本文選題：氮雜環(huán)丁烷 + 手性有機(jī)鋅配合物��； 參考：《西南大學(xué)》2017年碩士論文

【摘要】：氮雜環(huán)丁烷衍生物在醫(yī)藥領(lǐng)域有潛在的應(yīng)用價(jià)值,是有機(jī)合成化學(xué)研究的重要領(lǐng)域。同時(shí),這類化合物還具有結(jié)構(gòu)剛性、空間位阻易調(diào)及叔胺氮原子配位能力強(qiáng)等特點(diǎn),是優(yōu)良的金屬配合物配體,但目前有關(guān)它們衍生的金屬配合還很少報(bào)道。因此,本論文主要是利用手性氮雜環(huán)丁烷衍生的磺酰胺類,Schiff類配體跟二乙基鋅的反應(yīng),制備出一系列新型手性有機(jī)鋅金屬配合物,同時(shí)研究這些配合物對丙交酯開環(huán)聚合反應(yīng)的催化性能。首先以3-氨基氮雜環(huán)丁烷為手性源合成一系列磺酰胺類(1aH-1fH)和Schiff類(2aH-2dH)化合物。并將它們與當(dāng)量的二乙基鋅反應(yīng)制備出一系列有機(jī)鋅配合物(1-11),配合物的結(jié)構(gòu)受配體的空間位阻的影響很大,比如,磺酰胺類配體(1aH,1cH,1eH,1fH)與二乙基鋅反應(yīng),分別得到二聚金屬配合物{(1a)ZnEt}2(1)、{(1c)ZnEt}2(3)、{(1e)ZnEt}2(5)、{(1f)ZnEt}2(6),而磺酰胺配體(1bH,1dH)與二乙基鋅反應(yīng),卻分別得到無活性乙基的多核金屬配合物(2)和(4)。另外,我們還發(fā)現(xiàn)與磺酰胺類配體不同,Schiff類配體(2aH-2dH)與二乙基鋅反應(yīng),分別得到無活性乙基的bis-ligated配合物(2a)2Zn(7)、{(2b)ZnEt}2(8)、(2b)2Zn(9)、(2c)2Zn(10)、{(2d)ZnEt}(11),并且這些配合物的中心金屬離子都沒有與叔氮配位。所有的配體和有機(jī)鋅配合物都通過了各種光譜、元素分析和核磁共振的鑒定,部分配合物結(jié)構(gòu)通過了X-單晶衍射的證實(shí)。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)是外消旋丙交酯開環(huán)聚合反應(yīng)的活性催化劑,在催化過程中表現(xiàn)出了較高的反應(yīng)活性和選擇性,同時(shí)催化劑的活性受溶劑類型的影響較大。
[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.
【學(xué)位授予單位】：西南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O641.4

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 趙耀明,麥杭珍,陳軍武,高茜斐;生物降解材料──聚丙交酯合成的研究[J];華南理工大學(xué)學(xué)報(bào)(自然科學(xué)版);2000年10期

，

本文編號：2016696