Elucidation of the Diels–Alder Reaction Kinetics between Diphenylfulvene and Maleimide by Mechanochemistry and in Solution

Abstract

The Diels−Alder reaction kinetics between diphenylfulvene and maleimide using mechanochemistry and in liquid state is described. This reaction was carried out in solid state using a modified vibratory ball-mill with temperature control and in solution with toluene as solvent. The effect of temperature, ball mass, material, additives, and aging reaction were studied. We reported for the first time the kinetics of a mechanochemical reaction depending on the ratio ball mass/mass of the reagent. A new kinetic model has been established that corresponds well to our experimental data and allows an estimation of the global activation energy. In solution, the retro Diels−Alder reaction was observed. The reaction was second order for the formation of endo and exo and first order for the retro Diels−Alder reaction. The grinding method shows many advantages compared to solution: shorter reaction time, total reaction, and better selectivity.

Regioselectivity Switch Towards the Development of Innovative Diels‐Alder Cycloaddition and Productive Applications in Organic Synthesis

“…Next, diverse hypotheses were formulated with regards to selectivity concerns to obtain Diels‐Alder cycloaddition product where diene‐HOMO and dienophile‐LUMO facilitate the orbital overlap. Herein, an electronic distribution among diene and dienophile found to undergoes synchronized pericyclic movement [51–53] . However, remarkable discovery was reported by Brassard and co‐workers demonstrating the regiocontrolled selectivity where vinylogous ketene acetals and their derivatives underwent DA cycloaddition with haloquinones for the subsequent production of anthraquinone nucleus (see Scheme 2).…”

“…Herein, an electronic distribution among diene and dienophile found to undergoes synchronized pericyclic movement. [51][52][53] However, remarkable discovery was reported by Brassard and co-workers demonstrating the regiocontrolled selectivity where vinylogous ketene acetals and their derivatives underwent DA cycloaddition with haloquinones for the subsequent production of anthraquinone nucleus (see Scheme 2). [54] Further extension of their results were studied by Blas Flores-Perez and co-workers in 2016 to demonstrate the remarkable regioselectivity pattern followed in Brassard diene (see Scheme 2a).…”

A Review on Mechanochemistry: Approaching Advanced Energy Materials with Greener Force

“…[29,30] The kinetic energy generated during mechanochemical reactions promotes the wear, fracture, and refinement of a chemical system's microstructure. [31,32] Most importantly, the specific surface area of materials can be significantly increased by the generation of new interfaces during fracture, which increases the contact probability between different components. Since reactions usually occur on the surface or boundaries of different components, [33,34] chemical reactions are accelerated by kinetic energy.…”

Mechanochemical synthesis of (4S)-N-alkyl-4,5-bis-sulfooxypentanamideviaa one-pot sequential aminolysis-sulfation reaction of (S)-γ-hydroxymethyl-γ-butyrolactone (2H-HBO)

“…Many advantages were observed for the mechanochemical process, such as better selectivity, shorter reaction time and full conversion. 6 In the context of development of petroleum-derived surfactant alternatives, we have previously synthesized and described different families of glycolipids. 7 Sugar-based amphiphiles were prepared by condensation of a lipid chain in the anomeric position of an aldose via an amide function.…”

“…Many advantages were observed for the mechanochemical process, such as better selectivity, shorter reaction time and full conversion. 6…”