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Molecular interactions with CO2 for controlling the regioselectivity of liquid phase hydrogenation of 2,4-dinitroaniline
| Title: | Molecular interactions with CO2 for controlling the regioselectivity of liquid phase hydrogenation of 2,4-dinitroaniline |
| Authors: | Yoshida, Hiroshi Browse this author →KAKEN DB | | Tomizawa, Akitoshi Browse this author | | Tachikawa, Hiroto Browse this author →KAKEN DB | | Fujita, Shin-ichiro Browse this author →KAKEN DB | | Arai, Masahiko Browse this author →KAKEN DB |
| Issue Date: | 22-Jul-2014 |
| Publisher: | Royal Society of Chemistry |
| Journal Title: | Physical Chemistry Chemical Physics |
| Volume: | 16 |
| Issue: | 35 |
| Start Page: | 18955 |
| End Page: | 18965 |
| Publisher DOI: | 10.1039/c4cp02114b |
| PMID: | 25092019 |
| Abstract: | The catalytic hydrogenation of 2,4-dinitroaniline using a 0.5 wt% Pt/TiO2 catalyst was investigated in a multiphase medium of tetrahydrofuran (THF) pressurized by CO2 at different pressures and at 323 K. When CO2 pressure was increased, the overall rate of hydrogenation simply decreased but the selectivity to the desired product of 4-nitro-1,2-phenylenediamine increased. The noticeable enhancement of the selectivity to 4-nitro-1,2-phenylenediamine can be explained by chemical reactivities of CO2 molecules. In situ high-pressure FTIR and molecular simulations demonstrate that the dissolved CO2 molecules may interact with amino groups of the substrate and weaken the intra-hydrogen bonding between the amino and 2-nitro groups, which results in the change in the relative reactivity of the two nitro groups, yielding the desired product in a higher selectivity. The change in the intra-and inter-molecular interactions between the substrate and CO2 molecules was theoretically examined by DFT calculations. |
| Type: | article (author version) |
| URI: | http://hdl.handle.net/2115/59539 |
| Appears in Collections: | 工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 荒井 正彦
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