638. The separation of polar and steric effects. Part IV. The kinetics of the alkaline hydrolysis of methyl arylaliphatic carboxylates, and the ionization of arylaliphatic carboxylic acids

Author(s):  
K. Bowden ◽  
N. B. Chapman ◽  
J. Shorter
1962 ◽  
Vol 16 ◽  
pp. 1927-1935 ◽  
Author(s):  
Bertil Hansen ◽  
Peter Klæboe ◽  
Lynn Wolf ◽  
Carl Djerassi ◽  
Olof Theander ◽  
...  

1966 ◽  
Vol 44 (6) ◽  
pp. 661-669 ◽  
Author(s):  
Keith Bowden

The rate coefficients for the acid-catalyzed esterification in methanol at 35.0° of fourteen 3-substituted acrylic acids have been determined. Rate coefficients have also been determined for the alkaline hydrolysis in 70% v/v dioxin–water at 18.8° of 13 methyl esters and the carbonyl-stretching frequencies of the esters have been examined. The effect of trans-substitution is assessed by use of the Hammett equation. In the alkaline hydrolysis, the transmission of polar effects is approximately 1.9 that of the meta- and para-substituted benzoates. An analysis of the steric effects in the cis-isomers in both reactions shows that the steric effects of the halogeno-substituents in the two reactions differ and an explanation is offered. The application of the Taft–Ingold equation to ortho-substituted benzoates is criticized. The carbonyl-stretching frequencies of the cis-halogeno-esters exhibit a shift of +8 cm−1 compared with the trans-isomers; this shift is attributed to an electrostatic effect.


1980 ◽  
Vol 45 (11) ◽  
pp. 2873-2882
Author(s):  
Vladislav Holba ◽  
Ján Benko

The kinetics of alkaline hydrolysis of succinic acid monomethyl and monopropyl esters were studied in mixed aqueous-nonaqueous media at various temperatures and ionic strengths. The results of measurements are discussed in terms of electrostatic and specific interactions between the reactants and other components of the reaction mixture. The kinetic parameters in the media under study are related to the influence of the cosolvent on the solvation sphere of the reactants.


1963 ◽  
Vol 28 (10) ◽  
pp. 2825-2828 ◽  
Author(s):  
Stanley G. Smith ◽  
Marion O'Leary

2013 ◽  
Vol 60 (2) ◽  
pp. 43-48
Author(s):  
Stankovičová M. ◽  
Bezáková Ž. ◽  
Beňo P. ◽  
Húšťavová P.

Abstract The substance BK 129 - 1-[2-(2-pentyloxyphenylcarbamoyloxy)-(2-methoxymethyl)-ethyl]-perhydroazepinium chloride was prepared in terms of influence of the connecting chain between the carbamate functional group and the basic part of molecule on biological activity. Such a structural feature is important with regard to its stability. In this work we determined the rate constants of alkaline hydrolysis of this compound at increased temperature under isothermal and non-isothermal conditions. The hydrolysis was also performed in buffer solutions with the purpose of evaluating its stability. Non-isothermal tests of stability enable to reduce the number of analyses. The necessary data for stability of compound are in this way achieved in a short time.


1992 ◽  
Vol 271 ◽  
Author(s):  
Charles D. Gagliardi ◽  
Dilum Dunuwila ◽  
Beatrice A. Van Vlierberge-Torgerson ◽  
Kris A. Berglund

ABSTRACTTitanium alkoxides modified by carboxylic acids have been widely studied as the molecular precursors to ceramic materials. These alkoxide complexes have also been very useful in the formation of stable, porous, optically clear films having many novel applications such as chemical sensors, catalytic supports, and ion-exchange media. To improve the processing of these materials, it is essential to better understand the kinetics of the chemical transformations which occur.The kinetics of the hydrolysis reaction are studied for selected carboxylic acids using Raman spectroscopy to probe the chemistry of the process. The study has a special emphasis on the titanium isopropoxide-valeric acid system due to the superior quality of these films over other carboxylates. Greater knowledge of the hydrolysis kinetics allows increased control over the quality of the film materials and should be of general interest to those working with modified metal alkoxides.


2000 ◽  
Vol 49 (2) ◽  
pp. 265-269
Author(s):  
L. Ya. Zakharova ◽  
F. G. Valeeva ◽  
L. A. Kudryavtseva ◽  
V. E. Bel'skii ◽  
E. P. Zhil'tsova ◽  
...  

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