【作者】 张雅然；

【导师】 赵继全；

【作者基本信息】 河北工业大学 ， 应用化学， 2006， 硕士

【摘要】 以对羟基苯甲酸和环己二胺为原料,合成了一种带有较强吸电子基酯基的新型Schiff碱配体N,N′-双（3-甲酰基-4-羟基苯甲酸甲酯）缩环己二胺及其Mn³⁺、Fe³⁺、Ni²⁺离子的配合物,并用元素分析、红外光谱、核磁共振、紫外可见光谱、热重—差热分析等手段对其结构进行了鉴定。 合成了两种新型水杨醛衍生物5-叔丁基-3-甲酰基-4-羟基苯甲酸及其甲酯。将其与（1R,2R）-环己二胺缩合制备出新型手性Shift碱配体,利用该配体合成了Mn³⁺、Fe³⁺、Ni²⁺、Cu²⁺手性配合物。通过元素分析、¹H NMR、FT-IR、UV-Vis等手段对配体和配合物结构进行了表征。研究发现,Salen-Mn（Ⅲ）配合物对多种底物烯烃在不同环氧化体系中的不对称环氧化反应,均有很高的催化活性和对映体选择性。例如,1,2-二氢化萘作底物时,在一定的反应条件下e.e.值可达90.3%;顺-β-甲基苯乙烯作底物时,在一定的反应条件下e.e.值可达83.9%。 采用接枝法制备出介孔分子筛MCM-41固载的C₂-不对称型Salen-Mn（Ⅲ）非均相催化剂,利用FT-IR、XRD、DR UV-Vis、TG-DTA、N₂吸附和ICP对非均相催化剂进行了表征。通过设计单因素实验,找到了催化空气环氧化环己烯反应的最佳条件:环己烯20mmol,异丁醛50mmol,Salen-Mn（Ⅲ）/MCM-41 0.03g（0.02mmol）,乙腈50mL,反应温度35℃,反应时间8h。在此最佳反应条件下,环己烯的转化率为100%,环氧环己烷的选择性为90.7%。在此最佳反应条件下,循环使用6次,催化剂仍然具有较高的催化活性。此催化剂对降冰片烯、1,2-二氢化萘、苯乙烯、α-甲基苯乙烯也具有很高的催化活性和选择性。 设计并制备了两种固载催化剂:一是采用化学键连和溶胶—凝胶技术相结合的方法,制备了带锚链固定的多相化手性Salen-Mn（Ⅲ）催化剂;二是将手性Salen-Mn（Ⅲ）配合物固载在介孔分子筛MCM-41内表面上。采用FT-IR、DR UV-Vis、XRD、N₂吸附、TG-DTA、ICP等手段对固载催化剂进行了表征。通过在不同反应条件下的烯烃不对称环氧化反应评价了它们的催化性能。研究表明,后者的催化效果明显高于前者。后者在一定的反应条件下催化1,2-二氢化萘不对称环氧化反应,收率45.9%,e.e.值84.3%。更多还原

【Abstract】 A new schiff base ligand was synthesized by the condensation of methyl 3-formyl-4-hydroxylbenzoate with 1,2-diaminocyclohexane. Three complexes of Mn(Ⅲ), Fe(Ⅲ) and Ni(Ⅱ) were also prepared from the ligand. The new ligand and complexes were characterized by elementary analysis, FT-IR, ~1H NMR, UV-Vis and TG-DTA.Two new salicylaldehyde derivatives, 5-(1,1-dimethylethyl)-3-fcrmyl-4-hydroxybenzoic acid and methyl ester, were synthesized, and a novel chiral ligand was obtained by reaction of the ester with (1R,2R)-1,2-diaminocyclohexane. Then four chiral complexes of Mn(Ⅲ), Fe(Ⅲ), Ni(Ⅱ) and Cu(Ⅱ) were prepared from the chiral ligand. The chiral ligand and complexes were characterized by elementary analysis, ~1H NMR, FT-IR and UV-Vis. From experiments, it was found that the homogenous catalyst exhibited relatively high catalytic activity and enantioselectivity in asymmetric epoxidation of different alkenes under various conditions. For example, the e.e. were 90.3% and 83.9% respectively with 1,2-dihydronaphthalene and cis-P-methylstyrene as substrates in certain conditions.A C2-unsymmetric Manganese(Ⅲ) Salen complex was anchored onto the surface of MCM-41 by a multi-step grafting method. The resulting material was characterized by FT-IR, XRD, DR UV-Vis, nitrogen adsorption and ICR It was found that the conversion of cyclohexene can reach 100%) with 90.7% selectivity under the optimum conditions, which are cyclohexene 20 mmol, isobutraldehyde 50 mmol and the heterogenized catalyst 0.02 mmol in acetonitrile 50 mL at 35 ℃ for 8 h. This catalyst can be reused by simple filtration up to 6 times without much loss of activity though Mn leaching took place in some degree. Furthermore, it also showed relativelyhigh activity and epoxide selectivity in the aerobic epoxidation of norbornylene, 1,2-dihydronaphthalene, styrene and a-methylstyrene.Two chiral heterogenized catalysts were designed and synthesized. One was prepared by the combination method of anchoring and sol-gel technique, the other was prepared by immobilizing the Salen-Mn(III) complex on the channels of MCM-41 molecular sieves modified with aminopropyl groups. The resulting catalysts were characterized by FT-IR, DR UV-Vis, XRD, TG-DTA, nitrogen adsorption and ICP. Their activities were investigated with the catalytic enantioselective epoxidation reactions. Experimental results showed that the catalytic properties of the latter were superior to that of the former. Under certain conditions, 45.9% yield and 84.3% e.e. were obtained with 1,2-dihydronaphthalene as substrate.更多还原