Aerobic Oxidation Catalyzed by Mixed Addenda Heteropolyoxometarates

混合附加物杂多酸催化的有氧氧化

基本信息

批准号：
06453143
负责人：
ISHII Yasutaka
金额：
$ 2.94万
依托单位：
Kansai University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1995
项目状态：
已结题

项目摘要

Oxidations of variountaining vanadium and molybdenum were examined. In addition, the combination of Pd (II) with vanadomolybdophosphate (NPVMo) in the presence of hydroquinone was found to be an efficient catalytic system for the oxidation of alkenes with molecular oxygen. We have obtained the following results in this project.1. Oxidation of various organic substrates with molecular oxygen by NPVMoVanadomolybdophosphate (NPVMo), which can be shown as (NH_4) _5H_6PV_4Mo_8O_<40>, catalyzed the oxidation of aromatic amines, benzyl alcohols and phenols to the corresponding imines, bezaldehydes and quinoes with molecular oxygen under relatively mild conditions.2. Development of indirect oxidation using molecular oxygen as final oxidantHydroquinone was smoothly dehydrogenated with molecular oxygen to quinone by NPVMo. By combination of Pd (II) and this system, anew oxidation system has been developed. Thus, a variety of cycloalkenes such as cyclohexene underwent the acylation in acetic acid by Pd (II) /hydroquinone/NPVMo/O_2 system to form 3-acetoxy-1-cycloalkenes in quantitative yields. When ethyl acrylate and acrylonitrile was allowed to react in ehtanol by the use of this catalytic system, acetalization took place to form the corresponding acetals in good yields.3. Oxidation by the use of N-hydroxyphthalimide as catalystN-Hydroxyphthalimide (NHPI) was found to catalyze the oxidation of benzylic compounds with molecular oxygen to give alcohols or ketones in fair yields. This catalytic oxidation was found to be a novel aerobic oxidation system. The oxidation of alkanes such as cyclohexane was achieved by NHPI in the presence of Co (acac) n (n=2 or 3). For example, cyclohexane was converted to cyclohexanone and adipic acid in fair yields. This method was extended to the aerobic oxidation of various organic substrates.

检查了谷钒和钼的氧化。此外，发现PD（II）与氢二磷酸盐（NPVMO）的组合在氢喹酮存在下被发现是一种有效的催化系统，用于用分子氧氧化烯烃。我们在该项目中获得了以下结果。1。通过NPVMovanadomolybdophophathate（NPVMO）用分子氧对各种有机底物进行氧化，可以显示为（NH_4）_5H_4）_5H_6PV_4MO_8O_ <40>氧气在相对温和的条件下2。使用分子氧作为最终氧化乙醇喹酮的间接氧化的发展被NPVMO平滑地脱氢成喹酮。通过PD（II）和该系统的组合，已经开发了新的氧化系统。因此，诸如环己烯之类的多种环烯烃通过PD（II）/羟基酮/NPVMO/O_2系统在定量产率中形成3-乙氧基-1-氯烷烯。当丙烯酸乙酯和丙烯腈通过使用该催化系统在eHtanol中反应时，发生了乙酰化时，进行了乙酰化，以良好的产量形成相应的醋。3。发现通过使用N-羟基苯二甲胺作为催化剂 - 羟基苯胺（NHPI）氧化可催化用分子氧的苄基化合物的氧化，从而以公平的收益率促进醇或酮。发现这种催化氧化是一种新型的有氧氧化系统。 NHPI在CO（ACAC）N（N = 2或3）的存在下实现了烷烃（例如环己烷）的氧化。例如，将环己烷转化为环己酮和脂肪酸的公平产量。该方法扩展到各种有机底物的有氧氧化。