硝酸铁催化氧化合成异色满酮和杂蒽酮的研究

发布时间：2018-09-13 13:49

【摘要】：异色满酮和杂蒽酮类化合物已经广泛地应用于医药、农药、化学、材料等领域。因此,开发一种简单、高效制备异色满酮和杂蒽酮类化合物的方法具有重要的意义。本论文主要采用苄位氧化的方法一步合成异色满酮和杂蒽酮类化合物。首先,以苯乙醇类化合物为原料通过两步反应制备了异色满类化合物;以水杨醛和环己烯酮类化合物为原料通过氧化偶联反应制备了氧杂蒽类化合物;以硫杂蒽酮类化合物为原料通过还原的方法制备了硫杂蒽类化合物。其次,将Fe(NO_3)_3·9H_2O/KPF6/O_2的催化氧化体系应用于异色满酮类化合物的制备。以异色满为模型底物,考察了溶剂、催化剂、温度、氧气、催化剂的用量、强酸盐等条件对反应的影响。研究结果表明:以10 mol%的Fe(NO_3)_3·9H_2O为催化剂,15 mol%的KPF6为添加物,3 mL乙腈为溶剂,氧气为氧化剂,在80oC下反应5 h,异色满酮的分离收率为94%。该反应体系适用于大部分异色满类化合物,产物的分离收率为46-95%。随后,将Fe(NO_3)_3·9H_2O/KPF6/O_2的催化氧化体系应用于杂蒽酮类化合物的制备。对于大多数的底物,制备异色满酮的最优条件同样适用于杂蒽酮类化合物,并且反应时间缩减为2 h,分离收率为91-97%。对于某些在乙腈中溶解性较差的底物,需要增加乙腈和催化剂的用量,并延长反应时间。最后,我们根据文献并通过设计对照实验探讨了该体系的反应机理。总之,我们成功地开发了一种异色满酮和杂蒽酮的合成方法,该体系对于大多数的底物均表现出了较高的活性。但是,本论文的杂蒽酮只针对氧杂蒽酮和硫杂蒽酮,不包括氮杂蒽酮。
[Abstract]:Isomone and heteranthenone have been widely used in medicine, pesticide, chemistry, materials and so on. Therefore, it is of great significance to develop a simple and efficient method for the preparation of isocolone and heteranthenone compounds. In this paper, the benzyl oxidation method was used to synthesize isocolone and anthrone compounds in one step. Firstly, isocolor compounds were prepared from phenylethanes by two-step reaction, and oxy-heteranthracene compounds were prepared from salicylaldehyde and cyclohexene ketones by oxidative coupling reaction. Thioanthracene compounds were prepared by reduction from thioxanthrone compounds. Secondly, the catalytic oxidation system of Fe (NO_3) 3 9H_2O/KPF6/O_2 was applied to the preparation of isocolor ketones. The effects of solvent, catalyst, temperature, oxygen, amount of catalyst and strong acid salt on the reaction were investigated. The results showed that with 10 mol% Fe (NO_3) 3 9H_2O as catalyst, KPF6 of 15 mol% as additive, acetonitrile of 3 mL as solvent, oxygen as oxidant, reaction under 80oC for 5 h, the yield of isocolone was 94%. The reaction system is suitable for most heterocolor compounds and the separation yield of the product is 46-95. Subsequently, the catalytic oxidation system of Fe (NO_3) 3 9H_2O/KPF6/O_2 was applied to the preparation of heteranthrones. For most substrates, the optimum conditions for the preparation of isocolone are also suitable for heteranthenones, and the reaction time is reduced to 2 h, and the separation yield is 91-97. For some substrates with poor solubility in acetonitrile, the amount of acetonitrile and catalyst should be increased and the reaction time should be prolonged. Finally, the reaction mechanism of the system was discussed by designing a controlled experiment according to the literature. In conclusion, we have successfully developed a method for the synthesis of isocolone and heteranthronone, which shows high activity for most substrates. However, the heteroxanthrone in this thesis is only for oxyanthrone and thioxanthrone, excluding azanthronone.
【学位授予单位】：浙江工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.3

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