Abstract
Substituent effects on the electronic structure of 23 biologically active 4-aminoaryl (4-substituted aryl) sulphones were investigated by means of 1H n.m.r., 13C n.m.r., and i.r. spectroscopy, as well as by semiempirical all-valence CNDO/2 calculations, with and without sulphur d orbital participation. Good linear intercorrelations were found among the spectral data and between these and the computed electronic charges and the Hammett σp values. On this basis the substituent effects are interpreted in terms of electronic charge perturbation, which is linearly transmitted from the substituent to the whole molecule, bridging SO2 group included. The agreement between experimental and theoretical data is good and the trends do not depend on the inclusion or exclusion, in the calculations, of the sulphur d orbitals. Strong and linearly related σ–π electron interactions operate between C-1 and C-1′ in the C(1)SO2C(1′) moiety; thus Koch and Moffitt's qualitative π-electron conjugation model for Case 2 type sulphones seems inadequate.
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More From: Journal of the Chemical Society, Perkin Transactions 2
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