CN86106525A - 磷化合物 - Google Patents
磷化合物 Download PDFInfo
- Publication number
- CN86106525A CN86106525A CN86106525.5A CN86106525A CN86106525A CN 86106525 A CN86106525 A CN 86106525A CN 86106525 A CN86106525 A CN 86106525A CN 86106525 A CN86106525 A CN 86106525A
- Authority
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- China
- Prior art keywords
- alkyl group
- low alkyl
- aromatic base
- group
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- -1 Phosphorus compound Chemical class 0.000 title description 10
- 229910052698 phosphorus Inorganic materials 0.000 title description 3
- 239000011574 phosphorus Substances 0.000 title description 2
- 239000000126 substance Substances 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 50
- 125000003118 aryl group Chemical group 0.000 claims description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 30
- 239000003446 ligand Substances 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 229910052703 rhodium Inorganic materials 0.000 claims description 11
- 239000010948 rhodium Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical group 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000002585 base Substances 0.000 description 16
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 150000002596 lactones Chemical class 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- SERHXTVXHNVDKA-UHFFFAOYSA-N pantolactone Chemical compound CC1(C)COC(=O)C1O SERHXTVXHNVDKA-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- BEWYHVAWEKZDPP-UHFFFAOYSA-N bornane Chemical compound C1CC2(C)CCC1C2(C)C BEWYHVAWEKZDPP-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229940115458 pantolactone Drugs 0.000 description 2
- SIEVQTNTRMBCHO-UHFFFAOYSA-N pantolactone Natural products CC1(C)OC(=O)CC1O SIEVQTNTRMBCHO-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- BFMKBYZEJOQYIM-UCGGBYDDSA-N tert-butyl (2s,4s)-4-diphenylphosphanyl-2-(diphenylphosphanylmethyl)pyrrolidine-1-carboxylate Chemical compound C([C@@H]1C[C@@H](CN1C(=O)OC(C)(C)C)P(C=1C=CC=CC=1)C=1C=CC=CC=1)P(C=1C=CC=CC=1)C1=CC=CC=C1 BFMKBYZEJOQYIM-UCGGBYDDSA-N 0.000 description 2
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical compound C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 description 1
- HRTOQFBQOFIFEE-UHFFFAOYSA-N 2-dehydropantolactone Chemical compound CC1(C)COC(=O)C1=O HRTOQFBQOFIFEE-UHFFFAOYSA-N 0.000 description 1
- HQRSIMQXCAWAJB-UHFFFAOYSA-N 3,3,3-trifluoro-2-phenylpropanoic acid Chemical class OC(=O)C(C(F)(F)F)C1=CC=CC=C1 HQRSIMQXCAWAJB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000283073 Equus caballus Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- XETQTCAMTVHYPO-UHFFFAOYSA-N Isocamphan von ungewisser Konfiguration Natural products C1CC2C(C)(C)C(C)C1C2 XETQTCAMTVHYPO-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UEDBHEFYEKZZBA-UHFFFAOYSA-N ac1np5zy Chemical compound C1=CC=[C+]=C[CH]1 UEDBHEFYEKZZBA-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229930006742 bornane Natural products 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- IAODRFIZLKITMK-UHFFFAOYSA-N furan-2,3-dione Chemical class O=C1OC=CC1=O IAODRFIZLKITMK-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 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
- 125000005842 heteroatom Chemical group 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 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
- CHOLPKIHPFNIPE-UHFFFAOYSA-N phosphanylphosphane rhodium Chemical compound [Rh].PP CHOLPKIHPFNIPE-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
-
- 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
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2291—Olefins
-
- 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
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- 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
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring 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
- B01J31/2495—Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
- C07F15/008—Rhodium compounds without a metal-carbon linkage
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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Abstract
本发明描述了如下一般化学式的新颖手性铑-二膦络合物:
[Rh(X)(Y)(Lo、1,2)]1,2其中X、Y和L具有权利要求I所描述的含意。而且,描述了这些络合物的制造方法及它们在不对称氢化作用方面的应用。
Description
本发明涉及到如下通式Ⅰ的新颖手性铑-二膦络合物:
其中可以任意固定到载体上的X代表化学式Z-Coo-的残基,残基中的Z表示下面的基团或芳香基,
其中R1、R2、R3=氢、卤素、低级烷基、芳香基-低级烷基、全氟-C1-20-烷基、芳香基或基团-OR7、-(CH2)n-COA或AOC-(CF2)n,但R1、R2和R3其中必须至少有一个代表-OR7或芳香基,
R4、R5、R6=氢、卤素、低级烷基、芳香基-低级烷基、全氟-C1-20-烷基、芳香基或基团-(CH2)n-COA或AOC-(CF2)n,
R7=氢、低级烷基、部分地或全部被卤化的低级烷基,芳香基或芳香基-低级烷基,
A=残基-OR或-NR′ 2,
R=氢、低级烷基、芳香基、芳香基-低级烷基或一种阳离子,
R′=氢、低级烷基、芳香基或芳香基-低级烷基和
n=0~20和其中:
以及R1、R2和R3代表卤素、低级烷基、全氟苯基、全氟-C1-20-烷基,氢或基团-COA或AOC-(CF2)n-其中A表示残基-OR或-NR′ 2,但取代基R1、R2和R3其中必须至少有一个表示氟,R表示氢、低级烷基或一种阳离子,R′表示氢或低级烷基和n表示1-20的数。
本发明也涉及化学式1的铑-二膦络合物的制造及其在不对称氢化作用方面的应用。
从文献资料中已经知道手性铑-二膦络合物及它们在不对称的氢化作用方面的应用。这些络合物通常是阳离子的,或当它们为中性时,含有作为配位体X的氯、溴或碘。这些络合物使用不对称氢化作用时所达到的光学收率处于最有利的情况,就酮潘妥内酯的氢化作用来说,大约为80-84%。
现在意外地发现,与早先已知的络合物比较,本发明化学式(1)的铑-二膦络合物是相当有效的和相当有对映选择的,尤其是,这意味着,当采用这些络合物时可以考虑作为少量催化剂来使用,反应的时间可能是较短的,以及光学收率可以达到95%以上。
术语“低级烷基”在本发明的范围内表示直链的或具有1-9个碳原子的分枝烷基团,例如甲基、乙基、丙基、异丙基、正-丁基、异丁基、叔丁基、戊基、己基、庚基、辛基、壬基等等。术语“卤素”表示氟、氯、溴和碘,以及氟为最佳。术语“全氟-C1-20-烷基”在本发明范围内表示不但是直链的,而且是支链的,还可能有光学活性,因此不是所有的氢原子需要被氟原子置换。于是,当不是所有的氢原子被氟原子置换时,尤其,在末端的氢原子是经常存在的。就X固定到载体上这一点来说,这是通过基团-COA来实现的。
关于化学式(1)的化合物所使用的术语“芳香基”在本发明的范围内,不但表示芳香烃,而且表示具有4-14个碳原子的芳香杂环。尤其可以把氧和氮考虑为杂原子。而且这些环既可以是未取代的,又可以是取代的,在那种情况下最好把囟素、羟基、低级烷基、全氟-低级烷基、低级烷氧基和甲酰考虑为取代基。并且芳香基的存在,可以络合成某种过渡金属,例如铬、铁或也可为镍的络合物。
关于化学式Ⅱ的化合物在下文所用的术语“芳香基”在本发明范围内表示苯基,该苯基可以任意地存在于下面一些化合物中:对-和/或间-位低级烷基或低级烷氧基、最好是甲基或甲氧基,或二-低级烷氨基,最好是二甲基氨基,以及羧基、氨基甲酰基、氰基或低级烷氧基羰基。而且,在相同磷原子上的二个芳香基通过邻-位置或也可通过亚甲基、乙稀或丙烯基团相互直接连接。术语“芳氧基”表示一种基团,其中芳香基残基具有上述的含意。
术语“低级烷氧基”表示基团,其中烷基残基具有上述的含意。并且,符号“
”表示该相应的残基位于该分子平面之上,而符号“≡”表示相应残基位于该分子平面之下。符号n代表0-20的数字,较好为1-12,最好为1-8。
术语“中性配位体”在本发明的范围内的表示很容易转换的配位体,例如链烯,比如乙烯、丙稀、环辛烯、1.5-己二烯、降冰片二烯、1.5-环辛二烯等等,一种腈比如乙腈和苄腈或也就是所采用的溶剂等等。在氢化作用的情况下,该配位体是可以转换的。在这种配位体有一个以上的情况下,这些配位体也可以是相互不同的。
在不对称氢化作用方面所已知的和也可以任意地固定到载体上的任何二膦配位体基本上可被用作手性二膦配位体。这种配位体是大家都知道的而且为本技术领域的人所容易理解的。例如,在本发明范围内所考虑的配位体出自下面的文献:马科.L.等著,“均相催化的特性”1981年4 P145-202,1978年4月6日的日本专利申请号67411(德温特8180C);西德公开说明书No2161200;欧洲专利公布号104375。特别合适的和最佳的配位体是手性膦,其一般化学式如下:
其中R8代表芳香基,R9代表基团-CO-R10,-SO2-R10,-PO(R10)2或-PS(R10)2,其中R10表示芳香基、低级烷基、二-芳氨基、二-低级烷基氨基、芳氧基或低级烷氧基。
化学式1的最佳铑二膦的络合物是那些其中Z代表基团
的络合物并且R1、R2和R3取代基中的一个表示残基-OR7,其他二个表示氟、氢、全氟-C1-20-烷基或者芳香基,以及那些其中R1、R2和R3取代基中的一个代表芳香基,其他二个代表氟、氢或全氟-C1-20-烷基,但它们其中必须至少有一个表示氟。在配位体X为手性的情况下,该配位体存在于外消旋形式之中,或最好是存在于光学活性形式之中。
化学式Ⅱ的最佳二膦配位体是那些其中R8代表苯基、对-甲苯基、间-甲苯基、或3.5-二甲苯基,以及R9残基中的R10表示苯基,对-甲苯基、间-甲苯基、对-低级烷氧基羰基苯基或叔-丁氧基。并且特别最佳的膦类是那些其中R9残基代表-PO(R10)2基团。下面可以举出一些最佳二膦配位体的实例:
(2S,4S)-4-(二-间-甲苯基膦基)-2-〔(二-间-甲苯基膦基)甲基〕-1-(二苯基膦酰基)-吡咯烷(mcH3-POPPM);
(2S,4S)-4-(二苯基膦基)-2-〔(二苯膦基)-甲基〕-1-(二苯基膦酰基)-吡咯烷;(POPPM);
(2S,4S)-4-(二-对-甲苯基膦基)-2-〔(二-对-甲苯基膦基)甲基〕-1-(二苯基膦酰基)吡咯烷;(PCH3-POPPM);
(2S,4S)-4-(二苯基膦基)-2-〔(二苯基膦基)-甲基〕-1-(二-对-甲氧甲酰苯基膦)-吡咯烷;
(2S,4S)-4-(二苯基膦基)-2-〔(二苯基膦基)-甲基〕-1-(叔丁氧基羰基)-吡咯烷(BPPM);
(2S,4S)-4-(二-间-甲苯基膦基)-2-〔(二-间-甲苯基膦基)甲基〕-1-(叔丁氧基羰基)-吡咯烷(mcH3-BPPM)。
化学式Ⅰ的特别最佳的铐二膦络合物是那些其中R1、R2和R3取代基中的一个表示残基-OR7,其他二个表示氟或一个表示三氟甲基和另一个表示苯基,以及那些其中R1、R2、和R3取代基中的一个代表苯基,其他二个代表氟或一个表示氢和另一个表示氟,该二膦配位体是mcH-POPPM。如下化学式的络合物是最最佳的:
可以用一个本质上为已知的方法来制造本发明化学式Ⅰ的铑-二膦络合物。例如可以按下面一些反应来制造这些络合物:
a)化学式(Ⅲ)的铑络合物与手性二膦配位体反应,
其中X和L具有与前面相同的含意,m表示1-4的数;
b)化学式(Ⅳ)的铑络合物与手性二膦配位体及含阴离子X的盐反应,
其中L和m具有与前面相同的含意,A-代表阴离子,特别BF-,ClO- 4,PF- 6或B(C6H5)- 4;
c)化学式(Ⅴ)的铑-二膦络合物与含阴离子X的盐反应,
其中L,Y和A-有与前面相同的含意,P代表1-3的数;
d)化学式(Ⅵ)的手性铑-二膦络合物与化学式(Ⅶ)的银盐或铊盐反应,
其中X表示囟,L和Y具有与前面相同的含意,
其中X具有与前面相同的含意。
化学式Ⅲ、Ⅳ、Ⅴ和Ⅵ的铑络合物的反应可以用某种已知的方法按a-d不同的反应来进行。这在某种惰性的有机溶剂中进行很方便。下面可列举这些溶剂的实例:芳香烃例如苯、甲苯等,酯类例如乙酸乙酯等,环醚类例如四氢呋喃或二噁烷、低级醇类例如甲醇、乙醇诸如此类或也可以为其混合物。该反应可以大约在℃-100℃的温度范围内进行,最佳的温度大约在15°-60℃范围内,但是氧被严格地排除在外。
术语“含阴离子X盐”在本发明范围内特别表示铵盐、碱金属盐,、碱土金属盐以及其他合适的金属盐类。这些盐类均属于已知的物质。如果需要增加这种盐类在某些溶剂中的溶解度,那么可以添加一种合适的冠醚。
化学式Ⅰ的铑-二膦络合物都是催化剂或其前体。因为不能肯定地给出它们准确的化学结构,所以铑-二膦络合物的特征也在于:按上述a)到d)的反应进行化学式Ⅲ-Ⅵ的铑络合物反应,它们是可以获得的。
用作原材料的化学式Ⅲ、Ⅳ、Ⅴ和Ⅵ的铑络合物均属于已知物质或类似的已知物质,这种类似的已知物质可容易地由类似于已知的物质来制备。
正如已经所提到的,本发明化学式Ⅰ的铑-二膦络合物可以用作不对称氢化作用中的催化剂。它们在α、β-不饱和和酸和酯类、α-酮-羧酸和酯类以及α-酮-内酯类的不对称氢化作用方面是特别重要的。尤其关于二氢-4,4-二甲基-2,3呋喃二酮(酮潘妥内酯)(Ketopantolactone)对相应的R-(α-羟基-β,β-二甲基-γ-丁内酯)〔R-(-)-潘妥内酯(Pantolactone)〕的不对称氢化作用它们显得很重要。
因此,为了进行上述不对称的氢化作用,可把化学式Ⅰ的络合物加到一种被氢化的不对称化合物的溶液中去。换句话说,在有被氢化的不对称化合物的情况下,也能就地产生不对称的氢化作用。
不对称氢化作用可以在合适的有机溶剂中进行,那些有机溶剂在其反应条件下是惰性的。照这样,下面的一些有机溶剂有可能被指定为溶剂:尤其是低级烷醇例如甲醇或乙醇,芳香烃例如苯或甲苯,环醚例如四氢呋喃或二噁烷,酯类例如乙酸乙酯或者其混合物,诸如此类。铑和配位体上的克分子比约适合在0.05-5之间,但最好约在0.5-2铑和残基X的克分子比约适合在0.01-20之间,但最佳约在0.5-10之间。化学式Ⅰ的铑络合物和被氢化的化合物重量百分数的比约适合在0.00001-5之间,但最好约在0.0001-0.01之间。
采用化学式Ⅰ的络合物适宜于大约在0℃-100℃温度情况下进行不对称的氢化作用。但最好温度约在20℃-70℃。在压力下,便于完成这些氢化作用,特别约在1-100巴的压力下,但最佳压力为2-50巴。
下面一些实例用来说明本发明,但决非受其限制。
在这些实例中,一些缩略语含有如下的含意:
COD=1,5-环辛二稀
BPPM;mCH-POPPM:为第6和7页上所提到的-二膦类
在25米毛细管柱上,用手性物相(Chiral Phase)(sP-300)通过(R)-和(S)-潘妥内酯的气相色谱法的测定来测量对映体组合物(对映体过量允许误差)。在几种情况下,在温度20℃和浓度3%的去离子水中,以589毫微米(D-线)来测定(R)-(-)-潘妥内酯的旋光度。最纯的(R)-(-)-潘妥内酯的光纯度值为〔α〕=-51.6°(C=3,H2O)。
实施例1
将100毫升玻璃烧瓶置于一个手套箱中(含氧量<1ppm)悬浮在手套箱中的该玻璃烧瓶内有含水的40%四丁铵氢氧化物溶液254.2毫克(0.389毫摩尔)、全氟苯氧基乙酸108.2毫克(0.389毫摩尔)、双-(1,5-环辛二烯)-铑(1)四氟硼酸盐157.8毫克(0.389毫摩尔)和(2S,4S)-4-(二-间-甲苯基膦基)-2-〔(二-间-甲苯基膦基)甲基〕-1-二苯基膦酰基-吡咯烷(mCH3-POPPM)281.7毫克(0.389毫摩尔)。它们悬浮于50毫升甲苯中。随后将此混悬浮液22-25℃搅拌16个小时,从而形成一种几乎透明的橙红色的催化剂溶液。
实施例2
把40克(0.31摩尔)酮潘妥内酯、160毫升甲苯和根据实施例1制备的50毫升催化剂溶于注入手套箱内的500毫升的高压釜中(含氧量<1ppm)。在40℃和40巴恒压氢的条件下进行氢化,并且在氢化的同时加以强烈地搅拌。1小时后该转化99.8%。经过4小时的总氢化时间后,黄色氢化溶液从高压釜中倾泻出来,随后高压釜用甲苯漂洗三次,每次用50毫升甲苯。在60℃、17毫巴的条件下,该化合物的甲苯溶液在旋转式汽化器上进行蒸发。在130-150℃(蒸浴温度)和12毫巴情况下,蒸馏42克残余物。最后得到具有92.8%(允许误差)的光纯度的40.3克(99.3%(R)-α-羟基-β,β-二甲基-γ-丁内酯〔(R)-(-)-潘妥内酯〕。
实施例3-29
用类似于实施例1的方法制备催化剂溶液,尔后按类似于实施例2的方法进行酮潘妥内酯的氢化作用。这些结果汇编在下面的表中。
实施例30
置于手套箱中的钢质高压釜内(含氧量<1ppm)注入的物质有:异丙基α-氧代-γ-(1.3-二氧-2-异氮杂茚基)-丁酸酯30克(0.104摩尔)、甲苯110毫升和催化剂溶液,这种催化剂溶液是由如下物质按类似于实施例1的方法制备而成的:含40%四丁铵氢氧化物溶液165克(0.292毫摩尔)、(S)-α-甲氧基-α-三氟甲基苯乙酸68.3毫克(0.292毫摩尔)、双-(1,5-环辛二烯)-铑(1)四氟硼酸酯118.4毫克(0.292毫摩尔)和(2S,4S)-1-叔丁氧基羰基-4-二苯基膦基-2-二苯基膦基甲基-吡咯烷164.7毫克(0.292毫摩尔)。在40℃和10巴恒压氢的条件下进行氢化,并且在氢化的同时强烈地搅拌24小时。蒸发氢化溶液,用硅胶对该残余物进行色谱分析,并且蒸发含有成品的馏分。最终获得29.5克(97.4%)异丙基(R)-α-羟基-γ-(1,3-二氧-2-异氮茚基)-丁酸酯,为淡黄色的晶体。熔点为78-82℃,对映体纯度为78.5%(如同莰烷酸酯,在21米毛细管柱Se54〕上按气相色谱法测定)。〔α〕20 D=-4.4°(C=1,CH3OH);光纯度79.0%。
Claims (10)
1、一种手性铑-二膦络合物有一般化学式:
其中可以任意固定到载体上的X代表化学式Z-C00的残基,残基中Z表示下面的基团或芳香基:
其中R1、R2、R3=氢、卤素、低级烷基、芳香基-低级烷基、全氟-C1-20-烷基,芳香基或基团-OR7、-(CH2)n-COA或AOC-(CF2)n,但R1、R2和R3其中必须至少有一个代表-OR7或芳香基,
R4、R5、R6二氢、卤素、低级烷基、芳香基-低级烷基、全氟-C1-20-烷基、芳香基或基团-(CH2)n-COA或AOC(CF2)n,
R7=氢、低级烷基、部分或全部地囟代的低烷基、芳香基或芳香基-低级烷基,
A=残基-OR或-NR1 2,
R=氢、低级烷基、芳香基、芳香基-低级烷基或一种阳离子,
R′=氢、低级烷基、芳香基或芳香基-低级烷基和
n=0-20,和其中:
Y=代表一种手性二膦配位体和
L代表中性的配位体,除化学式Ⅰ的那些络合物之外,其中可以任意固定到载体上的X代表化学式Z-COQ-的残基,残基中的Z表示下面的基团
、全氟苯基、全氟二苯基或为下面化学式的一种残基:
以及R1、R2和R3代表卤素、低级烷基、全氟苯基、全氟-C1-20-烷基、氢或基团-COA或AOC-(CF2)n-其中A表示残基-OR或-NR1 2,但取代基R1、R2和R3其中必须至少有一个表示氟,R表示氢、低级烷基或一种阳离子,R1表示氢或低级烷基和n表示1-20。
3、根据权利要求1或2所述的手性络合物,其中取代基R1、R2和R3中的一个表示残基-OR7和其他两个表示氟、氢、全氟-C1-20-烷基或芳香基以及R7与权利要求1所述相同。
4、根据权利要求1或2所述的手性络合物,其中取代基R1、R2和R3中的一个表示苯基和其他两个代表氟、氢或全氟-C1-20-烷基,但它们至少有一个表示氟。
6、根据权利要求5所述的手性络合物,其中R9代表基团-PO(R10)2。
7、根据权利要求5或6所述的手性络合物,其中R8表示苯基、对-甲苯基、间-甲苯基或3.5-二甲苯基,以及R10表示苯基、对-甲苯基、间-甲苯基、对-低级烷氧羰基苯基或叔丁氧基。
8、一种制造下面一般化学式的手性铑-二膦络合物的方法,
其中可以任意固定在载体上的X代表化学式Z-COO的残基,残基中Z代表下面的基团:
或芳香基,其中
R1、R2、R3=氢、卤、低级烷基、芳香基-低级烷基、全氟-C1-20-烷基、芳香基或基团-OR7、-(CH2)n-COA或AOC-(CF2)n,但R1、R2和R3其中必须至少有一个代表-OR7或芳香基,R4、R5、R6=氢、卤素、低级烷基、芳香基-低级烷基、全氟-C1-20-烷基、芳香基或基团-(CH2)n-COA或AOC-(CF2)n,
R=氢、低级烷基、部分或全部地囟化的低级烷基、芳香基或芳香基-低级烷基,
A=残基-OR或-NR′ 2,
R=氢、低级烷基、芳香基、芳香基-低级烷基或一种阳离子,
R′=氢、低级烷基、芳香基或芳香基-低级烷基和
n=0-20的数,和其中:
Y代表一种手性二膦配位体和
L代表中性的配位体,
除化学式Ⅰ的那些络合物之外,其中可以任意固定到载体上的X代表化学式Z-COO--的残基,残基中Z表示下面的基团:
全氟苯基、全氟二苯基或为下面化学式的一种残基:
以及R1、R2和R3代表卤、低级烷基、全氟苯基、全氟-C1-20-烷基、氢或基团-COA或AOC-(CF2)n-其中A表示残基-OR或-NR′ 2,但取代基R1、R2和R3其中必须至少有一个表示氟,R表示氢、低级烷基或一种阳离子,R1表示氢或低级烷基和n表示1-20,
其中方法包括:
的铑络合物与手性二膦配位体反应,
其中X和L具有与前面相同的含意,m表示1-4的数;
的络合物与手性二膦配位体及阴离子X的盐反应,
其中L和m具有与前面相同的含意,A-代表阴离子,特别是BF- 4Clo- 4、PF- 6或B(C6H5)- 4;
的铑-二膦络合物与含阴离子X的盐反应,
其中L、Y和A-具有与前面相同的含意,P代表1-3的数;
的手性铑-二膦络合物与
的银盐或铊盐反应,
其中X1表示卤素,L和Y具有与前面相同的含意,
其中X具有与前面相同的含意。
9、根据权利要求8所述的方法可以得到权利要求1-7的一般化学式的手性铑-二膦络合物。
10、根据权利要求1-7所述的化学式Ⅰ的手性铑-二膦络合物可以用作不对称氢化作用中的催化剂。
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CH4498/85 | 1985-10-18 | ||
CH449885 | 1985-10-18 |
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US (1) | US5142063A (zh) |
EP (1) | EP0218970B1 (zh) |
JP (1) | JP2546830B2 (zh) |
CN (1) | CN1008095B (zh) |
AT (1) | ATE77383T1 (zh) |
DE (1) | DE3685713D1 (zh) |
DK (1) | DK464586A (zh) |
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EP0348351A1 (de) * | 1988-06-22 | 1989-12-27 | Ciba-Geigy Ag | Verfahren zur Herstellung von substituierten Aniliden |
KR0144567B1 (ko) * | 1989-03-03 | 1998-07-15 | 오노 알버어스 | 카르보닐화촉매시스템 |
US5110955A (en) * | 1989-04-14 | 1992-05-05 | Hoffmann-La Roche Inc. | Tocopherol synthesis: chromane cyclization and catalysis |
FR2651152B1 (fr) * | 1989-08-23 | 1991-11-29 | Elf Aquitaine | Perfectionnement a la preparation de catalyseurs chiraux a base de complexes du ruthenium et du phosphore. |
DE4001019A1 (de) * | 1990-01-16 | 1991-07-18 | Degussa | Verfahren zur asymmetrischen hydrierung von (alpha)-ketocarbonylverbindungen zu optisch aktiven (alpha)-hydroxycarbonylverbindungen |
GB9002521D0 (en) * | 1990-02-05 | 1990-04-04 | Shell Int Research | Carbonylation catalyst system |
GB9111583D0 (en) * | 1991-05-30 | 1991-07-24 | Shell Int Research | Carbonylation catalyst system |
ES2054519T3 (es) * | 1991-02-15 | 1994-08-01 | Shell Int Research | Sistema de catalizador de carbonilacion. |
US5258546A (en) * | 1991-05-30 | 1993-11-02 | Shell Oil Company | Carbonylation catalyst system |
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US3660493A (en) * | 1967-10-17 | 1972-05-02 | British Petroleum Co | Hydroformylation process |
FR1601121A (zh) * | 1968-10-01 | 1970-08-10 | ||
GB1368431A (en) * | 1970-07-22 | 1974-09-25 | Johnson Matthey Co Ltd | Rhodium complex and methods of preparing the complex |
US3954821A (en) * | 1975-06-30 | 1976-05-04 | E. I. Du Pont De Nemours And Company | Carbon dioxide complexes of Rh, Ir, Ni, Pd, and Pt |
US4343741A (en) * | 1981-04-22 | 1982-08-10 | Hoffmann-La Roche Inc. | Chiral phosphines |
US4539411A (en) * | 1982-02-05 | 1985-09-03 | Hoffmann-La Roche Inc. | Rhodium complexes of chiral phosphines |
DE3574704D1 (de) * | 1984-04-19 | 1990-01-18 | Hoffmann La Roche | Chirale rhodium-diphosphinkomplexe fuer asymmetrische hydrierungen. |
DE3783084T2 (de) * | 1986-06-25 | 1993-04-15 | Kazuo Achiwa | Chirale phosphinopyrrolidin-verbindungen und ihre verwendung fuer asymetrische synthese optisch aktiver verbindungen. |
JPH0713076A (ja) * | 1993-06-29 | 1995-01-17 | Minolta Co Ltd | コンパクトな高変倍実像式ファインダー |
-
1986
- 1986-09-26 EP EP86113271A patent/EP0218970B1/de not_active Expired - Lifetime
- 1986-09-26 AT AT86113271T patent/ATE77383T1/de not_active IP Right Cessation
- 1986-09-26 DE DE8686113271T patent/DE3685713D1/de not_active Expired - Fee Related
- 1986-09-29 DK DK464586A patent/DK464586A/da not_active Application Discontinuation
- 1986-10-16 CN CN86106525.5A patent/CN1008095B/zh not_active Expired
- 1986-10-17 JP JP61245604A patent/JP2546830B2/ja not_active Expired - Lifetime
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CN100406118C (zh) * | 2003-10-01 | 2008-07-30 | 陶氏环球技术公司 | 制备阳离子铑配合物的方法 |
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ATE77383T1 (de) | 1992-07-15 |
EP0218970A2 (de) | 1987-04-22 |
EP0218970A3 (en) | 1989-10-25 |
DE3685713D1 (de) | 1992-07-23 |
JP2546830B2 (ja) | 1996-10-23 |
DK464586D0 (da) | 1986-09-29 |
EP0218970B1 (de) | 1992-06-17 |
DK464586A (da) | 1987-04-19 |
US5142063A (en) | 1992-08-25 |
CN1008095B (zh) | 1990-05-23 |
JPS6295140A (ja) | 1987-05-01 |
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