中心为氨基、末端为硝基的苯乙炔树枝状分子的合成  

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

作　　者：陈梦琳[1] 池春彦[1] 王献红[1] 赵晓江[1] 李季[1] 王佛松[1] 

机构地区：[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

出　　处：《高等学校化学学报》2004年第7期1359-1362,MJ06,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金 (批准号 :2 0 0 740 3 6);国家杰出青年科学基金 (批准号 :2 0 2 2 5 414 )资助

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A rapid and convenient solid-supported iterative divergent/convergent approach was utilized to prepare the nitro-capped phenylacetylene-monodendrons I-G1-(NO 2) 2 and I-G2-(NO 2) 4, which were transformed into the expected amino-centered, nitro-capped monodendrons NH 2-G1-(NO 2) 2 and NH 2-G2-(NO 2) 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-(NO 2) 2 and P-G2-(NO 2) 4, which was the characteristic of the stretching vibration for the terminal nitro groups. Both NH 2-G1-(NO 2) 2 and NH 2-G2-(NO 2) 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-(NO 2) 4 and NH 2-G2-(NO 2) 4 showed a blue shift of (20±1) nm for the absorption peaks, compared with those of I-G1-(NO 2) 2 and NH 2-G1-(NO 2) 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 NH 2-G1-(NO 2) 2 and NH 2-G2-(NO 2) 4 showed a red shift of (6±1) nm for the absorption peaks, compared with those of I-G1-(NO 2) 2 and I-G2-(NO 2) 4.

关 键 词：苯乙炔 树枝状分子 氨基 硝基 合成 固定相合成 “收敛/发散”法 偶联反应 

分 类 号：O632.17[理学—高分子化学]