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Influence of substituent and push‐pull effect on the chemical shifts of the carbon in bridging bond of 1‐furyl/thienyl‐2‐arylethylene
Author(s) -
Cao Chaotun,
Yan Lu,
Cao Chenzhong,
Qu Junyan
Publication year - 2021
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.4160
Subject(s) - substituent , chemistry , chemical shift , excited state , crystallography , double bond , resonance (particle physics) , reaction rate constant , carbon atom , stereochemistry , organic chemistry , atomic physics , kinetics , ring (chemistry) , physics , quantum mechanics
Sixty‐six samples of 1‐furyl/thienyl‐2‐arylethylene model compounds XCHCHArY (abbreviated XEBY) were synthesized. The nuclear magnetic resonance spectra (NMR) of model compounds were determined. The chemical shift δ C (X) and δ C (Y) of the carbon atoms in bridging bond CHCH which connected to the X group and the ArY group, respectively, were confirmed with the two‐dimensional NMR method. The effect of substituent on the δ C (X) and δ C (Y) was studied, meanwhile, the push‐pull effect of substituent on Δ δ C = δ C (Y) − δ C (X) and δ C (Y/X) = δ C (Y)/ δ C (X) were discussed. The results show the following: (a) Both the δ C (X) and δ C (Y) are affected by excited‐state substituent constant σ CC ex X of group X, Hammett constant σ (Y), and excited‐state substituent constantσ CC ex Y of group Y. The effect of σ (Y) on the δ C (X) is positive, whereas that on the δ C (Y) is negative. That is to say, the σ (Y) of group Y has an alternative influence on the δ C (X) and δ C (Y). (b) Compared with furyl, there is a p‐d effect formed by the 3d orbit of S atom and the p electron of the π system in thienyl, which increase the chemical shift of the carbon atoms in bridging bond. (c) The push‐pull effect between substituent X and Y is not only affected by the σ parameter but also related to the σ CC ex parameter, which results from the combined effect of the two parameters σ and σ CC ex . The observation of this paper provides a new perspective in understanding the push‐pull effect of substituent.