BF3•Et2O促进的双烯酮-酚重排合成具有聚集诱导发光(AIE)效应的磷杂七元环化合物

doi:10.6023/cjoc202204012

有机化学 ›› 2022, Vol. 42 ›› Issue (8): 2481-2487.DOI: 10.6023/cjoc202204012 上一篇下一篇

研究论文

BF₃•Et₂O促进的双烯酮-酚重排合成具有聚集诱导发光(AIE)效应的磷杂七元环化合物

郭泽, 吴迪, 王丽丽^*(), 段征^*()

郑州大学化学学院绿色催化研究中心国际磷化学实验室河南省有机磷功能分子国际联合实验室郑州 450001

收稿日期:2022-04-06 修回日期:2022-05-01 发布日期:2022-05-17
通讯作者: 王丽丽, 段征
基金资助:
国家自然科学基金(22171245); 国家自然科学基金(22101262); 国家自然科学基金(21672193); 河南省科技攻关(202102310327); 郑州大学资助项目

BF₃•Et₂O Promoted Dienone-Phenol Type Rearrangement to Synthesize Phosphepine with Aggregation Induced Luminescence (AIE) Effect

Ze Guo, Di Wu, Lili Wang(), Zheng Duan()

International Joint Research Laboratory for Functional Organophosphorus Materials of Henan Province, International Phosphorus Laboratory, Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou 450001

Received:2022-04-06 Revised:2022-05-01 Published:2022-05-17
Contact: Lili Wang, Zheng Duan
Supported by:
National Natural Science Foundation of China(22171245); National Natural Science Foundation of China(22101262); National Natural Science Foundation of China(21672193); Key Scientific and Technological Project of Henan Province(202102310327); Zhengzhou University

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摘要/Abstract

磷杂环庚三烯类化合物作为一类新兴的发光分子吸引了人们研究的兴趣. 因其合成路线非常有限, 对其结构与发光性能相关性的探索还远远落后于相应的磷杂五、六元环类化合物. 双烯酮化合物在酸或碱的促进下发生重排反应被广泛用于酚类化合物的制备. 利用螺环双烯酮磷杂六元环化合物在BF₃•Et₂O作用下发生双烯酮-酚重排反应合成了一系列具有聚集诱导发光(AIE)效应的磷杂七元环化合物.

关键词: 双烯酮-酚重排反应, 磷杂七元环, 聚集诱导发光(AIE), BF₃•Et₂O

Very recently, phosphepines has emerged as a new luminogen. Further explorations of this new motif in optical materials have been hampered by the lack of general and practical methods for their synthesis and derivation. The rearrangement of dienones promoted by acid or base is widely used in the preparation of phenols. A series of phosphepines with aggregation induced luminescence (AIE) effect were synthesized by the dienone-phenol rearrangement reaction of spirodienone six-membered phosphacycles in the presence of BF₃•Et₂O.

Key words: dienone-phenol rearrangement, phosphepine, aggregation-induced emission (AIE), BF₃•Et₂O

引用此文

郭泽, 吴迪, 王丽丽, 段征. BF₃•Et₂O促进的双烯酮-酚重排合成具有聚集诱导发光(AIE)效应的磷杂七元环化合物[J]. 有机化学, 2022, 42(8): 2481-2487.

Ze Guo, Di Wu, Lili Wang, Zheng Duan. BF₃•Et₂O Promoted Dienone-Phenol Type Rearrangement to Synthesize Phosphepine with Aggregation Induced Luminescence (AIE) Effect[J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2481-2487.

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图/表 8

图式1. 磷杂七元环的合成方法

Scheme 1. Synthesis of phosphepines

图式2. 螺环双烯酮酚重排反应及在磷杂七元环的合成中的应用

Scheme 2. Spirocyclic dienone-phenol rearrangement reactions and their applications in the synthesis of phosphepines

图1. 化合物3a和3d的单晶结构

Figure 1. Crystal structures of compounds 3a and 3d

图式3. BF3促进的双烯酮-酚重排反应合成磷杂七元环化合物

Scheme 3. BF3-promoted dienone-phenol rearrangements for the synthesis of phosphepines

图式4. 双烯酮-酚重排反应可能的反应机理

Scheme 4. Plausible mechanisms for the dienone-phenol rearrangements

图2. 常温下二氯甲烷溶液中3a~3h的(a)紫外可见吸收光谱图和(b)荧光发射光谱图

Figure 2. UV-Vis absorption spectra (a) and fluorescence spectra (b) of 3a~3h in CH2Cl2 at room temperature

Compound	λ_abs/nm	λ_ex/nm	λ_em/nm
3a	315	250	390
3b	309	300	388
3c	308	260	390
3d	308	290	397
3e	313	260	402
3f	321	260	398
3g	314	260	390
3h	310	260	395

表1. 3a~3h的光物理数据a

Table 1. Photophysical datas of 3a~3h

图3. (a)化合物3h在不同比例的水/THF混合溶液中的荧光发射光谱图及(b)荧光强度与含水量的关系图

Figure 3. (a) Fluorescence emission spectra of compound 3h in different ratios of water/THF solution, and (b) fluorescence intensity versus water content

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BF₃•Et₂O促进的双烯酮-酚重排合成具有聚集诱导发光(AIE)效应的磷杂七元环化合物

BF₃•Et₂O Promoted Dienone-Phenol Type Rearrangement to Synthesize Phosphepine with Aggregation Induced Luminescence (AIE) Effect

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