Influence Of Substituent Effects On The NMR And UV Spectra Properties Of N-(Phenyl-ethylene)-anilines

In this work, 61 samples of substituted N-(phenyl-ethylene)-anilines(XPEAYs) were synthesized, and which have been confirmed by NMR. The data of NMR chemical shifts, UV absorption and ORP were obtained by measurement. Comparison the difference of substituents effects between N-(phenyl-ethylene)-anilines and N-(benzylidene)-anilines(XBAYs), then try to make an explanation for the differences.Comparison of 13 C NMR of C=N bond chemical shifts δc(C=N) in XPEAYs with that in XBAYs was carried out. The results shows the factors affecting the δC(C=N) of XPEAYs are quite different from that of XBAYs. A penta-parameter correlation equation was obtained, which has correlation coefficient 0.9922, standard error 0.12 ppm. The result indicates that in XPEAYs, the inductive effects of substituents X and Y are major factors affecting the δC(C=N), while the conjugative effect of them have very little effect on the δC(C=N) and can be ignored. The substituent specific cross-interaction effects between X and Y and between Me of C=N bond and substituent Y are important factors affecting the δC(C=N). Also, the excited-state substituent parameter of substitute Y has certain contribution to the δC(C=N).The regularity of substituents effects on the UV spectra of XPEAYs has been studied. The quantitative equation has good linear relation,which confirmed that there are some differences in substituents effects affecting the UV spectra between in XPEAYs and in XBAYs. The UV spectra of XPEAYs have not only been affected by the substituents conjugative effects and inductive effects, but also the excited-substituents effects and the cross-interaction of excited-substituents effects. It make differences that the specific substituents cross-interaction effects of polarity parameters do little effects on the UV spectra of the target compounds, that can be ignore, but it would have certain effects on that of XBAYs.The Oxidation-Reduction Potential(OPR) of XPEAYs are measured by CV in(n-Bu)4NPF6/CH3 CN, the experimental results show that the electrode reaction of XPEAYs is an irreversible one which has only a reduction potential E(Red). Primary researching on regularity of the substituents effects which affecting the E(Red) of 30 samples of XPEAYs, as it shows the factors of substituents effects affecting the E(Red) are complex. As the results show that the polarity parameters are still important factors, as the same as the excited-substituents effect parameters. While the substituents specific cross-interaction effects of polarity parameters, the substituents specific cross-interaction effects of excited-substituents effect parameters and the substituents specific cross-interaction effects between Me and substituent Y are all make certain contributions to E(Red). Moreover, we find there isn’t any direct relationship between the dC(C=N) and E(Red) of XPEAYs by contrastive analyzing them. It also means that there is no direct relation between E(Red) of C=N bond in XPEAYs and their dC(C=N), that will not agree with the classics theory.