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关于磺酸与醇酯化反应机理的密度泛函理论研究

A DFT study on the mechanism of the sulfonic acid + alcohol esterification reaction.

作者信息

Salvatella Luis

机构信息

Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza Pedro Cerbuna 12 E-50009 Zaragoza Spain

出版信息

RSC Adv. 2018 Jan 22;8(7):3828-3832. doi: 10.1039/c7ra09833b. eCollection 2018 Jan 16.

DOI:10.1039/c7ra09833b
PMID:35542947
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9077688/
Abstract

Four alternative mechanisms for the benzenesulfonic acid + methanol esterification reaction have been studied at the B3LYP/aug-cc-pVTZ level. The participation of a pentacoordinate sulfur intermediate (in either neutral or protonated form) can be disregarded according to energy considerations. Instead, results show a low activation barrier for the S1 pathway (through a sulfonylium cation intermediate) and a moderate barrier for the S2 path (involving protonated methanol as an alkylating reagent).

摘要

在B3LYP/aug-cc-pVTZ水平上研究了苯磺酸与甲醇酯化反应的四种替代机理。根据能量考虑，五配位硫中间体（中性或质子化形式）的参与可以忽略不计。相反，结果表明S1途径（通过锍阳离子中间体）的活化能垒较低，而S2途径（涉及质子化甲醇作为烷基化试剂）的能垒适中。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a630/9077688/99a9887e0c4e/c7ra09833b-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a630/9077688/21fa1c7f2b88/c7ra09833b-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a630/9077688/828cb3e0cbae/c7ra09833b-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a630/9077688/bfa2e9d143e9/c7ra09833b-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a630/9077688/a3659aa57c63/c7ra09833b-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a630/9077688/99a9887e0c4e/c7ra09833b-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a630/9077688/21fa1c7f2b88/c7ra09833b-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a630/9077688/828cb3e0cbae/c7ra09833b-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a630/9077688/bfa2e9d143e9/c7ra09833b-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a630/9077688/a3659aa57c63/c7ra09833b-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a630/9077688/99a9887e0c4e/c7ra09833b-f4.jpg

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本文引用的文献

1
Hydrogen bonding in the sulfuric acid-methanol-water system: a matrix isolation and computational study.硫酸 - 甲醇 - 水体系中的氢键：基质隔离与计算研究
J Phys Chem A. 2015 Mar 19;119(11):2271-80. doi: 10.1021/jp505965z. Epub 2014 Sep 25.
2
Quantum chemical study of atmospheric aggregates: HCl•HNO3•H2SO4.大气聚集体的量子化学研究：HCl•HNO3•H2SO4
J Mol Model. 2014 Jun;20(6):2232. doi: 10.1007/s00894-014-2232-6. Epub 2014 May 21.
3
The endocyclic restriction test: the geometries of nucleophilic substitutions at sulfur(VI) and sulfur(II).
环内限制试验：硫（VI）和硫（II）亲核取代的几何结构
J Org Chem. 2008 Dec 19;73(24):9627-32. doi: 10.1021/jo8016428.
4
Nucleophilic identity substitution reactions. The reaction between water and protonated alcohols.
Org Biomol Chem. 2003 Aug 21;1(16):2935-42. doi: 10.1039/b302268d.
5
Nafion-H catalysed sulfonylation of aromatics with arene/alkenesulfonic acids for the preparation of sulfones1a.用于制备砜1a的、由Nafion-H催化的芳烃与芳烃/烯烃磺酸的磺酰化反应。
Chem Commun (Camb). 2001 Sep 7(17):1696-7. doi: 10.1039/b104603a.
6
Reaction of amino acids with alkyl p-toluenesulfonates.氨基酸与对甲苯磺酸烷基酯的反应。
Chem Pharm Bull (Tokyo). 1985 Apr;33(4):1711-5. doi: 10.1248/cpb.33.1711.