77541-40-3Relevant academic research and scientific papers
CORRELATION OF KINETIC DATA OF 1,3-DIPOLAR CYCLOADDITIONS OF C-BENZOYL-N-PHENYLNITRONES WITH THE HOMO ENERGIES OF FURAN DERIVATIVES
Fisera, Lubor,Gaplovsky, Anton,Timpe, Hans-Joachim,Kovac, Jaroslav
, p. 1504 - 1512 (2007/10/02)
Application of PMO treatment to 1,3-dipolar cycloaddition of C-benzoyl-N-phenylnitrone with furan derivatives is described.Ionisation 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 furanderivatives were determined from IP and energies of ?-?*transitions using empirical equation ΔE(?-?*)=IP-EA-450.58 kJ mol-1.
1,3-DIPOLAR CYCLOADDITION OF C-BENZOYL-N-PHENYLNITRONE WITH FURAN DERIVATIVES. ANOMALOUS DEHYDROGENATION OF CYCLOADDUCTS WITH 2,3-DICHLORO-5,6-DICYANO-1,4-BENZOQUINONE
Fisera, Lubor,Lesko, Jan,Dandarova, Miloslava,Kovac, Jaroslav
, p. 3546 - 3556 (2007/10/02)
C-Benzoyl-N-phenylnitrone reacted with 2-R-substituted (R=phenyl,CH2OH,CH2OCOCH3,CH2SH)furan derivatives at 55 deg C by a 3-dipolar cycloaddition reaction to the unsubstituted furan double bond to give mono- and bisadducts. 2,5-Dimethylfuran afforded monoadduct only.Dehydrogenations of monoadducts of 5-R-2-phenyl-3-benzoyl-3a,6a-dihydrofuroisoxazolines with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone proceeded anomously at 60 deg C: dehydrogenation followed by electrocyclic opening afforded the corresponding ketonitrones.This method of dehydrogenation offersa new preparation of nitrones and further exemplifies the exploitation of products of 1,3-dipolar cycloaddition for synthetic purposes.
