DFT investigation of the reaction mechanism for the guanidine catalysed ring-opening of cyclic carbonates by aromatic and alkyl-amines

被引：49

作者：

Alves, M. ^{[1
]}

Mereau, R. ^{[1
]}

Grignard, B. ^{[2
]}

Detrembleur, C. ^{[2
]}

Jerome, C. ^{[2
]}

Tassaing, T. ^{[1
]}

机构：

[1] Univ Bordeaux, Inst Sci Mol, UMR CNRS 5255, 351 Cours Liberat, F-33405 Talence, France

[2] Univ Liege, Ctr Educ & Res Macromol, CESAM Res Unit, Batiment B6a, B-4000 Liege, Sart Tilman, Belgium

来源：

RSC ADVANCES | 2017年 / 7卷 / 31期

关键词：

NON-ISOCYANATE POLYURETHANES; CHEMICAL FIXATION; NONISOCYANATE POLYURETHANES; URETHANE FORMATION; DIOXIDE; CYCLOCARBONATES; ROUTE; POLYMERIZATION; EPOXIDES; KINETICS;

D O I：

10.1039/c7ra00220c

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The guanidine catalysed aminolysis of propylene carbonate has been investigated using density functional theory (DFT) and highlights that different reaction pathways are involved, depending on the aromatic or aliphatic nature of the amine. The structural ability of 1,5,7-triazabicyclo[4.4.0] dec-5-ene (TBD) to simultaneously give and receive protons was demonstrated by a detailed mechanistic investigation. The bifunctional activity (base/H-bond donor) of TBD significantly reduces the Gibbs energy of the reaction and allows understanding of its higher efficiency compared to its methyl counterpart (MTBD).

引用

页码：18993 / 19001

页数：9

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