手性氮杂环丁烷衍生的锌配合物的合成、结构及催化丙交酯聚合研究

发布时间：2018-06-14 08:08

本文选题：氮杂环丁烷 + 手性有机锌配合物　；参考：《西南大学》2017年硕士论文

【摘要】：氮杂环丁烷衍生物在医药领域有潜在的应用价值,是有机合成化学研究的重要领域。同时,这类化合物还具有结构刚性、空间位阻易调及叔胺氮原子配位能力强等特点,是优良的金属配合物配体,但目前有关它们衍生的金属配合还很少报道。因此,本论文主要是利用手性氮杂环丁烷衍生的磺酰胺类,Schiff类配体跟二乙基锌的反应,制备出一系列新型手性有机锌金属配合物,同时研究这些配合物对丙交酯开环聚合反应的催化性能。首先以3-氨基氮杂环丁烷为手性源合成一系列磺酰胺类(1aH-1fH)和Schiff类(2aH-2dH)化合物。并将它们与当量的二乙基锌反应制备出一系列有机锌配合物(1-11),配合物的结构受配体的空间位阻的影响很大,比如,磺酰胺类配体(1aH,1cH,1eH,1fH)与二乙基锌反应,分别得到二聚金属配合物{(1a)ZnEt}2(1)、{(1c)ZnEt}2(3)、{(1e)ZnEt}2(5)、{(1f)ZnEt}2(6),而磺酰胺配体(1bH,1dH)与二乙基锌反应,却分别得到无活性乙基的多核金属配合物(2)和(4)。另外,我们还发现与磺酰胺类配体不同,Schiff类配体(2aH-2dH)与二乙基锌反应,分别得到无活性乙基的bis-ligated配合物(2a)2Zn(7)、{(2b)ZnEt}2(8)、(2b)2Zn(9)、(2c)2Zn(10)、{(2d)ZnEt}(11),并且这些配合物的中心金属离子都没有与叔氮配位。所有的配体和有机锌配合物都通过了各种光谱、元素分析和核磁共振的鉴定,部分配合物结构通过了X-单晶衍射的证实。其中,{(1a)ZnEt}2(1)、{(1c)ZnEt}2(3)、{(1e)ZnEt}2(5)、{(1f)ZnEt}2(6)、(2a)2Zn(7)、{(2b)ZnEt}2(8)、{(2d)ZnEt}(11)是外消旋丙交酯开环聚合反应的活性催化剂,在催化过程中表现出了较高的反应活性和选择性,同时催化剂的活性受溶剂类型的影响较大。
[Abstract]:Nitrogen heterocyclic butane derivatives have potential application value in the field of medicine, which is an important field of organic synthesis chemistry. At the same time, these compounds have the advantages of rigid structure, easy adjustment of steric hindrance and strong coordination ability of tertiary amine nitrogen atom, etc. They are excellent metal coordination ligands, but the metal complexes derived from them are seldom reported at present. In this thesis, a series of novel chiral organozinc complexes were prepared by the reaction of sulfamides and diethyl zinc with chiral azacyclic butane derivatives. The catalytic properties of these complexes for ring-opening polymerization of lactide were also studied. First, a series of sulfonamide (1 aH-1fH) and Schiff class (2aH-2dH) compounds were synthesized from 3-amino-azacyclic butane as chiral source. A series of organic zinc complexes were prepared by reacting them with diethylzinc. The structure of the complexes was greatly affected by the space steric resistance of ligands, such as the reaction of sulfonamide ligands 1aHn1cHn1eHn1fH) with diethylzinc, and their structures were greatly affected by the space steric hindrance of the ligands, for example, the sulfonamide ligands (1 aH1) reacted with diethylzinc. The dimeric metal complexes {1 ~ 1a ~ (-1) ZnEt} _ 2H ~ (-1), {~ (1) C ~ (2 +) ZnEt} ~ (2) ~ (3) ~ (3), {~ (1) E ~ (2 +) ZnEt} _ 2 ~ (5), {~ (1) f ~ (ZnEt)} ~ (2) ~ (6), while the sulfonamide ligand ~ (1) BH ~ (1dH) reacted with diethylzinc, respectively, and obtained a polyethyl polynuclear metal complex (~ (2) and (~ (4) ~ (4) ~ (4), respectively. In addition, we have also found that different from sulfonamide ligands, Schiff ligands (2aH-2dH) reacted with diethylzinc, and the non-active ethylated bis-ligated complexes, 2ah2ZnH7, {2bOZnEt} 2BX, 2Zn92ZnC2ZnO10H, {2dntZnEt} have not coordinated with tertiary nitrogen, respectively, and the central metal ions of these complexes are not coordinated with tertiary nitrogen. All the ligands and organozinc complexes were identified by various spectra, elemental analysis and nuclear magnetic resonance (NMR). Some of the complexes were confirmed by X-ray diffraction. Among them, {1a ~ (1a) ZnEt} 2H ~ (1), {~ (1) C ~ (1) ZnEt} ~ (2) ~ (3) ~ (3), {~ (1) e ~ (1) ~ (ZnEt)} ~ (2) ~ (5) ~ (5), {~ (1) F ~ (2 +) ZnEt} ~ 2 ~ (2 +) ~ (2) ~ (2 +) ~ (2), {~ (2) bZnEt} ~ (28), {~ (2) d ~ (2 d) ZnEt} ~ (11) are active catalysts for the ring-opening polymerization of racemic lactide, and the activity of the catalyst is greatly influenced by the solvent type in the process of the catalytic process, and the activity of the catalyst is greatly influenced by the solvent type at the same time.
【学位授予单位】：西南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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