445-09-0Relevant articles and documents
Dual Reactivity of the Formyl Cation as an Electrophile and a Broensted Acid in Superacids
Tanaka, Mutsuo,Fujiwara, Masahiro,Ando, Hisanori
, p. 3846 - 3850 (2007/10/02)
The nature of the formyl cation in the Gattermann-Koch formylation was studied by comparing the formylation with the acetylation and sulfonation in CF3SO3H-SbF5 and FSO3H-SbF5, respectively.The results of the kinetic studies in CF3SO3H-SbF5 showed that the formyl cation has dual reactivity as an electrophile and as a Broensted acid.Upon comparing the formylation with the sulfonation in FSO3H-SbF5, it was found that the protonated aromatic compounds also act as Broensted acids to produce formyl cations.Therefore, the formylation has a priority over other typical electrophilic substitutions under conditions where most of aromatic compounds are protonated because the formyl cation is reproduced close to the aromatic compounds by the protonation of CO with not only superacids but also protonated aromatic compounds.
OXIDATION OF METHYL-SUBSTITUTED BENZENESULFONYL FLUORIDES IN THE PbO2-HSO3F SYSTEM
Arapov, O. V.,Rudenko, A. P.,Zarubin, M. Ya.
, p. 152 - 163 (2007/10/02)
The transformations of the sulfonyl fluorides of methyl-substituted benzenes in the PbO2-HSO3F system were studied.They take place through a stage involving the one-electron oxidation of the substrate to aromatic radical-cations.One of the transformation paths of the latter is realized through the elimination of a proton from the methyl groups involved to the greatest degree in the delocalization of the unpaired electron.This leads to the formation of diarylmethanes and the fluorosulfonates of substituted benzyl alcohols, which give substituted tolylsultones and benzyl alcohols during hydrolysis of the acid solution and methyl ethers of benzyl alcohols during methanolysis.The other path, which arises during localization of the unpaired electron in the unsubstituted positions of the benzene ring, leads to biaryls.