The alternating of substituent effect on the ¹³C NMR shifts of all bridge carbons in cinnamyl aniline derivatives.
Bridge carbon (13)C NMR shifts of a wide set of substituted cinnamyl anilines p-XC(6)H(4)CHCHCHNC(6)H(4)Y-p (XNO(2), Cl, H, Me, MeO, or NMe(2); YNO(2), CN, CO(2)Et, Cl, F, H, Me, MeO or NMe(2)) had been used as a probe to study the change of substituent effect in the conjugated system. The goal of this work was to study the difference among the substituent effect on SCS of all bridge carbons, and find the alternating of substituent effect in this model compounds. In this study, it was found that the change of the inductive effect and the conjugative effect on different bridge carbons is related to the bond number (m) from the substituent to the corresponding carbon, and the adjusted parameters σ(F(rel))(∗) and σ(R(ver))(∗) can be suitable to scale the difference of the inductive effect and the conjugative effect on bridge carbons. Moreover, because of the difference of substituent effect on bridge carbons, the substituent cross-interaction item Δσ(2)(Δσ(2) = (σ(F(rel))(∗)(X) + σ(R(ver))(∗)(X) - σ(F(rel))(∗)(Y) - σ(R(ver))(∗)(Y))(2)) was not suitable simply to scale the interaction between substituents X and Y for all bridge carbons, so the Δσ(2) was recommended to be divided into two parts: Δσ(F(rel))(2) (Δσ(F(rel))(2) = σ(F(rel))(∗)(X) - σ(F(rel))(∗)(Y))(2)) and Δσ(R(ver))(2) (Δσ(R(ver))(2) = (σ(R(ver))(∗)(X) - σ(R(ver))(∗)(Y))(2)). With σ(F(rel))(∗), σ(R(ver))(∗), Δσ(F(rel))(2), Δσ(R(ver))(2), and δ(C,parent), the obtained correlation equation can be used to correlate with the 159 sorts of SCS of the different bridge carbon in cinnamyl aniline derivatives. The correlation coefficient is 0.9993, and the standard deviation is only 0.53 ppm. The multi-parameter correlation equation can be recommended to predict well the corresponding bridge carbons SCS of disubstituted cinnamyl anilines.
School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Key Laboratory of Theoretical, Chemistry and Molecular Simulation of Ministry of Education, Hunan Provincial University Key Laboratory of QSAR/QSPR, Xiangtan 411201, China.
Guanfan
G
Chen
Chenzhong
C
Cao
Yun
Y
Zhu
Zhenxing
Z
Wu
Xiangsi
X
Wu
D000465:Algorithms; D000814:Aniline Compounds / Q000737:chemistry*; D002247:Carbon Isotopes / Q000032:analysis; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*
D000814:Aniline Compounds; D002247:Carbon Isotopes