离子液体负载TEMPO催化醇氧化.pdfVIP

符号说明 TEMPO: 2,2,6,6-Tetramethyl-1-piperidinyloxy, 2,2,6,6- 四甲基哌啶-N-氧自由基 GC: Gas chromatography, 气相色谱仪 TPO: Tertiary phosphine oxide, 叔膦氧化物 NHPI: N-Hydroxyphthalimide, N-羟基邻苯二甲酰亚胺 Bpy: bipyridine, 2,2-联吡啶 VAL: 4-Hydroxy-3-methoxybenzyl, 香草醇 VN: Vanillin, 香草醛 DES: Deep Eutectic Solvents, 低共熔溶剂 DCC: N,N-dicyclohexylcarbodiimide, 二环己基碳二亚胺 DMAP: 4-dimethylaminopyridine，4-二甲氨基吡啶 NMR: Nuclear Magnetic Resonance, 核磁共振 FTIR: Fourier Transform Infrared Spectrometer, 傅里叶变换红外光谱仪 UV: Ultraviolet and visible spectrum, 紫外和可见光谱 TMS: Tetramethylsilane, 四甲基硅烷 DMF: N,N-Dimethylformamide, N,N-二甲基甲酰胺 DMC: Dimethyl carbonate, 碳酸二甲酯 目录 中文摘要·························································································I Abstract ··························································································III 1 前言·····························································································1 1.1 醇的绿色催化氧化 1 1.2 过渡金属/分子氧催化醇氧化 1 1.3 TEMPO 催化醇氧化 4 1.3.1 TEMPO 的结构与性质 4 1.3.2 TEMPO 催化体系研究进展 5 1.3.2.1 过渡金属/TEMPO 催化体系 6 1.3.2.2 无过渡金属/TEMPO 催化体系 9 1.3.2.3 负载型TEMPO 催化剂11 1.4 离子液体 12 1.4.1 酸性离子液体 13 1.4.2 碱性离子液体 13 1.4.3 离子液体在绿色化学中的应用 14 1.4.4 离子液体参与的TEMPO 催化体系 15 1.5 12-羟基硬脂酸甲酯的氧化 17 1.6 本课题的意义及研究内容 18 2 材料与方法····················································································20 2.1 实验仪器与试剂 20 2.2 实验操作 21 2.2.1 IL-TEMPO-NO2 催化剂的制备 21 2.2.2 [PyS][OTf]助催化剂的制备 22 2.2.3 12-羟基硬脂酸甲酯的制备与提纯 23 2.2.4 12-羟基硬脂酸甲酯的氧化 23 2.2.5 醇的选择性氧化探究 23 2.2.6 N-丁基吡啶离子液体助催化剂的制备 24 2.3 分析测试方法 24 2.3.1 IL-TEMPO-NO2 的表征 24 2.3.2 [PyS][OTf]、N-丁基离子液体及产物的表征 25 2.3.3 醇氧化产物的GC 测定 25 3 结果与分析 ···················································································26 3.1 IL-TEMPO-NO2 催化剂的制备与表征 26 3.1.1 IL-TEMPO-NO2 催化剂的制备 26 3.1.2 IL-TEMPO-NO2 催化剂的表征 26 3.2 [PyS][OTf]助催化剂的制备与表征 28 3.2.1 [Py