有机酸催化剂存在下的聚氨酯合成——一项计算研究

Urethane Synthesis in the Presence of Organic Acid Catalysts-A Computational Study.

作者信息

Waleed Hadeer Q, Viskolcz Béla, Fiser Béla

机构信息

Institute of Chemistry, University of Miskolc, 3515 Miskolc-Egyetemváros, Hungary.

Higher Education and Industrial Cooperation Centre, University of Miskolc, 3515 Miskolc-Egyetemváros, Hungary.

出版信息

Molecules. 2024 May 17;29(10):2375. doi: 10.3390/molecules29102375.

DOI:10.3390/molecules29102375

PMID:38792235

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11123846/

Abstract

A general mechanism for catalytic urethane formation in the presence of acid catalysts, dimethyl hydrogen phosphate (DMHP), methanesulfonic acid (MSA), and trifluoromethanesulfonic acid (TFMSA), has been studied using theoretical methods. The reaction of phenyl isocyanate (PhNCO) and butan-1-ol (BuOH) has been selected to describe the energetic and structural features of the catalyst-free urethane formation. The catalytic activities of DMHP, MSA, and TFMSA have been compared by adding them to the PhNCO-BuOH model system. The thermodynamic properties of the reactions were computed by using the G3MP2BHandHLYP composite method. It was revealed that in the presence of trifluoromethanesulfonic acid, the activation energy was the lowest within the studied set of catalysts. The achieved results indicate that acids can be successfully employed in urethane synthesis and the mechanism was described.

摘要

采用理论方法研究了在酸催化剂（磷酸二氢甲酯（DMHP）、甲磺酸（MSA）和三氟甲磺酸（TFMSA））存在下催化生成聚氨酯的一般机理。选择苯基异氰酸酯（PhNCO）和丁醇-1（BuOH）的反应来描述无催化剂生成聚氨酯的能量和结构特征。通过将DMHP、MSA和TFMSA添加到PhNCO-BuOH模型体系中，比较了它们的催化活性。采用G3MP2BHandHLYP复合方法计算了反应的热力学性质。结果表明，在三氟甲磺酸存在下，在所研究的催化剂组中活化能最低。所得结果表明，酸可成功用于聚氨酯合成，并描述了其机理。