本科生综合实验: 4-[二(4-甲基苯)氨基]苯甲醛合成与变色性能研究

doi:10.3724/SP.J.1123.2023.11009

摘要/Abstract

摘要：

针对有机合成实验缺少性质研究、仪器分析实验分析方法相对独立的问题,本项目基于机械致荧光变色材料在化学前沿领域的研究,设计了一个本科生综合实验。以4,4'-二甲基三苯胺为原料,通过Vilsmeier-Haack反应合成了4-[二(4-甲基苯)氨基]苯甲醛,并通过质谱、红外吸收光谱和核磁共振波谱对其结构进行了表征;然后通过紫外-可见吸收光谱、荧光光谱等对其溶剂化变色和机械致荧光变色现象进行了研究,并通过X射线粉末衍射对其机械致荧光变色机理进行了探讨。本项目将有机合成与仪器分析实验相结合,形成合成及变色性能一体化研究,实验综合性强,现象有趣,是一个兼具趣味性、科学性和综合性的本科生创新实验。该实验可以很好地激发学生对化学研究的兴趣,锻炼多项实验操作能力,提升学生的综合科研素质。

关键词: 综合性实验, 三苯胺类化合物, 溶剂化变色, 机械致荧光变色

Abstract:

To solve the problems of the lack of property research in organic synthesis experiments and the relative independence of instrumental analytical methods in experiments, we designed a comprehensive undergraduate experiment based on mechanofluorochromic materials. In this project, 4-[bis(4-methylphenyl)amino] benzaldehyde was synthesized via the Vilsmeier-Haack reaction using 4,4'-dimethyltriphenylamine as the raw material. The product was then characterized by mass spectrometry, infrared absorption spectroscopy, and nuclear magnetic resonance spectroscopy. The solvatofluorochromism and mechanofluorochromism of the target material were studied using ultraviolet-visible absorption spectroscopy, fluorescence spectroscopy, etc. Furthermore, the mechanism of mechanofluorochromism was determined using powder X-ray diffraction. Organic synthesis and a series of instrumental analytical methods were combined to form an integrated experiment. The experiment is interesting, scientific, and comprehensive for undergraduates as a creative exercise; moreover, it can inspire their interest in chemical research, cultivate a variety of experimental operation abilities, improve creative-thinking skills, and encourage the development of effective solutions to existing problems in chemical experiments.

Key words: comprehensive experiment, triphenylamine compounds, solvatofluorochromism, mechanoflurochromism

中图分类号:

O658

潘玉珍, 薛寒, 高雅琳, 胡舒蕊, 张文珠. 本科生综合实验: 4-[二(4-甲基苯)氨基]苯甲醛合成与变色性能研究[J]. 色谱, 2024, 42(3): 304-309.

PAN Yuzhen, XUE Han, GAO Yalin, HU Shurui, ZHANG Wenzhu. Comprehensive undergraduate experiment: synthesis and chromism of 4-[bis(4-methylphenyl)amino] benzaldehyde[J]. Chinese Journal of Chromatography, 2024, 42(3): 304-309.

图/表 9

图 1 (a)4-[二(4-甲基苯)氨基]苯甲醛的合成路线与(b)Vilsmeier-Haack反应机理图

Fig. 1 (a) Synthesis of 4-[bis(4-methylphenyl)amino] benzaldehyde and (b) mechanism diagram of Vilsmeier-Haack reaction

图 2 BMABA的质谱图

Fig. 2 Mass spectrum of BMABA

图 3 DMTPA和BMABA的红外吸收光谱图

Fig. 3 IR spectra of DMTPA and BMABA

图 4 BMABA的氢核磁共振波谱图

Fig. 4 1H nuclear magnetic resonance spectrum of BMABA

图 5 BMABA在(a)可见光和(b)紫外光(365 nm)照射下在不同溶剂中的照片图

Fig. 5 Photographic images in different solvents under (a) ambient light and (b) UV light irradiation (λex=365 nm) The solvents from left to right: n-hexane, ethyl acetate, tetrahydrofuran, chloroform, acetone, dichloromethane.

图 6 BMABA在不同溶剂中的(a)紫外吸收光谱图和(b)荧光发射光谱图

Fig. 6 (a) UV-Vis absorption spectra and (b) fluorescence emission spectra of BMABA in different solvents The maximum absorption peaks in the ultraviolet absorption spectra of n-hexane, acetone, ethyl acetate, tetrahydrofuran, dichloromethane, and chloroform are as follows, 353, 354, 355, 357, 361, 367 nm. The maximum emission peaks in fluorescence emission spectra of n-hexane, acetone, ethyl acetate, tetrahydrofuran, dichloromethane, and chloroform are as follows, 424, 542, 502, 507, 546, 538 nm.

图 7 不同条件下的BMABA照片

Fig. 7 Photographic images of BMABA under different conditions a. original sample under ambient light; b. original sample under UV light (365 nm); c. ground sample under UV light (365 nm); d. fumed by CH2Cl2.

图 8 BMABA在初始、研磨、溶剂熏蒸状态下的荧光发射光谱图

Fig. 8 Fluorescence emission spectra of BMABA under different conditions of original, ground and fumed by solvent

图 9 BMABA机械摩擦前后的X射线粉末衍射图

Fig. 9 XRD diagrams of BMABA original and ground

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