18294-87-6Relevant articles and documents
A comparative LSER study of the reactivity of 2-substituted cyclohex- 1-eneacetic and 2-substituted phenylacetic acids with diazodiphenylmethane in various solvents
Nikolic,Uscumlic,Juranic, Ivan O.
, p. 613 - 622 (2009)
The rate constants for the reaction of 2-substituted cyclohex-1-eneacetic and 2- substituted phenylacetic acids with diazodiphenylmethane were determined in various aprotic solvents at 30°C. To explain the kinetic results through solvent effects, the second-order rate constants of the examined acids were correlated using the Kamlet-Taft solvatochromic equation. The correlations of the kinetic data were carried out by means of multiple linear regression analysis, and the solvent effects on the reaction rates were analyzed in terms of initial and transition state contributions. The opposite signs of the electrophilic and the nucleophilic parameters are in agreement with the well-known mechanism of the reaction of carboxylic acids with diazodiphenylmethane. The quantitative relationship between the molecular structure and the chemical reactivity is discussed, as well as the effect of the molecular geometry on the reactivity of the examined compounds.
EtAlCl2/2,6-Disubstituted Pyridine-Mediated Carboxylation of Alkenes with Carbon Dioxide
Tanaka, Shinya,Watanabe, Kota,Tanaka, Yuuki,Hattori, Tetsutaro
supporting information, p. 2576 - 2579 (2016/06/15)
α-Arylalkenes and trialkyl-substituted alkenes undergo carboxylation with CO2 in the presence of EtAlCl2 and 2,6-dibromopyridine to afford the corresponding α,β- and/or β,γ-unsaturated carboxylic acids. This reaction is suggested to proceed via the electrophilic substitution of EtAlCl2 with the aid of the base, followed by the carbonation of the resulting ate complex. This reaction can be applied to terminal dialkylalkenes by using a mixture of 2,6-di-tert-butylpyridine and 2,6-dibromopyridine.
Solvent and structural effects on the activation parameters of the reaction of carboxylic acids with diazodiphenylmethane
Nikolic,Uscumlic
, p. 256 - 265 (2013/04/24)
The kinetics of the reaction of benzoic, 2-methylbenzoic, phenylacetic, cyclohex-1-enecarboxylic, 2-methylcyclohex-1-enecarboxylic, and cyclohex-1-eneacetic acids with diazodiphenylmethane was studied at 30, 33, 37, 40, and 45°C in a set of 12 protic and aprotic solvents. The reactions were found to follow the second-order kinetics. The activation energy as well as the activation parameters, such as the standard entropy, the standard enthalpy, and the standard Gibbs energy of the activation, was calculated from the second-order rate constants. The solvent and structural effects on the activation energy and the standard Gibbs energy of activation, for each examined compound, were analyzed. The results of Kamlet-Taft multiple correlation analysis show that the specific solvent-solute interactions play a dominant role in the governing of the reaction. The signs of the equation coefficients support the proposed reaction mechanism.