T:Toxic;
106-49-0Relevant articles and documents
Zeolite-Catalyzed Isomerization of Aromatic Amines to Methyl-Aza-Aromatics
Stamm, T.,Kouwenhoven, H. W.,Seebach, D.,Prins, R.
, p. 268 - 282 (1995)
The scope and mechanism of the isomerization of arylamines to methyl-substituted aromatic heterocycles have been studied.Aniline, toluidines, naphthylamines and m-phenylenediamine all reacted to the corresponding ortho-methyl-substituted aza-aromatiics when exposed to high NH3 pressure and elevated temperature in the presence of acid catalysts.Zeolites with a three-dimensional pore structure, especially H-ZSM-5, showed the best performance.Optimum reaction conditions are around 600 K and 10 MPa.Two mechanisms which had been proposed earlier for this apparent N-ortho C exchange reaction proved untenable.Neither incorporation of the N atom into the aromatic ring nor a mechanism based on an intramolecular Ritter reaction could explain the required high NH3 pressure or the product distribution.Two new mechanisms are proposed which can explain all observations.In both mechanisms, reaction starts with addition of NH3 to the arylamine, followed by ring opening.In one mechanism an alkyno-imine intermediate is formed; in the other mechanism an enamino-imine intermediate is formed through a reverse aldol reaction.In both cases ring closure and NH3 elimination lead to the required aromatic heterocycles.The high NH3 pressure is explained by the need to add NH3 to the aromatic ring, and the high temperature by the need to desorb NH3 from the acid sites.
Copper-catalysed reductive amination of nitriles and organic-group reductions using dimethylamine borane
Van Der Waals, Dominic,Pettman, Alan,Williams, Jonathan M. J.
, p. 51845 - 51849 (2014)
A heterogeneous copper catalyst, formed in situ, has been shown to dehydrocouple commercially available amine boranes whilst transferring hydrogen for the reduction of selected organic functional groups in an aqueous medium. The catalytic system has also been shown to promote the reductive amination of aryl nitriles. This journal is
Microbial deoxygenation of N-oxides with Baker's yeast-NaOH
Baik, Woonphil,Kim, Dong Ik,Koo, Sangho,Rhee, Jong Uk,Shin, Sung Hee,Kim, Byeong Hyo
, p. 845 - 848 (1997)
The microbial deoxygenation of a series of aromatic and heteroaromatic N-oxide compounds, including quinoline N-oxides, isoquinoline N-oxides, 2-aryl-2H-benzotriazole 1-oxides, benzo[c]cinnoline N-oxide and azoxybenzenes, has been performed with bakers'yeast-NaOH.
Intermetallic Nanocatalysts from Heterobimetallic Group 10-14 Pyridine-2-thiolate Precursors
Adamson, Marquix A. S.,Chen, Yunhua,Daniels, Carena L.,Dorn, Rick W.,Fan, Huajun,Knobeloch, Megan,Rossini, Aaron J.,Vela, Javier,Wu, Hao,Yox, Philip,Zhou, Guoquan
, (2020)
Intermetallic compounds are atomically ordered inorganic materials containing two or more transition metals and main-group elements in unique crystal structures. Intermetallics based on group 10 and group 14 metals have shown enhanced activity, selectivity, and durability in comparison to simple metals and alloys in many catalytic reactions. While high-temperature solid-state methods to prepare intermetallic compounds exist, softer synthetic methods can provide key advantages, such as enabling the preparation of metastable phases or of smaller particles with increased surface areas for catalysis. Here, we study a generalized family of heterobimetallic precursors to binary intermetallics, each containing a group 10 metal and a group 14 tetrel bonded together and supported by pincer-like pyridine-2-thiolate ligands. Upon thermal decomposition, these heterobimetallic complexes form 10-14 binary intermetallic nanocrystals. Experiments and density functional theory (DFT) computations help in better understanding the reactivity of these precursors toward the synthesis of specific intermetallic binary phases. Using Pd2Sn as an example, we demonstrate that nanoparticles made in this way can act as uniquely selective catalysts for the reduction of nitroarenes to azoxyarenes, which highlights the utility of the intermetallics made by our method. Employing heterobimetallic pincer complexes as precursors toward binary nanocrystals and other metal-rich intermetallics provides opportunities to explore the fundamental chemistry and applications of these materials.
Simple and efficient reduction of aromatic nitro compounds using recyclable polymer-supported formate and magnesium
Abiraj, Keelara,Srinivasa, Gejjalagere R.,Gowda, D. Channe
, p. 149 - 151 (2005)
Aromatic nitro compounds were chemoselectively reduced to the corresponding amines using recyclable polymer-supported formate as a hydrogen donor in the presence of low-cost magnesium powder at room temperature. Use of the immobilized hydrogen donor affords the product amine in excellent yield (90-97%) without the need for any Chromatographic purification steps. This method was found to be highly facile with selectivity over several other functional groups, such as halogen, alkene, nitrile, carbonyl, ester, amide, methoxy, phenol, and hydroxyl groups. CSIRO 2005.
Process development of 4-[N-methyl-N-(tetrahydropyran-4-yl)aminomethyl]aniline dihydrochloride: A key intermediate for TAK-779, a small-molecule nonpeptide CCR5 antagonist
Hashimoto, Hideo,Ikemoto, Tomomi,Itoh, Tatsuya,Maruyama, Hideaki,Hanaoka, Tadashi,Wakimasu, Mitsuhiro,Mitsudera, Hiroyuki,Tomimatsu, Kiminori
, p. 70 - 73 (2002)
A new and efficient synthesis of 4-[N-methyl-N-(tetrahydropyran-4-yl)aminomethyl]aniline dihydrochloride, a key intermediate for the CCR5 antagonist TAK-779, is described. Reductive alkylation of methylamine with tetrahydro-4H-pyran-4-one followed by alkylation of N-methyl-N-(tetrahydropyran-4-yl)amine with 4-nitrobenzylbromide and reduction of N-(4-nitrobenzyl)-N-(tetrahydropyran-4-yl)amine results in a 78% isolated yield from the starting materials by a scalable method, using only commercially available reagents.
Rapid, efficient and selective reduction of aromatic nitro compounds with hydrazine hydrate in the presence of the plain and supported platinum nanoparticles as catalysts
Mehdizadeh, Soofia,Ahmadi, Seyed Javad,Sadjadi, Sodeh,Outokesh, Mohammad
, p. 1587 - 1592 (2014)
The current study aimed at application of the plain and supported platinum nanoparticles as a heterogenous catalyst for the reduction of aromatic nitro compounds. Monodispersed platinum nanoparticles were synthesized by reduction of H2PtCl6 by ethanol in the presence of polyvinyl pyrrolidone as a stabilizer, and then were immobilized on four types of zeolites. The obtained catalyst granules were characterized by X-ray diffractometry and transmission electron microscopy. The study then focused on elaboration of the catalytic activity of the nano catalysts under different operational conditions. It was found that reaction is adequately rapid at ambient temperature, and by utilizing a sufficient amount of catalyst, can be completed in nearly 30 min. Among the utilized zeolitic supports, zeolite 4A had the highest performance, but the mechanism of its synergetic effect on the activity of platinum nano catalyst was not found and requires more investigation.
Sodium dithionite reduction of nitroarenes using viologen as an electron phase-transfer catalyst
Park, Kwanghee Koh,Oh, Chang Hun,Joung, Won Kyou
, p. 7445 - 7446 (1993)
Various aromatic nitro compounds were reduced conveniently to the corresponding aniline derivatives with sodium dithionite using dioctyl viologen as an electron-transfer catalyst in dichloromethane- water two-phase system.
Mild and general procedure for Pd/C-catalyzed hydrodechlorination of aromatic chlorides
Sajiki, Hironao,Kume, Akira,Hattori, Kazuyuki,Hirota, Kosaku
, p. 7247 - 7250 (2002)
A mild and efficient one-pot hydrodechlorination using a Pd/C-Et3N system proceeds at room temperature, which is general for the dechlorination of a variety of aromatic chlorides.
GRAPHITE CATAlYZED REDUCTION OF AROMATIC AND ALIPHATIC NITRO COMPOUNDS WITH HYDRAZINE HYDRATE
Han, Byung Hee,Shin, Dae Hyun,Cho, Sung Yun
, p. 6233 - 6234 (1985)
Aromatic and aliphatic nitro compounds were readily reduced to amino compounds in excellant yields with graphite and hydrazine hydrate.
