取代基效應對1,2-二苯基丙烯類化合物譜學性能的影響
發(fā)布時間：2018-12-13 19:22
【摘要】：本文設計合成了44個目標化合物1,2-二苯基丙烯XArC(Me)=CHAr Y(XSMBY)。測定了目標化合物的熔點、核磁共振氫譜和碳譜、紫外吸收光譜、電化學還原電位和紅外吸收光譜。采用定量結構-性能相關分析方法,研究了取代基效應對目標化合物的譜學性能的影響規(guī)律。研究了44種XSMBY的紫外吸收光譜的ν_(max)受取代基效應影響的變化規(guī)律,并與XArCH=CHArY(XSBY)的ν_(max)變化規(guī)律進行比較,發(fā)現(xiàn)XSMBY與XSBY的ν_(max)沒有線性關系,影響兩類化合物的ν_(max)的因素有差異。橋基上甲基的引入使得取代基X和Y的基態(tài)極性電子效應(σ)對ν_(max)也有重要影響,然而在XSBY體系中,X、Y的σ常數(shù)對ν_(max)的影響可以忽略。對于母體結構不同的兩類化合物XSMBY和XSBY,可以由一個統(tǒng)一的方程來關聯(lián)取代基對ν_(max)的影響,且相關性良好。XSMBY橋基上甲基引起的立體效應,導致其UV吸收λ_(max)藍移。對目標化合物XSMBY橋基上三個碳的化學位移δC分別進行定量分析,并與希夫堿類化合物的δC進行了比較研究。通過回歸分析分別提出了XSMBY的三個定量相關方程,其相關系數(shù)分別達到了0.9945、0.9974和0.9701,并成功的將其應用于化合物的碳化學位移的預測,得到了良好的結果。雖然化合物XSMBY的橋基因甲基的引入而使橋基帶有一定極性,但是取代基效應對該類化合物的影響規(guī)律不同于希夫堿類化合物。化合物XSMBY中,對X端橋基碳的δC(X)來說,取代基X的共軛效應σR(X)起重要作用且貢獻最大;對Y端橋基碳的δC(Y)來說,取代基X的誘導效應σF(X)、共軛效應σR(X)以及取代基Y的誘導效應σF(Y)同時起重要作用;對橋基上甲基碳的δC(Me)來說,除了Hammett常數(shù)外激發(fā)態(tài)取代基參數(shù)同樣是重要的影響因素。對化合物XSMBY的還原電位Ered的數(shù)據(jù)進行分析,發(fā)現(xiàn)除了用取代基X和Y的Hammett常數(shù)和激發(fā)態(tài)取代基常數(shù)定量相關外,橋基上甲基與取代基Y之間的相互作用也是重要的影響因素。其Ered的影響因素明顯不同于希夫堿類化合物,不能用希夫堿化合物的回歸方程對化合物XSMBY進行模擬。二苯乙烯類化合物的橋基碳碳雙鍵比希夫堿類化合物的碳氮雙鍵更難于還原。研究了化合物XSMBY的C=C橋鍵紅外吸收νC=C的變化規(guī)律,結果表明,XSMBY的C=C橋鍵紅外吸收νC=C可以用一個六參數(shù)的相關方程進行定量相關,方程的相關性良好,相關系數(shù)達到了0.9158。除了Hammett常數(shù)和激發(fā)態(tài)取代基常數(shù)以外,橋基上甲基與取代基X之間的相互作用項對νC=C也有影響,且貢獻最大,是主要的影響因素。
[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.
【學位授予單位】：湖南科技大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O625.12
本文編號：2377081
[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.
【學位授予單位】：湖南科技大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O625.12
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