100-60-7Relevant articles and documents
One pot catalytic NO2 reduction, ring hydrogenation, and N-alkylation from nitroarenes to generate alicyclic amines using Ru/C-NaNO 2
Oh, Seung Geun,Mishra, Vivek,Cho, Jin Ku,Kim, Baek-Jin,Kim, Hoon Sik,Suh, Young-Woong,Lee, Hyunjoo,Park, Ho Seok,Kim, Yong Jin
, p. 79 - 83 (2014)
A report to produce alicyclic amines and subsequent N-alkylation with alcohols using Ru/C-NaNO2 catalyzed facile transformation of nitrobenzene was investigated. Effects of solvent, temperature, pressure, reaction time, and molar-ratio of substrate/catalyst on product composition were also studied. These mechanistic studies explain that nitrobenzene undergoes hydrogenation reaction in the following order; -NO2 reduction to -NH2, aromatic ring-hydrogenation to alicyclic, and from the reaction of alcohol to give N-alkylated amines. This investigation shed lights on possible application to polyurethane chemistry since these amines are used as important precursors for diisocyanates.
Reductive N-methylation of amines with calcium hydride and Pd/C catalyst
Guyon, Carole,Duclos, Marie-Christine,Métay, Estelle,Lemaire, Marc
, p. 3002 - 3005 (2016)
The methylation of amines by paraformaldehyde in the presence of calcium hydride as a source of hydrogen and palladium on charcoal as catalyst was studied. Depending on the quantity of paraformaldehyde, monomethylated and dimethylated amines were selectively and efficiently prepared in one pot with good yields.
Commercial Pd/C-Catalyzed N-Methylation of Nitroarenes and Amines Using Methanol as Both C1 and H2 Source
Goyal, Vishakha,Gahtori, Jyoti,Narani, Anand,Gupta, Piyush,Bordoloi, Ankur,Natte, Kishore
, p. 15389 - 15398 (2019)
Herein, we report commercially available carbon-supported-palladium (Pd/C)-catalyzed N-methylation of nitroarenes and amines using MeOH as both a C1 and a H2 source. This transformation proceeds with high atom-economy and in an environmentally friendly way via borrowing hydrogen mechanism. A total of >30 structurally diverse N-methylamines, including bioactive compounds, were selectively synthesized with isolated yields of up to 95%. Furthermore, selective N-methylation and deuteration of nimesulide, a nonsteroidal anti-inflammatory drug, were realized through the late-stage functionalization.
Zinc-promoted, iridium catalyzed reductive alkylation of primary amines with aliphatic ketones in aqueous medium
da Silva, Renato A.,Bieber, Lothar W.
, p. 689 - 691 (2010)
The reductive alkylation of primary aromatic and aliphatic amines with aliphatic ketones has been achieved in aqueous acidic medium using commercially available, non-activated zinc dust catalyzed by a very small quantity of iridium bromide. Anilines react well in aqueous formic acid, whereas monoalkylamines require 1,4-dioxane as a co-solvent and sulfuric acid as the proton source. A plausible mechanism via low-valent iridium hydride species is proposed.
Dual pathways for the desilylation of silylamines by singlet oxygen
Baciocchi, Enrico,Del Giacco, Tiziana,Lapi, Andrea
, p. 1783 - 1786 (2006)
A kinetic and product study has been carried out for the reactions of silylamines 1a and 1b with 1O2 in MeCN and (80:20) MeCN-MeOH. Indications suggesting an electron-transfer step following exciplex (I) formation have been obtained. However, the fate of the radical cation is solvent dependent. The radical cation undergoes desilylation in MeCN-MeOH and deprotonation in MeCN.
Dichlorobis(1,4-diazabicyclo[2.2.2]octane)(tetrahydroborato)zirco- nium(IV), [Zr(BH4)2Cl2(dabco)2](ZrBDC), as a new, stable, and versatile bench top reducing agent: Reduction of imines and enamines, reductive amination of aldehydes and ketones and reductive methylation of amines
Firouzabadi, Habib,Iranpoor, Nasser,Alinezhad, Heshmatollah
, p. 143 - 151 (2003)
The reducing agent is easily prepared in an almost quantitative yield from commercially available starting materials. This compound is stable under mild aqueous acidic conditions (pH 4-6) and survives in H2O for several days without losing its reducing abilities. ZrBDC has been successfully used for the reduction of imines and enamines, reductive amination of aldehydes and ketones, and reductive methylation of amines.
Identification of Novel Bacterial Members of the Imine Reductase Enzyme Family that Perform Reductive Amination
France, Scott P.,Howard, Roger M.,Steflik, Jeremy,Weise, Nicholas J.,Mangas-Sanchez, Juan,Montgomery, Sarah L.,Crook, Robert,Kumar, Rajesh,Turner, Nicholas J.
, p. 510 - 514 (2018)
Reductive amination of carbonyl compounds constitutes one of the most efficient ways to rapidly construct chiral and achiral amine frameworks. Imine reductase (IRED) biocatalysts represent a versatile family of enzymes for amine synthesis through NADPH-mediated imine reduction. The reductive aminases (RedAms) are a subfamily of IREDs that were recently shown to catalyze imine formation as well as imine reduction. Herein, a diverse library of novel enzymes were expressed and screened as cell-free lysates for their ability to facilitate reductive amination to expand the known suite of biocatalysts for this transformation and to identify more enzymes with potential industrial applications. A range of ketones and amines were examined, and enzymes were identified that were capable of accepting benzylamine, pyrrolidine, ammonia, and aniline. Amine equivalents as low as 2.5 were employed to afford up to >99 % conversion, and for chiral products, up to >98 % ee could be achieved. Preparative-scale reactions were conducted with low amine equivalents (1.5 or 2.0) of methylamine, allylamine, and pyrrolidine, achieving up to >99 % conversion and 76 % yield.
Ceria supported Ru0-Ruδ+ clusters as efficient catalyst for arenes hydrogenation
Cao, Yanwei,Zheng, Huan,Zhu, Gangli,Wu, Haihong,He, Lin
, p. 770 - 774 (2021)
Selective hydrogenation of aromatic amines, especially chemicals such as aniline and bis(4-aminocyclohexyl)methane for non-yellowing polyurethane, is of particular interests due to the extensive applications. To conquer the existing difficulties in selective hydrogenation, the Ru0-Ruδ+/CeO2 catalyst with solid frustrated Lewis pairs was developed for aromatic amines hydrogenation with excellent activity and selectivity under relative milder conditions. The morphology, electronic and chemical properties, especially the Ru0-Ruδ+ clusters and reducible ceria were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS), CO2 temperature programmed desorption (CO2-TPD), H2 temperature programmed reduction (H2-TPR), H2 diffuse reflectance Fourier transform infrared spectroscopy (H2-DRIFT), Raman, etc. The 2% Ru/CeO2 catalyst exhibited good conversion of 95% and selectivity greater than 99% toward cyclohexylamine. The volcano curve describing the activity and Ru state was found. Owning to the “acidic site isolation” by surrounding alkaline sites, condensation between the neighboring amine molecules could be effectively suppressed. The catalyst also showed good stability and applicability for other aromatic amines and heteroarenes containing different functional groups.
Electrocatalytic Dealkylation of Amines Mediated by Ferrocene
Torriero, Angel A. J.,Morda, Joanne,Saw, Jessica
, p. 4280 - 4287 (2019)
The homogeneous catalytic oxidation of dicyclohexylamine (DCHA), N,N-dimethylcyclohexylamine (DMCHA) and N,N-dicyclohexylmethylamine (DCHMA) has been investigated in the presence of electrochemically generated ferrocenium ions as the catalyst. Mechanistic details for this electrocatalytic process have been scrutinized with the use of cyclic voltammetry, bulk electrolysis, and digital simulations techniques. A one-electron catalytic process between ferrocene and the respective amines was observed. The products obtained from bulk electrolysis were isolated and identified by FTIR, 1H and 13C NMR spectroscopy, and mass spectrometry. Both DCHMA and DMCHA proceed to yield a secondary amine product by the elimination of one methyl group. In the absence of this group, as in the case of DCHA, the cycloalkyl group is then eliminated. The catalytic efficiency and the second-order rate constants were estimated and found to follow the order DCHA ≤ DMCHA DCHMA. The results presented in this work should open up a new avenue to achieve simple, low-cost, and efficient amine oxidation, which could be useful in several areas of chemistry.
Catalytic reduction of the arene ring, and other functionalities, of organic substrates using formic acid and palladium on carbon
Alper, Howard,Vampollo, Guiseppe
, p. 7477 - 7480 (1992)
The arene ring in a variety of compounds with functionalities which contain nitrogen is reduced in good yields using formic acid and Pd/C in methanol.
