izopropilbenzol).
Poželjni ne-koordinirajući anioni A su trifluoroacetat, trifluorometan, sulfonat, BF4, ClO4, PF6, SbF6 i BAr4.
Različiti molekuli, atomi ili ioni pojedinačnih komponenti M, P, L, S i A mogu biti uključeni unutar pojedinačnih kompleksnih spojeva.
Među kompleksnim spojevima koji sadrže ione, poželjni su spojevi tipa [RhP(dien)]+A-, u kojima P predstavlja ligand formule (I) – (IV) sukladno predmetnom izumu.
Priprava spojeva koji sadrže komplekse metal-ligand odigrava se in situ reakcijom soli metala ili odgovarajućeg preliminarnog kompleksa s ligandima opće formule (I) – (IV). Osim toga, spojevi kompleksa metal-ligand mogu se dobiti reakcijom soli metala ili odgovarajućeg preliminarnog kompleksa s ligandima opće formule (I) – (IV) nakon izoliranja koje potom slijedi.
Primjeri soli metala su metalni kloridi, bromidi, jodidi, cijanidi, nitrati, acetati, acetilacetonati, heksafluoroacetilacetonati, teterafluoroborati, perfluoroacetati ili triflati, posebice paladija, platine, rodija, rutenija, osmija, iridija, kobalta, nikla ili bakra.
Primjeri odgovarajućih preliminarnih kompleksa su :
Ciklooktadienpaladij klorid, ciklooktadienpaladij jodid, 1,5-heksadienpaladij klorid, 1,5-heksadienpaladij jodid, bis(dibenzilidenaceton)paladij, bis(acetonitril)paladij(II) klorid, bis(acetonitril)paladij(II) bromid, bis(benzonitril)paladij(II) klorid, bis(benzonitril)paladij(II) bromid, bis(benzonitril)paladij(II) jodid, bis(alil)paladij, bis(metalil)paladij, alilpaladij klorid dimer, metalilpaladij kloridni dimer, teterametiletilendiaminpaladij diklorid, teterametiletilendiaminpaladij dibromid, teterametiletilendiaminpaladij dijodid, teterametiletilendiaminpaladij dimetil, ciklooktadienplatina klorid, ciklooktadienplatina jodid, 1,5-heksadienplatina klorid, 1,5-heksadienplatina jodid, bis(ciklooktadien)platina, kalij (etilentrikloroplatinat), ciklooctadienrodij(I) kloridni dimer, norbornadienrodij(I) kloridni dimer, 1,5-heksadienrodij(I) kloridni dimer, tris(trifenilfosfan)rodij(I) klorid, hidridokarboniltris(trifenilfosfan)rodij(I) klorid, bis(ciklooktadien)rodij(I) perklorat, bis(ciklooktadien)rodij(I) teterafluoroborat, bis(ciklooktadien)rodij(I) triflat, bis(acetonitrilciklooktadien)rodij(I)perklorat, bis(acetonitrilciklooktadien)rodij(I)teterafluoroborat, bis(acetonitrilciklooktadien)rodij(I) triflat, ciklopentadienrodij(III) kloridni dimer, pentametilciklopentadienrodij(III) kloridni dimer, (ciklooktadien)Ru(η3-alil)2, ((ciklooktadien)Ru)2(acetat)4, ((ciklooktadien)Ru)2(trifluoroacetat)4, RuCl2(aren) dimer, tris(trifenilfosfan)rutenij(II) klorid, ciklooctadienrutenij(II) klorid, OsCl2(aren) dimer, ciklooktadieniridij(I) kloridni dimer, bis(ciklookten)iridij(I) kloridni dimer, bis(ciklooktadien)nikal, (ciklododekatrien)nikal, tris(norbornen)nikal, nikal teterakarbonil, nikal(II) acetilacetonat, (aren)bakar triflat, (aren)bakar perklorat, (aren)bakar trifluoroacetat, kobalt karbonil.
Kompleksni spojevi koji imaju jedan ili više metala iz skupine metalnih elemenata, posebno iz skupine koju čine Ru, Co, Rh, Ir, Ni, Pd, Pt i Cu, mogu već sami biti katalizatori ili se mogu koristi za dobivanje katalizatora koji sadrže jedan ili više metala iz skupine metalnih elemenata, posebno iz skupine koju čine Ru, Co, Rh, Ir, Ni, Pd, Pt i Cu. Svi su ti kompleksni spojevi posebice prikladni kod asimetrične hidrogenacije C=C-, C=O- ili C=N-veze, gdje pokazuju visoku aktivnost i selektivnost, kao i kod reakcije asimetrične hidroformilacije. Naročito pogodnim pokazala se činjenica da se ligandi opće formule (I) – (IV) mogu vrlo dobro prilagoditi, sterički i elektronski, konkretnom supstratu i katalitičkoj reakciji zaradi njihove jednostavne adaptibilnosti širokog spektra.
Odgovarajući katalizatori sadrže najmanje jedan kompleksni spoj sukladno predmet-nom izumu.
Kako je već naznačeno, uporaba kompleksa ili katalizatora sukladno predmetnom izumu posebice je prikladna za hidrogenaciju mješavine E/Z prokiralnih N-acetiliranih βaminoakrilnih kiselina ili njihovih derivata. Acetil, formil ili uretan ili zaštitine skupine za karbamoil ovdje se poželjno mogu koristiti kao acilna skupina.
U principu se ligandi i kompleksi/katalizatori koriste na način koji je poznat stručnjacima u obliku reakcije transfer hidrogenacije ("Asymmetric transfer hydrogenation of C=O and C=N bonds", M. Wills et al. Tetrahedron: Asymmetry 1999, 10, 2045; "Asymmetric transfer hydrogenation catalyzed by chiral ruthenium complexes" R. Noyori et al. Acc. Chem. Res. 1997, 30, 97; "Asymmetric catalysis in organic synthesis", R. Noyori, John Wiley & Sons, New York, 1994, p.123; "Transition metals for organic Synthesis" Ed. M. Beller, C. Bolm, Wiley-VCH, Weinheim, 1998, vol. 2, p.97; "Comprehensive Asymmetric Catalysis" Ed.: Jacobsen, E.N.; Pfaltz, A.; Yamamoto, H., Springer-Verlag, 1999), ali se također može koristiti elementarni vodik. Postupak se može izvoditi ili hidrogenacijom s vodikovim plinom ili transfer hidrogenacijom.
Kod enantioselektivne hidrogenacije, poželjan je postupak otapanje substrata koji se treba hidrogenirati i kompleksa/katalizatora u otapalu. Kako je navedeno gore, katalizator se poželjno tvori iz preliminarnog katalizatora u prisutnosti kiralnog liganda, reakcijom ili procesom pre-hidrogenacije prije dodavanja supstrata. Potom se hidrogenacija izvodi pod tlakom vodika od 0,1 do 10 bara, poželjno od 0,5 do 5 bara.
Tijekom hidrogenacije, odabire se ona temperatura pri kojoj se reakcija odvija dovoljno brzo s poželjenim enantiomeričkim viškom, ali pri tom treba izbjegavati sporedne reakcije najvećoj mogućoj mjeri. Korisno je da se reakcija odvija na temperaturama od –20°C do 100°C, poželjno od 0°C do 50°C. Odnos supstrata prema katalizatoru određen je ekonomskim čimbenicima. Reakcija se treba odvijati dovoljno brzo s najnižom mogućom koncentracijom kompleksa/katalizatora. Medjutim, poželjno je odvijanje reakcija pri omjeru koncentracije supstrat/katalizator izmedju 10000:1 i 10:1, a poželjno je od 1000:1 i 50:1.
Upraba liganda ili kompleksa koji se vežu za polimer korisna je za katalitičke procese koji se odvijaju u membranskom reaktoru. Ako je potrebno, osim rada u šaržama i polukontinuiranog rada, reaktor može raditi i kontinuirano, putem filtracije poprečnim protokom (Sl. 2) ili tzv. “dead-end“ filtracijom (Sl. 1).
Obje su varijante procesa u principu opisane u prethodnom stanju tehnike (Engineering Processes for Bioseparations, Ed.: L.R. Weatherley, Heinemann, 1994, 135-165; Wandrey et al., Tetrahedron Asymmetry 1999, 10, 923928).
Da bi neki kompleks/katalizator bio prikladan za upotrebu u membranskom reaktoru, mora ispuniti mnogo različitih kriterija. S jedne strane, na primjer, treba se osigurati da postoji dovoljno visok retencijski kapacitet za kompleks/katalizator koji se veže na polimer, tako da postoji zadovoljavajuća aktivnost u reaktoru tijekom željenog perioda, a da se pri tom ne mora stalno dodavati kompleks/katalizator, što je štetno glede ekonomičnosti postupka (DE19910691). Osim toga, katalizator koji se koristi u postupku mora imati odgovarajuću tof (turn over frequency, frekvenciju obratovanja), kako bi mogao prevesti supstrat u proizvod unutar ekonomski prihvatljivog perioda.
Općenito, prekusori β-amino kiselina dobivaju se prema opisima iz literature. Za sinteze spojeva treba slijediti smjernice u okviru općenitih specifikacija koje navode Zhang i dr. (G. Zhu, Z. Chen, X. Zhang J. Org. Chem. 1999, 64, 6907-6910) i Noyori et al. (W. D. Lubell, M. Kitamura, R. Noyori Tetrahedron: Asymmetry 1991, 2, 543-554), kao i Melillo et al. (D. G. Melillo, R. D. Larsen, D. J. Mathre, W. F. Shukis, A. W. Wood, J. R. Colleluori J. Org. Chem. 1987 52, 5143-5150). Polazeći od prikladnih 3-ketokarboksilata, dobivaju se željeni prokiralni enamidi reakcijom s amonij acetatom i potom acilacijom. Proizvodi dobiveni hidrogenacijom mogu se prevesti u β-aminokiseline postupcima koji su poznati stručnjacima (analogno dobivanju α-aminokiselina).
U okviru predmetnog izuma, mješavine polimera- povećanog polimerskog lanaca upućuju na činjenicu da se pojedinačni polimeri različitog podrijetla polimeriziraju zajedno u blok polimere. Također su moguće nasumce stvorene mješavine monomera u polimeru.
Povećanje polimerskog lanca u okviru predmetnog izuma odnosi se na činjenicu da se jedna ili više aktivnih jedinica koje uzrokuju kiralnu indukciju (liganda) kopolimeriziraju u odgovarajućem obliku s ostalim monomerima ili s onim ligandima koji su spojeni za postojeći polimer postupcima poznatim stručnjacima. Oblici aktivnih jedinica koji su pogodni za kopolimerizaciju dobro su poznati stručnjaku u predmetnom području, koji ih može odabirati po vlastitom nahođenju. Postupak je poželjno takav da se molekul derivira sa skupinama koje su sposobne za kopolimerizaciju, sukladno tipu kopolimerizacije, na primjer, u slučaju kopolimerizacije s (met)akrilatima, spajanjem na molekule akrilata.
Metil, etil, npropil, izopropil, nbutil, izobutil, sekbutil, tercbutil, pentil, heksil, heptil ili oktil, zajedno sa svim njihovim vezanim izomerima, smatraju se (C1C8)-alkil radikalima. (C1C8)-alkoksi radikal odgovara (C1C8)-alkil radikalu, pod uvjetom da je ovaj vezan za molekul preko atoma kisika.
Kada je riječ o (C2C8)-alkoksialkilu, alkilni lanac radikala prekida se s najmanje jednim atomom kisika, pri čemu se dva atoma kisika ne mogu vezati jedan na drugi. Broj atoma ugljika daje ukupan broj atoma ugljika koji su sadržani u radikalu.
(C3-C5)-alkilenski most je ugljični lanac s tri do pet C atoma, a taj lanac je spojen na molekul preko dva različita C atoma.
Maloprije opisani radikali mogu biti mono- ili polisupstituirani s halogenima i/ili radikalima koji sadrže atome N, O, P, S ili Si. Uglavnom su to alkil radikali gore spomenutog tipa, s jednim ili više spomenutih heteroatoma u svom lancu ili su vezani na molekul preko nekog od ovih heteroatoma.
(C3C8)-Cikloalkil označava ciklopropil, ciklobutil, ciklopentil, cikloheksil ili ciklo-heptil radikale itd. Isti se mogu supstituirati s jednim ili više halogena i/ili radikala koji sadrže N, O, P, S ili Si atome i/ili mogu imati N, O, P ili S atome u prstenu, poput primjerice, 1-, 2-, 3-, 4-piperidil, 1-, 2-, 3-pirolidinil, 2-, 3-teterahidrofuril, 2-, 3-, 4-morfolinil.
(C3-C8)-cikloalkil-(C1-C8)-alkil radikal odnosi se na cikloalkil radikal na gore opisani način, koji je vezan za molekul preko alkil radikala.
U okviru predmetnog izuma, (C1C8)-aciloksi označava alkil radikal kako je definiran gore, s najviše 8 C atoma, koji je vezan na molekul preko COO- .
U okviru predmetnog izuma (C1C8)-acil označava alkil radikal kako je definiran gore, s najviše 8 C atoma, koji je vezan na molekul preko CO-.
(C6-C18)-aril radikal označava aromatični radikal sa 6 do 18 C atoma. Tu posebice spadaju spojevi poput fenila, naftila, antrila, fenantrila ili bifenil radikala, koji se u obliku prstena vežu za molekul, poput primjerice, indenilnih sustava, koji su po izboru supstituirani s (C1C8)-alkil, (C1C8)-alkoksi, NR1R2, (C1C8)-acil ili (C1C8)-aciloksi.
(C7C19)aralkil radikal predstavlja (C6C18)aril radikal koji je vezan na molekul preko (C1C8)alkil radikala.
U okviru predmetnog izuma (C3C18)heteroaril radikal odnosi se na petero-, šestero- ili sedmeročlani aromatični prstenasti sustav od 3 do 18 C atoma, koji sadrži heteroatome poput, primjerice, dušika, kisika ili sumpora u prstenu. Posebice se radikali poput 1, 2, 3furila, 1, 2, 3pirolila, 1, 2, 3tienila, 2, 3, 4piridila, 2, 3, 4, 5, 6, 7indolila, 3, 4, 5pirazolila, 2, 4, 5imidazolila, akridinila, kinolinila, fenantridinila i 2, 4, 5, 6pirimidinila smatraju takovim heteroaromatičnim radikalima.
(C4C19)heteroaralkil označava heteroaromatični sustav koji odgovara (C7C19)aralkil radikalu.
Fluor, klor, brom i jod predstavljaju halogene (Hal).
PEG označava polietilen glikol.
U okviru predmetnog izuma, pojam “obogaćen enantiomerima“ ili “enantiomerički višak“ označava odnos enantiomera u mješavini s optičkim antipodom u opsegu između >50 % i <100 %. Vrijednost ee izračunava se na sljedeći način:
([Enantiomer1]-[Enantiomer2])/([Enantiomer1]+[Enantiomer2])=ee vrijednost
Davanje naziva kompleksima i ligandima sukladno predmetnom izumu obuhvaća sve moguće dijastereomere, a dva optička antipoda bilo kojeg dijastereomera također su obuhvaćeni predmetnim izumom.
Ovdje opisani kompleksi i katalizatori svojom konfiguracijom određuju optičku indukciju u proizvodu. Podrazumijeva se da katalizatori, kada se koriste racemski, također daju racemski proizvod. Naknadno razdvajanje racemata ponovno daje proizvode obogaćenih enantiomerima. To je, medjutim, opće mjesto poznato svakom stručnjaku.
N-Acil skupine predstavljaju zaštitne skupine koje se obično koriste u kemiji amino-kiselina za zaštitu atoma dušika. Posebice se u toj funkciji mogu spomenuti sljedeće skupine: formil, acetil, Moc, Eoc, ftalil, Boc, Alloc, Z, Fmoc, itd.
Reference iz literature koje se navode u ovom dokumentu sadržane su u okviru predmetnog izuma.
U okviru predmetnog izuma, membranski reaktor označava bilo koju reakcijsku posudu u koju se stavlja katalizator s povećanom molekulskom težinom dok se tvari male molekulske težine dodaju u reaktor ili se iz njega izvlače. Membrana može biti integrirana izravno u reakcijsku komoru ili se može instalirati izvan nje u odvojenom modulu za filtraciju, gdje reakcijska otopina neprekidno ili s prekidima protječe kroz modul za filtraciju, a retentat se ponovo reciklira u reaktor. Prikladna su utjelovljenja opisana, medju ostalim, u WO98/22415 i u Wandrey i dr., u Jahrbuch 1998, Verfahrenstechnik und Chemieingenieurwesen, VDI p. 151 ff.; Wandrey et al., u Applied Homogeneous Catalysis with Organometallic Compounds, Vol. 2, VCH 1996, p. 832 ff.; Kragl et al., Angew. Chem. 1996, 6, 684 f..
U okviru predmetnog izuma, ligand/kompleks sa polimernim lancem označava polimerni lanac kojem je povećana molekulska težina stvaranjem kovalentne veze za ligandom.
Opis slika:
Sl. 1 prikazuje membranski reaktor s tzv. “dead-end“ filtracijom. Supstrat 1 se prenosi pomoću pumpe 2 u reakcijsku komoru 3, s membranom 5. U reaktoru s mješalicom se, osim otapala, nalaze se i katalizator 4, proizvod 6 i neizreagirani supstrat 1. Tvari male molekulske težine 6 uglavnom se filtriraju kroz membranu 5.
Sl. 2 prikazuje membranski reaktor s filtracijom s poprečnom strujom. Supstrat 7 se prenosi pomoću pumpe 8 u reakcijsku komoru s mješalicom, u kojoj se također nalaze katalizator 9 i proizvod 14. Pomoću pumpe 16 prilagođava se protok otapala, koje prolazi po izboru dodanom izmjenjivaču toplote 12 u ćeliji za filtraciju s poprečnom strujom 15. Ovdje se proizvod male molekulske mase 14 odvaja pomoću membrane 13. Katalizator velike molekulske mase 9 se nakon toga propušta natrag u reaktor 10 s protokom otapala, po izboru ponovo preko izmjenjivača toplote 12, ili po izboru preko ventila 11.
Primjeri:
Opći prikaz
Reakcije spojeva koji su osetljivi na zrak odvijaju se u komori napunjenoj argonom ili u standardnim Schlenkovim epruvetama. Otapala teterahidrofuran (THF), dietil eter i diklorometan se otpline i pročiste pomoću opreme za sušenje otapala (Innovative Technologies) filtracijom kroz kolonu napunjenu aktiviranim aluminij oksidom; toluen i pentan se naknadno oslobadjaju kisika na koloni napunjenoj katalizatorom od bakra.
Namjena sljedećih primjera jest bolje objasniti predmetni izum. Oni ni u kom smislu ne predstavljaju ograničenje predmetnog izuma.
Primjer 1
(R,R)-2,5-Dimetil-1-fenil-fosfolan
Ekvivalent n-BuLi (8.9 ml, 1.6 M. otopina u n-heksanu) polagano se dodaje u otopinu 1.57 g fenilfosfina (14.3 mmol) u 100 ml THF-a na –78 °C. Ta se mješavina potom miješa sljedeća dva sata na sobnoj temperaturi. Nakon ponovnog hladjenja do –78 °C, dodaje se preko kanule ekvivalent cikličkog sulfata 1 u 10 ml THF i reakcija se pusti dovršiti nakon 3 h na 25°C. Prije dodavanja dodatnih 1.2 ekv. n-BuLi (9.8 ml) brizgalicom, mješavina se ponovno ohladi, dodaje se n-BuLi i miješanje se nastavlja tijekom noći. Za dobivanje proizvoda, otapalo se uklanja in vacuo i ostatak se sipa u 5 ml vode i ekstrahira s 50 ml metilen klorida. Nakon razdvajanja faza, uklanja se otapalo i ostatak se destilira in vacuo. Dobiva se obojeni sirup u 71 %-tnom prinosu (1.95 g).
Bp0.7 = 105°C; 1H-NMR (CDCl3): 7.51-7.45 (2H, m, arom. H), 7.35-7.30 (3H, m, arom. H), 2.70 (1H, m, CH-P), 2.31 (1H, m, Ha-CH2), 2.22 (1H, m, CH-P), 1.97 (1H, m, Hb-CH2), 1.47 (1H, m, Ha-CH2), 1.34 (1H, m, Hb-CH2), 1.33 (3H, dd, CH3, 3JH,P = 19.0 Hz, 3JH,H = 7.1 Hz), 0.79 (3H, dd, CH3, 3JH,P = 11.5 Hz, 3JH,H = 7.1 Hz); 13C-NMR (u CDCl3): 137.7 (d, ipso-C, 1JC,P= 25.7 Hz), 134.1 (d, orto-C, 2JC,P = 18.1 Hz), 128.4 (s, para-C), 127.8 (d, meta-C, 3JC,P = 6.6 Hz), 36.9 (d, CH2, 2JC,P = 3.8 Hz), 36.8 (s, CH2), 35.3 (d, CH-P, 1JC,P = 11.4 Hz), 34.8 (d, CH-P, 1JC,P= 8.6 Hz), 21.0 (d, CH3, 2JC,P = 33.4 Hz), 15.1 (s, CH3); 31P-NMR (u CDCl3): 10.9; C12H17P (192.237).
Primjer 2
(R,R)-2,5-Dimetil-1-trimetilsilil-fosfolan
Prema opisu Burk i dr. (Tetrahedron: Asymmetry 1991, 2, 569-592), 3.06 g (15.9 mmol) (R,R)-2,5-dimetil-1-fenil-fosfolana u približno 100 ml THF-a uzima se na sobnoj temperaturi i tome se dodaje 2.5 ekvivalenta litija. Mješavina se miješa tijekom noći. Dobivena se suspenzija tamnocrvene boje odvaja od litija korišćenjem kanule, a 2 ekvivalenta klorotrimetilsilana (3.46 g) se lagano dodaju na 0°C uporabom brizgalice. Kako se reakcija bliži kraju, reakcijska otopina sve više postaje obojena. Otopina se koncentrira in vacuo do 60-70% od ukupne zapremine, a nataložene soli litija se isfiltriraju. Nakon što je proces isparavanja dovršen, ostatak se destilira pod sniženim tlakom i dobiva se silil u prinosu od 1.43 g (48%) u vidu bezbojnog spoja u tečnom stanju. 31P-NMR spektar pokazuje prisutnost dvije vrste u približnom omjeru od 3:1. Na osnovu procjene NMR signala, očigledno je da se radi o željenom kiralnom silil fosfolanu i odgovarajućem mezo-spoju. Reakcije izomerizacije ovog tipa već su opisane od strane Burka (Tetrahedron: Asymmetry 1991, 2, 569-592). Budući da se tijekom sljedeće reakcije s anhidridom dikloromaleinske kiseline kristalizira samo jedan dijastereomer, mješavina ovih izomera može se koristiti za nukleofiline reakcije bez daljeg odvajanja.
Bp15 = 72-80°C; 1H-NMR (CDCl3): 2.54-1.20 (6H, m, CH-P, CH2), 1.25-1.15 (6H, m, CH3), 0.20 (d, Si(CH3)3, 3JH,P = 4.2 Hz), 0.15 (d, mezo-Si(CH3)3, 3JH,P = 4.2 Hz), 13C-NMR (u CDCl3): 40.1 (d, CH2, 2JC,P = 4.8 Hz), 38.9 (s, CH2), 37.5 (s, mezo-CH2), 33.6 (d, CH-P, 1JC,P = 11.4 Hz), 31.3 (d, CH-P, 1JC,P = 7.6 Hz), 30.5 (d, mezo-CH-P, 1JC,P = 7.6 Hz), 23.4 (d, mezo-CH3, 2JC,P = 30.5 Hz), 22.8 (d, CH3, 2JC,P = 30.5 Hz), 18.0 (d, CH3, 2JC,P = 1.9 Hz), -0.2 (d, Si(CH3)3, 2JC,P = 11.4 Hz), -1.8 (d, mezo-Si(CH3)3, 2JC,P = 10.5 Hz); 31P-NMR (u CDCl3): -53.1 (mezo), -54.5; C9H21PSi (188,322);
Primjer 3
(R,R)-2,5-Dimetil-1-trimetilsilil-fosfolan
U otopinu 9.50 g tris(trimetilsilil)fosfina (37.9 mmol) u 300 ml THF, na sobnoj temperaturi polagano se dodaje 1.05 ekv. MeLi (28.4 ml, 1.4 M otopina u eteru). Miješanje se nakon toga nastavlja tijekom noći na sobnoj temperaturi, a nakon toga se otapalo uklanja pod vakuumom. Ostatak se sipa u 300 ml etera i dodaje se ekvivalent cikličkog sulfata (6.83 g u 100 ml etera) u kapima u otopinu litijeve soli. Nakon tri sata, ponovo se dodaje 28.4 ml otopine MeLi u reakcijsku mješavinu uz pomoć brizgalice. Da bi se reakcija završila, mješavina se miješa tijekom noći. Otapalo se uklanja in vacuo, a ostatak se pažljivo destilira in vacuo. Dobiva se bezbojan, tečniji sirup u 70%-tnom prinosu (5.0 g).
Bp20 = 93°C; 1H-NMR (CDCl3): 2.54-1.20 (6H, m, CH-P, CH2), 1.25-1.15 (6H, m, CH3), 0.20 (9H, d, Si(CH3)3, 3JH,P = 4.2 Hz), 13C-NMR (u CDCl3): 40.1 (d, CH2, 2JC,P = 4.8 Hz), 38.9 (s, CH2), 33.6 (d, CH-P, 1JC,P = 11.4 Hz), 31.3 (d, CH-P, 1JC,P = 7.6 Hz), 22.8 (d, CH3, 2JC,P = 30.5 Hz), 18.0 (d, CH3, 2JC,P = 1.9 Hz), -0.2 (d, Si(CH3)3, 2JC,P = 11.4 Hz), 31P-NMR (u CDCl3): -54.5; C9H21PSi (188,322);
Primjer 4
Anhidrid 2,3-Bis[(R,R)-2,5-dimetil-fosfolanil]maleinske kiseline
Prema opisu Fenske i dr.(Chem. Ber. 1974, 107, 117-122), dodaje se 450 mg (2.4 mmol) dijastereomeričke mješavine silila 3 u kapima uporabom brizgalice tijekom perioda od 15 minuta u otopinu 200 mg anhidrida 2,3-dikloromaleinske kiseline (0.5 eq.) u 5 ml dietil etera na 0°C. Mješavina se nakon toga tijekom noći drži na –78°C. Nataloženi kristali tamne crveno-smeđe izoliraju se iz otapala filtracijom pomoću filter torbe i potom se suše. Prinos iznosi 190 mg (49%).
Na NMR-u izoliranog spoja, može se detektirati samo jedan dijastereomer C2-simetričnog spoja. To je dokaz kako odgovarajući mezo-sililfosfin, koji se dodaje u reakciju u nedovoljnoj količini, ili nije reagirao ili da se odgovarajući dijastereomerički proizvodi ne kristaliziraju. Uz ovu primjedbu, djelomična racemizacija kod sinteze (R,R)-2,5-dimetil-1-trimetilsilil-fosfolana također se može isključiti. Nakon fosfinili-zacije, njegova uporaba dovodi do tvorbe dijastereomeričkih bisfosfolana, koji nisu detektirani.
1H-NMR (CDCl3): 3.32 (2H, m, CH2), 2.49-1.25 (10H, m, CH-P, CH2), 1.22 (6H, dd, CH3, 3JH,P = 20.4 Hz, 3JH,H = 7.3 Hz), 1.07 (6H, dd, CH3, 3JH,P = 10.5 Hz, 3JH,H = 7.2 Hz); 13C-NMR (u CDCl3): 163.7 (s, C=O), 37.7 (s, CH2), 36.9 (s, CH2), 36.6 (m, CH-P), 31.5 (s, CH-P), 20.5 (m, CH3), 16.9 (s, CH3); 31P-NMR (u CDCl3): -2.2; C16H24O3P2 (326,307);
Primjer 5
Kompleksi rodija dobiveni reakcijom liganda s [Rh(COD)2]BF4
190 mg (0.58 mmol) bisfosfolana se otopi u 2 ml THF-a i polagano dodaje u otopinu jednog ekvivalenta [Rh(COD)2]BF4 (236 mg) na približno -20o C. Spomenuta se otopina pusti zagrijati do sobne temperature i nakon toga se miješa sljedećih 90 min. Polagano se tvori talog smeđe boje, koji se potom isfiltrira i dva puta ispere s eterom.
1H-NMR (aceton-d6): 5.85 (2H, s(br), =CH), 5.15 (2H, s(br), =CH), 3.07 (2H, m, CH-P), 2.67-1.50 (18 H, m, CH-P, CH2), 1.57 (6H, dd, CH3, 3JH,P = 19.5 Hz, 3JH,H = 7.0 Hz), 1.23 (6H, dd, CH3, 3JH,P = 16.0 Hz, 3JH,H = 7.1 Hz);13C-NMR (u acetonu-d6): 165.1 (m, C=C),160.1 (m, C=O), 108.5 (=CH), 94.9 (=CH), 40.8 (m, CH-P), 38.0 (m, CH-P), 37.7 (s, CH2), 36.4 (s, CH2), 32.8 (s, CH2), 29.0 (s, CH2), 17.6 (m, CH3), 14.1 (s, CH3); 31P-NMR (u CDCl3): 63.8 (d, 1JP,Rh= 151 Hz, [Rh(P-P)(COD)]BF4);
Primjer 6
Hidrogenacija
Uvjeti: Katalizator:supstrat: 200:1; 1 mmol substrata, 15 ml metanola ili THF, 25°C, 1.5 bar vodika.
[image]
Primjer 7
Hidrogenacija prekusora β-aminokiselina
Uvjeti: 0.005 mmol katalizatora, 0.5 mmol supstrata, 7.5 ml otapala, 1 bar vodika, 25°C
[image]
Claims (24)
1. Enantiomerički obogaćeni bidentatni organofosforni ligandi opće formule (I),
[image]
naznačen time, da
R1, R2, R3, R4, svaki za sebe predstavljaju, (C1C8)-alkil, (C2C8)-alkoksialkil, (C6C18)-aril, (C7C19)-aralkil, (C3C18)-heteroaril, (C4C19)-heteroaralkil, (C1C8)-alkil-(C6C18)-aril, (C1C8)-alkil(C3C18)-heteroaril, (C3C8)-cikloalkil, (C1C8)-alkil(C3C8)-cikloalkil, (C3C8)-cikloalkil(C1C8)alkil,
ili R1 i R2 i/ili R3 i R4 predstavljaju (C3-C5)-alkilenski most mono-ili polisupstituiran sa (C1C8)alkil, HO-(C1-C8)-alkil, (C1C8)alkoksi, (C2C8)alkoksialkil, (C6C18)aril, (C7C19)aralkil, (C1C8)alkil(C6C18)aril, (C3C8)cikloalkil, (C1C8)alkyl(C3C8)cikloalkil ili (C3C8)cikloalkil(C1C8)alkil, koji su po izboru vezani za polimerni lanac,
i gdje A označava jednu od sljedećih struktura
[image]
u kojima R označava H, (C1C8)alkil, (C6C18)aril, (C7C19)aralkil, (C1C8)alkil(C6C18)aril, (C3C8)cikloalkil, (C1C8)alkil(C3C8)cikloalkil, (C3C8)cikloalkil(C1C8)alkil, ili vezu sa polimerom, a Q = O, NH, NR.
2. Ligandi prema patentnom zahtjevu 1, naznačeni time, da odgovaraju općoj formuli (II),
[image]
u kojoj
A ima značenje kao i u patentnom zahtjevu 1,
R5 do R12, svaki za sebe, predstavljaju (C1C8)alkil, HO-(C1-C8)-alkil, (C1C8)alkoksi, (C2C8)alkoksialkil, (C6C18)aril, (C7C19)aralkil, (C1C8)alkil(C6C18)aril,(C3C8)cikloalkil, (C1C8)alkil(C3C8)cikloalkil, (C3C8)cikloalkil(C1C8)alkil,
ili su vezani za polimerni lanac.
3. Ligandi prema patentnom zahtjevu 1 i/ili 2, naznačeni time, da se polimerni lanac formira od poliakrilata, poliakrilamida, polivinilpirolidinona, polisiloksana, polibutadiena, poliizopropena, polialkana, polistirena, polioksazolina ili polietera, ili mješavine istih.
4. Ligandi prema patentnom zahtjevu 1, 2 i/ili 3 naznačeni time, da su vezani za polimerni lanac preko linkera koji je odabran od skupine
a) -Si(R2)-b) -(SiR2-O)n- n=1-10000
c) -(CHR-CHR-O)n- n=1-10000d) -(X)n- n=1-20e) Z-(X)n- n=0-20f) -(X)n-W n=0-20g) Z-(X)n-W n=0-20gdje
R označava H, (C1-C8)-alkil, (C6-C18)-aril, (C7-C19)-aralkil, ((C1-C8)-alkil)13-(C6-C18)-aril,
X označava (C6-C18)-arilen, (C1-C8)-alkilen, (C1-C8)-alkenilen, ((C1-C8)-alkil)13-(C6-C18)-arilen, (C7-C19)-aralkilen,
Z, W označavaju svaki za sebe, -C(=O)O-, -C(=O)NH-, -C(=O)-, NR, O, CHR, CH2, C=S, S, PR.
5. Ligandi prema jednom ili više od gore spomenutih patentnih zahtjeva, naznačeni time, da predstavljaju katalizatore koji su otopljeni u homogenoj fazi.
6. Ligandi prema patentnom zahtjevu 5, naznačeni time, da je prosječna molekulska masa katalizatora u opsegu od 5,000 – 300,000 g/mol.
7. Ligandi, prema jednom ili više od gore spomenutih patentnih zahtjeva, naznačeni time, da odgovaraju općoj formuli (III) ili (IV)
[image]
gdje
A i Q imaju značenje kao u patentnom zahtjevu 1,
R‘ = H ili R, i gdje
R, u svakom slučaju nezavisno jedan od drugog, označava (C1C8)alkil, HO-(C1-C8)-alkil, (C2C8)alkoksialkil,
(C6C18)aril, (C7C19)aralkil, (C1C8)alkil(C6C18)aril, (C3C8)cikloalkil, (C1C8)alkil(C3C8)cikloalkil ili (C3C8)cikloalkil(C1C8)alkil.
8. Ligandi prema patentnom zahtjevu 7, naznačeni time, da R može biti metil, etil, propil, izo-propil, terc.-butil ili fenil.
9. Ligandi prema jednom ili više od gore spomenutih patentnih zahtjeva, naznačeni time, da Q označava kisik ili NR‘, gdje R‘ može biti (C1-C8)-alkil, (C6C18)aril ili benzil.
10. Ligandi prema jednom ili više od gore spomenutih patentnih zahtjeva, naznačeni time, da Q označava kisik ili NR‘, gdje R‘ može biti metil, etil, propil, izo-propil, terc.-butil, fenil, naftil, fluorenil ili benzil.
11. Ligandi prema jednom ili više od gore spomenutih patentnih zahtjeva, naznačeni time, da spojevi formule (I) do (IV) posjeduju enantiomeričko obogaćenje od >90 %, poželjno > 98%.
12. Kompleks koji sadrži ligande prema patentnim zahtjevima 1 – 11, naznačen time, da sadrži najmanje jedan prijelazni metal.
13. Kompleks koji sadrži ligande prema patentnim zahtjevima 1 – 11, naznačen time, da sadrži paladij, platinu, rodij, rutenij, osmij, iridij, kobalt, nikal ili bakar.
14. Postupak za proizvodnju liganda prema patentnim zahtjevima 1 – 11, naznačen time, da se odgovarajući fosfini dobivaju reakcijom LiP(SiMe3)2 s prikladnim ko-reaktantima koji posjeduju nukleofugalne odlazeće skupine u prisutnosti organometalne baze.
15. Postupak za proizvodnju liganda prema patentnim zahtjevima 1 – 11, naznačen time, da odgovarajući trimetilsililfosfini iz patentnog zahtjeva 14 reagiraju s odgovarajućim dihalogenskim derivatima iz skupine A prema patentnom zahtjevu 1, a atomi halogena zauzimaju položaje sa slobodnim valencama struktura prikazanih u skupini A u patentnom zahtjevu 1.
16. Uporaba kompleksnog spoja prema patentnom zahtjevu 12 ili 13, naznačena time, da se isti rabi kao katalizator za asimetrične reakcije.
17. Uporaba kompleksnog spoja prema patentnom zahtjevu 12 ili 13, naznačena time, da se isti rabi kao katalizator za asimetričnu hidrogenaciju, hidroformilaciju, premještanje (skupina), alilnu alkilaciju, ciklopropanaciju, hidrosililaciju, hidridne transfere, hidroboraciju, hidrocijanaciju, hidrokarboksilaciju, aldolne reakcije ili Heckovu reakciju.
18. Uporaba kompleksnog spoja prema patentnom zahtjevu 12 ili 13, naznačena time, da se isti rabi kao katalizator za asimetričnu hidrogenaciju i/ili hidroformilaciju.
19. Uporaba prema patentnom zahtjevu 18, naznačena time, da se E/Z mješavina prokiralnih, N-aciliranih βaminoakrilnih kiselina ili njihovih derivata hidrogenizira.
20. Uporaba prema jednom ili više patentnih zahtjeva 17 - 19, naznačena time, da se postupak može izvesti ili hidrogenacijom s plinom vodikom ili transfer hidrogenacijom.
21. Uporaba prema patentnom zahtjevu 20, naznačena time, da kada se odnosi na hidrogenaciju s plinom vodikom, spomenuta se hidrogenacija odvija pod tlakom vodika od 0.1 do 10 bar-a, poželjno od 0.5 do 5 bar-a.
22. Uporaba prema patentnom zahtjevu 21, naznačena time, da se hidrogenacija odvija na temperaturama od –20°C do 100°C, poželjno 0°C do 50°C.
23. Uporaba prema jednom ili više patentnih zahtjeva 16 - 22, naznačen time, da je omjer supstrat/katalizator odabran izmedju 10000:1 i 10:1, a poželjno je 1000:1 i 50:1.
24. Uporaba prema jednom ili više patentnih zahtjeva 16 - 23, naznačena time, da se katalizator dobiva u membranskom reaktoru.
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DE10214988 | 2002-04-04 | ||
PCT/EP2003/002162 WO2003084971A1 (en) | 2002-04-04 | 2003-03-03 | Bisphosphines as bidentate ligands |
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EP (1) | EP1490379B1 (hr) |
JP (1) | JP2005529868A (hr) |
KR (1) | KR20040097265A (hr) |
CN (1) | CN1318433C (hr) |
AT (1) | ATE468346T1 (hr) |
AU (1) | AU2003212297A1 (hr) |
BR (1) | BR0308970A (hr) |
CA (1) | CA2481037A1 (hr) |
DE (2) | DE10309356A1 (hr) |
HR (1) | HRP20040904A2 (hr) |
IL (1) | IL164342A0 (hr) |
RU (1) | RU2004132221A (hr) |
WO (1) | WO2003084971A1 (hr) |
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DE10058383A1 (de) | 2000-11-24 | 2002-05-29 | Oxeno Olefinchemie Gmbh | Neue Phosphininverbindungen und deren Metallkomplexe |
DE10210918B4 (de) | 2002-03-13 | 2004-06-03 | Oxeno Olefinchemie Gmbh | Verfahren zur Herstellung von Bisphosphiten |
ATE468346T1 (de) * | 2002-04-04 | 2010-06-15 | Evonik Degussa Gmbh | Bisphosphine als bidentat liganden |
DE10223593A1 (de) * | 2002-05-27 | 2003-12-11 | Degussa | Hydroxydiphosphine und deren Verwendung in der Katalyse |
JP2005537330A (ja) | 2002-08-31 | 2005-12-08 | オクセノ オレフィンヒェミー ゲゼルシャフト ミット ベシュレンクテル ハフツング | 環状カルボン酸エステルの存在で非変性金属錯体により触媒活性されるオレフィン不飽和化合物のヒドロホルミル化によりアルデヒドを製造する方法 |
CA2496838A1 (en) | 2002-08-31 | 2004-03-11 | Oxeno Olefinchemie Gmbh | Process for the hydroformylation of olefinically unsaturated compounds, in particular olefins, in the presence of cyclic carbonic esters |
DE10353831A1 (de) * | 2003-11-18 | 2005-06-23 | Degussa Ag | Verfahren zur Herstellung von Bisphospholanliganden |
DE10360772A1 (de) * | 2003-12-23 | 2005-07-28 | Oxeno Olefinchemie Gmbh | Verfahren zur Herstellung von Organoacylphosphiten |
DE10360771A1 (de) * | 2003-12-23 | 2005-07-28 | Oxeno Olefinchemie Gmbh | Verfahren zur Herstellung von dreiwertigen Organophosphor-Verbindungen |
DE102004013514A1 (de) * | 2004-03-19 | 2005-10-06 | Oxeno Olefinchemie Gmbh | Verfahren zur Hydroformylierung von Olefinen in Anwesenheit von neuen phosphororganischen Verbindungen |
EP1595888A1 (en) * | 2004-05-11 | 2005-11-16 | Degussa AG | Cycloolefin phosphine ligands and their use in catalysis |
DE102004051456A1 (de) * | 2004-10-22 | 2006-04-27 | Degussa Ag | Neue Bisphosphankatalysatoren |
DE102005014054A1 (de) * | 2005-03-23 | 2006-09-28 | Degussa Ag | Elektronenarme Bisphospholanliganden und -katalysatoren |
DE102005014055A1 (de) * | 2005-03-23 | 2006-09-28 | Degussa Ag | Unsymmetrisch substituierte Phospholankatalysatoren |
WO2006116344A2 (en) * | 2005-04-22 | 2006-11-02 | Dow Global Technologies Inc. | Asymmetric hydroformylation process |
WO2007007646A1 (ja) * | 2005-07-07 | 2007-01-18 | Takasago International Corporation | 均一系不斉水素化反応用触媒 |
US7608709B2 (en) * | 2005-07-25 | 2009-10-27 | National University Corporation Chiba University | 2, 3-bis(dialkylphosphino)pyrazine derivative, process of producing the same, and metal complex having the same as ligand |
DE102005042464A1 (de) * | 2005-09-07 | 2007-03-08 | Oxeno Olefinchemie Gmbh | Carbonylierungsverfahren unter Zusatz von sterisch gehinderten sekundären Aminen |
DE102005053079A1 (de) | 2005-11-04 | 2007-05-10 | Degussa Gmbh | Halogenphospholane und deren Herstellung |
DE102006034442A1 (de) * | 2006-07-26 | 2008-01-31 | Oxeno Olefinchemie Gmbh | Katalysatorvorstufe für einen Rh-Komplexkatalysator |
DE102006058682A1 (de) * | 2006-12-13 | 2008-06-19 | Evonik Oxeno Gmbh | Bisphosphitliganden für die übergangsmetallkatalysierte Hydroformylierung |
DE102007023514A1 (de) * | 2007-05-18 | 2008-11-20 | Evonik Oxeno Gmbh | Stabile Katalysatorvorstufe von Rh-Komplexkatalysatoren |
DE102008002188A1 (de) * | 2008-06-03 | 2009-12-10 | Evonik Oxeno Gmbh | Verfahren zur Abtrennung von 1-Buten aus C4-haltigen Kohlenwasserstoffströmen durch Hydroformylierung |
US8308832B2 (en) | 2009-02-16 | 2012-11-13 | Samsung Electronics Co., Ltd. | Dust separating and collecting apparatus of vacuum cleaner |
WO2013043785A2 (en) * | 2011-09-20 | 2013-03-28 | Dow Corning Corporation | Nickel containing hydrosilylation catalysts and compositions containing the catalysts |
CN105849221B (zh) | 2013-09-27 | 2019-06-18 | 乔治洛德方法研究和开发液化空气有限公司 | 胺取代的三甲硅烷基胺和三-二甲硅烷基胺化合物 |
EP3029044B1 (de) | 2014-12-04 | 2019-05-01 | Evonik Degussa GmbH | Bisphosphite die einen unsymmetrischen biaryl-zentral-baustein aufweisen |
US9777025B2 (en) | 2015-03-30 | 2017-10-03 | L'Air Liquide, Société pour l'Etude et l'Exploitation des Procédés Georges Claude | Si-containing film forming precursors and methods of using the same |
CN110340793A (zh) * | 2019-07-02 | 2019-10-18 | 宝钢湛江钢铁有限公司 | 一种涂镀类生产线apc塔顶辊辊面清洁装置及其控制系统 |
CN114931961B (zh) * | 2022-06-10 | 2024-02-27 | 万华化学集团股份有限公司 | 一种氢甲酰化催化剂及其应用 |
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US5171892A (en) * | 1991-07-02 | 1992-12-15 | E. I. Du Pont De Nemours And Company | Chiral phospholanes via chiral 1,4-diol cyclic sulfates |
DE19918420A1 (de) | 1999-04-23 | 2000-10-26 | Aventis Res & Tech Gmbh & Co | Bidentate Organophosphorliganden und ihre Verwendung |
DE10052868A1 (de) | 2000-10-25 | 2002-05-29 | Aventis Res & Tech Gmbh & Co | Bidentate Phosphorliganden und ihre Verwendung in der Katalyse |
DE10100971A1 (de) | 2001-01-11 | 2002-07-18 | Degussa | Verfahren zur Herstellung enantiomerenangereicherter beta-Aminosäure |
CA2458430A1 (en) * | 2001-10-05 | 2003-04-17 | Solvias Ag | Ligands for asymmetric reactions |
ATE468346T1 (de) | 2002-04-04 | 2010-06-15 | Evonik Degussa Gmbh | Bisphosphine als bidentat liganden |
DE10353831A1 (de) | 2003-11-18 | 2005-06-23 | Degussa Ag | Verfahren zur Herstellung von Bisphospholanliganden |
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2003
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- 2003-03-03 JP JP2003582168A patent/JP2005529868A/ja not_active Withdrawn
- 2003-03-03 DE DE10309356A patent/DE10309356A1/de not_active Withdrawn
- 2003-03-03 CA CA002481037A patent/CA2481037A1/en not_active Abandoned
- 2003-03-03 KR KR10-2004-7015675A patent/KR20040097265A/ko not_active Application Discontinuation
- 2003-03-03 BR BR0308970-3A patent/BR0308970A/pt not_active IP Right Cessation
- 2003-03-03 IL IL16434203A patent/IL164342A0/xx unknown
- 2003-03-03 AU AU2003212297A patent/AU2003212297A1/en not_active Abandoned
- 2003-03-03 EP EP03708169A patent/EP1490379B1/en not_active Expired - Lifetime
- 2003-03-03 DE DE60332610T patent/DE60332610D1/de not_active Expired - Lifetime
- 2003-03-03 CN CNB038075555A patent/CN1318433C/zh not_active Expired - Fee Related
- 2003-03-03 RU RU2004132221/04A patent/RU2004132221A/ru not_active Application Discontinuation
- 2003-03-03 US US10/508,537 patent/US20050209455A1/en not_active Abandoned
- 2003-03-03 WO PCT/EP2003/002162 patent/WO2003084971A1/en active Application Filing
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US20070179301A1 (en) | 2007-08-02 |
WO2003084971A1 (en) | 2003-10-16 |
EP1490379A1 (en) | 2004-12-29 |
US20050209455A1 (en) | 2005-09-22 |
IL164342A0 (en) | 2005-12-18 |
ATE468346T1 (de) | 2010-06-15 |
US7361786B2 (en) | 2008-04-22 |
BR0308970A (pt) | 2005-01-11 |
CN1646547A (zh) | 2005-07-27 |
RU2004132221A (ru) | 2005-09-10 |
AU2003212297A1 (en) | 2003-10-20 |
KR20040097265A (ko) | 2004-11-17 |
JP2005529868A (ja) | 2005-10-06 |
DE60332610D1 (de) | 2010-07-01 |
DE10309356A1 (de) | 2003-11-20 |
EP1490379B1 (en) | 2010-05-19 |
US7589215B2 (en) | 2009-09-15 |
CN1318433C (zh) | 2007-05-30 |
US20070123733A1 (en) | 2007-05-31 |
CA2481037A1 (en) | 2003-10-16 |
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