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    • 7. 发明授权
    • Preparation of metallated and substituted alkynes
    • 金属化和取代炔烃的制备
    • US5162562A
    • 1992-11-10
    • US697867
    • 1991-05-09
    • Frederick L. HermanAnn C. L. SavocaMark L. Listemann
    • Frederick L. HermanAnn C. L. SavocaMark L. Listemann
    • C07F1/04C07F7/08C07F7/30
    • C07F1/04C07F7/0801C07F7/0827C07F7/30
    • A process is provided for making metallated and substituted alkynes from feedstocks which include alkadienes containing allenic unsaturation or such alkadienes in a mixture with alkynes having either internal or terminal unsaturation, such as a mixture of propadiene and propyne. This reaction involves an initial step in which the allenic hydrocarbon and any internal alkyne is isomerized and simultaneously the resultant terminal alkynes are metallated with an alkali metal. The reaction is carried out at relatively low temperatures in a suitable inert solvent such as diethylether. When metallation is complete the reaction mixture can be contacted directly with any suitable electrophile, such as a halo silane, for example, chlorotrimethylsilane, and the alkali metal on the terminal alkyne is replaced with the desired substituent. The products thus formed are useful as monomers for preparing polymers having a variety of properties, for example, as asymmetric membranes for gas separation.
    • 提供了一种用于从原料制备金属化和取代的炔烃的方法,其包括含有不饱和烯烃的链烯二烯或与具有内部或末端不饱和键(例如丙二烯和丙炔的混合物)的炔烃的混合物。 该反应包括初步步骤,其中烯烃和任何内炔异构化,同时所得的末端炔烃用碱金属进行金属化。 该反应在相当低的温度下在合适的惰性溶剂如二乙醚中进行。 当金属化完成时,反应混合物可以与任何合适的亲电试剂例如卤代硅烷(例如氯代三甲基硅烷)直接接触,并且末端炔上的碱金属被所需的取代基取代。 由此形成的产物可用作制备具有各种性质的聚合物的单体,例如用作气体分离的不对称膜。