高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (7): 1359.

• 研究论文 • 上一篇    下一篇

中心为氨基、末端为硝基的苯乙炔树枝状分子的合成

陈梦琳, 池春彦, 王献红, 赵晓江, 李季, 王佛松   

  1. 中国科学院长春应用化学研究所高分子化学与物理国家重点实验室, 长春 130022
  • 收稿日期:2003-03-26 出版日期:2004-07-24 发布日期:2004-07-24
  • 通讯作者: 王献红(1966年出生),男,博士,研究员,博士生导师,主要从事导电高分子及二氧化碳固定的研究.E-mail:xhwang@ciac.jl.cn E-mail:xhwang@ciac.jl.cn
  • 基金资助:

    国家自然科学基金(批准号:20074036);国家杰出青年科学基金(批准号:20225414)资助

Synthesis of Amino-centered, Nitro-capped Phenylacetylene-monodendrons

CHEN Meng-Lin, CHI Chun-Yan, WANG Xian-Hong, ZHAO Xiao-Jiang, LI Ji, WANG Fo-Song   

  1. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  • Received:2003-03-26 Online:2004-07-24 Published:2004-07-24

摘要: 将固定相合成与“收敛/发散”方法相结合,合成了第一、二代苯乙炔树枝状分子.通过Heck-Cassar-Sonogashira-Hagihara偶联反应,将其中心和末端分别修饰上供电子的氨基和拉电子的硝基,得到第一、二代中心为氨基、末端为硝基的苯乙炔树枝状分子NH2-G1-(NO2)2和NH2-G2-(NO2)4.用傅里叶变换红外光谱跟踪了整个固定相合成过程.苯乙炔树枝状分子的紫外-可见吸收光谱呈现出规律性变化.

关键词: 固定相合成, &ldquo, 收敛/发散&rdquo, 方法, 苯乙炔树枝状分子, 偶联反应

Abstract: A rapid and convenient solid-supported iterative divergent/convergent approach was utilized to prepare the nitro-capped phenylacetylene-monodendrons I-G1-(NO2)2 and I-G2-(NO2)4, which were transformed into the expected amino-centered, nitro-capped monodendrons NH2-G1-(NO2)2 and NH2-G2-(NO2)4 by Heck-Cassar-Sonogashira-Hagihara coupling reactions. Transmittance FTIR spectroscopy followed the whole solid-phase approach. The absorption peaks at 2 157(1) and 3 311(1) cm-1 were the characteristic of the stretching vibration for the carbon-carbon triple bond in trimethylsilyl-protected acetylene and the carbon-hydrogen bond in the terminal acetylene after desilylation, respectively. Upon coupling reaction, the peak at 1 343(1) cm-1 was observed in P-G1-(NO2)2 and P-G2-(NO2)4, which was the characteristic of the stretching vibration for the terminal nitro groups. Both NH2-G1-(NO2)2 and NH2-G2-(NO2)4 were confirmed by UV-Vis, IR, NMR, EI-MS and ESI-MS techniques. UV-Vis spectra of the obtained monodendrons showed a good relationship with their structures. Both I-G2-(NO2)4 and NH2-G2-(NO2)4 showed a blue shift of (20±1) nm for the absorption peaks, compared with those of I-G1-(NO2)2 and NH2-G1-(NO2)2, which is probably due to the increase in the number of the terminal nitro groups. Upon coupling with the electron donor-amino group, both NH2-G1-(NO2)2 and NH2-G2-(NO2)4 showed a red shift of (6±1) nm for the absorption peaks, compared with those of I-G1-(NO2)2 and I-G2-(NO2)4.

Key words: Solid-phase synthesis, Iterative divergent/convergent, Phenylacetylene-monodendron, Coupling reactions

中图分类号: 

TrendMD: