Nitroso-trifluoromethane

Finally mixing of aliphatic or aromatic nitroso compounds with benzene sulfinic acid leads immediately to formation of benzene-sulfonylaminyloxides75. Aminyl-oxide anion 62 was detected when nitrosobenzene was allowed to react with aqueous hydrogensulfite in presence of lead dioxide76. With nitroso trifluoromethane radical 63 was formed. With tetraphenylarsonium cation this radical anion even formed a solid, paramagnetic precipitate77. ... 

Trifluoronitrosomethane, CFsNO, mw 99.02 bright blue, fairly stable gas, very irritant fr p —150°, bp —84°. Can be prepd by interaction of iodo (or bromo) trifluoromethane with nitric oxide in the presence of UV light. Serves as a monomer for nitroso rubber as a military poison Refs 1) Beil 1, il05i <99 > 2) Cond-... 

Pyruvate ketals can be synthesized [161] by direct condensation of a pyruvate ester with a diol in the presence of a Lewis acid, but this is less preferred because of the electron-withdrawing effect of the adjacent carboxylate group [162,163]. Therefore, several indirect methods for the acetalization have been introduced including condensation with pyruvate derivatives [164,165] or generation of the carboxylate group by oxidation of a suitable precursor [166,167,168,169]. A more efficient route to pyruvic acid acetals starts from silylated diols [170] or by the reaction between diols and methyl pyruvate dialkyl dithioacetal [171,172] activated by methyl triflate, dimethyl(methylthio)sulfonium trifluoromethane sulfonate (DMTST), nitroso tetraflu-oroborate (NOBF4), S02Cl2-trifluoromethanesulfonic acid, or Al-Iodosuccinimide (NIS) and trifluoromethanesulfonic acid [173] (O Scheme 24). 

Photolysis of perfluoroalkylsulfonyl bromide (11) [10], perfluoroazoalkanes (12) [11], hexafluoroacetone (13) [12], and N-nitroso-N-(trifluoromethyl)trifluoromethane sulfonamide (14) [13] also generates Rf radicals (Scheme 1.67). 

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