Kinetics and thermodynamics of keto-enol tautomerism of simple carbonyl compounds: an approach based on a kinetic study of halogenation at low halogen concentrations

1981 ◽  
Vol 103 (18) ◽  
pp. 5393-5401 ◽  
Author(s):  
Jacques Emile Dubois ◽  
Mohiedine El-Alaoui ◽  
Jean Toullec
1980 ◽  
Vol 58 (1) ◽  
pp. 55-59 ◽  
Author(s):  
Bernard Boyer ◽  
Gérard Lamaty ◽  
Jean-Pierre Roque ◽  
Patrick Geneste

A kinetic study of the addition reactions of borohydride and sulfite ions and of hydroxylamine to a number of stereospecifically deuterated carbonyl compounds (3,3,5,5-tetramethyl cyclohexanone, 7,7-d2-bicyclo[2,2,1]-2-bornanone) leads to the observation of a distant secondary deuterium isotope effect. The results obtained reveal the intervention of a directional effect in the steric origin of these isotope effects. In particular, this study shows the importance of the orientation of the vibrations brought into play by a C—D bond during the reaction process. (Journal translation)


2011 ◽  
Vol 8 (3) ◽  
pp. 1102-1107
Author(s):  
B. Mohammed Nawaz ◽  
K. Subramani ◽  
Mansur Ahmed

Pyridinium fluorochromate (PFC) oxidation of pentaamminecobalt(III) complexes of α-hydroxy acids in micellar medium yielding nearly 100% of carbonyl compounds are ultimate products. The decrease in UV-visible absorbance at λ=502 nm for Co(III) complex corresponds to nearly 100% of the initial absorbance. The stoichiometry of unbound ligand and cobalt(III) complex is accounting for about 100% reduction at the cobalt(III) centre. The kinetic and stoichiometric results have been accounted by a suitable mechanism.


1966 ◽  
Vol 44 (23) ◽  
pp. 2793-2803 ◽  
Author(s):  
A. William Johnson ◽  
Simon C. K. Wong

The pKa values of two series of iminophosphoranes, N-(substituted phenyl)-iminotriphenylphosphoranes (VI) and N-phenyliminotri-(substituted phenyl)-phosphoranes (VII), have been correlated with σ0 and σ, respectively, giving ρ values of +3.5 and +9.3. A kinetic study of the reaction of VI and VII with benzaldehydes indicates that a betaine intermediate (V) is involved. The rate-limiting step of the reaction changes, the result of a delicate balance between the nucleophilicity of the nitrogen atom and the electrophilicity of the phosphorus atom. The involvement of dπ–pπ bonding is indicated.


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