Mechanism of oxidation of trialkylamines by ferricyanide in aqueous solution

1983 ◽  
Vol 48 (7) ◽  
pp. 992-995 ◽  
Author(s):  
Elizabeth P. Burrows ◽  
David H. Rosenblatt
Keyword(s):  
Aqueous Solution ◽  
Mechanism Of Oxidation

Study of aerobic oxidation of phenyl PtII complexes (dpms)PtIIPh(L) (dpms = di(2-pyridyl)methanesulfonate; L = water, methanol, or aniline)

2009 ◽  
Vol 87 (1) ◽  
pp. 110-120 ◽  
Author(s):  
Julia R Khusnutdinova ◽  
Peter Y Zavalij ◽  
Andrei N Vedernikov
Keyword(s):  
Aqueous Solution ◽  
Aerobic Oxidation ◽  
Reductive Elimination ◽  
High Yield ◽  
Ambient Conditions ◽  
Activation Barriers ◽  
Methanol Solutions ◽  
Anionic Species ◽  
Mechanism Of Oxidation ◽  
Solution Mechanism

Oxidation of phenyl PtII complexes K[(dpms)PtIIPh2], 1, (dpms)PtIIPh(MeOH), 2, (dpms)PtIIPh(OH2), 3, and methyl PtII complex (dpms)PtIIMe(NH2Ph), 6, with O2 in aqueous or methanol solutions under ambient conditions leads to corresponding (dpms)PtIVR(X)OH complexes (R = X = Ph, 7; R = Ph, X = OH, 8; R = Ph, X = OMe, 9; R = Me, X = NHPh; 11; dpms = di(2-pyridyl)methanesulfonate). Complexes 7–9 could be isolated in high yield. Complex 11 as well as its phenyl analogue (dpms)PtIVPh(NHPh)OH, 10 can be prepared in high yield by oxidation of corresponding (dpms)PtIIR(NH2Ph) with H2O2 in methanol. Phenyl PtII complexes (dpms)PtIIPh(HX) derived from HX = aniline and DMSO, 4 and 5, respectively, are inert toward O2. The rate of oxidation of 1–5 with O2 decreases in the order 1 > 3 ~ 2 » 4, and 5 is unreactive. Methyl analogues are significantly more reactive compared with their phenyl counterparts. Proposed mechanism of oxidation with O2 includes formation of anionic species (dpms)PtIIR(X)– responsible for reaction with dioxygen. Attempts at C–O and C–N reductive elimination from phenyl PtIV complexes 7–10 do not lead to phenyl derivatives PhX at 80–100 °C, consistent with the results of the DFT estimates of corresponding activation barriers, ΔG0 exceeding 28 kcal/mol.Key words: platinum phenyl complexes, oxidation, dioxygen, aqueous solution, mechanism.

ChemInform Abstract: STUDY OF THE KINETICS AND MECHANISM OF OXIDATION OF 1,1-DIMETHYLHYDRAZINE BY OZONE IN AN AQUEOUS SOLUTION

1976 ◽  
Vol 7 (16) ◽  
pp. no-no
Author(s):  
T. F. LYSENKO ◽  
L. F. ATYAKSHEVA ◽  
B. V. STRAKHOV ◽  
G. I. EMEL'YANOVA
Keyword(s):  
Aqueous Solution ◽  
Kinetics And Mechanism ◽  
Mechanism Of Oxidation

Amine autoxidation in aqueous solution

1983 ◽  
Vol 36 (4) ◽  
pp. 719 ◽  
Author(s):  
ALJ Beckwith ◽  
PH Eichinger ◽  
BA Mooney ◽  
RH Prager
Keyword(s):  
Aqueous Solution ◽  
Electron Transfer ◽  
Free Radical ◽  
Electron Acceptors ◽  
Hydroxyl Groups ◽  
Free Base ◽  
Strong Electron ◽  
Radical Initiators ◽  
Mechanism Of Oxidation ◽  
Radical Traps

The uncatalysed autoxidation of aqueous solutions of tertiary aliphatic amines has been studied in order to obtain information concerning the mechanism of oxidation of Sirotherm resins. Oxidation occurs most rapidly in the free base, and the general correlation of rate with pK, or ionization potential suggests that electron transfer to form an aminium radical cation is rate-determining. The reaction is not initiated by free radical initiators, nor inhibited by radical traps. It is significantly catalysed by strong electron acceptors and by light and is moderately inhibited by the electron donor N-phenylanthranilic acid. Pyrrolidines and hexahydroazepines are oxidized faster than piperidines, and hydroxyl groups on β-carbons increase the rate of oxidation, while those on γ-carbons decrease it. The major products of autoxidation of alkyl pyrrolidines in water were found to be N-oxides. Various pyrrolidinones were isolated in smaller yield.

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