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α、ω-双香豆素长链化合物激基缔合物的研究 总被引:1,自引:0,他引:1
通过α、ω-双香豆素长链化合物详细研究了香豆素激基缔合物的荧光行办,通过吸收光谱、荧光光谱和激发光谱,考察了香豆素激基缔合物的发光位置与激发波长,借助单光子技术确定了形成的是分子内的激基缔合物,通过1HNMR谱研究了不同双香豆素长链化合物的构象分布,揭示了在水溶液中由于疏水相互作用促进了长链化合物分子内激基缔合物的形成. 相似文献
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A novel approach to double bond location in long-chain olefinic acids has been elaborated by means of “remote functional group modification”. This method consists in converting the carboxylic acid into corresponding 2-alkenyl substituted heterocycle followed by measuring its 70 eV electron-impact mass spectrum. The inherited tendency of random migration of the double bond along the aliphatic chain under electron impact is strongly suppressed by incorporating the terminal carboxyl group into a heterocycle. The derivatives thus prepared show more informative spectra which clearly indicate the site of unsaturation of the parent acids. Submilligram scale derivatization of the olefinic acids, as exemplified by the model compound oleic acid, and a comparison of the spectra of the resulting heterocycles (3—10) as well as benzoxazole derivatives (3a—3d) of selected carboxylic acids is described in the present paper. 相似文献
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研究了一系列不同链长的对硝基苯酚羧酸酯在十种有机溶剂和水的二元混合溶剂中的水解反应,有机溶剂的体积含量分别为30%(Φ=0.30)和50%(Φ=0.50).结果表明,在Φ=0.50的各溶剂体系中,只有乙二醇-水和二甲亚砜-水体系,十六酸酯的水解速度才因受物分子的簇集绕曲而减慢.而在Φ=0.30的各溶剂体系中,除t-BuOH-H_2O体系外,十六酸酯全都存在簇集和绕曲现象,水解速度因此而受抑制的程度有如下次序:乙二醇>二甲亚砜>乙二醇单甲醚>二甲基甲酰胺~乙二醇二甲醚>二氧六环>乙醇~丙酮~乙腈>叔丁醇.如以log(k_(C8)/k_(a16))值作为衡量溶剂对受物的疏水-亲脂作用大小的定量标准,则发现各log(k_(C8)/k_(a16))和有机溶剂的介电常数ε,溶剂极性标度Kosower’s Z值,Dimroth’sE_T(30)值及Taft’s π值都不相关,但和Rekker的疏水常数f值却有较好的相关关系.这说明在这些“促簇性”溶剂中,控制长链酯水解的主要因素是疏水-亲脂相互作用,而和溶剂的极性无直接关系.此外,还讨论了不同比例的二元溶剂体系中水解的活化参数△S,△H.本工作首次提供了Rekker疏水常数应用于研究有机化合物反应性的实例. 相似文献
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