3-乙酰基-8-叔丁基香豆素晶体结构及密度泛函理论研究
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摘要
本文合成了3-乙酰基-8-叔丁基香豆素,并通过X-射线单晶衍射法测定分子结构,随后进行红外、核磁共振、紫外可见吸收光谱表征,并通过密度泛函理论(DFT)研究晶体中的分子间作用,模拟光谱并预测表面活性位点。结果表明,分子为大共轭平面结构,在晶体中主要以π-π堆积作用和氢键作用结合,结合能分别为17. 2和3. 9 kcal/mol。分子在近紫外可见光范围内的最大吸收波长在310nm,摩尔消光系数为16000L·mol-1·cm-1,主要对应苯环上π电子向内酯环以及羰基氧上的跃迁。该分子6号位碳最易发生芳环上亲电取代反应,内酯可发生水解、氨解等反应,苯环上氢、羰基氧均可形成氢键等弱相互作用。
3-Acetyl-8-tert-butylcoumarin was synthesized and characterized by single-crystal X-ray diffraction,IR spectroscopy and UV-Vis spectroscopy.Density functional theory was used to investigate the intermolecular weak interaction in crystal,simulate spectrum and predict active site which is possible to be attacked by electrophilic or nucleophile reagent.The results showed that the molecule is almost a planar structure which exists conjugation effect.Molecules in crystal are combined by π-π stacking between layers and hydrogen bonds in chains,and the binding energy of two molecules is 17.2 and 3.9 kcal/mol respectively.The wavelength of maximum absorption in the scope of near ultraviolet and visible light is about 310 nm,and molar absorption coefficient is 16000 L·mol-1·cm-1,which was caused by π-electron of benzene ring transferring to inner ester ring and the oxygen atom of aldehyde group.No.6 carbon is the most likely site to be attacked by electrophilic reagent in benzene ring.Inner ester is able to undergo hydrolysis or aminolysis reaction.The hydrogen atoms in the benzene ring and the oxygen atoms of carbonyl groups can both form weak interaction such as hydrogen bond.
3-Acetyl-8-tert-butylcoumarin was synthesized and characterized by single-crystal X-ray diffraction,IR spectroscopy and UV-Vis spectroscopy.Density functional theory was used to investigate the intermolecular weak interaction in crystal,simulate spectrum and predict active site which is possible to be attacked by electrophilic or nucleophile reagent.The results showed that the molecule is almost a planar structure which exists conjugation effect.Molecules in crystal are combined by π-π stacking between layers and hydrogen bonds in chains,and the binding energy of two molecules is 17.2 and 3.9 kcal/mol respectively.The wavelength of maximum absorption in the scope of near ultraviolet and visible light is about 310 nm,and molar absorption coefficient is 16000 L·mol-1·cm-1,which was caused by π-electron of benzene ring transferring to inner ester ring and the oxygen atom of aldehyde group.No.6 carbon is the most likely site to be attacked by electrophilic reagent in benzene ring.Inner ester is able to undergo hydrolysis or aminolysis reaction.The hydrogen atoms in the benzene ring and the oxygen atoms of carbonyl groups can both form weak interaction such as hydrogen bond.
引文
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[7]M Doludda,F Kastenholz,E Lewitzki et al.J.Fluoresc.,1996,6(3):159~163.
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