Oxidation of Cyclanols by V^V

Abstract

The kinetics of oxidation of cyclanols by Vv in acetic acid ‐ water mixtures at constant acidity is reported. The results are discussed in the light of I strain hypothesis. The postulated mechanism of Waters for cyclanol oxidation is also discussed with reference to this series of alcohols.

Oxidation of aniline and other primary aromatic amines by manganese dioxide

“…Those substituents that are considered classical electron-withdrawing groups make reductive dissolution of manganese dioxide by phenol or aniline more difficult by decreasing electron density, while the opposite effect on dissolution rate occurs for classical electron-donating groups. Similar orders of relative reactivity have been obtained for the oxidation of substituted anilines in dilute acetic acid medium by thallium triacetate and sodium iodate (16,17).…”

“…Toxic metals such as As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Se, U, and Zn from fossil-and nuclear-fuel cycle waste streams, geothermal fluids, and electroplating wastes are currently removed by coprecipitation with ferric iron or are under consideration for such treatment (3,(15)(16)(17).…”

Structure−Reactivity Correlation of Anilines in Acetic Acid

“…The oxidations by hydrogen peroxide catalyzed by methylrhenium trioxide (methanol, F ) -1.2), 13 peracetic acid (ethanol, F ) -1.9), 14 iodosobenzene (chloroform, F ) -1.6; manganese(III)salen complex-catalyzed, methylene chloride, F + ) -0.8), 15 lead-(IV) acetate (chloroform-acetic anhydride, F ) -2.4), 16 and pyridinium chlorochromate (chlorobenzene-nitrobenzene, 10 3 [Cl 2 CHCOOH] ) 3 ( 0.5 mol dm -3 , F -) -3.8) 17 were in nonaqueous media. Similar studies in acid medium include chloramine-T (aqueous acetic acid, 10 2 -[HClO 4 ] ) 0.62-5.0 mol dm -3 ), 18 N-chlorosuccinimide (acetic acid, F ) -1.5), 19 bromate ion (aqueous acetic acid, F ) 1.7), 20 iodate catalyzed by ruthenium(III) (aqueous acetic acid, 10 2 [HClO 4 ] ) 1.0 mol dm -3 , F ) -2.8), 21 periodate (aqueous acetic acid, F + ) -2.3), 22 peroxodisulfate (aqueous acetic acid, F ) 1.9), 23 thallium(III) (aqueous acetic acid, [HClO 4 ] ) 1.0 mol dm -3 , F ) -3.0), 24 thallium(III) catalyzed by ruthenium(III) (aqueous acetic acid, [HClO 4 ] ) 1.0 mol dm -3 , F ) -0.8), 24 and iron(III)bipyridyl (aqueous methanol, 10 2 [HClO 4 ] ) 1.2 mol dm -3 , F + ) -3.1). 25 But the present study reveals that the hitherto followed method of correlation of the reaction rates in acidic solution is erroneous and presents a modified approach.…”