HYDROGEN-PEROXIDE OXIDATION CATALYZED BY HETEROPOLY ACIDS COMBINED WITH CETYLPYRIDINIUM CHLORIDE - EPOXIDATION OF OLEFINS AND ALLYLIC ALCOHOLS, KETONIZATION OF ALCOHOLS AND DIOLS, AND OXIDATIVE CLEAVAGE OF 1,2-DIOLS AND OLEFINS
HYDROGEN-PEROXIDE OXIDATION CATALYZED BY HETEROPOLY ACIDS COMBINED WITH CETYLPYRIDINIUM CHLORIDE - EPOXIDATION OF OLEFINS AND ALLYLIC ALCOHOLS, KETONIZATION OF ALCOHOLS AND DIOLS, AND OXIDATIVE CLEAVAGE OF 1,2-DIOLS AND OLEFINS
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DOI：
10.1021/jo00250a032
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发表时间：
1988-07-22
影响因子：
3.6
通讯作者：
OGAWA, M
中科院分区：
文献类型：
--
作者：
ISHII, Y;YAMAWAKI, K;OGAWA, M
以过氧化氢为氧化剂，研制了一种通用、易降解的氧化催化剂.在两相条件下，使用氯仿作为溶剂，使用Mo-或W-基杂多酸H3 PMo 12 O 40（MPA）或H3 PW 12 O 40（WPA）与合适的铵盐如氯化十六烷基吡啶鎓（CPC）的组合，用市售的过氧化氢（30- 35%H2O2）将烯烃和烯丙醇环氧化（表I和II）。三（十六烷基吡啶鎓）12-钨磷酸盐（CWP），[7 r-C5 H5 N+（CH 2）15 CH 3] 3-（PW 12 O 40）2，独立于WPA和3当量CPC，催化醇和二醇的仲羟基在均相条件下用H2 O2使用叔丁醇作为溶剂的有效酮化（表III）。在相同条件下，通过CWP-H2 O2系统成功地进行了邻二醇的氧化裂解，以良好的产率得到羧酸（表IV）。该催化剂-氧化剂体系对于烯烃的碳-碳双键的氧化裂解也是有效的，这提供了烯烃到羧酸的新的有价值的转化（表V）。
A general and versatileoxidation catalyst has been developed by using hydrogen peroxide as the oxidant. Olefins and allylic alcohols were epoxidized with commercially available hydrogen peroxide (30-35% H202) using a combination of Mo-or W-based heteropoly acids, H3PMo1204o (MPA) or H3PW1204o (WPA), with an appropriate ammonium salt such as cetylpyridinium chloride (CPC), under two-phase conditions using chloroform as the solvent (Tables I and II). The tris (cetylpyridinium) 12-tungstophosphate (CWP),[7r-C5H5N+(CH2) 15CH3] 3-(PW1204o)^, preparedindependently from WPA and 3 equiv of CPC, catalyzes the efficient ketonization of the secondary hydroxy group of alcohols and diols with H202 under homogeneous conditions using fert-butyl alcohol as the solvent (Table III). Under the same conditions, oxidative cleavage of vic-diols was successfully conducted by the CWP-H202 system to give carboxylic acids in good yields (Table IV). This catalyst-oxidant system was also efficient for the oxidative cleavage of carbon-carbondouble bonds of olefins which provides a new valuable conversion of olefins to carboxylic acids (Table V).