【作者】 崔鹏；

【导师】 汤杰；

【作者基本信息】 华东师范大学 ， 有机化学， 2006， 硕士

【摘要】 本论文主要有由两部分内容组成：（1）离子液体／HOAc／CO²⁺／AIBN体系中芳烃侧链分子氧选择性氧化反应研究（2）季铵盐在芳烃侧链分子氧选择性氧化反应中的应用。 一、离子液体／HOAc／Co²⁺／AIBN体系中芳烃侧链分子氧选择性氧化反应研究 在课题组前期工作的基础上，研究了在不同离子液体／催化剂体系中的芳烃侧链分子氧选择性氧化反应，考察了影响反应转化率和选择性的因素。主要结果如下： （1）发展了一种新的[Hex-mim]⁺BF₄^-／Co（OAc）₂／HOAc／／NaBr／AIBN反应体系。在该体系中，对二甲苯可在常压下高效地被分子氧选择性氧化为相应的醛和醇。对二甲苯的转化率高达95.9％，优于我们课题组前期结果。 （2）发展了通过向反应体系中加适量水调整产物选择性的方法。随着体系中水量的增加，产物中醛的选择性随之增加，但反应的转化率却随之降低。当体系中的水量为离子液体用量的70％时，在保持中等转化率（43％）的同时，醛的选择性可提高到67％。 （3）条件试验表明，增加反应体系的酸度能够提高反应的转化率，以对二甲苯为底物，当反应在[Hmim]⁺CF₃COO^-／CF₃COOH=2／1的体系中进行时，反应的转化率提高到89.7％，对甲基苄醇醋酸酯的选择性高达98.2％!这为芳烃侧链分子氧催化氧化法制备芳香醇或芳香醇的醋酸酯提供了一条新途径。而延长反应时间和增加离子液体的用量对反应的转化率和选择性几乎都没有影响。 （4）不同底物的反应结果表明，电子效应对转化率有显著影响。底物芳环上的给电子基团有利于反应进行；反之，吸电子基团则使转化率降低。 二、季铵盐在芳烃侧链分子氧选择性氧化反应中的应用 首次采用季铵盐作为反应的催化剂和深度氧化的抑制剂，研究了芳烃侧链分子氧选择性氧化反应，初步结果令人鼓舞。 通过初步筛选发现，在醋酸水溶液中，催化量（底物的5％）的四丁基溴化铵作为催化剂和深度氧化的抑制剂，调控体系的酸度和水量，同样可使芳烃侧链更多还原

【Abstract】 This dissertation consists of two parts: （1） selective oxidation of alkylarenes with molecular oxygen in ionic liquid/HOAc/Co²⁺ /AIBN; （2） the application of quaternary ammonium salts in the selective oxidation of alkylarenes with molecular oxygen.Part I. Selective oxidation of alkylarenes with molecular oxygen in ionic liquid/HOAc/Co²⁺ /AIBN.Selective oxidations of alkylarenes with molecular oxygen in different ionic liquid/catalysts systems were investigated, and the influence factors for the selectivity and conversion were inspected. The main results were as follows:1. We developed a new reaction system [Hex-mim]⁺BF₄^-/Co（OAc）₂/ HOAc//NaBr/AIBN, in which p-xylene could be oxidized effectively to the corresponding aldehyde and alcohol by molecular oxygen under atmospheric pressure. The conversion was up to 95.9%, and it was superior obviously to the earlier results.2. We also developed one method for adjusting the selectivity by adding right amount of water to the reaction system. The selectivity for the product aldehyde was enhanced while increased the quantity of water, however, the conversion was decreased under this condition. When the ratio of water to ionic liquid was 7/10, both of the selectivity and conversion were satisfactory.3. The experimental showed that the conversion could be improved while increasing the acidity, but it was nearly not changed when the acidity was increased to a certain degree. Continuation of increasing the acidity led to the formation of aromatic acid. Lengthening the reaction time and increasing the quantity of ionic liquid did not influence the conversion and selectivity.4. The oxidation of different substrates indicated that the conversion was influenced obviously by electronic effect. The electron-donating groups on aromatic ring was favorable to the reaction, contrarily, the electron-withdrawing groups decreased the conversion.Part II. The application of quaternary ammonium salts in the selective oxidation更多还原