6111-88-2Relevant articles and documents
Reaction of Azoalkanes with Isolable Cation Radical Salts
Engel, Paul S.,Robertson, Donald M.,Scholz, John N.,Shine, Henry J.
, p. 6178 - 6187 (2007/10/02)
Three tertiary azoalkanes related in the sense acyclic, cyclic, and bicyclic are shown to evolve nitrogen upon oxidation with stable cation radical salts.Thus azo-tert-octane (ATO), 3,3,6,6-tetramethyl-1,2-diazacyclohexene (TMDAC), and 1,4-dimethyl-2,3-diazabicyclooct-2-ene (Me2DBO) react rapidly with thianthrenium perchlorate (Th(.1+)ClO4(1-)), tris(p-bromophenyl)aminium hexachloroantimonate (TBPA(.1+)SbCl6(1-)), and TBPA(.1+)SbF6(1-).The ether and olefin products, which are formed in high yield in CH2Cl2/MeOH solvent, are not those expected from the usual free-radical decomposition of azoalkanes but instead implicate carbocations.Althrough the reaction stoichiometry clearly requires 2 equiv of cation radical salt to one of azoalkane, the mechanism is not yet clearly defined.A complication in these studies is found in the ability of certain cation radical salts to oxidize more azoalkane than expected based on the 2:1 stoichiometry.
MECHANISMS OF FREE-RADICAL REACTIONS. XV. SELECTIVITY OF THE FREE-RADICAL CHLORINATION OF ALIPHATIC HYDROCARBONS BY ARYLCHLOROIODONIUM CHLORIDES
Dneprovskii, A. S.,Krainyuchenko, I. V.,Kasatochkin, A. N.
, p. 437 - 440 (2007/10/02)
The free-radical chlorination of 2,3-dimethylbutane, 2,2,4-trimethylpentane, adamantane, and cyclohexane by arylchloroiodonium chlorides was investigated by the method of competing reactions.It was shown that the introduction of electron-withdrawing substituents into the arylchloroiodonium chloride leads to an increase in the sensitivity of the process to the polar effect of the substituents in the substrate and to a decrease of the selectivity toward variation in the dissociation energy of the C - H bond.The importance of steric effects in the reaction was noted.
