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    • 5. 发明授权
    • Haloporphyrins and their preparation and use as catalysts
    • 卤卟啉及其制备和用作催化剂
    • US5663328A
    • 1997-09-02
    • US672202
    • 1996-06-27
    • Paul E. Ellis, Jr.James E. Lyons
    • Paul E. Ellis, Jr.James E. Lyons
    • B01J31/18C07D487/22C07C29/50C07C31/12
    • B01J31/1815B01J2231/70B01J2531/025B01J2531/16B01J2531/26
    • The invention provides novel catalyst compositions, useful in the oxidation of hydrocarbons with air or oxygen to form hydroxy-group containing compounds and in the decomposition of hydroperoxides to form hydroxy-group containing compounds. The catalysts comprise transition metal complexes of a porphyrin ring having 1 to 12 halogen substituents on the porphyrin ring, at least one of said halogens being in a meso position and/or the catalyst containing no aryl group in a meso position. The compositions are prepared by halogenating a transition metal complex of a porphyrin. In one embodiment, a complex of a porphyrin with a metal whose porphyrin complexes are not active for oxidation of hydrocarbons is halogenated, thereby to obtain a haloporphyrin complex of that metal, the metal is removed from the haloporphyrin complex to obtain the free base form of the haloporphyrin, and a metal such as iron whose porphyrin complexes are active for oxidation of hydrocarbons and for the decomposition of alkyl hydroperoxides is complexed with the free base to obtain an active catalyst for oxidation of hydrocarbons and decomposition of alkyl hydroperoxides.
    • 本发明提供了新的催化剂组合物,其可用于用空气或氧气氧化烃以形成含羟基化合物,并在氢过氧化物的分解中形成含羟基化合物。 催化剂包括在卟啉环上具有1至12个卤素取代基的卟啉环的过渡金属络合物,所述卤素中的至少一个在中间位置和/或在中间位置不含芳基的催化剂。 通过卤化卟啉的过渡金属络合物制备组合物。 在一个实施方案中,卟啉与卟啉络合物对于烃的氧化不起作用的金属的络合物被卤化,从而获得该金属的卤卟啉络合物,从卤卟啉络合物中除去金属,得到游离碱形式 卤卟啉和卟啉配合物对烃的氧化和烷基氢过氧化物的分解具有活性的金属如铁,与游离碱络合,得到烃的氧化和烷基氢过氧化物的分解的活性催化剂。