Page 191 - 《精细化工》2020年第3期

第 37 卷第 3 期 精 细 化 工 Vol.37, No.3
202 0 年 3 月 FINE CHEMICALS Mar. 2020

特种染料与颜料
双羟基七甲川菁染料的合成及其光谱性能研究

1
刘占会 ，鲍利红 1,2*
（1. 北京服装学院 材料设计与工程学院，北京 100029；2. 北京市服装材料研发与评价重点实验室，北
京 100029）

摘要：通过分子设计，分别以 2,3,3-三甲基吲哚和 1,1,2-三甲基-1H-苯并[e]吲哚为原料，首先合成两种季铵盐，
再分别同 2-氯-1-甲酰-3-羟基亚甲基环己烯缩合，利用 Suzuki-Miyaura 反应实现染料中位 C—C 偶联，以超过 70%
的收率制备了 4 种带有活性羟基的七甲川菁染料。利用核磁和高分辨率质谱对染料结构进行了表征。以乙醇为
溶剂，用紫外-可见光谱仪考察了染料的光谱性能。采用电流为 13.4 A 的高压氙灯为光源，考察了染料的光稳定
性。探究了 pH 对染料颜色的影响，并尝试推论变色机理。结果表明，4 种七甲川菁染料均在近红外区产生较强
吸收，在无水乙醇中均具有良好的光稳定性。不同 pH 下，染料的光谱性能研究发现，七甲川菁染料吸收光谱
受 pH 影响较大，在 pH=5~7 时，染料在近红外区有最佳吸收。
关键词：七甲川菁染料；Suzuki-Miyaura 反应；光谱性能；光稳定性；pH 稳定性
中图分类号：TQ613.5 文献标识码：A 文章编号：1003-5214 (2020) 03-0609-06

Synthesis and spectral properties of dihydroxy heptamethine cyanine dyes

1
LIU Zhanhui , BAO Lihong 1,2*
（1. School of Materials Design and Engineering, Beijing Institute of Fashion Technology, Beijing 100029, China; 2. Beijing
Key Laboratory of Clothing Materials R & D and Assessment, Beijing 100029, China）

Abstract: Four heptamethine cyanine dyes with active hydroxyl groups were prepared by molecular design
using 2, 3, 3-trimethylindole and 1, 1, 2-trimethyl-1H-benzo [e] indole as raw materials and their yields
were over 70%. First, two kinds of quaternary ammonium salts were synthesized and then condensed with
2-chloro-1-formyl-3-hydroxymethylene cyclohexene, respectively. Finally, median C-C coupling of dyes
1
was carried out by Suzuki-Miyaura coupling reaction. The structures of dyes were characterized by HNMR
and FTMS spectra. The absorption spectra of four dyes were determined by UV-Vis spectrometer with
ethanol as solvent. The light stability of dyes was investigated by using a high voltage xenon lamp with a
current of 13.4 A as the source of the light. The effect of pH on the color of dye was studied, and the
mechanism of color change was deduced. The results showed that four heptamethine cyanine dyes had
strong absorption peaks in the near infrared region and exhibited good light stability in anhydrous ethanol.
Their absorption spectra were greatly affected by pH value. These dyes had the best absorption in the near
infrared region when pH value was in the range from 5 to 7.
Key words: heptamethine cyanine dyes; Suzuki-Miyaura coupling reaction; spectral property; light stability;
pH stability

无机类近红外吸收材料因生产成本相对较高， 菁染料由两端含氮杂环通过共轭七甲川链连接在一
又含有金属元素，无法在生物体内或者大自然中分 起而形成。杂环既可以作为电子供体，也可以作为
解，会导致一定的危险和环境隐患。而有机近红外 电子受体，在整个分子中形成推拉电子体系，从而
吸收材料生物相容性和可降解性相对优越。七甲川 实现对近红外光的吸收 [1-2] ，目前已经在分析、生物

收稿日期：2019-06-03; 定用日期：2019-09-18; DOI: 10.13550/j.jxhg.20190499
基金项目：北京服装学院高水平教师队伍建设专项资金（BIFTXZ201808）
作者简介： 刘占会（1993—），男，硕士生，E-mail：1803194570@qq.com。联系人：鲍利红（1978—），女，教授，E-mail：clyblh@ bift.edu.cn。