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    • 42. 发明授权
      EP0938459B1 VERFAHREN ZUR HERSTELLUNG VON AROMATISCHEN OLEFINEN MITTELS KATALYSE DURCH PALLADAPHOSPHACYCLOBUTANE 失效
    • VERFAHREN ZUR HERSTELLUNG VON AROMATISCHEN OLEFINEN MITTELS KATALYSE DURCH PALLADAPHOSPHACYCLOBUTANE
    • 工艺制备芳族烯烃期催化BY palladaphosphacyclobutanes
    • EP0938459B1
    • 2002-07-31
    • EP97950185.5
    • 1997-11-13
    • Degussa AG
    • GEISSLER, Holger , GROSS, Peter , GUCKES, Bianca , KLIMPEL, Michael
    • C07B37/04
    • B01J31/26 , B01J31/24 , B01J31/2409 , B01J31/2423 , B01J31/2447 , B01J2231/4261 , B01J2531/0205 , B01J2531/824 , B01J2540/225 , C07B37/04 , C07C67/343 , C07C69/734
    • A process is disclosed for preparing monofunctional, bifunctional and polyfunctional aromatic olefins of formula (I), in which R?1a to R5a¿ independently represent hydrogen, C¿1?-C8-alkyl, (C1-C8)-alkoxy, (C1-C8)-acyloxy, O-phenyl, phenyl, fluorine, chlorine, bromine, iodine, OH, NO2, OSO2CF3, CN, COOH, CHO, SO3H, SO2R, SOR, NH2, NH-(C1-C8)-alkyl, N-(C1-C8)-alkyl2-, CHal3, NHCO-(C1-C4)-alkyl, N-(C1-C4)-alkyl-CO-(C1-C4)-alkyl, COO-(C1-C8)-alkyl, CONH2, CO-(C1-C8)-alkyl, NHCOH, NCOO-(C1-C4)-alkyl, CO-phenyl, COO-phenyl, CHCH-CO2-(C1-C8)-alkyl, CHCHCO2H, PO-phenyl2, PO-(C1-C4)-alkyl2, OSO2-phenyl, OSO2CH3, or of formula (Ia), in which R?6a¿ stands for hydrogen, (C¿1?-C8)-alkyl, phenyl, O-(C1-C8)-alkyl, fluorine; R?7a and R8a¿ independently represent hydrogen, CN, CO¿2?H, CO2-(C1-C8)-alkyl, CONH2, CONH-(C1-C4)-alkyl, CON(C1-C4)-(alkyl)2, fluorine, CO2-phenyl, alkyl, (C1-C8)-phenyl, PO(phenyl), PO-(C1-C4)-(alkyl)2, CO-phenyl, CO-(C1-C4)-alkyl, O-(C1-C4)-alkyl, NH-(C1-C4)-alkyl, PO3H, SO3H, SO3-(C1-C4)-alkyl, SO2-(C1-C4)-alkyl, O-phenyl, (C1-C8)-alkyl, by reacting halogenated aromatic compounds of general formula (II) with olefins of general formula (III), in which R?1a to R8a¿ have the above-mentioned meanings, X having the same meaning as radicals R?1a to R5a¿. This process is characterised in that a palladium compound of general formula (IV) is used as catalyst. In formula (IV), R1, R2 independently represent hydrogen, (C¿1?-C4)-alkyl, (C3-C12)-cycloalkyl, (C1-C4)-alkoxy, fluorine, N-(C1-C4)-(alkyl)2, CO2-(C1-C4)-alkyl, OCO-(C1-C4)-alkyl or aryl; R?3, R4, R5, R6¿ independently represent (C¿1?-C8)-alkyl, (C3-C12)-cycloalkyl, aryl; or in which R?1 and R2, R1 or R2 and R3 or R4, R3 and R4, R3 or R4 and R5 or R6, R5 and R6¿ form together an aliphatic ring, or in which R?5 and R6, R3 or R4 and R5 or R6¿ form together an aromatic ring, and Y stands for an anion of an inorganic or organic acid.
    • 基本信息 添加关注 加入工作空间 PDF全文 PDF下载 全文下载 相似专利 双屏查看 权利要求书 说明书全文 Global Dossier Espacenet 法律信息 同族专利 专利引用
    • 47. 发明公开
      EP0633062A1 Fluorous multiphase catalyst or reagent systems, and processes using them 失效
    • Fluorous multiphase catalyst or reagent systems, and processes using them
    • Fluorierter mehrphasiger Katalysator oder Reagenzsystem und Verfahren zu dessen Verwendung。
    • EP0633062A1
    • 1995-01-11
    • EP94304877.7
    • 1994-07-04
    • EXXON RESEARCH AND ENGINEERING COMPANY
    • Horvath, Istvan Tamas , Rabai, Jozsef
    • B01J31/16 , B01J31/02
    • C07F9/1411 , B01J31/183 , B01J31/185 , B01J31/20 , B01J31/2234 , B01J31/24 , B01J31/4046 , B01J2231/321 , B01J2231/70 , B01J2531/025 , B01J2531/822 , B01J2531/842 , B01J2531/845 , B01J2531/847 , B01J2531/94 , B01J2531/98 , B01J2540/225 , B01J2540/64 , C07C17/38 , C07C45/50 , C07C315/02 , C07D303/32 , C07D333/76 , C07F9/091 , C07F9/5004 , Y02P20/582 , Y02P20/584 , C07C317/14 , C07C47/02
    • Stoichiometric and catalytic chemical transformations may be carried out in solution using novel fluorous multiphase systems (FMS). "Fluorous" denotes a carbon-fluorine bond rich organic molecule derived by replacing hydrogen atoms bonded to carbon atoms with fluorine. The FMS consists of a fluorous phase containing a fluorous solvent, typically a fluorocarbon or a fluorohydrocarbon (with or without substituent groups), and a reagent or a catalyst containing a sufficient number of fluorous moieties to render it preferentially soluble in the fluorous solvent and located at the interface of the fluorous and nonfluorous phases. The nonfluorous (i.e. the second) solvent, may be any known organic or nonorganic solvent(s) with limited or no solubility in the fluorous solvent that is effective for dissolving the reactants and/or separating the reaction products (e.g., a nonfluorous solvent having a Hildebrand solubility parameter of at least about 18.0 MPa ½ ). The reaction can occur simultaneously in the fluorous phase and at the interface of the phases. The FMS reagents and FMS catalysts contain sufficient number of fluorous moieties to render them preferentially soluble into the fluorous phase and at the interface without impairing the efficacy or participation of the catalyst or reagent in the reaction which is maintained in a liquid or fluid phase. The preferred fluorous moieties are linear, branched and carbocyclic fluorocarbon alkyl chains with high carbon numbers that enable the catalyst or reagent to remain fluorous-phase compatible. The fluorous moieties may also contain O, S, N, P, As and Si, that assist in rendering the catalysts and reagents fluorous phase compatible. The FMS reagents and catalysts can be prepared by (1) fluorination (i.e., replacement of C-H bonds with fluorine); (2) fluorofunctionalization, e.g., the attachment of fluorous moieties to the reagents or catalysts; or (3) by total synthesis.
      The fluorous multiphase systems have utility to facilitate the separation of the FMS catalyst or spent FMS reagent, which has utility in the design and synthesis of catalysts and reagents with high product selectivity, resulting in especially environmentally friendly processes.
    • 使用新型氟多相体系（FMS）可在溶液中进行化学计量和催化化学转化。 “氟”表示通过用氟取代与碳原子键合的氢原子得到的富含碳 - 氟的有机分子。 FMS由含氟溶剂，通常为碳氟化合物或氟代烃（具有或不具有取代基）的氟相和含有足够数量的氟部分的试剂或催化剂组成，使其优先溶于氟溶剂并定位 在氟和非氟相的界面处。 非氟（即第二）溶剂可以是在氟溶剂中溶解有限或不溶性的任何已知的有机溶剂或非有机溶剂，其有效溶解反应物和/或分离反应产物（例如，具有 Hildebrand溶解度参数为至少约18.0MPa 1/2）。 反应可以在氟相和相的界面同时进行。 FMS试剂和FMS催化剂含有足够数量的氟部分，使它们优先溶于氟相和界面，而不损害催化剂或试剂在保持在液相或流体相中的反应中的功效或参与。 优选的氟部分是具有高碳数的直链，支链和碳环碳氟烷基链，使得催化剂或试剂保持与氟相容。 氟部分还可以含有O，S，N，P，As和Si，这有助于使催化剂和试剂氟相相容。 FMS试剂和催化剂可以通过（1）氟化（即用氟取代C-H键）来制备; （2）氟官能化，例如将氟部分连接到试剂或催化剂上; 或（3）全合成。 氟多相体系具有促进FMS催化剂或废FMS试剂分离的作用，其在设计和合成具有高产物选择性的催化剂和试剂中具有效用，从而导致特别环境友好的方法。
    • 基本信息 添加关注 加入工作空间 PDF全文 PDF下载 全文下载 相似专利 双屏查看 权利要求书 说明书全文 Global Dossier Espacenet 法律信息 同族专利 专利引用
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