Kinetics and mechanisms of oxidation of 1-octene and heptanal by crown ether-solubilized potassium permanganate in non-aqueous solvents

The kinetics of oxidation of 1-octene and heptanal by 18-crown-6-ether-solubilized KMnO₄ in benzene and CH₂Cl₂ have been investigated. In benzene, the oxidation of 1-octene is first order with respect to the oxidant and zero order with respect to the substrate, whereas in CH₂Cl₂ the reaction is first order with respect to both substrate and oxidant. The reaction of heptanal followed different kinetics being first order with respect to both substrate and oxidant, regardless of whether benzene or CH₂Cl₂ was employed as the solvent. The values of activation energy E _a, standard enthalpy H ^*, standard entropy change S ^*, and standard free energy G ^*, for the reaction, are reported. Mechanistic pathways for the studied reactions are also proposed.     

Osmium(VIII)-Catalyzed Oxidation of Some Cyclic Amines by Potassium Hexacyanoferrate(III) in Alkaline Media: a Kinetics and Mechanistic Study

Reactions of morpholine, piperidine, and piperazine with Os(VIII)-catalyzed hexacyanoferrate(III) in alkaline media to produce the corresponding lactam have been studied at constant temperature and ionic strength. The reactions followed first-order kinetics with respect to [amine] and [Os(VIII)] but were independent of [Fe(CN)₆ ^3-] and [OH^-]. The effects of introduced electrolytes, potassium hexacyanoferrate(II), relative permitivity, and temperature have also been studied. A mechanism accounting for these results has been proposed.     

Reaction of octafluorotoluene, 3,5-dichlorotrifluoropyridine, 3-chlorotetrafluoro-yridine and tetrafluoropyrimidine with alkali-metal oximates

Treatment of octafluorotoluene (2) with approximately one-molar equivalents of the oximates R¹R²C = NO~ M⁺ (R¹ = R²=Me;R¹ = R² = Ph; R¹ = Me, R² = Ph;M = Na) (6a-c) in diethyl ether gives 4-(R¹R²C = NO)C₆F₄CF₃ (7a-c) as the only isolated products. Corresponding reaction of 3,5-dichlorotrifluoropyridine (3) with the oximates 6a-c affords 4-and 2-(R¹R²C = NO)C5F₂C12N (8a-c) and (9a-c), respectively (4-/2ratios at −35 °C: 65:35; 30:70; 12:88) ; the lithium oximates (R¹ = R² =Ph ; R¹ = Me, R² = Ph; M = Li) (6d) and (6e) give comparable results. With 3-chlorotetrafluoropyridine (4), treatment with sodium oximate 6c gives 4-(PhCMe = NO)-3-ClC₅F₃N (10) and 2-(PhCMe = NO)-5ClC₅F₃N (11) (ratio 44:56 at −35 °C). Such competition between S_NAr attack of these alkali-metal oximates at the C-4 and C-2 positions of chlorofluoropyridines 3 and 4 can be rationalized by invoking chelation of an alkali-metal cation with ring nitrogen in the transition state leading to formation of an orthio-quinonoidal σ-complex. Exclusive initial attack at the C-4 ring site appears to occur in the reaction of tetrafluoropyrimidine (5) with oximates 6a and 6c to afford 4-(MeC = NO)C₄F₃N₂ (12a) and 4-(PhCMe=NO)C₄F₃NN₂ (12b), respectively; Some further attack on product 12b by oximate 6c at the C-6 site takes place to give the disubstituted derivative 4,6-(PhCMe=NO)₂C₄F₂N₂ (13).