ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Reactions of the dimedone anion with X-benzyl chlorides. Effect of substituents upon the carbon/oxygen product ratio and its theoretical interpretation

P. Hrnčiar and P. Zahradník

Department of Organic Chemistry, Faculty of Natural Sciences, Komenský University, 81631 Bratislava

Abstract: Reactions of the dimedone anion with XC6H4CH2Cl(I; X = H, 3- and 4-halo, 3- and 4-MeO, etc.) in acetone have been performed. The ration of C- to O-benzylation depends on X; log C/O = f(σ*). Using the semiempirical CNDO/2 method, the quantum chem. characteristics of I have been calcd. A linear correlation of Hammett σp* consts. and charge densities at the electrophilic C atom, virtual orbital energies , and calcd. polarities of C-Cl linkages in I have been found.

Full paper in Portable Document Format: 351a105.pdf

Chemical Papers 35 (1) 105–111 (1981)