D. L. Rakhmankulov

1,3-Dioxacycloalkyl groups as substituents in aromatic molecules and radical ions

Conclusions1.In the reaction of the dipotassium salt of the cyclooctatetraene dianion with 2-(nitrophenyl)-1,3-diheterocycloalkanes, radical anions are formed. These radical anions are stable from −50 to +40‡.C and are oxidized monoelectronically in the presence of proton donors with quantitative formation of the starting compounds.2.According to the data of PMR, EPR, and mass spectrometry, 1,3-dihetero-2-cycloalkyl substituents exert a donor effect on theπ-electron system of the nitrophenyl group in the basic, radical-cation, and radicalanion states of the molecules, i.e., the CH group in the 2 position of 1,3-diheterocycloalkane is not a barrier for bonding of the unshared electron pairs of the hetero atoms with theπ-electron system of the nitrophenyl ring system.

Effect of high pressure on radical isomerization of 2-isopropyl-1,3-dioxolane

1. n nPressure decreases the rate of forming ethyl isobutyrate during the homolytic liquid-phase isomerization of 2-isopropyl-1,3-dioxolane. n n n n n2. n nThe volume effect for the activation of the decomposition of di-tert-butyl peroxide to 2-isopropyl-1,3-dioxolane at 130° is characterized by a substantial value (11 cm3/mole).