Radical intermediates of low temperature radiolysis of di-tert-butylcyclohexano-18-crown-6/1-octanol extractant

Abstract

AbstractIntermediates of low temperature (77 K) X-rays radiolysis of 1-octanol and di-tert-butylcyclohexano-18-crown-6 solutions in 1-octanol were studied by ESR spectroscopy. Hydroxyalkyl CH3(CH2)6C•HOH and interior-type alkyl R1C•HR2OH radicals were found to be main paramagnetic products stabilized in 1-octanol irradiated at 77 K. In addition to abovementioned radicals, macrocyclic –O–CH2–C•H– and acyclic –C•H–C(H)=O radicals produced from crown ether were identified in irradiated 1.0 M DtBuCH18C6 solution in octanol. No deviation in radiation-chemical yield of the stabilized acyclic radicals from the value expected in accord with “additive” rule was observed in the latter case. It was supposed that macrocycle cleavage in DtBuCH18C6 occurred at early stages of radiolysis rather than in secondary radical reactions between products of 1-octanol radiolysis and crown ether. Meanwhile, alkyl radicals formed from 1-octanol can react with crown ether, resulting in formation of macrocyclic products of radiolysis.