Collect. Czech. Chem. Commun. 1981, 46, 1504-1512

Correlation of kinetic data of 1,3-dipolar cycloadditions of C-benzoyl-N-phenylnitrones with the homo energies of furan derivatives

Lubor Fišeraa, Anton Gáplovskýb, Hans-Joachim Timpec and Jaroslav Kováča

a Department of Organic Chemistry, Slovak Institute of Technology, 880 37 Bratislava
b Institute of Chemistry, Comenius University, 816 00 Bratislava
c Department of Photochemie, TH Leuna Merseburg, DDR-42 Merseburg


Application of PMO treatment to 1,3-dipolar cycloaddition of C-benzoyl-N-phenylnitrone with furan derivatives is described. Ionization potentials of 2-R-substituted furan derivatives (R = H, CH3, C2H5, CH2OH, CH2OCOCH3, C6H5, CHO) and 2,5-dimethylfurane representing experimental values of the HOMO energies have been determined from energies of the respective charge-transfer complexes with TCNE. Good correlation between IP and k2 rate constants indicates that the reaction is controlled by the LUMO(nitrone)/HOMO(furan deriv.) interaction. Electron affinities of the furan derivatives were determined from IP and energies of π-π* transitions using empirical equation ΔE(π-π*) = IP-EA-450.58 kJ mol-1.