20972-43-4Relevant academic research and scientific papers
An FTIR spectroscopic study of the selective oxidation of nitrosobenzne to nitrobenzene by metal oxides
Meijers,Ponec
, p. 1 - 9 (1996)
Catalytic conversion of nitro- into nitrosobenzene by transition metal oxides is of considerable practical and theoretical interest. Therefore, the surface chemistry of nitrosobenzene on various metal oxides has been studied using IR spectroscopy. The main products of surface reactions are nitrobenzene and azoxybenzene. Findings of this study are compared with the results of a mass spectroscopic study carried out with nitrosobenzene on the same oxides. Molecularly adsorbed nitrosobenzene is found to be coordinated to metal cations by σ-N as well as σ-O bonds. Also the cis-dimer of nitrosobenzene is detected. As a reference, the spectra of adsorbed nitrosobenzene were compared with the spectra of monomeric nitrosobenzene dissolved in benzene and dimeric nitrosobenzene dissolved in ethanol. Some IR absorptions not reported earlier are assigned to C-N stretching and ring vibrations of σ-O coordinated and dimeric nitrosobenzene. The coordination modes of nitrosobenzene observed with the different oxides, and the reverse relationship found between ν(N=O) and ν(C-N) are in agreement with the observations made with nitroso compounds coordinated as ligands in organometallic complexes. A link to the catalytic behavior of nitrosobenzene on oxides is indicated.
A novel intermediate in allylic amination catalyzed by iron salts
Srivastava,Khan,Nicholas
, p. 3311 - 3312 (1996)
Our initial probe of the aminations catalyzed by iron salts excluded the intermediacy of free ArNO, suggesting that a coordinated organonitrogen species could be the active aminating agent. To elucidate the mechanism of these latter reactions we report herein (a) the isolation and first structural elucidation of a metal complex of a C-nitroso dimer (1), and (b) evidence that this novel compound is the key aminating agent in allylic aminations catalyzed by iron salts. We have established with 1 the first structurally verified metal complex of a C-nitroso dimer and its unprecedented reactivity and selectivity for the allylic N-functionalization of olefins. Its involvement as the aminating agent in FeX2,3-catalyzed allylic amination also has been strongly implicated.
Concerning the baker's yeast (Saccharomyces cerevisiae) mediated reduction of nitroarenes and other N-O containing functional groups
Blackie, Josie A.,Turner, Nicholas J.,Wells, Andrew S.
, p. 3043 - 3046 (1997)
Nitro- and nitrosoarenes can be reduced using baker's yeast (Saccharomyces cerevisiae) under two distinct sets of conditions, one of which is in fact a well established non-enzymic process. In order to clarify reports in the literature a comparison of the two methods has been made.
MARKED METAL ION EFFECTS IN ELECTRON TRANSFER FROM REDUCED FLAVIN TO AROMATIC NITRO COMPOUNDS IN ETHANOL
Yano, Yumihiko,Sakaguchi, Terukiyo,Nakazato, Michiaki
, p. 595 - 600 (1984)
The reduction of p-chloronitrobenzene by a reduced flavin has been investigated kinetically in the presence of divalent metal ions in EtOH under anaerobic conditions.A large rate acceleration due to the metal ions was observed; 1(none) : 32 Zn(2+) : 420 Ni(2+) : 1 000 Co(2+) : 12 Mn(2+).The role of the metal ions is proposed.The reducing ability of metal-chelated flavin radicals has been briefly examined by employing 2,4-dinitrochlorobenzene as an electron acceptor.
Zr(OH)4-Catalyzed Controllable Selective Oxidation of Anilines to Azoxybenzenes, Azobenzenes and Nitrosobenzenes
Long, Yu,Luo, Nan,Ma, Jiantai,Qin, Jiaheng,Sun, Fangkun,Wang, Wei David,Zhou, Pan-Pan
supporting information, (2021/12/09)
The selective oxidation of aniline to metastable and valuable azoxybenzene, azobenzene or nitrosobenzene has important practical significance in organic synthesis. However, uncontrollable selectivity and laborious synthesis of the expensive required catalysts severely hinders the uptake of these reactions in industrial settings. Herein, we have pioneered the discovery of Zr(OH)4 as an efficient heterogeneous catalyst capable of the selective oxidation of aniline, using either peroxide or O2 as oxidant, to selectively obtain various azoxybenzenes, symmetric/unsymmetric azobenzenes, as well as nitrosobenzenes, by simply regulating the reaction solvent, without the need for additives. Mechanistic experiments and DFT calculations demonstrate that the activation of H2O2 and O2 is primarily achieved by the bridging hydroxyl and terminal hydroxyl groups of Zr(OH)4, respectively. The present work provides an economical and environmentally friendly strategy for the selective oxidation of aniline in industrial applications.
Rhodium-terpyridine Catalyzed Transfer Hydrogenation of Aromatic Nitro Compounds in Water
Liu, Yuxuan,Miao, Wang,Tang, Weijun,Xue, Dong,Xiao, Jianliang,Wang, Chao,Li, Changzhi
supporting information, p. 1725 - 1729 (2021/06/01)
A rhodium terpyridine complex catalyzed transfer hydrogenation of nitroarenes to anilines with i-PrOH as hydrogen source and water as solvent has been developed. The catalytic system can work at a substrate/catalyst (S/C) ratio of 2000, with a turnover frequency (TOF) up to 3360 h?1, which represents one of the most active catalytic transfer hydrogenation systems for nitroarene reduction. The catalytic system is operationally simple and the protocol could be scaled up to 20 gram scale. The water-soluble catalyst bearing a carboxyl group could be recycled 15 times without significant loss of activity.
NaI/PPh3-Mediated Photochemical Reduction and Amination of Nitroarenes
Qu, Zhonghua,Chen, Xing,Zhong, Shuai,Deng, Guo-Jun,Huang, Huawen
supporting information, p. 5349 - 5353 (2021/07/21)
A mild transition-metal- and photosensitizer-free photoredox system based on the combination of NaI and PPh3 was found to enable highly selective reduction of nitroarenes. This protocol tolerates a broad range of reducible functional groups such as halogen (Cl, Br, and even I), aldehyde, ketone, carboxyl, and cyano. Moreover, the photoredox catalysis with NaI and stoichiometric PPh3 provides also an alternative entry to Cadogan-type reductive amination when o-nitrobiarenes were used.
Yeast supported gold nanoparticles: an efficient catalyst for the synthesis of commercially important aryl amines
Krishnan, Saravanan,Patel, Paresh N.,Balasubramanian, Kalpattu K.,Chadha, Anju
supporting information, p. 1915 - 1923 (2021/02/06)
Candida parapsilosisATCC 7330 supported gold nanoparticles (CpGNP), prepared by a simple and green method can selectively reduce nitroarenes and substituted nitroarenes with different functional groups like halides (-F, -Cl, -Br), olefins, esters and nitriles using sodium borohydride. The product aryl amines which are useful for the preparation of pharmaceuticals, polymers and agrochemicals were obtained in good yields (up to >95%) using CpGNP catalyst under mild conditions. The catalyst showed high recyclability (≥10 cycles) and is a robust free flowing powder, stored and used after eight months without any loss in catalytic activity.
Modified mesoporous y zeolite catalyzed nitration of azobenzene using NO2as the nitro source combined with density functional theory studies
Chen, Lei,Guo, Chuanzhou,Guo, Jiaming,Peng, Xinhua
, p. 21389 - 21394 (2021/12/04)
A modified mesoporous Y zeolite is developed to catalyze high ortho regioselective nitration of azobenzene with NO2 as the nitro source. The mesoporous Y zeolite is modified by the ion exchange method and characterized by various analyses involving FT-IR spectroscopy, and XPS and BET analyses. The ortho/para ratio of mononitration products is improved from 0.70 to 2.39 in the presence of the catalyst. Based on density functional theory (DFT), the active sites of nitration reaction are calculated by combining the electrostatic potential with the average local ionization energy, which are further support the electrophilic substitution mechanism of azobenzene in the catalytic nitration reaction. This journal is
Catalytic Selective Oxidative Coupling of Secondary N-Alkylanilines: An Approach to Azoxyarene
Ke, Lei,Zhu, Guirong,Qian, Hui,Xiang, Guangya,Chen, Qin,Chen, Zhilong
supporting information, p. 4008 - 4013 (2019/06/04)
Azoxyarenes are among important scaffolds in organic molecules. Direct oxidative coupling of primary anilines provides a concise fashion to construct them. However, whether these scaffolds can be prepared from secondary N-alkylanilines is not well explored. Here, we present a catalytic selective oxidative coupling of secondary N-alkylaniline to afford azoxyarene with tungsten catalyst under mild conditions. In addition, azoxy can be viewed as a bioisostere of alkene and amide. Several "azoxyarene analogues" of the corresponding bioactive alkenes and amides showed comparable promising anticancer activities.
