基于铱催化剂对新型苯硼酸（酯）的合成研究

发布时间：2019-01-30 18:34

【摘要】：芳基硼酸类化合物是有机合成反应中一类重要的中间体,它能够与芳基卤代物发生偶合反应,生成联芳基类化合物。Suzuki反应的报道,使芳基硼酸类化合物的合成一度成为有机合成的热点。苯硼酸作为芳基硼酸的重要分支,它的合成方法和工艺日渐成熟,应用领域也不断地扩展。目前,苯硼酸类化合物的主要合成方法有:格氏试剂法、钯催化氧硼基化法、有机锂试剂法。但是,这三类传统的合成方法具有相同的弊端:硼酸(酯)基团引入的位置由底物中卤原子(溴和碘)位点决定,这增加了合成苯硼酸的难度,并限制了苯硼酸的多样性。近几年,报道了苯硼酸的新合成方法:以联硼酸频那醇酯(频那醇硼烷)为硼源试剂,在铱催化剂(二(1,5-环辛二烯)二-Μ-甲氧基二铱(I))的作用下,可以直接活化C-H键而在苯环上引入硼酸酯基团。该制备方法不受苯环上卤素位点的制约,这使得苯硼酸类化合物的合成再次引起人们的关注。本课题组受贵州省威顿晶磷电子材料有限公司委托,基于铱催化剂开发10-15个苯硼酸类化合物的合成工艺。最终得到5个系列,共14个化合物,经纯化和波谱表征确证了其结构,讨论了溶剂、配体、温度、投料比例等因素对反应的影响,并对其合成工艺进行优化。其中有7个化合物无CAS号,分别是A3、B1、C3、C4、D1、D2和F1;3个化合物有CAS号,但无合成方法报道,分别是A4、A5和C1;4个化合物,有合成方法报道,本文对其合成工艺进行了改进,分别是A_1、A_2、C_2和F_2。
[Abstract]:Aryl boric acid compounds are important intermediates in organic synthesis. They can be coupled with aryl halides to form biaryl compounds. Suzuki reaction is reported. The synthesis of aryl boric acid compounds has become a hot spot in organic synthesis. Phenylboric acid is an important branch of aryl boric acid. At present, the main synthesis methods of phenylboric acid compounds are Grignard reagent method, palladium catalyzed oxyborylation method, organic lithium reagent method. However, these three traditional methods have the same disadvantages: the position of boric acid (ester) group is determined by the sites of halogen atoms (bromine and iodine) in the substrate, which increases the difficulty of synthesizing phenylboric acid and limits the diversity of phenylboric acid. In recent years, a new synthesis method of phenoboric acid was reported. The boron source reagent was phenanolyl biborate (phenoxanolyl biborate) under the action of iridium catalyst (di (1 (1) (1) -cyclooctylene) di- 渭 -methoxy diiridium (I). The C-H bond can be activated directly and borate groups can be introduced into the benzene ring. This method is not restricted by halogen sites in benzene ring, which makes the synthesis of phenylboric acid compounds attract attention again. Our research group was commissioned by the Weiden Crystal phosphorus Electronic Materials Co. Ltd of Guizhou Province to develop the synthesis process of 10-15 phenylboric acid compounds based on iridium catalyst. Finally, five series of 14 compounds were obtained. Their structures were confirmed by purification and spectroscopic characterization. The effects of solvent, ligand, temperature and feed ratio on the reaction were discussed, and the synthesis process was optimized. Seven of them had no CAS number, which were A3OB1C3C4C4C4D1D1D2 and F1.The three compounds had CAS number, but no synthetic method was reported, which were A4A5 and C1, respectively. Four compounds, which have been reported as synthetic methods, have been improved in this paper. They are A _ 1 / A _ T _ 2C _ s _ 2 and F _ s _ 2s _ 2 respectively.
【学位授予单位】：贵州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36;TQ263.1

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