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    • 5. 发明授权
    • Cobalt-catalyzed one-step synthesis of annulated pyridines
    • 钴催化的一步合成环状吡啶
    • US4328343A
    • 1982-05-04
    • US54926
    • 1979-07-05
    • K. Peter C. VollhardtAlaric Naiman
    • K. Peter C. VollhardtAlaric Naiman
    • C07D217/02C07D217/14C07D217/16C07D217/22C07D221/04C07D455/04C07D471/04C07D495/04
    • C07D221/04C07D217/02C07D217/14C07D217/16C07D217/22C07D455/04C07D471/04C07D495/04
    • A method of synthesizing fused ring pyridines (annulated) by co-oligomerization of .alpha.,.omega.-diynes with about molar equivalents of nitriles using a Co.sup.+1 catalyst preferably cyclopentadienyl cobalt dicarbonyl. Additionally, new compounds of tricyclic quinolizine-4-ones were produced where excess cyanoacetic ester starting materials were utilized (about 2:1 equivalent nitriles:diyne). The results with the catalyst employed indicated a stepwise mechanism in which cobalt(I) catalyst first forms a metallocycle intermediate derived from the bisacetylene. This cobalt(III) intermediate reacts preferentially with nitriles to give the product annulated pyridines in good yield. Generally, preferred conditions indicated roughly molar equivalents of reactants with no substantial excess of either reactant for the bicyclic compounds. Preferred conditions include a moderate temperature (solvent reflux temperature) and a preferred solvent such as BTX-type solvent (xylene) or an alkane (N-octane) under an inert blanket (nitrogen) for a multi-day period.
    • 通过使用Co + 1催化剂,优选环戊二烯基二羰基钴将α,ω-二炔与约摩尔当量的腈共价低聚合成稠环吡啶(环化)的方法。 另外,生产出三价喹诺酮-4-酮的新化合物,其中使用过量的氰基乙酸酯原料(约2:1当量腈:二炔)。 所用催化剂的结果表明,其中钴(I)催化剂首先形成衍生自双乙炔的金属环中间体的逐步机理。 这种钴(III)中间体优先与腈反应,以良好的产率给出产物环状的吡啶。 通常,优选的条件表示大致摩尔当量的双环化合物的反应物基本上不超过任何一种反应物。 优选的条件包括中等温度(溶剂回流温度)和优选的溶剂如BTX型溶剂(二甲苯)或烷烃(N-辛烷)在惰性气氛下(氮气)下进行多天。