An analytical model for mechanochemical reaction kinetics

Author(s):  
Maria Carta ◽  
Francesco Delogu ◽  
Andrea Porcheddu

With its ability to enable solvent-free chemical reactions, mechanochemistry promises to open new and greener synthetic routes to chemical products of industrial interest. Its practical exploitation requires understanding the relationships...

2019 ◽  
Vol 16 (1) ◽  
pp. 130-135 ◽  
Author(s):  
Jack van Schijndel ◽  
Dennis Molendijk ◽  
Luiz Alberto Canalle ◽  
Erik Theodorus Rump ◽  
Jan Meuldijk

Aim and Objective: Because of the low abundance of 3,4-unsubstituted coumarins in plants combined with the complex purification process required, synthetic routes towards 3,4-unsubstituted coumarins are especially valuable. In the present work, we explore the possibilities of a solvent-free Green Knoevenagel condensation on various 2-hydroxybenzaldehyde derivatives and malonic acid without the use of toxic organocatalysts like pyridine and piperidine but only use ammonium bicarbonate as the catalyst. Materials and Methods: To investigate the scope of the Green Knoevenagel condensation for the synthesis of 3,4-unsubstituted coumarins, various 2-hydroxybenzaldehyde derivatives were screened as starting material in the optimized two-step procedure developed for 2-hydroxybenzaldehyde. </P><P> Results: This study shows that the intramolecular esterification and the decarboxylation are in competition, but show different temperature optima. In order to suppress premature decarboxylation and maximize the yield of coumarin, a two-step procedure was adopted. The reaction mixture containing ammonium bicarbonate is initially kept at 90ºC for 1 hour. After completion of the cyclization, the temperature of the reaction mixture is increased to 140ºC for 2 hours. Following this protocol, coumarin could be isolated with a yield of 95%. Conclusion: A two-step procedure for the solvent-free synthesis of several 3,4-unsubstituted coumarins was developed using ammonium bicarbonate, resulting in high yields of the desired products. Moreover, this procedure has a low E-factor and is, therefore an environmental friendly reaction in line with the principles of Green Chemistry. It was shown that by initially capping the temperature at 90ºC, premature decarboxylation can be suppressed. After full conversion to the intermediate 3-carboxycoumarin, the temperature can be increased to 140ºC finalizing the reaction. Ammonium bicarbonate was shown to catalyze both the Green Knoevenagel condensation and the decarboxylation step.


1981 ◽  
Vol 18 (01) ◽  
pp. 263-267 ◽  
Author(s):  
F. D. J. Dunstan ◽  
J. F. Reynolds

Earlier stochastic analyses of chemical reactions have provided formal solutions which are unsuitable for most purposes in that they are expressed in terms of complex algebraic functions. Normal approximations are derived here for solutions to a variety of reactions. Using these, it is possible to investigate the level at which the classical deterministic solutions become inadequate. This is important in fields such as radioimmunoassay.


2005 ◽  
Vol 237-240 ◽  
pp. 145-150 ◽  
Author(s):  
Sébastien Garruchet ◽  
A. Hasnaoui ◽  
Olivier Politano ◽  
Tony Montesin ◽  
J. Marcos Salazar ◽  
...  

In this paper we give a brief presentation of the approaches we have recently developed on the oxidation of metals. Firstly, we present an analytical model based on non-equilibrium thermodynamics to describe the reaction kinetics present during the oxidation of a metal. Secondly, we present the molecular dynamics results obtained with a code specially tailored to study the oxidation and growth of an oxide film of aluminium. Our simulations present an excellent agreement with experimental results.


2018 ◽  
Vol 14 ◽  
pp. 2396-2403 ◽  
Author(s):  
Md Toufique Alam ◽  
Saikat Maiti ◽  
Prasenjit Mal

Performing any synthesis using several arylamines and hypervalent iodine(V) reagents by direct mixing is unrealistic because of the high exothermic reaction or explosion. Herein we demonstrate, when anilines were substituted with an amide group at the ortho-position, successful chemical reactions could be performed due to intramolecular control. At maximum contact of the reacting substances, i.e., under solvent-free mechanochemical conditions, 2-aminobenzamides, aryl-, alkylaldehydes and the iodine(V) reagent o-iodoxybenzoic acid (IBX) led to substituted quinazolin-4(3H)-one derivatives in fair yields.


Author(s):  
W. Ronald Fawcett

The kinetics of chemical reactions were first studied in liquid solutions. These experiments involved mixing two liquids and following the change in the concentration of a reactant or product with time. The concentration was monitored by removing a small sample of the solution and stopping the reaction, for example, by rapidly lowering the temperature, or by following a physical property of the system in situ, for example, its color. Although the experiments were initially limited to slow reactions, they established the basic laws governing the rate at which chemical changes occur. The variables considered included the concentrations of the reactants and of the products, the temperature, and the pressure. Thus, the reacting system was examined using the variables normally considered for a system at equilibrium. Most reactions were found to be complex, that is, to be made up of several elementary steps which involved one or two reactants. As the fundamental concepts of chemical kinetics developed, there was a strong interest in studying chemical reactions in the gas phase. At low pressures the reacting molecules in a gaseous solution are far from one another, and the theoretical description of equilibrium thermodynamic properties was well developed. Thus, the kinetic theory of gases and collision processes was applied first to construct a model for chemical reaction kinetics. This was followed by transition state theory and a more detailed understanding of elementary reactions on the basis of quantum mechanics. Eventually, these concepts were applied to reactions in liquid solutions with consideration of the role of the non-reacting medium, that is, the solvent. An important turning point in reaction kinetics was the development of experimental techniques for studying fast reactions in solution. The first of these was based on flow techniques and extended the time range over which chemical changes could be observed from a few seconds down to a few milliseconds. This was followed by the development of a variety of relaxation techniques, including the temperature jump, pressure jump, and electrical field jump methods. In this way, the time for experimental observation was extended below the nanosecond range.


2011 ◽  
Vol 12 (1) ◽  
pp. 44-48 ◽  
Author(s):  
Dominik Cinčić ◽  
Ivana Brekalo ◽  
Branko Kaitner

2017 ◽  
Vol 53 (92) ◽  
pp. 12477-12480 ◽  
Author(s):  
Hui Xu ◽  
Hong-Wei Liu ◽  
Hao-Sheng Lin ◽  
Guan-Wu Wang

A solvent-free mechanochemical reaction of alkylidene oxindoles with enamino esters via an iodine-promoted tandem Michael/cyclization sequence has been developed to provide a variety of spirocyclic oxindoles in moderate to good yields with excellent diastereoselectivities.


2003 ◽  
Author(s):  
George S. Dulikravich ◽  
Marcelo J. Colac¸o

A complete and consistent mathematical model of multiphase flows allowing for chemical reactions and/or phase changes has been derived from basic continuum mechanics principles. Comparison of elements of this model with models published by other sources has been elaborated. A set of analytic relations linking mixture and fluid components has been derived. Conclusions about closure of the system have been drawn based on these derivations.


Sign in / Sign up

Export Citation Format

Share Document