30341-37-8Relevant academic research and scientific papers
Profiling the oxidative activation of DMSO-F6 by pulse radiolysis and translational potential for radical C-H trifluoromethylation
Santschi, Nico,Jelier, Benson J.,St?helin, Samuel,Nauser, Thomas
, p. 9734 - 9742 (2019)
The oxidative activation of the perfluorinated analogue of dimethyl sulfoxide, DMSO-F6, by hydroxyl radicals efficiently produces trifluoromethyl radicals based on pulse radiolysis, laboratory scale experiments, and comparison of rates of reaction for analogous radical systems. In comparison to commercially available precursors, DMSO-F6 proved to be more stable, easier to handle and overall more convenient than leading F3C-reagents and may therefore be an ideal surrogate to study F3C radicals for time-resolved kinetics studies. In addition, we present an improved protocol for the preparation of this largely unexplored reagent.
Cesium fluoride catalyzed trifluoromethylation of esters, aldehydes, and ketones with (trifluoromethyl)trimethylsilane
Singh, Rajendra P.,Cao, Ganfeng,Kirchmeier, Robert L.,Shreeve, Jean'ne M.
, p. 2873 - 2876 (2007/10/03)
The low reactivity of carboxylic esters toward (trifluoromethyl)trimethylsilane (TMS-CF3) was investigated. A universal cesium fluoride catalyzed procedure for nucleophilic trifluoromethylation was developed. At room temperature (25 °C, with catalytic amounts of cesium fluoride, carboxylic esters were found to react to give the silyl ether intermediates, which afforded the trifluoromethyl ketones after hydrolysis. Sulfonic, sulfinic, and selenic esters also show good reactivity, giving novel trifluoromethylated compounds. The trifluoromethylation method was also applied to aldehydes and ketones, which were transformed to trifluoromethyl silyl ether intermediates and afforded trifluoromethylated alcohols in excellent yields after acid hydrolysis. Ethylene glycol dimethyl ether was used as solvent for solid or high boiling substrates, and benzonitrile was used for the low boiling substrates.
Stable fluorinated sulfuranes and sulfurane oxides. Synthesis and reactions
Kitazume, Tomoya,Shreeve, Jean'ne M.
, p. 2173 - 2176 (2007/10/10)
Bis(trifluoromethyl) sulfide, tetrafluoro-1,3-dithietane, and bis(trifluoromethyl) sulfoxide undergo oxidative addition when photolyzed with trifluoromethyl hypochlorite to form a new family of sulfuranes, bis(trifluoromethyl)bis(trifluoromethoxy)sulfurane (1) and tetrafluoro-1,3-tetrakis(trifluoromethoxy)dithietane (3), and of sulfurane oxides, bis(trifluoromethyl)bis(trifluoromethoxy)sulfurane oxide (2). Compounds 1 and 2 are hydrolyzed to bis(trifluoromethyl) sulfoxide and bis(trifluoromethyl) sulfone, respectively. Pyrolysis of 1, 2, or 3 gives bis(trifluoromethyl) sulfide, bis(trifluoromethyl) sulfoxide, and tetrafluoro-1,3-dithietane, respectively, plus bis(trifluoromethyl) peroxide. With primary amines, 1 and 2 yield N-alkylbis(trifluoromethyl)sulfimides and sulfoxyimides, and with N,N′-diethylaminotrimethylsilane, imine formation occurs. Sulfurane oxide 2 forms a new type of stable sulfurane oxide (4), bis(trifluoromethyl)bis(hexafluoroisopropylidenimido)sulfurane oxide, with lithium hexafluoroisopropylidenimine. Sulfurane 1 acts in a similar manner with the nucleophile but the sulfurane 5 is not isolated. Compounds 1 and 2 form α,α,α-(trifluoromethyl)anisole derivatives with substituted phenols. Secondary and tertiary alcohols are dehydrated by 1 or 2 to olefins but symmetrical alkyl ethers result when primary alcohols are reacted.
Trifluoromethanesulfonates of iodine
Dalziel,Aubke
, p. 2707 - 2711 (2008/10/08)
Iodine tris(trifluoromethanesulfonate), I(OSO2CF3)3, is obtained in the oxidation of iodine by stoichiometric amounts of S2O6F2 in trifluoromethanesulfonic acid, as a sparingly soluble precipitate. The compound is thermally stable up to +170° and its vibrational spectrum indicates the presence of both monodentate and bidentate bridging SO3CF3 groups. Reaction with the stoichiometric amount of iodine at +140° results in the formation of iodine(I) trifluoromethanesulfonate. Several routes to salts of the type MI[I(OSO2CF3)4], with MI = K, Rb, or Cs, are also described. Vibrational spectra for these and for IOSO2CF3 are reported.
