On the isolation and characterization of methyl (trifluoromethyl) dioxirane

Thianthrene 5‐Oxide as a Mechanistic Probe in Oxygen Transfer Reactions: The Case of Carbonyl Oxides versus Dioxiranes Revisited

“…The concentration of the dioxiranes in the ketone solution was determined iodometrically. Caroate (potassium monoperoxysulfate, the triple salt 2KHSO,~KHSO,.K,SO,) for the synthesis of DMD [28], TFD [29,20], and the other dioxiranes [30a] was obtained from Peroxid Chemie (D-82049 Pullach, Germany) and used as received. 1,l.l-Trifluoroacetone, which was usually not contamined by ether, was obtained from FLUKA [30b].…”

Competing [2 + 3] and [4 + 3] cycloadditions of C,N-diphenylnitrone with 1,3-dienes. Evidence for thermally nonequilibrated intermediates

“…Kinetics of the Cycloadditions and Thermolyses of the Cycloadducts: The Intermediate Diradicals Are Not Thermally Equilibrated. Second-order rate constants k2(2a) = 1.1 X M-ls-l, k2(2b) = 3.3 X 10"' M-ls-l, and k2(2f) = 4.4 X M-ls-l were determined for the reactions of diphenylnitrone 1 with the dipolaro- (11) Morita, T.; Okamoto, Y.; Sakurai, H. Synthesis 1981, 32. (12) Estimated from kz at 100 O C assuming AS* = -28 cal mol-' K-l: (13) At somewhat higher temperature (100 "C), rearrangements and/or decompositions of some of the cycloadducts take place, as shown in Table V.…”

Dioxirane oxidation of sulfur-containing organic compounds

“…Another widely used dioxirane is methyl(trifluoromethyl)dioxirane (TFD) (2) first synthesized in the laboratory of Mello 25 by the oxidation of 1,1,1-trifluoropropanone with potassium monoperoxysulfate. Its concentration was ca.…”