取代基效应对1,2-二苯基丙烯类化合物谱学性能的影响

发布时间：2018-12-13 19:22

【摘要】：本文设计合成了44个目标化合物1,2-二苯基丙烯XArC(Me)=CHAr Y(XSMBY)。测定了目标化合物的熔点、核磁共振氢谱和碳谱、紫外吸收光谱、电化学还原电位和红外吸收光谱。采用定量结构-性能相关分析方法,研究了取代基效应对目标化合物的谱学性能的影响规律。研究了44种XSMBY的紫外吸收光谱的ν_(max)受取代基效应影响的变化规律,并与XArCH=CHArY(XSBY)的ν_(max)变化规律进行比较,发现XSMBY与XSBY的ν_(max)没有线性关系,影响两类化合物的ν_(max)的因素有差异。桥基上甲基的引入使得取代基X和Y的基态极性电子效应(σ)对ν_(max)也有重要影响,然而在XSBY体系中,X、Y的σ常数对ν_(max)的影响可以忽略。对于母体结构不同的两类化合物XSMBY和XSBY,可以由一个统一的方程来关联取代基对ν_(max)的影响,且相关性良好。XSMBY桥基上甲基引起的立体效应,导致其UV吸收λ_(max)蓝移。对目标化合物XSMBY桥基上三个碳的化学位移δC分别进行定量分析,并与希夫碱类化合物的δC进行了比较研究。通过回归分析分别提出了XSMBY的三个定量相关方程,其相关系数分别达到了0.9945、0.9974和0.9701,并成功的将其应用于化合物的碳化学位移的预测,得到了良好的结果。虽然化合物XSMBY的桥基因甲基的引入而使桥基带有一定极性,但是取代基效应对该类化合物的影响规律不同于希夫碱类化合物。化合物XSMBY中,对X端桥基碳的δC(X)来说,取代基X的共轭效应σR(X)起重要作用且贡献最大;对Y端桥基碳的δC(Y)来说,取代基X的诱导效应σF(X)、共轭效应σR(X)以及取代基Y的诱导效应σF(Y)同时起重要作用;对桥基上甲基碳的δC(Me)来说,除了Hammett常数外激发态取代基参数同样是重要的影响因素。对化合物XSMBY的还原电位Ered的数据进行分析,发现除了用取代基X和Y的Hammett常数和激发态取代基常数定量相关外,桥基上甲基与取代基Y之间的相互作用也是重要的影响因素。其Ered的影响因素明显不同于希夫碱类化合物,不能用希夫碱化合物的回归方程对化合物XSMBY进行模拟。二苯乙烯类化合物的桥基碳碳双键比希夫碱类化合物的碳氮双键更难于还原。研究了化合物XSMBY的C=C桥键红外吸收νC=C的变化规律,结果表明,XSMBY的C=C桥键红外吸收νC=C可以用一个六参数的相关方程进行定量相关,方程的相关性良好,相关系数达到了0.9158。除了Hammett常数和激发态取代基常数以外,桥基上甲基与取代基X之间的相互作用项对νC=C也有影响,且贡献最大,是主要的影响因素。
[Abstract]:In this paper, we have designed and synthesized 44 target compounds, 1h2- diphenylpropene XArC (Me) = CHAr Y (XSMBY). The melting point, nuclear magnetic resonance (NMR) and carbon spectrum, UV absorption spectrum, electrochemical reduction potential and infrared absorption spectrum of the target compounds were determined. The influence of substituent effect on the spectroscopic properties of the target compounds was studied by quantitative structure-performance correlation analysis. In this paper, we studied the variation law of XSMBY's UV absorption spectrum, which was influenced by substituent effect, and compared with that of XArCH=CHArY (XSBY) 's (max). It was found that there was no linear relationship between XSMBY and XSBY's XSMBY. The factors affecting the (max) of the two kinds of compounds are different. The introduction of methyl on the bridge makes the ground state polar electron effect (蟽) of the substituents X and Y also have an important effect on (max). However, in the XSBY system, the 蟽 constant of XY can be neglected. For two classes of compounds with different parent structures, XSMBY and XSBY, can be correlated by a unified equation to relate the influence of substituents on v _ (max), and there is a good correlation between them. This results in the absorption of 位 _ (max) blue shift by its UV. The chemical shift 未 C of three carbon compounds on the XSMBY bridged base was quantitatively analyzed and compared with that of Schiff base compounds. Three quantitative correlation equations of XSMBY were put forward by regression analysis. The correlation coefficients were 0.9945% 0.9974 and 0.9701, respectively. It was successfully applied to predict the carbon chemical shift of compounds, and good results were obtained. Although the bridged gene methyl of XSMBY has some polarity, the influence of substituent effect on these compounds is different from that of Schiff base compounds. In compound XSMBY, the conjugate effect 蟽 R (X) of substituted group X plays an important role and contributes most to 未 C (X) of X-terminal bridged carbon. For 未 C (Y) of Y-terminal bridged carbon, the inductive effect 蟽 F (X), conjugate effect 蟽 R (X) of substituent X and the inductive effect 蟽 F (Y) of substituent Y play an important role at the same time. For 未 C (Me) of methyl carbon on the bridge, the excited state substituent parameter is also an important factor in addition to the Hammett constant. The data of reduction potential Ered of compound XSMBY are analyzed. It is found that in addition to the quantitative correlation between the Hammett constant and the excited state substituent constant of X and Y, the interaction between methyl and substituent Y on the bridge is also an important factor. The influencing factors of Ered are obviously different from those of Schiff base compounds. The XSMBY can not be simulated by the regression equation of Schiff base compounds. The bridged carbon-carbon double bond of stilbenes is more difficult to reduce than that of Schiff base compounds. The variation rule of infrared absorption of XSMBY C bridge bond was studied. The results showed that the infrared absorption of XSMBY C bridge bond could be quantitatively correlated with a six-parameter correlation equation. The correlation coefficient of the equation was good, and the correlation coefficient reached 0.9158. In addition to the Hammett constant and the excited state substituent constant, the interaction term between methyl and substituent X on the bridge has an effect on Hammett C, and its contribution is the largest, which is the main influencing factor.
【学位授予单位】：湖南科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O625.12

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