Stable radicals are generated by oxidation of s-butyl-lithium with transition-metal ions ; the e.s.r. spectra of these radicals are discussed. THE oxidation of intermediate anions to radicals has been postulated in many oxidation reactions catalysed by metal ions.l Using a flow system, the e.s.r. spectrum has been obtained for the radical CH,*CH,-CO,Me, a rearranged oxidation product of the anion of l-methoxycyclopropanoL2 FIGURE. E.s.r. signaE of Bu*Li-DIPS.This heniiacetal is quantitatively oxidized by Ce4+, Cu2+, and Fe3+, ions; the process is catalytic as the oxygen
The nitrile and several esters of 1-nitrosocyclohexanecarboxylic acid all gave the expected nitroxides upon thermal decomposition in toluene. These bis(1-substituted cyclohexyl) nitroxides could not be isolated from the decomposition product and were therefore prepared in the pure form by another route, involving peracid-oxidation of the corresponding bis(1-substituted cyclohexyl) amines. The nitroxides were stable in the solid state, but in solution a slow decomposition occurred. Hydrogenation of the nitroxides yielded the corresponding hydroxylamines. The ESR parameters of the nitroxides are given.
IntroductionRecently it was shown that many C-nitroso compounds form stable nitroxide radicals upon decomposition 1-5. The presence of the nitroxides in solutions of partly decomposed C-nitroso compounds is clearly shown by ESR spectroscopy. For the decomposition of the C-nitroso compounds either heat 4 or light of a suitable wave length can be usedIn the course of our work on I-nitrosocarboxylic acids 6 we prepared several derivatives of 1 -nitrosocyclohexanecarboxylic acid, such as the nitrile I a and the esters 1 b-d. We found that these C-nitroso compounds also form nitroxides upon thermal decomposition.
IFrom the ESR and W spectra the complex TiCI,(CH,CN), is shown, by means of the crystal-field theory, to have the configuration with Czv symmetry rather than that with C,, symmetry. The ESR and W spectra of the ion [TiCI,(CH,CN),]+, formed by adding a chlorine ion acceptor (e.g. TiCI,, SnCI,, AICI,, FeCI,) to a solution of anhydrous TiCI, in acetonitrile, could be calculated from the crystal-field parameters, which were determined from the spectra of TiCI, (CH,CN)
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