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Substituent effect study on 13 C β SCS of styrene series. A Yukawa–Tsuno model and Reynolds dual substituent parameter model investigation
Author(s) -
Saleh Basil A.,
AlShawi Sabih A.,
Fadhil Ghazwan F.
Publication year - 2008
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.1272
Subject(s) - substituent , chemistry , dihedral angle , side chain , heteroatom , crystallography , stereochemistry , ring (chemistry) , computational chemistry , organic chemistry , molecule , hydrogen bond , polymer
The Yukawa–Tsuno (Y–T) and Reynolds dual substituent parameter (DSP) models have been used to model 13 C substituent chemical shift (SCS) of the C β atom of 19 series of para ‐substituted styrenes (X‐C 6 H 4 CRCYW) with variable electronic and structural demands in the side‐chain. The best fit of the Y–T model was better than that of the Reynolds DSP model for most of the studied series. A high correlation was found between the ρ value of the Y–T model and ρ F value of the Reynolds DSP model. The ρ value, which reflects the sensitivity of 13 C β SCS to the substituent field effect, was found to be influenced by the group W on the C β atom. A W group that enhances the para ‐substituent π ‐polarization of the side‐chain has a higher ρ value than its counterpart W groups that induce counter π ‐polarization in the side‐chain. The series with W in an E ‐configuration to the aryl ring has higher ρ value than corresponding Z series. A lower ρ value is observed when W induces a counter π ‐polarization of the side‐chain (as with NO 2 and COMe) or when the R substituent imposes a 65° dihedral angle between the side‐chain and the para ‐substituted benzene ring (as with t ‐Bu). When the W group is a heterocyclic ring, the closer the heteroatom is to C β , the lower the ρ value is due to the greater counter π ‐polarization. The two components of the substituent effect on 13 C β SCS, namely the field effect and resonance effect, behave inversely. The resonance demand ( r + value) increases, as the Y and/or W groups become more electron‐withdrawing (EW). The series with W as a hetrocyclic ring develop negative charge at the carbon atom of the hetrocyclic ring adjacent to C β (and to which the styryl moiety is attached) and has a lower r + value than those which fail to do so. The lowest r + value was for those series with a 65° dihedral angle. Copyright © 2007 John Wiley & Sons, Ltd.