含不同核心第一代π-共轭不对称树状化合物的合成

doi:10.3724/SP.J.1095.2013.20466

摘要/Abstract

摘要： 以3,5-二叔丁基苯酚、三氟甲基磺酸酐和4,5-二乙炔基-2-甲氧基苯酚为原料，合成了4,5-双（3′,5′-二叔丁基苯基乙炔基）-2-甲氧基苯酚（单分子枝），单分子枝的酚羟基用三氟甲基磺酸酐酯化得到磺酸酯，后者再分别与偶氮苯、联苯、蒽和芘发色团偶联，得到含不同核心的第一代π-共轭不对称树状化合物。目标化合物的组成和结构分别经1H NMR谱、13C NMR谱、IR光谱和元素分析予以表征。其溶解性测试表明，相对于核（不同的发色团），所有树状化合物均能溶于常用的有机溶剂，并显示出良好的热稳定性。这将有利于其掺杂入其它材料和器件中。

关键词: 不对称共轭树状化合物, 发色团偶联, 合成, 表征

Abstract: 4,5-Bis(3′,5′-di-tert-butylphenylethynyl)-2-methoxyphenol(dendron) was synthesized from 3,5-di-tertbutyl phenol, trifluoromethanesulfonic anhydride and 4,5-diethynyl-2-methoxyphenol. The phenolic hydroxyl group was subsequently esterified by trifluoromethanesulfonic anhydride. By coupling different chromophores(biphenyl, azobenzene, anthracene, pyrene) on the as-obtained sulfonic esters, π-conjugate unsymmetrical dendrimers with different cores were obtained. 1H NMR, 13C NMR spectroscopy, FT-IR spectroscopy and element analysis were deployed to characterize the resultant products. The solubility of the dendrimers reveals that, compared to the cores(varieties of chromophores), all dendrimers are soluble in most common organic solvents. Meanwhile, the dendrimers show improved thermostability. These two characters make the dendrimers to be easily blended with other materials or added into equipments.

Key words: unsymmetrical conjugate dendrimers, chromophores coupling, synthesis, characterization

中图分类号:

O625.1

彭晓春, 伍建华, 肖竹平, 谢碧桃, 吴芳, 赵寒霜. 含不同核心第一代π-共轭不对称树状化合物的合成[J]. 应用化学, DOI: 10.3724/SP.J.1095.2013.20466.

PENG Xiaochun*, WU Jianhua, XIAO Zhuping, XIE Bitao, WU Fang, ZHAO Hanshuang. Synthesis of the First Generation π-Conjugate Unsymmetrical Dendrimers with Different Cores[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2013.20466.

参考文献

[1] Tomalia D A. Birth of a New Macromolecular Architecture:Dendrimer as Quantized Building Blocks for Nanoscale Synthetic Polymer Chemistry[J]. Prog Polym Sci,2005,30:294-324.

[2] WU Anqi,WANG Song,HUANG Haiqin. Research Development of Dendritic-linear Hybrid Copolymers at Home and Abroad[J]. Mater Rev,2008,22(6):54-57,60(in Chinese).

吴安琪,王嵩,黄海琴. 树枝状线性杂化共聚物国内外研究进展[J]. [HTK]材料导报[HTSS],2008,22(6):54-57,60.

[3] ZHAO Liwen,FAN Qinghua,ZHOU Haifeng. Study of Dendrimers as Supports for Organic Synthesis Progress in Chemistry[J]. Prog Chem,2006,18(1):317-320(in Chinese).

赵立文,范青华,周海峰. 树状大分子在有机合成中的应用[J]. [HTK]化学进展[HTSS],2006,18(1):317-320.

[4] LIU Haifeng,WANG Yurong,REN Yan. Development of Dendrimers′ Practical Using Research[J]. Polym Bull,2005,6(3):116-118(in Chinese).

刘海峰,王玉荣,任艳. 树枝状聚合物的应用研究进展[J]. [HTK]高分子通报[HTSS],2005,6(3):116-118.

[5] Vgtle F,Gestermann R,Hesse H,et al. Functional Dendrimers[J]. Prog Polym Sci,2000,25:987-1041.

[6] Hecht S. Functionalizing the Interior of Dendrimers:Synthetic Challenges and Applications[J]. J Polym Sci Part A:Polym Chem,2003,41(8):1047-1058.

[7] Akai I,Miyanari K,Shimamotol T,et al. Rapid Energy Transfer in a Dendrimer Having π-Conjugated Light-harvesting Antennas[J]. New J Phys,2008,10:125024.

[8] Wang J L,Zhou Y,Li Y F,et al. Solution-Processable Gradient Red-Emitting π-Conjugated Dendrimers Based on Benzothiadiazole as Core:Synthesis, Characterization, and Device Performances[J]. J Org Chem,2009,74:7449-7456.

[9] Liu R,Xiao Q,Li Y H,et al. Phenylene Ethynylene Azobenzenes with Symmetrical Peripheral Chromophores:Synthesis, Optical Properties and Photoisomerization Behaviors Study[J]. Dyes Pigm,2011,92:626-632.

[10] Raquel Gimenez,Milagros Pinol,Jose Luis Serrano. Luminescent Liquid Crystals Derived from 9,10-Bis(Phenylethynyl)-anthracene[J]. Chem Mater,2004,16:1377-1383.

[11] Oh J W,Lee Y O,Kim T H. Enhancement of Electrogenerated Chemiluminescence and Radical Stability by Peripheral Multidonors on Alkynylpyrene Derivatives[J]. Angew Chem,Int Ed,2009,48(14):2522-2524.

[12] Wu K C,Ku P J,Lin C S. The Photophysical Properties of Dipyrenylbenzenes and Their Application as Exceedingly Efficient Blue Emitters for Electroluminescent Devices[J]. Adv Funct Mater,2008,18(1):67-75.

[13] Stéphanie Leroy-Lhez,Frédéric Fages. Synthesis and Photophysical Properties of a Highly Fluorescent Ditopic Ligand Based on 1,6-Bis(ethynyl)pyrene as Central Aromatic Core[J]. Eur J Org Chem,2005,13:2684-2688.

[1]	李佳铮, 何述钟. 天然产物Polygalolides的全合成研究进展[J]. 应用化学, 2023, 40(5): 615-624.
[2]	刘振邦, 张硕, 包宇, 马英明, 梁蔚淇, 王伟, 何颖, 牛利. 深度学习在化学信息学中的应用研究进展[J]. 应用化学, 2023, 40(3): 360-373.
[3]	刘洋, 张海宝, 陈强. 纳秒脉冲介质阻挡放电等离子体合成氨工艺条件优化[J]. 应用化学, 2023, 40(2): 268-276.
[4]	曹蓉, 夏杰桢, 廖漫华, 赵路超, 赵晨, 吴琪. 单原子催化剂在电化学合成氨中的理论研究进展[J]. 应用化学, 2023, 40(1): 9-23.
[5]	田秦秦, 张佳, 陈峙, 何炜, 张生勇. 泊沙康唑的合成、检测及其临床应用研究进展[J]. 应用化学, 2022, 39(8): 1177-1189.
[6]	孟丹, 郑开元, 陈珊珊, 卓钊龙, 王丽丽. 硅、氮共掺杂碳点荧光粉的制备及发光性能[J]. 应用化学, 2022, 39(11): 1766-1773.
[7]	吴之强, 韩新宁, 刘阳, 王刚, 詹海鹃, 刘万毅. 水相或无溶剂绿色催化合成双吲哚基甲烷研究进展[J]. 应用化学, 2021, 38(8): 881-896.
[8]	薄纯辉, 姜维佳, 王玉高, 石利红, 董川. 煤基碳量子点合成研究进展[J]. 应用化学, 2021, 38(7): 767-788.
[9]	刘洋, 张海宝, 陈强. 低温等离子体合成氨研究进展[J]. 应用化学, 2021, 38(6): 622-636.
[10]	刘玉婷, 孙嘉希, 尹大伟. 含二茂铁基聚合物的合成及应用研究进展[J]. 应用化学, 2021, 38(4): 343-366.
[11]	谢志琦, 张婷, 李英崴, 王周君, 代飞, 张瑞锐, 刘瑞霞. 钒磷氧合成条件对丁烷选择性氧化催化性能的影响[J]. 应用化学, 2021, 38(4): 414-421.
[12]	毕一飘, 宫雪, 杨发, 阮明波, 宋平, 徐维林. 多价MnO_x/C电催化剂用于高效氮还原反应[J]. 应用化学, 2020, 37(9): 1048-1055.
[13]	张宝华, 史兰香. 一锅法合成芳(杂环)胺亚甲基双膦酸四乙酯[J]. 应用化学, 2020, 37(8): 877-882.
[14]	孟雅婷, 焦媛, 张羱, 高艺芳, 路雯婧, 刘洋, 董川. 红色荧光碳点的制备及其对过硫酸根的检测[J]. 应用化学, 2020, 37(6): 719-725.
[15]	张转芳, 郑建华, 辛建娇, 赵楠, 陈洁, 许芮. Keggin型多酸基晶态材料的合成及催化性能[J]. 应用化学, 2020, 37(4): 481-488.