文献类型：期刊文献

英文题名：Insight into the Interactions between Azole-Anion-Based Ionic Liquids and Propargylic Alcohol: Influence on the Carboxylative Cyclization of Propargylic Alcohol with Carbon Dioxide

作者：Liu, Jiajia[1];Tang, Xiaochen[1];Lu, Huiling[1];Xu, Yingjie[1]

机构：[1]Shaoxing Univ, Dept Chem, Shaoxing 312000, Zhejiang, Peoples R China

年份：2021

卷号：9

期号：14

起止页码：5050

外文期刊名：ACS SUSTAINABLE CHEMISTRY & ENGINEERING

收录：SCI-EXPANDED(收录号：WOS:000640356500012)、、EI(收录号：20211810296769)、Scopus(收录号：2-s2.0-85104925308)、WOS

基金：This work was supported by the National Natural Science Foundation of Zhejiang Province (No. Y18B060014) and National Natural Science Foundation of China (No. 21978172). The authors also thank Prof. Y. Wang at Zhejiang University for providing the Gaussian 09 suite of programs.

语种：英文

外文关键词：Ionic liquids; Hydrogen bond; CO2 conversion; Carboxylative cyclization; Propargylic alcohol; Spectroscopy

外文摘要：To reveal the interactions between azole-anion-based ionic liquids (AILS) and propargyl alcohol (PA) and their effect on the carboxylative cyclization reaction of PA with CO2, three AILs, namely, [P-66614] [Im], [P-66614] [4-MeIm], and [P-66614] [4-BrIm], were synthesized and characterized. The interactions between the AILs with 2-methyl-3-butyn-2-ol (MBY) were investigated through IR and H-1 NMR spectra and DFT calculations. The results indicate that azole-based anions can form H-bonds with the hydroxyl (O-H) and the alkynyl hydrogen atoms (C C-H) of MBY simultaneously, with the former much stronger than the latter, which is supported by the interaction energy and the distance of the H-bond from DFT calculations. Interestingly, the strength of the former always increases with the mole fraction of AIL (x(AIL)), while that of the latter first decreases and then increases, reaching a minimum at x(AIL) approximate to 0.4. Furthermore, the order of the strength of the two H-bonds is as follows: [P-66614] [IM] > [P-66614] [4-MeIM] > [P-66614][4-BrIm], which is in good agreement with their basicity. According to the interactions between the AILs with MBY and combined with the reaction mechanism of MBY with CO2 promoted by AILs, it is evident that the increase in the basicity of the AILs enhances the H-bond between the AILs with O-H, thereby enhancing the activation of MBY and the subsequent CO2 conversion. However, this will also increase the interaction between AILS and C C-H, resulting in the deprotonation of C=C-H and hindering the activation of MBY. Therefore, choosing a suitable basic AIL and controlling its ratio are the keys to the reaction of PA and CO2.