The role of aromatic groups in the Tobey-Simon additivity rule for vinylic protons.

The Tobey-Simon (additivity) rule for aromatic groups which was devised about 40 years ago has been found to need revision. The rule shows an aromatic group attached to a C==C double bond as causing a downfield chemical shift of a cis-related vinylic proton and a small upfield shift of a trans-related proton. A search of data in the recent literature has shown that this rule should apply mainly to monosubstituted phenyl groups and some polynuclear aromatics. In contrast with them, 2,6-disubstituted phenyl, 2,4,6-trisubstituted phenyl and 9-anthracenyl groups cause cis-related vinylic protons to resonate upfield of comparable trans-related protons. Further, the current rule for o-substituted phenyl groups has been found to be inaccurate. In writing a rule for aromatic groups, therefore, greater attention needs to be given to the diversity of effects that these groups have on chemical shifts of vinylic protons.