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    • 4. 发明授权
    • Synthesis of diaza crown ethers
    • 二氮冠醚的合成
    • US5247078A
    • 1993-09-21
    • US694706
    • 1991-05-02
    • Donald H. ChampionGeorge P. SperanzaTerry L. Renken
    • Donald H. ChampionGeorge P. SperanzaTerry L. Renken
    • C07D273/00C07D273/08
    • C07D273/00
    • Poly(ethyleneoxy)amines, such as those having the structure:H.sub.2 N--(CH.sub.2).sub.a --(OCH.sub.2 CH.sub.2).sub.b --NH--(CH.sub.2 CH.sub.2 O).sub.c --(CH.sub.2).sub.d --Rwhere a and d are independently 2 to 3; b and c are independently 1 to 4 and R is --OH or --NH.sub.2, may be reacted over a transition metal catalyst such as one containing nickel to produce diaza crown ethers, such as, for example 4,13-diaza-18-crown-6. If the poly(ethyleneoxy)amine is a diamine having a hydroxyl group of the above formula, the reaction may produce the corresponding triamine in the presence of ammonia. These triamines also readily form diaza crown ethers at near complete conversions simply from nickel, platinum, and palladium metal catalysts alone or with other transition metals such as copper and/or chromium. The process avoids tedious, multiple step procedures and the high dilutions that accompany prior diaza crown ether preparations.
    • 聚(乙烯氧基)胺,例如具有以下结构的那些:H 2 N - (CH 2)a - (OCH 2 CH 2)b -NH-(CH 2 CH 2 O)c - (CH 2)d -R,其中a和d独立地为2至3; b和c独立地为1至4并且R为-OH或-NH 2,可以在过渡金属催化剂如含镍的反应物上反应以制备二氮杂冠醚,例如4,13-二氮杂-18-冠 -6。 如果聚(乙烯氧基)胺是具有上式的羟基的二胺,则反应可在氨的存在下产生相应的三胺。 这些三胺也可以简单地从镍,铂和钯金属催化剂单独或与其它过渡金属如铜和/或铬接近完全转化形成二氮冠醚。 该过程避免了繁琐的多步骤程序和伴随以前的碳酸乙醚制备的高稀释度。
    • 7. 发明授权
    • Process for the preparation of polyoxyalkylene polyamines
    • 聚氧化烯多胺的制备方法
    • US4766245A
    • 1988-08-23
    • US707126
    • 1985-03-01
    • John M. LarkinTerry L. Renken
    • John M. LarkinTerry L. Renken
    • C08G65/32C08G65/325C07C85/02C07C85/06
    • C08G65/3255
    • An improved method for the manufacture of high molecular weight polyoxyalkylene amines wherein a hydroxy-terminated polyoxyalkylene compound having a molecular weight of at least 500 is reacted with ammonia in the presence of hydrogen and Raney nickel/aluminum under anhydrous reductive amination conditions to provide the corresponding polyoxyalkylene amine in good yield and selectivity.The Raney nickel/aluminum is a nickel/aluminum alloy treated with a base, such as sodium hydroxide, so as to only partially leach the aluminum from the alloy, such that the final product contains from about 60 wt. % to about 75 wt. % of nickel and, correspondingly, from about 25 wt. % to about 40 wt. % of aluminum and is preferably used in nugget form.
    • 制备高分子量聚氧化烯胺的改进方法,其中分子量至少为500的羟基封端的聚氧化烯化合物在无水还原胺化条件下在氢和阮内镍/铝的存在下与氨反应,以提供相应的 聚氧亚烷基胺具有良好的收率和选择性。 阮内镍/铝是用碱如氢氧化钠处理的镍/铝合金,以便仅从合金中部分浸出铝,使得最终产物含有约60wt。 %至约75wt。 的镍,相应地为约25wt。 %至约40wt。 铝的百分比,优选以熔核形式使用。