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    • 84. 发明申请
    • Synthesis of ruthenium of osmium metathesis catalysts
    • 锇复分解催化剂钌的合成
    • US20020022733A1
    • 2002-02-21
    • US09967198
    • 2001-09-28
    • California Institute of Technology
    • Robert H. GrubbsTomas R. BelderrainSeth N. BrownThomas E. Wilhelm
    • C07F015/00
    • B01J31/2404B01J31/2265B01J31/2295B01J31/24B01J2231/14B01J2231/54B01J2231/543B01J2531/821B01J2531/825C07F15/002C07F15/0046
    • The present invention relates to the synthesis of highly active ruthenium and osmium carbene metathesis catalyst in good yield from readily available starting materials. The catalysts that may be synthesized are of the general formula 1 wherein: M is ruthenium or osmium; X and X1 are independently any anionic ligand; L and L1 are any neutral electron donor ligand; and, R and R1 are each hydrogen or one of the following substituent groups: C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl. Optionally, the substituent group may be substituted with one or more groups selected from C1-C5 alkyl, halogen, C1-C5alkoxy, and aryl. When the substitute aryl group is phenyl, it may be further substituted with one or more groups selected from a halogen, a C1-C5 alkyl, or a C1-C5 alkoxy. Specific synthetic protocols for vinyl alkylidene catalysts wherein R is hydrogen and R1 is nullCHCR12R13 and non-vinyl alkylidene catalysts are also disclosed. In addition to the ease of synthesis (typically a one-step synthesis), the reactions generally may be run at or above room temperature and the resulting products usually may be used without extensive post synthesis purification.
    • 本发明涉及从容易获得的原料合成高活性钌和碳卡因复分解催化剂的良好产率。 可以合成的催化剂具有以下通式:其中:M是钌或锇; X和X1独立地为任何阴离子配体; L和L1是任何中性电子给体配体; C 1 -C 20烷基,C 1 -C 20烷基,C 1 -C 20烷基,C 1 -C 20羧酸酯,C 1 -C 20烷氧基,C 2 -C 20链烯氧基,C 2 -C 20炔基, C20炔氧基,芳氧基,C2-C20烷氧基羰基,C1-C20烷硫基,C1-C20烷基磺酰基和C1-C20烷基亚磺酰基。 任选地,取代基可以被一个或多个选自C 1 -C 5烷基,卤素,C 1 -C 5烷氧基和芳基的基团取代。 当取代芳基为苯基时,可以进一步被一个或多个选自卤素,C 1 -C 5烷基或C 1 -C 5烷氧基的基团取代。 还公开了其中R为氢且R 1为-CHCR 12 R 13的乙烯基亚烷基催化剂和非乙烯基亚烷基催化剂的具体合成方案。 除了易于合成(通常是一步合成)之外,反应通常可以在室温或更高的温度下进行,所得产物通常可以在没有广泛的后合成纯化的情况下使用。