95115-18-7Relevant academic research and scientific papers
MECHANISM OF CATALYSIS BY 4-DIMETHYLAMINOPYRIDINE IN THE REACTION OF 4-DIMETHYLAMINOBENZOYL CHLORIDE WITH BENZYL ALCOHOLS IN METHYLENE CHLORIDE
Drizhd, L. P.,Bondarenko, L. I.,Litvinenko, L. M.,Savelova, V. A.,Kirichenko, A. I.
, p. 2181 - 2187 (2007/10/02)
The rate constants were measured for the forward and reverse reactions of the equilibrium process leading to the formation of the stable acylammonium salt from 4-dimethylaminobenzoyl chloride and 4-dimethylaminopyridine in methylene chloride at 25 deg C.The process is characterized by a high equilibrium constant (1.7*104 liter/mole).The kinetics of the reaction of the acylammonium salt N-(4-dimethylaminobenzoyl)-4-dimethylaminopyridinium chloride with benzyl alcohols RC6H4CH2OH (R = 4-CH3, H, 4-Br) under the same conditions were studied.It was shown that the process takes place by a stage mechanism; initially the adduct forms a complex with the alcohol reversibly, and the complex then dissociates into the final products in the slow rate-determining stage.This is a feature of nucleophilic catalysis by pyridine bases in the acylation of alcohols by carboxylic acid halides in a proton-inert medium.
NUCLEOPHILIC CATALYSIS IN THE FORMATION OF ESTERS. THE EFFECT OF THE CHARACTERISTICS OF THE MEDIUM
Drizhd, L. P.,Bondarenko, L. I.,Savelova, V. A.,Litvinenko, L. M.,Kirichenko, A. I.,Yakovets, A. A.
, p. 2187 - 2193 (2007/10/02)
The rate constants were determined for the individual stages of nucleophilic catalysis by 4-dimethylaminopyridine in the reaction of 4-dimethylaminobenzoyl chloride with benzyl alcohol in volume mixtures of methylene chloride with benzene (1:1, 1:5, 1:9) at 25 deg C.The corresponding acylpyridinium salt is formed in all the solvents.In the subsequent fast equilibrium stage it forms a complex, which dissociates slowly into the final reaction products.Suggestions are made about the structures of the respective transition states on the basis of the nature of variation in the rate constants of the individual stages as a function of the solvating power of the medium.
