【作者】 黄明刚；

【导师】 宋航；

【作者基本信息】 四川大学 ， 应用化学， 2005， 硕士

【摘要】 手性分子对映异构体有几乎完全相同的物理、化学性质,甚至有相同的光谱,但是它们之间的旋光性不同,在新药研究和新型材料开发方面具有重要的价值,所以研究手性分子对映异构体已经成为当今研究的一个重要课题。本文主要是合成手性物5-(10)-十一烯乙酰胺基苊的同系物。最近的研究观察到手性对映体5-(10)-十一烯乙酰胺基苊有在非手性溶剂中转化的现象,根据该手性对映体的化学结构特点,设计了两种苊衍生的酰胺型手性化合物5-(10)-十一烯异丁酰胺基苊和5-(10)-十一烯丙酰胺基苊,该两种物质的合成是以苊为原料,经过苊环碳原子上的Fridel-Crafts酰基化反应、酮的还原胺化反应和胺的酰化反应制得。最后经过柱层析进行纯化,得到纯度较高的产品。目前在国内外的文献中,还没有报道对于5-(10)-十一烯异丁酰胺基苊和5-(10)-十一烯异丁酰胺基苊的高效液相色谱分析。本文实验使用高效液相色谱手性柱和在线旋光仪分析这两种手性化合物,考察了不同的手性柱对手性物的拆分,以及流动相的组成、柱温对溶质在色谱柱中分离的影响。实验结果表明,5-(10)-十一烯丙酰胺基苊的色谱条件是:流速2.0ml/min,柱温20.0℃,流动相为:异丙醇:正己烷=6.0:94.0,宜用DNB-PG手性柱分析,对映体的的第一个色谱峰是左旋;5-(10)-十一烯异丁酰胺基苊的色谱条件是:流速2.0ml/min,柱温20.0℃,流动相异丙醇:正己烷=4.0:96.0,DNB-PG手性柱,它的第一个物质峰是右旋。两种手性物第一个对映体物质峰的旋光性不同,很可能在于手性碳所链接的唯一不同基团,该基团的位阻和极化度影响造成。此外,在本实验室已经研究了5-(10)-十一烯乙酰胺基苊的基础上,通过改变手性碳原子所连接的长碳烯链的长度,即把10-十一烯碳链变为烯丙基短链,同时酰胺基团变为仲胺基团,合成了烯丙基-(苊基)—仲乙胺,目的更多还原

【Abstract】 Enantiomers have same physical and chemical properties and spectra expect rotary property, which have important applications to development of new drugs and functional materials. So study of enantiomers has been important field nowadays. In this paper, it is mainly about the synthesis of homologue compounds of 5-(10)-undecenacetamido-acenaphthene. Recent study showed that 5-(10)-undecena cetamido-acenaphthene is likely to invert in achiral solvents. According to previous study, two new compounds 5-(10)-undecenisobutyramido-acenaphthene and 5-(10)-undecenpropeonamido-acenaphthene derived from acenaphthene were designed. The synthetical processes of the compounds were via acenaphthene as material, the Fridel-Crafts acetylation reaction to the carbon of the acenaphthene ring, deoxi dization reaction to the ketone, acetylation reaction to the amidocyanogen, and final purification by flash chromatography. The higher pure products were obtained. So far, in all kinds of literature in domestic and abroad, there had been no report on HPLC analysis of 5-(10)-undecenisobutyramidoacenaphthene and 5-(10)-undecenpropionamido-acenaphthene. In this paper, the result of two enantiomers were analysed by high performance liquid chromatography and on-line polariscope. The effect of different CSP columns, different percentage of mobile phase (isopropyl alcohol and n-hexane) and temperature to the analysis were investigated experimentally. The results of the experiment showed that the analytical conditions of 5-(10)-undecenylpropionamido-acenaphthene as follows: flow rate 2.0ml/min, temperature 20.0℃, mobile phase, isopropyl alcohol: n-hexane=6.0:94.0, DNB-PG CSP column, laevorotation; the analytical conditions of 5-(10)-undecenisobutyr -amido-acenaphthene as follows: flow rate 2.0ml/min, temperature 20.0℃, mobile phase, isopropyl alcohol: n-hexane=4.0:96.0, DNB-PG CSP column, dextrorotation. For the chiral carbon is linked with the only different isopropyl and ethyl, its steric block and polarizable groups has effecton rotative way. In addition, in order to observe its separation due to functional group variation, allyl-acenaphthene-ethelamido enantiomer was synthesized, on the basis 5-(10)-undecenacetamido-acenaphthene, by means of replacing allyl chloride with 10-undecenyl, and amide being turned into amine. Several new enantiomer compounds synthesized could be not only linked with silica gel for preparing novel Pirkle CSPs, but also as potential enantiomers for investigation of the enantiomer inversion in achiral solvents. It has greatly practical significance.更多还原