【摘要】：通過(guò)3-異氰酸酯基丙基三乙氧基硅烷與5-氨基-1,10-菲咯啉的加成反應(yīng),制備了1-(1,10-菲咯啉-5-基)-3-(3-(三乙氧硅基)丙基)脲配體(Phen-Si),后者與介孔材料MCM-41在甲苯中縮合固載,再經(jīng)Me3SiCl硅化,制備了1,10-菲咯啉基功能化的MCM-41介孔材料(MCM-41-Phen)。將此功能化的介孔材料(MCM-41-Phen)分別與CuSO4和CuI反應(yīng),合成了MCM-41-Phen-CuSO4和MCM-41-Phen-CuI兩種新型負(fù)載銅配合物催化劑,對(duì)它們的結(jié)構(gòu)用元素分析、ICP-AES、XRD等方法進(jìn)行了表征。研究了在MCM-41-Phen-CuSO4存在下,芳基硼酸與硫酚在室溫下的Chan-Lam交叉偶聯(lián)反應(yīng)。結(jié)果表明該負(fù)載銅催化劑具有很高的催化活性,以40%氫氧化四丁銨為堿,各種芳基硼酸和硫酚在乙醇中室溫下能順利進(jìn)行C S交叉偶聯(lián)反應(yīng),以良好產(chǎn)率生成各種不對(duì)稱二芳基硫醚,該多相C S鍵形成反應(yīng)具有較寬的底物范圍和良好的功能基容忍性。該負(fù)載銅催化劑可以通過(guò)簡(jiǎn)單過(guò)濾與產(chǎn)物分離,經(jīng)循環(huán)使用8次后其催化活性基本保持不變。研究了在MCM-41-Phen-CuI存在下,芳基碘和脂肪族醇之間的C O偶聯(lián)反應(yīng)。以Cs2CO3為堿、脂肪族醇或甲苯為溶劑,發(fā)現(xiàn)該負(fù)載銅催化劑能有效催化各種芳基碘與不同脂肪族醇的C O交叉偶聯(lián)反應(yīng),以良好至優(yōu)異的產(chǎn)率生成各種芳基烷基醚。除簡(jiǎn)單的一級(jí)脂肪族醇外,二級(jí)脂肪族醇、芐醇、烯丙醇均是好的底物。循環(huán)試驗(yàn)表明,該新型負(fù)載銅催化劑能通過(guò)簡(jiǎn)單過(guò)濾與產(chǎn)物分離,回收的催化劑可循環(huán)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)化物與多氟苯甲酸鉀之間的脫羧C C交叉偶聯(lián)反應(yīng)。結(jié)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為溶劑,各種芳基碘/溴化物與不同的多氟苯甲酸鉀在130oC或160oC能順利經(jīng)歷脫羧C C交叉偶聯(lián)反應(yīng),以優(yōu)異產(chǎn)率生成各種多氟聯(lián)苯類(lèi)化合物。該負(fù)載銅催化劑可循環(huán)使用6次其催化活性基本保持不變,因而為多氟聯(lián)苯類(lèi)化合物的合成提供了一條實(shí)用的綠色新途徑。按文獻(xiàn)方法[149],縮合固載了3-(2-氨乙基氨基)丙基三甲氧基硅烷與介孔材料MCM-41,再經(jīng)三甲基氯硅烷硅化,制備了(MCM-41-2N)雙氮功能化的介孔材料,Cu(OAc)2和后者發(fā)生反應(yīng),MCM-41負(fù)載雙齒氮銅(II)配合物得以制備。研究了2-酰基吡啶與水合肼進(jìn)行“一鍋”氧化成環(huán)反應(yīng)生成[1,2,3]三唑并[1,5-a]吡啶類(lèi)化合物,在MCM-41-2N-Cu(OAc)2催化下。結(jié)果表明,該負(fù)載銅催化劑表現(xiàn)出良好催化活性,各種2-酰基吡啶與水合肼能順利進(jìn)行氧化成環(huán)反應(yīng),以良好至優(yōu)異的產(chǎn)率生成各種[1,2,3]三唑并[1,5-a]吡啶衍生物。該負(fù)載銅催化劑可循環(huán)使用8次其催化活性基本保持不變。
[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.
【學(xué)位授予單位】：廣東藥科大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O621.251

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