Ion radicals. XXXV. Reactions of thianthrene and phenoxathiin cation radicals with ketones. Formation and reactions of .beta.-ketosulfonium perchlorates and ylides

Oxidative Cleavage ofβ-Keto Sulfones via Nitrous Acid

“…-Keto sulfones 3a-e were synthesized by the reaction of 2-bromo-1-arylethanone 1a-e with the appropriate sodium arylsulfinate 2a, b according to the reported method [10][11][12][13][14][15]. Treatment of -keto sulfones 3a-e with sodium nitrite, in acetic acid containing sulfuric acid, afforded the corresponding carboxylic acids 12a-e in addition to formic acid (14) and benzene/4-toluenesulfinic acid 15a, b (Figure 1).…”

“…Ethanones 3a-f. These compounds were prepared according to the reported method [10][11][12][13][14][15].…”

“…To a stirred cold solution of -keto sulfones 3a-f [10][11][12][13][14][15] (10 mmol) in glacial acetic acid (20 mL), sulfuric acid (1 mL, 50%) was added. Then cold solution of sodium nitrite (0.7 g, 10 mmol) in water (5 mL) was added dropwise with stirring at such a rate that the temperature remains in the range 0-5 ∘ C. Over a period of 30 min, a light blue solution of nitrous acid is produced.…”

Hypervalent Iodine(III) Sulfonate Mediated Synthesis of α‐Thiocynanatoketones in a Task‐Specific Ionic Liquid [bmim]SCN

“…The resulting residue was chromatographed on silica gel column eluting with AcOEt: n-hexane (1:1) to give 3a, mp 69-70°C (lit. 12…”

Reactions of thianthrene cation radical tetrafluoroborate with aldehydes: formation of α-(5-thianthreniumyl)aldehyde tetrafluoroborates – a facile synthesis of α-ketols through Lobry de Bruyn–van Ekenstein rearrangement

“…About 30 years ago, one of us reported that reactions of thianthrene-(Th •+ ), phenoxathiin-, N-methylphenothiazine-, and N-phenylphenothiazine cation radical perchlorates with ketones gave β-ketosulfonium salts 1-4 ( Figure 1) (1)(2)(3)(4). The reactions were described as probably beginning with the addition of the cation radical to the enolic form of the ketone (3), which has been supported in later work by Wayner (5).…”