61628-75-9Relevant academic research and scientific papers
Selective Aerobic Oxidation of 4-Ethylnitrobenzene to 4-Nitroacetophenone Promoted by Metalloporphyrins
Yang, Yuning,Li, Guijie,Mao, Xinbiao,She, Yuanbin
supporting information, p. 1078 - 1086 (2019/03/26)
A solvent-free and environment-friendly process for the oxidation of 4-ethylnitrobenzene to 4-nitroacetophenone promoted by metalloporphyrins was developed in a pressure reactor using O2 as a clean oxidant. The activities and reaction selectivities of the metalloporphyrins could be significantly affected by their central metal ions as well as the nature and position of the substituted groups, which were systematically investigated by employing more than 60 metalloporphyrins. Generally, the Fe(III)- and Mn(II)-porphyrins exhibited high activities. Moreover, metalloporphyrins with electron-withdrawing substituents on the para-positions of the phenyl rings showed activities in the order T(p-Br)PPM T(m-Cl)PPM > T(p-Cl)PPM and T(o-OMe)PPM T(m-OMe)PPM T(p-OMe)PPM were observed. Furthermore, selectivities over 90.0% and a TON of 5370 could be achieved for the desired ketone. Especially, the T(p-Cl)PPMn demonstrated a selectivity of up to 93.6% and a conversion of 51.9% with only 3.3% acid and no alcohol observed, and the selectivity was nearly the same for a large-scale experiment (100 g).
Electron-Transfer Substitution Reactions: Stereochemistry
Kornblum, Nathan,Wade, Peter A.
, p. 5301 - 5305 (2007/10/02)
Substitution of the aliphatic nitro group of optically active 2-(p-nitrophenyl)-2-nitrobutane (II) by sodium azide, sodium thiophenoxide, sodium benzenesulfinate, and the lithium salt of 2-nitropropane invariably occurs with complete loss of optical activity.Furthermore, levorotatory II is racemized by sodium nitrite.These facts support the view that substitution reactions in p-nitrocumyl systems proceed via the electron-transfer chain mechanism of eq 2-5.
The Correlation of Regiochemistry with Structure in the SRN1 Reaction of aci-Nitronates with p-Nitrobenzylic Substrates
Norris, Robert K.,Randles, David
, p. 1621 - 1633 (2007/10/02)
The rate and regiochemistry of the SRN1 reactions of aci-nitronates with p-nitrobenzylic substrates are profoundly affected by branching at the positions adjacent to the reaction sites (Cβ).Definitive rules which predict whether C-alkylation will occur in the association step involving p-nitrobenzylic radicals and aci-nitronate ions are formulated. β-Branching causes O-alkylation or reductive processes to increase.In some cases no recognizable product formation results.Benzylic alcohols, p-nitrophenyl alkyl ketones and/or their oximes, and p-nitrophenol are among the products which result from subsequent reactions of the O-alkylation products, aci-nitronic esters of benzylic alcohols.
