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    • 1. 再颁专利
    • Ferrocenyl diphosphines as ligands for homogeneous catalysts
    • 二茂铁基二膦作为均相催化剂的配体
    • USRE37344E1
    • 2001-08-28
    • US09572931
    • 2000-05-18
    • Antonio TogniFelix SpindlerNadia ZanettiAmina Tijani
    • Antonio TogniFelix SpindlerNadia ZanettiAmina Tijani
    • C07F1702
    • C07F17/02B01J31/2291B01J31/2295B01J31/2409B01J31/2471B01J2231/643B01J2231/645B01J2531/0205B01J2531/0286B01J2531/822B01J2531/827B01J2531/842C07C67/303C07C67/31C07C209/52C07C231/18Y10S526/943C07C69/34C07C69/732
    • Compounds of formula I wherein R1 is C1-C8alkyl, phenyl or phenyl which is substituted by 1 to 3 C1-C4alkyl or C1-C4alkoxy groups; R2 and R3 are identical and are C1-C12alkyl, C5-C12cycloalkyl or C1-C4alkyl- or C1-C4alkoxy-substituted C5-C12cycloalkyl, or phenyl which is substituted by one to three identical or different members selected from the group consisting of C1-C4alkyl, C1-C4alkoxy, —SiR4R5R6, halogen, —SO3M, —CO2M, —PO3M, —NR7R8 and —[⊕NR7R8R9]X⊖; or R2 and R3 are different and are C1-C12alkyl, C5-C12cycloalkyl, C1-C4alkyl- or C1-C4-alkoxy-substituted C5-C12cycloalkyl, phenyl or phenyl which is substituted by one to three identical or different members selected from the group consisting of C1-C4alkyl, C1-C4alkoxy, —SiR4R5R6, halogen, —SO3M, —CO2M, —PO3M2, —NR7R8 and —[⊕NR7R8R9]X⊖; or the group —PR2R3 is a radical of formula II and R4, R5 and R6 are each independently of one another C1-C12alkyl or phenyl, R7 and R8 are H, C1-C2alkyl, phenyl or R7 and R8, taken together, are tetramethylene, pentamethylene or 3-oxa-1,5-pentylene, R9 is H or C1-C4alkyl, M is H or an alkali metal, X⊖ is the anion of a monobasic acid, and * is a stereogenic carbon atom, in the form of their racemates and diastereomers or mixtures of diastereoisomers. Rhodium and iridium complexes with these ligands are suitable for use as homogeneous enantioselective catalysts for the hydrogenation of prochiral compounds, containing carbon double bonds or carbon/hetero atom double bonds.
    • 其中R 1为C 1 -C 8烷基,苯基或被1至3个C 1 -C 4烷基或C 1 -C 4烷氧基取代的苯基的式I化合物; R 2和R 3相同,为C 1 -C 12烷基,C 5 -C 12环烷基或C 1 -C 4烷基 - 或C 1 -C 4烷氧基取代的C 5 -C 12环烷基或被一至三个相同或不同的选自C1- C4烷基,C1-C4烷氧基,-SiR4R5R6,卤素,-SO3M,-CO2M,-PO3M,-NR7R8和 - [⊕R7R8R9]X⊖; 或R 2和R 3不同,为C 1 -C 12烷基,C 5 -C 12环烷基,C 1 -C 4烷基 - 或C 1 -C 4 - 烷氧基取代的C 5 -C 12环烷基,苯基或被一至三个相同或不同的基团取代的苯基, 由C1-C4烷基,C1-C4烷氧基,-SiR4R5R6,卤素,-SO3M,-CO2M,-PO3M2,-NR7R8和 - [⊕R7R8R9]X⊖组成; 或基团-PR 2 R 3是式II的基团,R 4,R 5和R 6各自独立地为C 1 -C 12烷基或苯基,R 7和R 8为H,C 1 -C 2烷基,苯基或R 7和R 8一起为四亚甲基, 五亚甲基或3-氧杂-1,5-亚戊基,R9为H或C1-C4烷基,M为H或碱金属,X为一元酸的阴离子,*为立体碳原子,为 它们的外消旋体和非对映异构体或非对映异构体的混合物。 与这些配体的铑和铱络合物适合用作含有碳双键或碳/杂原子双键的前手性化合物氢化的均匀对映选择性催化剂。
    • 2. 发明授权
    • Ferrocenyl diphosphines as ligands for homogeneous catalysts
    • 二茂铁基二膦作为均相催化剂的配体
    • US5563309A
    • 1996-10-08
    • US459435
    • 1995-06-02
    • Antonio TogniFelix SpindlerNadia ZanettiAmina Tijani
    • Antonio TogniFelix SpindlerNadia ZanettiAmina Tijani
    • B01J31/22B01J31/24C07B35/02C07B41/02C07B43/04C07B53/00C07B61/00C07C45/41C07C45/64C07C49/245C07C67/303C07C67/31C07C209/52C07C217/08C07C231/18C07C235/16C07F17/02C07F19/00C07C5/02C07F17/00
    • C07F17/02B01J31/2291B01J31/2295B01J31/2409B01J31/2471C07C209/52C07C231/18C07C67/303C07C67/31B01J2231/643B01J2231/645B01J2531/0205B01J2531/0286B01J2531/822B01J2531/827B01J2531/842Y10S526/943
    • Compounds of formula I ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.8 alkyl, phenyl or phenyl which is substituted by 1 to 3 C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy groups; R.sub.2 and R.sub.3 are identical and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl or C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy,--SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M,--CO.sub.2 M,--PO.sub.3 M,--NR.sub.7 R.sub.8 and --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ; or R.sub.1 and R.sub.3 are different and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy,--SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M,--CO.sub.2 M,--PO.sub.3 M.sub.2, --NR.sub.7 R.sub.8 and --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ; or the group --PR.sub.2 R.sub.3 is a radical of formula II ##STR2## and R.sub.4, R.sub.5 and R.sub.6 are each independently of one another C.sub.1 -C.sub.12 alkyl or phenyl, R.sub.7 and R.sub.8 are H, C.sub.1 -C.sub.12 alkyl, phenyl or R.sub.7 and R.sub.8, taken together, are tetramethylene, pentamethylene or 3-oxa-1,5-pentylene, R.sub.9 is H or C.sub.1 -C.sub.4 alkyl, M is H or an alkali metal, X.sup..crclbar. is the anion of a monobasic acid, and * is a stereogenic carbon atom, in the form of their racemates and diastereoisomers or mixtures of diastereoisomers. Rhodium and iridium complexes with these ligands are suitable for use as homogeneous enantioselective catalysts for the hydrogenation of prochiral compounds containing carbon double bonds or carbon/hereto atom double bonds.
    • 式I的化合物其中R 1是C 1 -C 8烷基,苯基或被1至3个C 1 -C 4烷基或C 1 -C 4烷氧基取代的苯基; R 2和R 3相同,为C 1 -C 12烷基,C 5 -C 12环烷基或C 1 -C 4烷基 - 或C 1 -C 4烷氧基取代的C 5 -C 12环烷基或被一至三个相同或不同的选自C1- C 1-4烷基,C 1 -C 4烷氧基,-SiR 4 R 5 R 6,卤素,-SO 3 M,-CO 2 M,-PO 3 M,-NR 7 R 8和 - [(+)NR 7 R 8 R 9] X( - )。 或R 1和R 3不同,为C 1 -C 12烷基,C 5 -C 12环烷基,C 1 -C 4烷基 - 或C 1 -C 4烷氧基取代的C 5 -C 12环烷基,苯基或被一至三个相同或不同的成员取代的苯基, C 1 -C 4烷基,C 1 -C 4烷氧基,-SiR 4 R 5 R 6,卤素,-SO 3 M,-CO 2 M,-PO 3 M 2,-NR 7 R 8和 - [(+)NR 7 R 8 R 9] X( - )。 或基团-PR 2 R 3是式II的基团(II),且R 4,R 5和R 6彼此独立地为C 1 -C 12烷基或苯基,R 7和R 8为H,C 1 -C 12烷基,苯基或R 7和R 8 一起是四亚甲基,五亚甲基或3-氧杂-1,5-亚戊基,R9是H或C1-C4烷基,M是H或碱金属,X( - )是一元酸的阴离子,*是 其外消旋体和非对映异构体形式的立体碳原子或非对映异构体的混合物。 与这些配位体的铑和铱络合物适合用作含碳双键或碳/原子双键的前手性化合物氢化的均匀对映选择性催化剂。
    • 3. 发明授权
    • Ferrocenyl diphosphines as ligands for homogeneous catalysts
    • 二茂铁基二膦作为均相催化剂的配体
    • US5463097A
    • 1995-10-31
    • US292150
    • 1994-08-17
    • Antonio TogniFelix SpindlerNadia ZanettiAmina Tijani
    • Antonio TogniFelix SpindlerNadia ZanettiAmina Tijani
    • B01J31/22B01J31/24C07B35/02C07B41/02C07B43/04C07B53/00C07B61/00C07C45/41C07C45/64C07C49/245C07C67/303C07C67/31C07C209/52C07C217/08C07C231/18C07C235/16C07F17/02C07F19/00C07F15/00
    • C07F17/02B01J31/2291B01J31/2295B01J31/2409B01J31/2471C07C209/52C07C231/18C07C67/303C07C67/31B01J2231/643B01J2231/645B01J2531/0205B01J2531/0286B01J2531/822B01J2531/827B01J2531/842Y10S526/943
    • A complex of the formula V or VI,[X.sub.1 M.sub.1 YZ]X.sub.1 M.sub.1 Y].sup..sym. A.sub.1.sup..crclbar.wherein X.sub.1 is two C.sub.2 -C.sub.12 olefins or one C.sub.5 -C.sub.12 diene, Z is Cl, Br or I, A.sub.1.sup..crclbar. is the anion of an oxyacid or complex acid, M.sub.1 is Rh or Ir, and Y is a compound of the formula I ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.8 alkyl, phenyl or phenyl which is substituted by 1 to 3 C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy groups; R.sub.2 and R.sub.3 are identical and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl or C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, --SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M, --CO.sub.2 M, --PO.sub.3 M, --NR.sub.7 R.sub.8 and --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ; or R.sub.2 and R.sub.3 are different and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, --SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M, --CO.sub.2 M, --PO.sub.3 M.sub.2, --NR.sub.7 R.sub.8 and --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ; or the group --PR.sub.2 R.sub.3 is a radical of formula II ##STR2## and R.sub.4, R.sub.5 and R.sub.6 are each independently of one another C.sub.1 -C.sub.12 alkyl or phenyl, R.sub.7 and R.sub.8 are H, C.sub.1 -C.sub.12 alkyl, phenyl or R.sub.7 and R.sub.8, taken together, are tetramethylene, pentamethylene or 3-oxa-1,5-pentylene, R.sub.9 is H or C.sub.1 -C.sub.4 alkyl, M is H or an alkali metal, X.sup..crclbar. is the anion of a monobasic acid, and * is a stereogenic carbon atom, in the form of their racemates and diastereoisomers or mixtures of diastereoisomers.
    • 式Ⅴ或Ⅵ的络合物[X1M1YZ] X1M1Y](+)A1( - )其中X1是两个C2-C12烯烃或一个C5-C12二烯,Z是Cl,Br或I,A1( - )是 含氧酸或络合酸,M1为Rh或Ir,Y为式Ⅰ化合物其中R 1为C 1 -C 8烷基,苯基或被1至3个C 1 -C 4烷基或C 1 -C 4烷基取代的苯基, C4烷氧基; R 2和R 3相同,为C 1 -C 12烷基,C 5 -C 12环烷基或C 1 -C 4烷基 - 或C 1 -C 4烷氧基取代的C 5 -C 12环烷基或被一至三个相同或不同的选自C1- C 1-4烷基,C 1 -C 4烷氧基,-SiR 4 R 5 R 6,卤素,-SO 3 M,-CO 2 M,-PO 3 M,-NR 7 R 8和 - [(+)NR 7 R 8 R 9] X( - )。 或R 2和R 3不同,为C 1 -C 12烷基,C 5 -C 12环烷基,C 1 -C 4烷基 - 或C 1 -C 4烷氧基取代的C 5 -C 12环烷基,被一至三个相同或不同的成员所取代的苯基或苯基,所述相同或不同的成员选自 C 1 -C 4烷基,C 1 -C 4烷氧基,-SiR 4 R 5 R 6,卤素,-SO 3 M,-CO 2 M,-PO 3 M 2,-NR 7 R 8和 - [(+)NR 7 R 8 R 9] X( - )。 或基团-PR 2 R 3是式II的基团(II),且R 4,R 5和R 6彼此独立地为C 1 -C 12烷基或苯基,R 7和R 8为H,C 1 -C 12烷基,苯基或R 7和R 8 一起是四亚甲基,五亚甲基或3-氧杂-1,5-亚戊基,R9是H或C1-C4烷基,M是H或碱金属,X( - )是一元酸的阴离子,*是 其外消旋体和非对映异构体形式的立体碳原子或非对映异构体的混合物。
    • 4. 发明授权
    • Ferrocenyl diphosphines as ligands for homogeneous catalysts
    • 二茂铁基二膦作为均相催化剂的配体
    • US5371256A
    • 1994-12-06
    • US037783
    • 1993-03-26
    • Antonio TogniFelix SpindlerNadia ZanettiAmina Tijani
    • Antonio TogniFelix SpindlerNadia ZanettiAmina Tijani
    • B01J31/22B01J31/24C07B35/02C07B41/02C07B43/04C07B53/00C07B61/00C07C45/41C07C45/64C07C49/245C07C67/303C07C67/31C07C209/52C07C217/08C07C231/18C07C235/16C07F17/02C07F19/00
    • C07F17/02B01J31/2291B01J31/2295B01J31/2409B01J31/2471C07C209/52C07C231/18C07C67/303C07C67/31B01J2231/643B01J2231/645B01J2531/0205B01J2531/0286B01J2531/822B01J2531/827B01J2531/842Y10S526/943
    • Compounds of formula I ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.8 alkyl, phenyl or phenyl which is substituted by 1 to 3 C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy groups; R.sub.2 and R.sub.3 are identical and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl or C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, --SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M, --CO.sub.2 M, --PO.sub.3 M,--NR.sub.7 R.sub.8 and --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ; or R.sub.2 and R.sub.3 are different and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, --SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M, --CO.sub.2 M, --PO.sub.3 M.sub.2, --NR.sub.7 R.sub.8 and --[.sup..sym.NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ; or the group --PR.sub.2 R.sub.3 is a radical of formula II ##STR2## and R.sub.4, R.sub.5 and R.sub.6 are each independently of one another C.sub.1 -C.sub.12 alkyl or phenyl, R.sub.7 and R.sub.8 are H, C.sub.1 -C.sub.2 alkyl, phenyl or R.sub.7 and R.sub.8, taken together, are tetramethylene, pentamethylene or 3-oxa-1,5-pentylene, R.sub.9 is H or C.sub.1 -C.sub.4 alkyl, M is H or an alkali metal, X.sup..crclbar. is the anion of a monobasic acid, and * is a stereogenic carbon atom, in the form of their racemates and diastereoisomers or mixtures of diastereoisomers. Rhodium and iridium complexes with these ligands are suitable for use as homogeneous enantioselective catalysts for the hydrogenation of prochiral compounds containing carbon double bonds or carbon/hetero atom double bonds.
    • 式I的化合物其中R 1是C 1 -C 8烷基,苯基或被1至3个C 1 -C 4烷基或C 1 -C 4烷氧基取代的苯基; R 2和R 3相同,为C 1 -C 12烷基,C 5 -C 12环烷基或C 1 -C 4烷基 - 或C 1 -C 4烷氧基取代的C 5 -C 12环烷基或被一至三个相同或不同的选自C1- C 1-4烷基,C 1 -C 4烷氧基,-SiR 4 R 5 R 6,卤素,-SO 3 M,-CO 2 M,-PO 3 M,-NR 7 R 8和 - [(+)NR 7 R 8 R 9] X( - )。 或R 2和R 3不同,为C 1 -C 12烷基,C 5 -C 12环烷基,C 1 -C 4烷基 - 或C 1 -C 4烷氧基取代的C 5 -C 12环烷基,被一至三个相同或不同的成员所取代的苯基或苯基,所述相同或不同的成员选自 C 1 -C 4烷基,C 1 -C 4烷氧基,-SiR 4 R 5 R 6,卤素,-SO 3 M,-CO 2 M,-PO 3 M 2,-NR 7 R 8和 - [(+)NR 7 R 8 R 9] X( - )。 或基团-PR 2 R 3是式II的基团(II),且R 4,R 5和R 6彼此独立地为C 1 -C 12烷基或苯基,R 7和R 8为H,C 1 -C 2烷基,苯基或R 7和R 8 一起是四亚甲基,五亚甲基或3-氧杂-1,5-亚戊基,R9是H或C1-C4烷基,M是H或碱金属,X( - )是一元酸的阴离子,*是 其外消旋体和非对映异构体形式的立体碳原子或非对映异构体的混合物。 与这些配体的铑和铱配合物适合用作含碳双键或碳/杂原子双键的前手性化合物氢化的均匀对映选择性催化剂。