Conformational and Electronic Interaction Studies of P-Substituted α-Phenoxyacetones

Abstract

The v_co analysis of p-substituted α-phenoxy-acetones X-θ-O-CH₂-C(O)-Me (1-6) indicates the existence of the cislgauche rotational isomerism. The nearly constant increase in the cislgauche population ratios for the whole series, on going from carbon tetrachloride to acetonitrile, and the small sensitivity of the carbonyl frequency shifts (Δv_c) for the cis rotamer, on going from electron-attracting to electron-donating substituents, are interpreted as an interplay of the Field (F) and the Inductive (-I) Effects, which originates an almost constant carbonyl bond order, and suggests that the cis rotamers have almost the same energy in the whole series. The decrease in the cislgauche population ratios, in all solvents, and the deshielding effects on the carbonyl carbon atom, and on the methylene carbon atom in a weaker extent, observed in the ¹³C NMR spectra, on going from electron-attracting to electron-donating substituents, are discussed in terms of φ*CO/ⁿO orbital and Ar^δ+ -O^δ- — C^δ+ =O^δ- Coulombic interactions, which stabilize the gauche rotamers of the investigated compounds.

Key Words:

• Conformational analysis
• Electronic interaction
• α-Phenoxyacetones