【作者】 苏金龙；

【导师】 傅相锴； 穆瑞珠；

【作者基本信息】 西南大学 ， 有机化学， 2009， 硕士

【摘要】 本论文一共分为四个部分:第一章过氧化氢在有机合成中的应用进展本章归纳了过氧化氢促进烯烃的环氧化、醇的选择氧化、硫化物到砜的转化、有机物的卤化等反应。所引用的文献都是国际重要期刊文献。第二章H₂O₂/V₂O₅催化体系促进汉斯酯1,4-二氢吡啶的芳构化我们以醛、乙酰乙酸乙酯、醋酸铵为原料,在80℃条件下,一锅煮合成了一系列的汉斯酯1,4-二氢吡啶化合物,该合成方法对环境友好。在考察过氧化氢芳构化汉斯酯1,4-二氢吡啶的过程中,我们尝试了多种催化剂来完成该反应。本章我们运用H₂O₂/V₂O₅体系在室温下完成汉斯酯1,4-二氢吡啶的芳构化,并且为本反应提出一个可能的反应机理。本反应使用的试剂价廉易得,反应条件温和,产物收率较高,该方法是对已有方法的一种有益补充。第三章H₂O₂/Ti（SO₄）₂催化体系促进汉斯酯1,4-二氢吡啶的芳构化我们使用5 mol%的Ti（SO₄）₂催化过氧化氢完成一系列汉斯酯1,4-二氢吡啶的芳构化,产物收率较高。反应过程中,我们考察了溶剂对反应的影响,最后选择乙腈做为该反应的溶剂。该反应在室温下进行8 h,所有的底物都可以转化为相应的产物。反应所用的催化剂和氧化剂便宜易得。第四章H₂O₂/Ti（SO₄）₂体系选择氧化醇的研究本章我们成功运用H₂O₂/Ti（SO₄）₂体系完成醇的选择性氧化。除了苯甲醇和对硝基苯甲醇收率不好之外,其它醇的氧化产物都得到很好的收率。本论文拓展了过氧化氢在有机合成中的应用,扩大了催化剂Ti（SO₄）₂、V₂O₅在有机合成中的应用范围,具有一定的参考价值。更多还原

【Abstract】 In this thesis, the following four parts are mainly included: ChapterⅠ: Recent progress of hydrogen peroxide in organic synthesisIn this chapter, epoxidation of alkenes, selective oxidation of alcohols, oxidation of sulfides to sulfoxides and sulphones, halogenation of organic compounds carried out using hydrogen peroxide were summarized. The references all were published in leading international journals. ChapterⅡ: Aromatization of Hantzsch 1,4-dihydropyridines by H₂O₂/V₂O₅A series of Hantzsch 1,4-dihydropyridines were synthesized in an environmentally benign method , by reacting aldehydes with acetoacetate esters and ammonium acetate at 80℃. We have chosed several catalysts and found that H₂O₂/V₂O₅ was a good system for the aromatization of Hantzsch 1,4-dihydropyridines to the correspondence pyridines. A possible reaction mechanism was also suggested. The cheapness, easy availability of the reagents, mild reaction conditions as well as excellent yields of the products are the advantages which make this protocol a useful addition to the existing methodologies. ChapterⅢ: Aromatization of Hantzsch 1,4-dihydropyridines by H₂O₂/Ti（SO₄）₂Hantzsch 1,4-dihydropyridines undergo smooth aromatization catalyzed by a catalytic amount （5mol%） of Ti（SO₂）₂ with H₂O₂ to afford the corresponding pyridine derivatives in high yields. Various solvent systems were tested. All the reactions were carried out in acetonitrile at room temperature for eight hours to complete conversion of the substrates. The cheapness of the catalyst and the oxidizer were employed. ChapterⅣ: Selective oxidation of alcohols to aldehydes and ketones with H₂O₂/Ti（SO₂）₂In this chapter, the selective oxidation of alcohols to aldehydes and ketones with H₂O₂/Ti（SO₄）₂ have been accomplished. All of the substrates gave the excellent yields except the p-nitrobenzyl alcohol and the benzyl alcohol.The above results reference values in enlarging the application field of hydrogen peroxide in organic synthesis. We think that the use of V₂O₅ and Ti（SO₄）₂ catalysts with hydrogen peroxide in organic synthesis were worth to being referred.更多还原