间位基团激发态取代基常数的扩展及应用

发布时间：2019-04-15 18:56

【摘要】：合成了七个系列含间位取代基X的二苯乙烯m-XArCH=CHArY-p(简称m-XSBY-p),其中X为NO_2、I、CHCH_2、Ph、Et、NMe_2和CCH。在无水乙醇中测定它们的紫外(UV)吸收光谱,得到紫外吸收最大波长λ_(max)(nm)。对λ_(max)的波数ν_(max)(cm~(-1))进行定量相关,采用曲线拟合方法,得到上述7个间位基团的激发态取代基常数σ_(CC(m))~(ex)。将对位基团和间位基团的σ_(CC)~(ex)与Hammett常数σ进行对比,表明σx_(CC)~(ex)与σ分别表达取代基不同的电子效应。另外,合成了含上述间位基团的二芳基希夫碱(10个)和二苯乙烯(14个),用所得σ_(CC(m))~(ex)预测它们的λ_(max),并用实验测定它们的λ_(max),结果表明预测值与实验值相吻合,验证了所得σ_(CC(m))~(ex)常数的可靠性。收集了225个化合物(涉及二取代苯及二苯乙烯)的ν_(max),建立了一个统一的定量方程来表达这些化合物ν_(max)的变化规律。
[Abstract]:Seven series of stilbene m-XArCH=CHArY-p (m-XSBY-p) containing intermediate substituents X were synthesized, in which X is NO_2,I,CHCH_2,Ph,Et,NMe_2 and CCH.. Their UV (UV) absorption spectra were determined in anhydrous ethanol, and the maximum UV absorption wavelength 位 _ (max) (nm). Was obtained. The wave number of 位 _ (max) v _ (max) (cm~ (- 1) is quantitatively correlated, and the excited state substituent constants 蟽 _ (CC (m) ~ (ex). Of the above seven intermediate groups are obtained by curve fitting method. By comparing 蟽 _ (CC) ~ (ex) with Hammett constant 蟽 _ (CC) ~ (ex) and 蟽 _ (CC) ~ (ex), it is shown that the electronic effects of substituents are different. In addition, diaryl Schiff bases (10) and stilbene (14) containing the above intermediate groups were synthesized. Their 位 _ (max), were predicted by 蟽 _ (CC (m) ~ (ex) and their 位 _ (max), were measured experimentally. The results show that the predicted values are in good agreement with the experimental values, and the reliability of the 蟽 _ (CC (m) ~ (ex) constant obtained is verified. Two hundred and twenty-five compounds (involving disubstituted benzene and stilbene) were collected, and a unified quantitative equation was established to express the variation rule of these compounds (v _ (max).
【作者单位】：湖南科技大学化学化工学院理论有机化学与功能分子教育部重点实验室分子构效关系湖南省普通高校重点实验室;
【基金】：国家自然科学基金(21272063,21672058) 湖南省教育厅科研项目(14C0466) 湖南省自然科学基金(14JJ3112)资助~~
【分类号】：O621.1

【参考文献】