The oxidation of ortho-anisidine in alkaline medium. A product characterization and an EPR study

1994 ◽  
Vol 72 (5) ◽  
pp. 1351-1356 ◽  
Author(s):  
Adele Bolognese ◽  
Marina Buonanno ◽  
Antonio Cantilena ◽  
Giovanni Musci ◽  
Angelo Alberti
Keyword(s):  
Aqueous Solution ◽  
Alkaline Medium ◽  
Potassium Ferricyanide ◽  
Azo Compounds ◽  
Radical Mechanism ◽  
Radical Species ◽  
Alkaline Aqueous Solution ◽  
Product Characterization ◽  
Alkaline Oxidation

Alkaline oxidation of ortho-anisidine by potassium ferricyanide in alkaline aqueous solution was examined. Azo compounds, a diamine, and para-iminoquinones were isolated from the highly coloured reaction mixture. The reaction was also carried out within the cavity of an EPR spectrometer and two radical species have been detected. Following these product results and EPR studies, a radical mechanism is proposed for the process.

Oxidation of polysubstituted pyridinium salts

1982 ◽  
Vol 47 (5) ◽  
pp. 1494-1502 ◽  
Author(s):  
Petr Nesvadba ◽  
Josef Kuthan
Keyword(s):  
Alkaline Medium ◽  
Electrophilic Substitution ◽  
Pyridine Ring ◽  
Potassium Ferricyanide ◽  
Pyridinium Salts ◽  
Complex Reaction

Oxidation of 1-substituted 2,4,6-triphenylpyridinium salts Ia-Ij with potassium ferricyanide in an alkaline medium was accompanied by contraction of the pyridine ring and formation of 1,2,3,5-tetrasubstituted pyrroles II. The derivative IIf underwent facile electrophilic substitution in the position 4. Contrary to compounds Ia-Ij, the 1-substituted-2,6-diphenylpyridinium salts IIIa,b were oxidized to give a complex reaction mixture containing 4-pyridones IVa,b.

Ruthenium catalysed oxidation of cyclohexanol

1982 ◽  
Vol 35 (6) ◽  
pp. 1245 ◽  
Author(s):  
P Becker ◽  
JK Beattie
Keyword(s):  
Aqueous Solution ◽  
Isotope Effect ◽  
Phosphate Buffer ◽  
Hydride Transfer ◽  
Deuterium Isotope Effect ◽  
Rate Law ◽  
Alkaline Aqueous Solution ◽  
Catalysed Oxidation

The oxidation of cyclohexanol by ferricyanide in alkaline aqueous solution is catalysed by micromolar concentrations of K3RuCl6. The rate law at 25.0�C in pH 11.9 phosphate buffer containing 0.50 M NaCl is -d[FeIII]/dt = [Ru](2klk2[alcohol][FeIII])/(2kl[alcohol] + k2[FeIII]) with kl 12 � 2 mol-1 1. s-1 and k2 (2.5 � 0.2) × 102 mol-1 1. s-1. A deuterium isotope effect of about 4 is observed when (D12)cyclohexanol is used. A mechanism consistent with these observations involves reduction of the RuIII catalyst by hydride transfer from the alcohol followed by reoxidation by ferricyanide to the original RulIII state.

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