蒽基查尔酮衍生物的合成、共晶的制备及其结构分析

Synthesis, Co-crystal Preparation and Structures Analysis of Chalcone Derivatives Containing Anthracene

以9-蒽醛和4-N,N-二甲氨基苯乙酮为原料,超声辅助、加热55℃条件下合成蒽基查尔酮衍生物E1,产率为83%;同样的方法,将9-乙酰基蒽和4-二甲氨基苯甲醛,在超声辅助室温条件下合成了同分异构的蒽基查尔酮衍生物E2,其产率为85%。目标产物经~1H NMR、 ESI-MS、 IR表征,确认了分子结构。化合物E1在日光下呈橘红色晶体,365 nm紫外灯下发出黄色荧光;化合物E2在日光下为橙色粉末,在365 nm紫外灯下发出亮绿色荧光。紫外可见吸收光谱E1在390 nm为最大吸收峰,在498 nm处为荧光发射峰;E2在412 nm处有最大吸收峰,荧光发射集中在495 nm。通过溶剂挥发法得到化合物E2与7,7,8,8-四氰基对苯二醌二甲烷(TCNQ)的黑色共晶,晶体解析发现,共晶化合物属于单斜晶系,在共晶中TCNQ分子与E2的N,N二甲基苯部分沿晶体a轴呈交替排列,E2的蒽环在共晶中不能形成长程有序排列。所用超声辅助合成方法绿色高效,为该类化合物的制备及结晶特性提供了参考数据。

In this paper, two chalcone derivatives containing anthracene were synthesized. Compound E1 was obtained from the reaction of 9-anthracene aldehyde with 4-dimethylamino-acetophenone by ultrasound-assisted method and heating at 55 ℃. The yield rate was 83%. Using the same method, the isomer anthracene chalcone E2 was synthesized with 9-acetyl anthracene and 4-dimethylaminobenzaldehyde by ultrasound at room temperature. The yield rate was 85%. The two products were characterized and confirmed by ~1H-NMR, IR, ESI-MS and UV-Vis. The compound E1 exhibits orange under daylight and Yellow fluorescence under 365 nm UV lamp. The compound E2 is orange powder under daylight and shows bright green fluorescence under 365 nm UV lamp. The maximum absorption peak of chalcone E1 was at 390 nm, and its emission was around 498 nm. The maximum absorption peak of chalcone E2 was at 412 nm, and its emission was around 495 nm. The black cocrystal E2-TCNQ was obtained for single crystal analysis by slow solvent-evaporation method. It is found that the cocrystal belong to monoclinic crystals. In addition, TCNQ molecules and N, N-dimethyl benzene part of E2 were arranged alternately along the a-axis of crystal, while the anthracene ring of E2 cannot form a long-term orderly arrangement in the cocrystal. The ultrasound-assisted synthesis method is green and efficient, which provides reference for the preparation, structural optimization and analysis of the crystallization characteristics of these compounds.