环状过氧化物对硫醚的氧化反应研究

发布时间：2018-01-07 03:10

本文关键词：环状过氧化物对硫醚的氧化反应研究　出处：《哈尔滨工业大学》2016年硕士论文　论文类型：学位论文

【摘要】：亚砜化合物已经广泛用于生物医药和有机化学研究,引起了多个领域研究人员的重视。常见的亚砜类药物有胃病良药奥美拉唑,神经性疾病药物莫达非尼和心血管疾病类药物磺吡酮等。同时,在有机化学中手性亚砜类化合物还可作为手性助剂、手性配体和手性催化剂广泛用于不对称合成中。制备亚砜类化合物最直接的方法是将硫醚类化合物进行氧化。近期,环状二酰基过氧化物已成功用于烯烃的双羟基化反应和碳氢键的氧化反应,表现出温和的氧化性能。本文以环状二酰基过氧化物为氧化剂,选择性地将硫醚类化合物氧化为亚砜类化合物,并对反应机理进行探讨。合成了两种环状二酰基过氧化物,邻苯二甲酰过氧化物(PPO)和环戊基丙二酰过氧化物(MPO)。以PPO为氧化剂对硫醚进行氧化,高选择性高收率地将硫醚类化合物氧化为亚砜,拓展了37个涵盖多种官能团的硫醚进行普适性研究。以MPO为氧化剂,在温和条件下高产率地合成了奥美拉唑。通过气-质检测、核磁验证和DFT计算等,对环状二酰基过氧化物的氧化机理进行了探讨,提出了可能的反应机理。以环状二酰基过氧化物为氧化剂,将硫醚类化合物氧化为亚砜,操作简单,无需使用其他催化剂和添加剂,氧化性能温和,可选择性地将硫醚氧化为亚砜,底物适应性广,具有良好的官能团容忍度。
[Abstract]:Sulfoxide compounds have been widely used in biomedical and organic chemistry research, which has attracted the attention of researchers in many fields. Common sulfoxide drugs include omeprazole, a good medicine for stomach diseases. At the same time, chiral sulfoxide compounds can be used as chiral auxiliaries in organic chemistry. Chiral ligands and chiral catalysts are widely used in asymmetric synthesis. The most direct way to prepare sulfoxides is to oxidize sulfides. Cyclic diacylperoxides have been successfully used in the dihydroxylation of olefins and the oxidation of hydrocarbon bonds, showing mild oxidation properties. In this paper, cyclic diacyl peroxides are used as oxidants. Sulfides were selectively oxidized to sulfoxide compounds and the reaction mechanism was discussed. Two cyclic diacyl peroxides were synthesized. Phthalyl peroxide (PPO) and cyclopentyl malonyl peroxide (PPO) were used to oxidize sulfides to sulfoxide in high selectivity and yield. 37 sulfides covering a variety of functional groups were expanded to study their universality. Omeprazole was synthesized with high yield under mild conditions using MPO as oxidant. The oxidation mechanism of cyclic diacylperoxides was discussed and the possible reaction mechanism was proposed. The cyclic diacyl peroxide was used as oxidant. The thioether compounds are oxidized to sulfoxide, which is easy to operate and does not need other catalysts and additives. The oxidation performance is mild and the sulfoxide can be oxidized to sulfoxide selectively. The substrate has wide adaptability. Good tolerance of functional groups.
【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.254.1

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