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

被引：22

作者：

Gonnet, Lori ^{[1
,2
]}

Chamayou, Alain ^{[1
]}

Andre-Barres, Christiane ^{[2
]}

Micheau, Jean-Claude ^{[3
]}

Guidetti, Brigitte ^{[2
]}

Sato, Tohru ^{[4
]}

Baron, Michel ^{[1
]}

Baltas, Michel ^{[2
]}

Calvet, Rachel ^{[1
]}

机构：

[1] Univ Toulouse, Ctr RAPSODEE, IMT Mines Albi, UMR CNRS 5302, Campus Jarlard,Allee Sci, F-81013 Albi 09, France

[2] Univ Toulouse, LSPCMIB, CNRS UMR 5068, Univ Toulouse III Paul Sabatier, F-31062 Toulouse, France

[3] Univ Toulouse, Lab IMRCP, CNRS UMR 5623, Univ Toulouse III Paul Sabatier, F-31062 Toulouse, France

[4] Kyoto Univ, Fukui Inst Fundamental Chem, Kyoto 6068103, Japan

来源：

ACS SUSTAINABLE CHEMISTRY & ENGINEERING | 2021年 / 9卷 / 12期

关键词：

Diels-Alder; Mechanochemistry; Ball-milling; Kinetics; Mechanisms; ARRHENIUS EQUATION; SOLVENT-FREE; ENERGY;

D O I：

10.1021/acssuschemeng.0c08314

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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.

引用

页码：4453 / 4462

页数：10

共 44 条

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