請用此 Handle URI 來引用此文件: http://hdl.handle.net/11455/16723
標題: 含NNO三牙Schiff-Base之鋅和鎂錯化合物的合成及結構鑑定: 乳酸交酯開環聚合反應的良好催化劑
Synthesis and Characterization of NNO-Tridentate Schiff-Base Zinc and Magnesium Complexes: Efficient Initiators for the Ring-Opening Polymerization of L-Lactide
作者: 洪文周
Hung, Wen-Chou
關鍵字: Schiff-Base
Schiff-Base
zinc
Magnesium
Ring-Opening Polymerization
Lactide


開環聚合反應
乳酸交酯
出版社: 化學系所
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摘要: 本研究之目的是(1) 探討取代基之電子效應對Schiff-base金屬化合物在環酯類聚合反應催化活性的影響 (2) 合成共聚合物使用在藥物傳遞系統。 雖然,Schiff-base金屬形式的催化劑已經被報導,但是對亞胺基碳上取代基立障和電子效應的研究卻是很少。為了此研究目的,一系列Schiff-base鋅[LZn(μ-OBn)]2 (1b-8b)和鎂LMg(μ-OBn)]2 (1c-9c)化合物被合成出來。二乙基鋅分別與配位基(L1H-L8H)反應產生[(μ-L)ZnEt]2 (1a-8a),接著化合物1a-8a與苯甲醇反應產生相對應化合物 [LZn(μ-OBn)]2 (1b-8b)。單晶繞射結構研究顯示化合物1a-8a都以酚基的氧原子為架橋之雙核結構,化合物1b-8b也是雙核構型但透過苄氧基的氧原子連接中心金屬。Mg(OBn)2 與等當量的Schiff-base配位基(L1H-L9H)在甲苯下產生錯合物[LMg(μ-OBn)]2 (1c-9c)。化合物2c、3c、5c、7c、8c經由單晶繞射研究顯示所有這些化合物為五配位雙核結構以苄氧基的氧原子連接的中心的鎂原子。化合物1b-8b及1c-9c在乳酸交酯的開環聚合反應有良好的反應性及分子量控制性,合成的聚合物分子分佈度很狹窄。實驗結果顯示鋅化合物1b-8b之亞胺基碳上官能基的變化對催化活性有顯著的影響。鎂化合物1c-9c催化活性受到配位基上電子效應的影響。 為了合成共聚合物使用在藥物傳遞系統,[(MPTHQ)ZnEt]類型的鋅錯合物被合成。2-(2-methoxyphenyl)-3-tosyl-1,2,3,4-tetrahydroquinazoline (MPTHQ) (L10H)和二乙基鋅在甲苯下產生化合物10,晶體結構顯示化合物10是雙核四配位結構經由磺胺基的氧原子連接金屬中心。化合物10在苯甲醇的存在下對開環聚合反應具有良好的控制性,隨著單體與起始劑的比例增加,數目平均分子量呈現性成長且分子量分布度很狹窄。此外poly-(ethylene glycol) methyl ether-b-poly(lactide) (PEG-b-PLA) 和 poly(lactide)-b-tocopheryl polyethylene glycol succinate (PLA-b-TPGS)共聚合物已經被合成且經由核磁共振鑑定。
The objectives of the present investigations are (1) to study the electronic effect of the substituents affecting the activity of Schiff-base metal complexes on the polymerization rate of cyclic ester and (2) to synthesize block copolymers for use in drug delivery system. Although, extensive investigations on the Schiff-base metal type catalysts have been reported, studies on the steric and electronic effect of the substituents on imine carbon are rare. For this purpose, a series of zinc(II) and magnesium(II) complexes of the type [LZn(μ-OBn)]2 (1b-8b) and LMg(μ-OBn)]2 (1c-9c) supported on NNO-tridentate Schiff-base ligands have been synthesized. The reactions of diethyl zinc (ZnEt2) L1H-L8H yielded [(μ-L)ZnEt]2 (1a-8a), respectively. Further reaction of compounds 1a-8a with benzyl alcohol (BnOH) produced the corresponding compounds of [LZn(μ-OBn)]2 (1b-8b), respectively. The X-ray crystal structural studies reveal that all of these compounds 1a-8a are dimeric bridging through the phenolato oxygen atoms. However, compounds 1b-8b are dimeric character bridging through the benzylalkoxy oxygen atoms. The reactions of Mg(OBn)2 with one molar equivalent of related Schiff-base ligands (L1H-L9H) in toluene produce [LMg(μ-OBn)]2 (1c-9c) complexes. The X-ray crystal structural studies of compounds 2c, 3c, 5c, 7c, and 8c reveal that all of these compounds are penta-coordinated dimmers with the central magnesium atoms bridging by the oxygen atoms of benzyl alkoxides. All the complexes 1b-8b and 1c-9c proceeds rapidly with good molecular weight control, and yields polymers with a very narrow molecular weight distribution toward the ring-opening polymerization of L-lactide. Experimental results show that for complexes 1b-8b, the substituents on the imine carbon of the NNO-ligand affect the reactivity of zinc complexes dramatically. For the complexes 1c-9c, the reactivity is affected by the electronic effect of the substituents on the Schiff-base ligands. To synthesize block copolymers for use in drug delivery system, zinc complex [(MPTHQ)ZnEt]2 10 supported by bidentate sulfonamide ligand is designed. The reaction of 2-(2-methoxyphenyl)-3-tosyl-1,2,3,4-tetrahydroquinazoline (MPTHQ) (L10H) with ZnEt2 in toluene produced [(MPTHQ)ZnEt]2 10, and the X-ray crystal structural studies reveals that complex 10 is dinuclear bridging through the sulfoxide oxygen atoms and tetra-coordinated around the central metal atom. In the presence of benzyl alcohol, metal complex 10 gives rise to controll the ring-opening polymerization of lactide as shown by the linear relationship between the monomer-to-initiator ratio and the number-average molecular weight with low polydispersity indexes. In addition, block copolymers such as poly-(ethylene glycol) methyl ether-b-poly(L-lactide) (PEG-b-PLA) and poly(lactide)-b-tocopheryl polyethylene glycol succinate (PLA-TPGS) have also been prepared and characterized by NMR spectroscopy. Experimental results indicate that these block copolymers are potentially useful for drug delivery systems.
URI: http://hdl.handle.net/11455/16723
其他識別: U0005-1407200912034900
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