糠醛和5-甲基-2-乙酰基呋喃的溶剂效应研究

发布时间：2018-06-25 02:20

本文选题：红外光谱 + 溶剂效应　；参考：《浙江工业大学》2014年硕士论文

【摘要】：本文运用红外光谱法(FT-IR)测定了呋喃类化合物糠醛(Furfural,FUR)和5-甲基-2-乙酰基呋喃(2-acetyl-5-methylfuran, AMF)在一元溶剂和二元溶剂体系中羰基的伸缩振动谱带(υC=O),研究了各羰基伸缩振动谱带的变化规律,探讨了FUR和AMF在不同溶剂中的溶质-溶剂相互作用。通过量子化学模拟氢键对羰基振动的影响,并计算了溶剂效应对溶质电子光谱的影响。在一元溶剂中,将四种单溶剂参数和两种多溶剂参数与溶质的u(C=O)作了相关性分析,并讨论各溶剂参数方程的适用性。结果表明,单溶剂参数中与溶质υ(C=0)的相关性以G值最好,多溶剂参数方程与溶质υC=O相关性良好,LSER关系式最适合描述溶剂效应。通过改变各组二元溶剂体系中极性溶剂与基础溶剂的体积比,讨论了溶质-溶剂相互作用类型。结果发现FUR和AMF在不同二元溶剂中除受溶剂场作用外,还与氯仿和乙醇之间都有氢键缔合物生成,与四氯化碳之间无此氢键作用。采用DFT及TD-DFT下的B3LYP/6-311++G(d,p)水平结合CPCM溶剂模型计算了FUR及AMF在各种溶剂中的构型及紫外吸收光谱。结果表明溶剂效应对FUR及AMF的构型、原子电荷分布、能量以及前线分子轨道能量等性质的变化具有一定的影响。并对AMF与乙醇之间形成的氢键作用结构进行了几何构型优化,并讨论了氢键对AMF分子羰基振动的影响。
[Abstract]:In this paper, infrared spectroscopy (FT-IR) has been used to determine the stretching vibrational bands of carbonyl groups in the mono-solvent and binary solvent systems, Furfuralfural (FUR) and 5-methyl-2-acetyl-5-methylfuran( AMF), and the variation of the vibrational bands of each carbonyl group has been studied. The solute-solvent interaction of FUR and AMF in different solvents was investigated. The effect of hydrogen bond on carbonyl vibration was simulated by quantum chemistry, and the influence of solvent effect on the electron spectrum of solute was calculated. The correlation of four single solvent parameters and two multisolvent parameters with the solute u (Con O) was analyzed and the applicability of each solvent parameter equation was discussed. The results show that the correlation between the single solvent parameter and solute v (C0) is the best in G value, and the relationship between the multisolvent parameter equation and solute v Cno is the best to describe the solvent effect. The type of solute-solvent interaction was discussed by changing the volume ratio of polar solvent to base solvent in each binary solvent system. The results show that FUR and AMF have hydrogen bond association with chloroform and ethanol in different binary solvents, but not with carbon tetrachloride. The configuration and UV absorption spectra of FUR and AMF in various solvents were calculated by using B3LYP / 6-311G (dapp) level and CPCM solvent model under DFT and TD-DFT. The results show that the solvent effect has a certain influence on the configuration of FUR and AMF, atomic charge distribution, energy and frontier molecular orbital energy. The structure of hydrogen bond formed between AMF and ethanol was optimized and the effect of hydrogen bond on carbonyl vibration of AMF molecule was discussed.
【学位授予单位】：浙江工业大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：R917

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