65538-01-4Relevant articles and documents
Novel reactions of perfluoroalkylphenyl sulfides with organolithium reagents
Munavalli, S.,Hassner, A.,Rossman, D. I.,Singh, S.,Rohrbaugh, D. K.,Ferguson, C. P.
, p. 7 - 12 (1995)
The reaction of anisole with organolithium reagents, commonly known as ortho-directed metallation, is of considerable synthetic utility in organic chemistry and as such has attracted considerable attention in recent years.Over the past 50 years, several mechanisms have been proposed to account for the observed regioselective metallation.For the first time, the reaction of perfluoroalkylphenyl sulfides with organolithium reagents has been investigated and found to furnish products resulting from the replacement of the perfluoroalkyl moieties with alkyl groups derived from the metallating agents.Phenyltrifluoromethyl ether, the anisole analog, failed to undergo metallation.A rationalization for the formation of unusual products via mediation of a single-electron-transfer process is presented in this paper together with the spectral data of the products. - Keywords: Reactions; Perfluoroalkylphenyl sulfides; Organolithium reagents; NMR spectroscopy; Mass spectrometry; Orthometallation
Ion-radical perfluoroalkylation. Part 11. Perfluoroalkylation of thiols by perfluoroalkyl iodides in the absence of initiators
Boiko, V. N.,Shchupak, G. M.
, p. 207 - 212 (2007/10/02)
Perfluoroalkylation of aliphatic, aromatic and heterocyclic thiols by perfluoroalkyl iodides in the presence of Et3N appears to occur spontaneously under daylight or the usual laboratory lighting conditions at 20-22 deg C and is complete in 10-15 min to 2-3 h.An exception to this rule are thiols with a low nucleophilicity.The reaction is accompanied by thiol oxidation (2percent-3percent) and depends directly on the temperature, lighting, solvent polarity and electronic properties of the perfluoroalkylating agents and of the thiol substituents.At the same time, formation of diaryl disulphides frequently occurs contrary to above rules.The reaction mechanism is discussed. - Keywords: Ion-radical perfluoroalkylation; Thiols; Perfluoroalkyl iodides; Reaction mechanism; Nucleophilicity; NMR spectroscopy
Phase-Transfer Catalysed Ion-Radical Perfluoroalkylation of Thiols
Popov, V. I.,Boiko, V. N.,Yagupolskii, L. M.
, p. 365 - 370 (2007/10/02)
It has been shown that under conditions of phase-transfer catalysis under UV-irradiation perfluoroalkyl iodides react with aliphatic and aromatic thiols in the water-organic solvent media to form alkyl or aryl perfluoroalkyl sulfides in 60-80 percent yields.
