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A DFT study of reduction of nitrobenzene to aniline with SnCl 2 and hydrochloric acid
Author(s) -
Yamabe Shinichi,
Yamazaki Shoko
Publication year - 2016
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3543
Subject(s) - chemistry , aniline , nitrobenzene , protonation , medicinal chemistry , hydride , hydrochloric acid , electrophile , proton , adduct , cationic polymerization , imine , inorganic chemistry , ion , polymer chemistry , organic chemistry , catalysis , physics , quantum mechanics , hydrogen
A fundamental reduction reaction , nitrobenzene to aniline in SnCl 2 and hydrochloric acid , was investigated by density functional theory (DFT) calculations. First, the change of SnCl 2 → SnCl 4 2− → Cl 4 SnH − was discussed, and the reaction path of SnCl 4 2− + H 3 O + → Cl 4 SnH − + H 2 O was obtained. Starting from nitrobenzene, six elementary processes were found so as to arrive at the protonated aniline. The hydride ion from Cl 4 SnH − is connected always to the cationic nitrogen, and the proton is always to oxygens. An intermediate PhN + H 2 OH was obtained, which is isomerized to the para OH adduct protonated imine via the Bamberger rearrangement . This species may undergo the H − acceptance at the sp 2 N + H 2 center. In the nitrobenzene reduction, the proton enhances the electrophilicity of the nitrogen center, which makes the hydride shift ready. NH bonds are formed, and NO bonds are cleaved both by the proton attach and subsequent H 2 O elimination and by the formal [1,5] OH shift. Copyright © 2016 John Wiley & Sons, Ltd.