5870-61-1Relevant academic research and scientific papers
Ground- and Excited-State Carboxylate Radical Chain Carriers. Radical Chain Substitution Reactions with Acyl Hypohalites
Skell, Philip S.,May, Donald D.
, p. 3999 - 4008 (1983)
Earlier work with aliphatic carboxylate radicals held no prospect that they could be used as hydrogen abstractors in substitution reactions.Contrary to this expectation, acetoxy, propionoxy, isobutyroxy, and pivaloxy are effective in this role.At low temperatures radical chain brominations of alkanes and haloalkanes occur in satisfactory yields when the acyl hypobromites, RCO2Br, are used; the selectivities are independent of the structure of R.Two distinctive hydrogen-abstracting RCO2. are involved in these chain reactions, either the ? or ?a electronic states; which electronic state is the chain carrier is determined in the step RCO2Br + X. -> RCO2. + XBr.These C? and C? radicals resemble tert-butoxy in their hydrogen-abstraction selectivities.The concordance of these results with a state-of-the-art calculation is discussed.
Selective oxidation of alkyl 2,2-dichlorovinyl sulfides to sulfoxides in polyfluorinated solvents
Shainyan,Danilevich
, p. 1749 - 1754 (2007/10/03)
2,2-Dichlorovinyl sulfides are oxidized to the corresponding sulfoxides or sulfones by hydrogen peroxide or tert-butyl hydroperoxide with extremely high selectivity, depending on the solvent. The oxidation in acetic acid yields exclusively sulfones, whereas sulfoxides are the only products obtained in trifluoroacetic acid, trifluoroethanol, and telomeric polyfluorinated alcohols of the general formula H(CF2)nCH2OH. The oxidation mechanism and dependences of the rates of the first and second oxidation stages on the substitution in the vinyl group and solvent nature are discussed. The reaction of ethyl 2,2-dichlorovinyl sulfoxide with bromine gives EtS(O)CHBrCBrCl2 adduct and products of its further transformations.
