Kinetics and mechanism of the oxidation of unsaturated carboxylic acids by methyltributylammonium permanganate in methylene chloride solutions

1987 ◽  
Vol 52 (15) ◽  
pp. 3239-3243 ◽  
Author(s):  
Joaquin F. Perez-Benito ◽  
Donald G. Lee
Keyword(s):  
Carboxylic Acids ◽  
Methylene Chloride ◽  
Kinetics And Mechanism ◽  
Chloride Solutions ◽  
Unsaturated Carboxylic Acids

Kinetics and Mechanism of Triphenylphosphine Quarternization with Unsaturated Carboxylic Acids in Various Media

2011 ◽  
Vol 186 (4) ◽  
pp. 857-859 ◽  
Author(s):  
Alexey V. Salin ◽  
Alexandr A. Sobanov ◽  
Yulia V. Bakhtiyarova ◽  
Azat A. Khabibullin ◽  
Vladimir I. Galkin ◽  
...  
Keyword(s):  
Carboxylic Acids ◽  
Kinetics And Mechanism ◽  
Unsaturated Carboxylic Acids

Homogeneous Hydrogenation of Unsaturated Carboxylic Acids Using Chlororhodate(I) Complexes and Rhodium(I) Diethylsulfide Complexes

1975 ◽  
Vol 53 (6) ◽  
pp. 797-804 ◽  
Author(s):  
Brian R. James ◽  
Flora T. T. Ng
Keyword(s):  
Carboxylic Acids ◽  
Rate Constants ◽  
Maleic Acid ◽  
Activation Parameters ◽  
Kinetic Studies ◽  
Homogeneous Hydrogenation ◽  
Chloride Solutions ◽  
Rate Determining Step ◽  
Square Planar ◽  
Unsaturated Carboxylic Acids

N,N-Dimethylacetamide solutions of the cyclooctene complex [Rh(C8H14)2Cl]2, in the presence of excess chloride or diethylsulfide, are effective for the homogeneous hydrogénation of unsaturated carboxylic acids at ca. 80 °C and 1 atm H2. Kinetic studies on the hydrogenation of maleic acid are consistent with a rate determining step involving oxidative addition of H2 to square planar rhodium(I) olefin species. Rate constants and activation parameters agree with those determined previously from similar studies using corresponding rhodium(III) complexes and give confirmation that rhodium(I) catalysts are involved in the rhodium(III) systems. Discussion of the systems is limited by the somewhat uncertain nature of the catalysts; however, chlororhodate(I) species are involved in the chloride solutions, and bis(diethylsulfide) complexes appear likely in the sulfide systems.

Solvent Effect on Kinetics and Mechanism of the Phospha-Michael Reaction of Tertiary Phosphines with Unsaturated Carboxylic Acids

2014 ◽  
Vol 25 (3) ◽  
pp. 205-216 ◽  
Author(s):  
Alexey V. Salin ◽  
Albert R. Fatkhutdinov ◽  
Anton V. II'in ◽  
Vladimir I. Galkin ◽  
Fanuza G. Shamsutdinova
Keyword(s):  
Solvent Effect ◽  
Carboxylic Acids ◽  
Michael Reaction ◽  
Kinetics And Mechanism ◽  
Tertiary Phosphines ◽  
Unsaturated Carboxylic Acids

Perturbation theory of substituent effect. Importance of the field effect in transmission of the substituent effect

1980 ◽  
Vol 45 (6) ◽  
pp. 1655-1661 ◽  
Author(s):  
Robert Ponec
Keyword(s):  
Perturbation Theory ◽  
Carboxylic Acids ◽  
Quantum Chemical ◽  
Substituent Effect ◽  
Field Effect ◽  
Adequate Description ◽  
Meta Position ◽  
Unsaturated Carboxylic Acids

Various quantum chemical approaches to the problem of transmission of the substituent effect were compared. It was shown that inclusion of the electronic repulsion (field effect) was necessary to give a true picture of differences in ρ constants for reactions of the cis and trans isomers of substituted unsaturated carboxylic acids; the same holds for an adequate description of transmission of the substituent effect from the meta position on a given skeleton.

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