MCM-41负载1,10-菲咯啉铜配合物在碳—碳、碳—杂键形成反应中的应用
发布时间：2019-01-08 10:19
【摘要】：通过3-异氰酸酯基丙基三乙氧基硅烷与5-氨基-1,10-菲咯啉的加成反应,制备了1-(1,10-菲咯啉-5-基)-3-(3-(三乙氧硅基)丙基)脲配体(Phen-Si),后者与介孔材料MCM-41在甲苯中缩合固载,再经Me3SiCl硅化,制备了1,10-菲咯啉基功能化的MCM-41介孔材料(MCM-41-Phen)。将此功能化的介孔材料(MCM-41-Phen)分别与CuSO4和CuI反应,合成了MCM-41-Phen-CuSO4和MCM-41-Phen-CuI两种新型负载铜配合物催化剂,对它们的结构用元素分析、ICP-AES、XRD等方法进行了表征。研究了在MCM-41-Phen-CuSO4存在下,芳基硼酸与硫酚在室温下的Chan-Lam交叉偶联反应。结果表明该负载铜催化剂具有很高的催化活性,以40%氢氧化四丁铵为碱,各种芳基硼酸和硫酚在乙醇中室温下能顺利进行C S交叉偶联反应,以良好产率生成各种不对称二芳基硫醚,该多相C S键形成反应具有较宽的底物范围和良好的功能基容忍性。该负载铜催化剂可以通过简单过滤与产物分离,经循环使用8次后其催化活性基本保持不变。研究了在MCM-41-Phen-CuI存在下,芳基碘和脂肪族醇之间的C O偶联反应。以Cs2CO3为碱、脂肪族醇或甲苯为溶剂,发现该负载铜催化剂能有效催化各种芳基碘与不同脂肪族醇的C O交叉偶联反应,以良好至优异的产率生成各种芳基烷基醚。除简单的一级脂肪族醇外,二级脂肪族醇、苄醇、烯丙醇均是好的底物。循环试验表明,该新型负载铜催化剂能通过简单过滤与产物分离,回收的催化剂可循环使用8次仍保持原有的催化活性。研究了在MCM-41-Phen-CuI催化下,芳基碘(溴)化物与多氟苯甲酸钾之间的脱羧C C交叉偶联反应。结果表明,在10-20 mol%MCM-41-Phen-CuI配合物存在下,以二甘醇二甲醚或DMAc为溶剂,各种芳基碘/溴化物与不同的多氟苯甲酸钾在130oC或160oC能顺利经历脱羧C C交叉偶联反应,以优异产率生成各种多氟联苯类化合物。该负载铜催化剂可循环使用6次其催化活性基本保持不变,因而为多氟联苯类化合物的合成提供了一条实用的绿色新途径。按文献方法[149],缩合固载了3-(2-氨乙基氨基)丙基三甲氧基硅烷与介孔材料MCM-41,再经三甲基氯硅烷硅化,制备了(MCM-41-2N)双氮功能化的介孔材料,Cu(OAc)2和后者发生反应,MCM-41负载双齿氮铜(II)配合物得以制备。研究了2-酰基吡啶与水合肼进行“一锅”氧化成环反应生成[1,2,3]三唑并[1,5-a]吡啶类化合物,在MCM-41-2N-Cu(OAc)2催化下。结果表明,该负载铜催化剂表现出良好催化活性,各种2-酰基吡啶与水合肼能顺利进行氧化成环反应,以良好至优异的产率生成各种[1,2,3]三唑并[1,5-a]吡啶衍生物。该负载铜催化剂可循环使用8次其催化活性基本保持不变。
[Abstract]:By the addition reaction of 3-isocyanate propyl triethoxy silane and 5-amino-1-phenanthroline, 1- (1-1-phenanthroline) -3- (3- (triethoxysilyl) propyl) urea ligand (Phen-Si) was prepared. The latter was immobilized in toluene by condensation with mesoporous material MCM-41 and then silicified by Me3SiCl to prepare the MCM-41 mesoporous material (MCM-41-Phen). Two novel supported copper complex catalysts, MCM-41-Phen-CuSO4 and MCM-41-Phen-CuI, were synthesized by reaction of this functionalized mesoporous material (MCM-41-Phen) with CuSO4 and CuI, respectively. Their structures were characterized by elemental analysis, ICP-AES,. XRD and other methods were used to characterize. The Chan-Lam cross-coupling reaction of aryl boric acid and thiophenol at room temperature in the presence of MCM-41-Phen-CuSO4 was studied. The results show that the supported copper catalyst has high catalytic activity. With 40% tetrabutylammonium hydroxide as the base, various aryl boric acid and thiophenol can successfully carry out C / S cross-coupling reaction at room temperature in ethanol. All kinds of asymmetric diaryl sulfides were produced in good yield. The formation reaction of the polyphase C / S bond has a wide substrate range and good functional tolerance. The supported copper catalyst can be separated from the product by simple filtration, and the catalytic activity of the catalyst remains basically unchanged after 8 cycles. The C-O coupling reaction between aryl iodine and aliphatic alcohols in the presence of MCM-41-Phen-CuI was studied. Using Cs2CO3 as base and aliphatic alcohol or toluene as solvent, it was found that the supported copper catalyst could effectively catalyze the cross-coupling reaction of aryl iodine with C / O of different aliphatic alcohols and produce various aryl alkyl ethers in good yields. In addition to simple primary aliphatic alcohols, secondary aliphatic alcohols, benzyl alcohols and allyl alcohols are good substrates. The cyclic test shows that the new supported copper catalyst can be separated from the product by simple filtration, and the recovered catalyst can be recycled for 8 times to maintain its original catalytic activity. The cross-coupling reaction between aryl iodide (bromine) and potassium polyfluorobenzoate was studied under the catalysis of MCM-41-Phen-CuI. The results show that in the presence of 10-20 mol%MCM-41-Phen-CuI complexes, in the presence of diethylene glycol dimethyl ether or DMAc as solvent, various aryl iodine / bromides and different potassium polyfluorobenzoate can successfully undergo decarboxylation C-C cross-coupling reaction in 130oC or 160oC. All kinds of polyfluorinated biphenyls are produced in excellent yield. The catalytic activity of the supported copper catalyst can be kept unchanged for 6 times, which provides a new practical green way for the synthesis of polyfluorinated biphenyls. (MCM-41-2N) diazo-functionalized mesoporous materials were prepared by condensation of 3- (2-aminoethylamino) propyltrimethoxy silane and mesoporous material MCM-41, via trimethylchlorosilane. Cu (OAc) _ 2 reacts with the latter and MCM-41 supported (II) complexes with didentate nitrogen and copper are prepared. The epoxidation of 2-acylpyridine with hydrazine hydrate in "one pot" to form [1 (2) (2) (3)] triazo [1 (5) a] pyridine compounds catalyzed by MCM-41-2N-Cu (OAc) _ (2) was studied. The results showed that the supported copper catalyst exhibited good catalytic activity, and all kinds of 2-acylpyridine and hydrazine hydrate could be oxidized smoothly to form epoxidation reaction. 3] triazo [1] pyridine derivative. The catalytic activity of the supported copper catalyst can be kept unchanged for 8 times.
【学位授予单位】：广东药科大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
本文编号：2404471
[Abstract]:By the addition reaction of 3-isocyanate propyl triethoxy silane and 5-amino-1-phenanthroline, 1- (1-1-phenanthroline) -3- (3- (triethoxysilyl) propyl) urea ligand (Phen-Si) was prepared. The latter was immobilized in toluene by condensation with mesoporous material MCM-41 and then silicified by Me3SiCl to prepare the MCM-41 mesoporous material (MCM-41-Phen). Two novel supported copper complex catalysts, MCM-41-Phen-CuSO4 and MCM-41-Phen-CuI, were synthesized by reaction of this functionalized mesoporous material (MCM-41-Phen) with CuSO4 and CuI, respectively. Their structures were characterized by elemental analysis, ICP-AES,. XRD and other methods were used to characterize. The Chan-Lam cross-coupling reaction of aryl boric acid and thiophenol at room temperature in the presence of MCM-41-Phen-CuSO4 was studied. The results show that the supported copper catalyst has high catalytic activity. With 40% tetrabutylammonium hydroxide as the base, various aryl boric acid and thiophenol can successfully carry out C / S cross-coupling reaction at room temperature in ethanol. All kinds of asymmetric diaryl sulfides were produced in good yield. The formation reaction of the polyphase C / S bond has a wide substrate range and good functional tolerance. The supported copper catalyst can be separated from the product by simple filtration, and the catalytic activity of the catalyst remains basically unchanged after 8 cycles. The C-O coupling reaction between aryl iodine and aliphatic alcohols in the presence of MCM-41-Phen-CuI was studied. Using Cs2CO3 as base and aliphatic alcohol or toluene as solvent, it was found that the supported copper catalyst could effectively catalyze the cross-coupling reaction of aryl iodine with C / O of different aliphatic alcohols and produce various aryl alkyl ethers in good yields. In addition to simple primary aliphatic alcohols, secondary aliphatic alcohols, benzyl alcohols and allyl alcohols are good substrates. The cyclic test shows that the new supported copper catalyst can be separated from the product by simple filtration, and the recovered catalyst can be recycled for 8 times to maintain its original catalytic activity. The cross-coupling reaction between aryl iodide (bromine) and potassium polyfluorobenzoate was studied under the catalysis of MCM-41-Phen-CuI. The results show that in the presence of 10-20 mol%MCM-41-Phen-CuI complexes, in the presence of diethylene glycol dimethyl ether or DMAc as solvent, various aryl iodine / bromides and different potassium polyfluorobenzoate can successfully undergo decarboxylation C-C cross-coupling reaction in 130oC or 160oC. All kinds of polyfluorinated biphenyls are produced in excellent yield. The catalytic activity of the supported copper catalyst can be kept unchanged for 6 times, which provides a new practical green way for the synthesis of polyfluorinated biphenyls. (MCM-41-2N) diazo-functionalized mesoporous materials were prepared by condensation of 3- (2-aminoethylamino) propyltrimethoxy silane and mesoporous material MCM-41, via trimethylchlorosilane. Cu (OAc) _ 2 reacts with the latter and MCM-41 supported (II) complexes with didentate nitrogen and copper are prepared. The epoxidation of 2-acylpyridine with hydrazine hydrate in "one pot" to form [1 (2) (2) (3)] triazo [1 (5) a] pyridine compounds catalyzed by MCM-41-2N-Cu (OAc) _ (2) was studied. The results showed that the supported copper catalyst exhibited good catalytic activity, and all kinds of 2-acylpyridine and hydrazine hydrate could be oxidized smoothly to form epoxidation reaction. 3] triazo [1] pyridine derivative. The catalytic activity of the supported copper catalyst can be kept unchanged for 8 times.
【学位授予单位】：广东药科大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
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