3,5-二氯苯胺合成的新方法及2-三氟甲基-1,3-共轭烯炔与亲核试剂反应研究

发布时间：2018-03-22 03:38

本文选题：3　切入点：5-二氯苯胺　出处：《华东师范大学》2017年硕士论文　论文类型：学位论文

【摘要】：3,5-二氯苯胺是一种医药、农药、染料的中间体,该化合物广泛用于医药、染料、颜料、光致变色材料、植物生长促进剂的合成。目前,由于环酰亚胺类农用杀菌剂产量的增加,其中间体3,5-二氯苯胺已成供不应求的趋势。因此,研究其简便、经济的合成方法并使之工业化具有一定的现实意义。另一方面,有机化合物分子中引入氟原子或含氟基团后,由于氟原子具有强吸点性和极小的原子半径,会造成氟化产物在理化性质上发生一定的改变,例如好的反应性,良好的亲酯性效应和代谢阻碍效应。尤其是许多含氟有机分子具有了一些不同于它们的非含氟类似物的生理活性,使得其在药物和生物领域得到越来越多的应用。因此,研究合成各类含氟化合物的方法有着十分重大的意义。论文第一部分工作研究了使用1,3,5-三氯苯一步合成3,5-二氯苯胺。发展了一种简便合成3,5-二氯苯胺的新方法。研究发现通过使用原料简单易得的1,3,5-三氯苯,在配体和钯金属催化剂的作用,加入氨气或者铵盐以及碱,就可以一步高产率合成3,5-二氯苯胺这类重要的药物中间体。论文的第二部分工作研究了银催化下2-三氟甲基-1,3-共轭烯炔与伯胺的串联氢胺化反应和环化反应规律。发展了两次串联氢胺化反应合成4-三氟甲基-2,4-二取代-2,5-二氢吡咯衍生物的新方法。研究发现4-三氟甲基-2,4-二取代-2,5-二氢吡咯衍生物是一类非常实用的有机合成中间体,可用来合成脯氨酸、吡咯烷酮、吡咯及氟吡咯衍生物。论文的第三部分工作研究了 2-三氟甲基-1,3-共轭烯炔与苯硫酚的选择性加成反应规律。研究发现2-三氟甲基-1,3-共轭烯炔与苯硫酚在不同溶剂的作用下,可以选择性得到1,2加成硫炔类产物和3,4加成双烯类加成产物。硫炔类型加成产物在碘单质的作用下可以得到罕见的含硫含碘四取代烯烃,这类型烯烃具有潜在的抗癌活性;双烯类型加成产物通过简单的Diels-Alder反应可以得到含氟六元碳环产物。
[Abstract]:The compound is widely used in the synthesis of pharmaceuticals, dyes, pigments, photochromic materials and plant growth promoters. At present, due to the increase in the production of cycloimide agricultural fungicides, Therefore, it is of practical significance to study its simple and economical synthesis method and to industrialize it. On the other hand, fluorine atoms or fluorine groups are introduced into organic compounds. Because fluorine atoms have strong absorption point and very small atomic radius, fluorinated products have some changes in physical and chemical properties, such as good reactivity. In particular, many fluorine-containing organic molecules have some physiological activities that are different from their non-fluorine analogues, which make them more and more widely used in the field of medicine and biology. It is of great significance to study the synthesis of various fluorine-containing compounds. In the first part of the thesis, we have studied the one-step synthesis of 3o 5-dichloroaniline using 1 ~ (3) C ~ (3 +) -trichlorobenzene and developed a simple and convenient method for the synthesis of 3H _ (5) -dichloroaniline. The study found that through the use of simple and easily available raw materials of 1, 3, 5-trichlorobenzene (trichlorobenzene), Adding ammonia or ammonium salts and alkali to the ligands and palladium metal catalysts, In the second part of this paper, the series hydroamination reaction and cyclization of 2-trifluoromethyl-1-trifluoromethyl-3-conjugated alkyne with primary amine catalyzed by silver were studied. A new method for the synthesis of 4- trifluoromethyl-2o-4-disubstituted-2-5-dihydropyrrole derivatives was developed. It was found that the 4-trifluoromethyl-2-pyrrolidene-4-disubstituted-2-dihydropyrrole derivative is a kind of very practical intermediate in organic synthesis. Can be used to synthesize proline, pyrrolidone, In the third part of the thesis, the selective addition reaction of 2-trifluoromethyl -1keto-3-conjugated alkyne with phenythiophenol was studied, and it was found that 2-trifluoromethyl -1-trifluoromethyl-3-conjugated alkyne and phenylthiophenol acted on them in different solvents. The thioacetylenes and the dienes can be selectively obtained. The thioacetylene type adducts can obtain rare tetrasubstituted alkenes containing sulfur and iodine under the action of iodide, and this type of olefins have potential anticancer activity. The addition products of diene type can be obtained by simple Diels-Alder reaction.
【学位授予单位】：华东师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25

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