C:Corrosive;
108-91-8Relevant articles and documents
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Smith et al.
, p. 294 (1952)
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A Selective Electrocatalytic Cleavage of the Benzyloxycarbonyl Group from Peptides
Casadei, M. Antonietta,Pletcher, D.
, p. 1118 - 1119 (1987)
An electrosynthetic procedure for the cleavage of the benzyloxycarbonyl group from protected amino acids and peptides is described.It is based on the use of a high surface area palladium cathode in methanol/acetic acid and gives an excellent selectivity under very mild conditions.
Formal asymmetric biocatalytic reductive amination
Koszelewski, Dominik,Lavandera, Ivan,Clay, Dorina,Guebitz, Georg M.,Rozzell, David,Kroutil, Wolfgang
, p. 9337 - 9340 (2008)
All for one: A combination of three biocatalysts (ω-transaminase, alanine dehydrogenase, and an enzyme such as formate dehydrogenase for cofactor recycling) catalyze a cascade to achieve the asymmetric transformation of a ketone into a primary α-chiral unprotected amine through a formal stereoselective reductive amination (see scheme). Only ammonia and the reducing agent (formate) are consumed during this reaction. (Chemical Equation Presented).
Anti-Markovnikov Hydroamination of Alkenes with Aqueous Ammonia by Metal-Loaded Titanium Oxide Photocatalyst
Park, Soyeong,Jeong, Jaeyoung,Fujita, Ken-Ichi,Yamamoto, Akira,Yoshida, Hisao
, p. 12708 - 12714 (2020)
A completely new route was established to synthesize valuable primary amines from alkenes by using aqueous ammonia, that is, a simple photocatalytic hydroamination of alkenes using aqueous ammonia with a metal-loaded TiO2 photocatalyst. Although the photochemical hydroamination prefers to form amines according to the Markovnikov rule, the new photocatalytic hydroamination gives anti-Markovnikov products predominantly. With an Au-loaded TiO2 photocatalyst, the amine yield reached up to 93% and the regioselectivity of anti-Markovnikov products was above 98%. The reaction mechanism was proposed for the new photocatalytic hydroamination.
Doped ordered mesoporous carbons as novel, selective electrocatalysts for the reduction of nitrobenzene to aniline
Daems, Nick,Risplendi, Francesca,Baert, Kitty,Hubin, Annick,Vankelecom, Ivo F. J.,Cicero, Giancarlo,Pescarmona, Paolo P.
, p. 13397 - 13411 (2018)
Ordered mesoporous carbons (OMCs) doped with nitrogen, phosphorus or boron were synthesised through a two-step nanocasting method and studied as electrocatalysts for the reduction of nitrobenzene to aniline in a half-cell setup. The nature of the dopant played a crucial role in the electrocatalytic performance of the doped OMCs, which was monitored by LSV with a rotating disk electrode setup. The incorporation of boron generated the electrocatalysts with the highest kinetic current density, whereas the incorporation of phosphorus led to the lowest overpotential. Doping with nitrogen led to intermediate behaviour in terms of onset potential and kinetic current density, but provided the highest selectivity towards aniline, thus resulting in the most promising electrocatalyst developed in this study. Density functional theory calculations allowed explaining the observed difference in the onset potentials between the various doped OMCs, and indicated that both graphitic N and pyrdinic N can generate active sites in the N-doped electrocatalyst. A chronoamperometric experiment over N-doped OMC performed at -0.75 V vs. Fc/Fc+ in an acidic environment, resulted in a conversion of 61% with an overall selectivity of 87% to aniline. These are the highest activity and selectivity ever reported for an electrocatalyst for the reduction of nitrobenzene to aniline, making N-doped OMC a promising candidate for the electrochemical cogeneration of this industrially relevant product and electricity in a fuel cell setup.
Selective reductions. Part 60: Chemoselective reduction of organyl azides with dichloroborane-dimethyl sulfide
Salunkhe, Ashok M.,Veeraraghavan Ramachandran,Brown, Herbert C.
, p. 10059 - 10064 (2002)
The rate and stoichiometry of the reduction of an organyl azide with BH3·THF was examined under standardized conditions at room temperature. Borane derivatives, such as dialkyl-, alkoxy-, and haloboranes were also examined for the reduction of azides. This study revealed BHCl2·SMe2 to be the most suitable reagent for the reduction of azides. The chemoselectivity of this reagent was also studied by reducing n-hexyl azide in the presence of representative series of functional groups, including esters, halides, nitriles, and nitro groups. BHCl2·SMe2 reduces azides in the presence of all of the above functional groups as well as olefins. Taking advantage of the differences in reactivity of BHCl2·SMe2 and BH3·THF or BH3·SMe2, it is now possible to reduce selectively an azide in the presence of olefins or to hydroborate an olefin in the presence of azides by a judicious choice of the reagent.
Fe/Fe2O3@N-dopped Porous Carbon: A High-Performance Catalyst for Selective Hydrogenation of Nitro Compounds
Yun, Ruirui,Hong, Lirui,Ma, Wanjiao,Jia, Weiguo,Liu, Shoujie,Zheng, Baishu
, p. 724 - 728 (2019)
Herein, we designed and prepared a novel Fe/Fe2O3-based catalyst, in which a remarkable synergistic effect has been revealed between Fe and Fe2O3 encapsulated in N-doping porous carbon. The Fe-based catalysts were fabricated via pyrolysis a mixture of MIL-101(Fe) and melamine. The catalyst exhibits exceptionally high catalytic activity (TOFs up to 8898 h?1 which is about 100 times higher than the similar kinds of catalysts) and chemoselectivity for nitroarene reduction under mild conditions.
Amberlyst-15(H+)-NaBH4-LiCl: An effective reductor for oximes and hydrazones
Baruah, Bipul,Dutta, Manu P.,Boruah, Anima,Prajapati, Dipak,Sandhu, Jagir S.
, p. 409 - 410 (1999)
A simple and mild procedure reduces oximes and hydrazones on amberlyst 15(H+) support with LiCl-NaBH4 to the corresponding amines and hydrazines respectively in high yield and purity.
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Schultz
, p. 1039,1040 (1960)
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Synthesis of 1,4-diaminocyclohexane in supercritical ammonia
Fischer,Mallat,Baiker
, p. 289 - 291 (1999)
The amination of 1,4-cyclohexanediol in supercritical ammonia has been studied in a continuous fixed-bed reactor at 135 bar. An unsupported cobalt catalyst stabilized by 5 wt% Fe afforded the main reaction products 4-aminocyclohexanol and 1,4-diaminocyclohexane with a cumulative selectivity of 97% at 76% conversion. Excess of ammonia and short contact time favored the desired reactions. At low and high conversions the amination selectivity decreased due to the formation of dimers and oligomers and degradation products. Recycling of the unreacted diol and amino alcohol intermediate can provide an alternative economic process for the synthesis of 1,4-diaminocyclohexane.
Instantaneous SmI2/H2O/amine mediated reduction of nitroalkanes and α,β-unsaturated nitroalkenes
Ankner, Tobias,Hilmersson, G?ran
, p. 5707 - 5710 (2007)
A rapid method for efficient reduction of nitroalkanes and α,β-unsaturated nitroalkenes using SmI2/H2O/amine has been developed.
Essential role of heterocyclic structure of N-alkylated 2-pyrrolidone derivatives for recycling uranium from spent nuclear fuels
Inoue, Tsubasa,Kazama, Hiroyuki,Takao, Koichiro,Tsushima, Satoru
, p. 846 - 853 (2020)
In a simple and versatile reprocessing method for recycling U and Pu from spent nuclear fuels, cyclic amides like Nalkylated 2-pyrrolidone derivatives (NRPs) are exclusively employed. However, there has been no convincing rational to explain why such a heterocyclic structure is required. To answer this question, we employed N-cyclohexyl-2-pyrrolidone (NCP) and N-cyclohexylformamide (NCF) as cyclic and acyclic monodentate amides, and focused on the following 3 topics in this study; (1) structural chemistry of their uranyl dinitrato complexes, (2) precipitation behavior of UO22+ from HNO3(aq) by using these amides, and (3) their chemical stability in HNO3(aq) simulating the reprocessing conditions for spent nuclear fuels. Fundamental coordination chemistry of UO2(NO3)2(L)2 (L = NCP, NCF) was found to be common to both L, regardless of the presence or absence of the pyrrolidone ring. Furthermore, both L exhibit comparable capability in precipitation of UO22+ from HNO3(aq). The most critical difference between NCP and NCF was found in their chemical stability in HNO3(aq), where NCF was gradually decomposed through acid-catalyzed hydrolysis, while NCP remained intact for at least 4 h. In conclusion, the pyrrolidone ring of NRPs plays an important role to sterically protect the carbonyl C from nucleophilic hydrolysis which initiates the amide C(=O)N bond cleavage.
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Breuer,Schnitzer
, p. 301,307 (1936)
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New and mild allyl carbamate deprotection method catalyzed by electrogenerated nickel complexes
Franco,Dunach
, p. 7333 - 7336 (2000)
A Ni(II)-catalyzed electrochemical procedure for the simple and mild deprotection of allyl carbamates to the corresponding amines is described. The amines are obtained in yields of 40-99% and the method is compatible with several functional groups. Electrolyses are carried out in DMF or in THF in single-compartment cells in the presence of a consumable zinc anode. (C) 2000 Elsevier Science Ltd.
A magnetically separable gold catalyst for chemoselective reduction of nitro compounds
Park, Sungho,Lee, In Su,Park, Jaiwook
, p. 395 - 399 (2013)
Magnetically separable gold-nanoparticle catalyst was prepared, and it showed excellent activity for chemoselective reduction of nitroarenes with hydrosilanes. The Royal Society of Chemistry 2013.
O-(DIPHENYLPHOSPHINYL)HYDROXYLAMINE: A NEW REAGENT FOR ELECTROPHILIC C-AMINATION
Colvin, Ernest W.,Kirby, Gordon W.,Wilson, Arthur C.
, p. 3835 - 3836 (1982)
O-(Diphenylphosphinyl)hydroxylamine efficiently aminates a variety of stabilised carbanions and certain Grignard reagents.
Low-temperature deacylation of N-monosubstituted amides
Spaggiari, Alberto,Blaszczak, Larry C.,Prati, Fabio
, p. 3885 - 3888 (2004)
(Chemical Equation Presented) The (PhO)3P-Cl2 reagent, prepared in situ by titrating a solution of triphenyl phosphite with chlorine, is used to convert N-monosubstituted amides into their corresponding amines. The reaction, if compared to other traditional methods, shows the advantage of very mild conditions and low temperature (-30°C→rt).
Highly selective one-step hydrogenation of nitrobenzene to cyclohexylamine over the supported 10% Ni/carbon catalysts doped with 3‰ Rh
Lu, Xinhuan,Chen, Yang,Zhao, Zhenshuang,Deng, Hao,Zhou, Dan,Wei, Changcheng,Nie, Renfeng,Xia, Qinghua
, p. 15354 - 15361 (2016)
The carbon supported 10% Ni catalysts doped with 3‰ Rh have been prepared by an impregnation method. These catalysts have been used to catalyze the one-step hydrogenation of nitrobenzene to cyclohexylamine. The results show that the 3‰ Rh-10% Ni/CSC (biocarbon) catalyst exhibits an excellent performance to achieve 100 mol% conversion of nitrobenzene and 91.6% selectivity of cyclohexylamine under reaction conditions of 3.5 MPa and 140 °C. The recycling tests reveal recyclable stability of 3‰ Rh-10% Ni/CSC. This catalyst is active for the hydrogenation of a series of electron-deficient nitrobenzenes. Some factors such as the type of carriers, the content of Ni and Rh, the type of metals and additives play important roles in controlling the selective hydrogenation.
Highly-dispersed and size-controlled ruthenium nanoparticles on carbon nanofibers: Preparation, characterization, and catalysis
Motoyama, Yukihiro,Takasaki, Mikihiro,Higashi, Kenji,Yoon, Seong-Ho,Mochida, Isao,Nagashima, Hideo
, p. 876 - 877 (2006)
Facile synthesis of ruthenium nanoparticles supported on the carbon nanofibers (CNFs) is accomplished by thermal decomposition of Ru 3(CO)12; ruthenium species on the platelet-type CNF are dispersed homogeneously and selectively on the edge of the graphite layers with narrow size distributions and behaves as an excellent catalyst for arene hydrogenation. Copyright
Fe/Fe3C Encapsulated in N-Doped Carbon Tubes: A Recyclable Catalyst for Hydrogenation with High Selectivity
Yun, Ruirui,Zhang, Shi,Ma, Wanjiao,Lv, Xiao,Liu, Shoujie,Sheng, Tian,Wang, Suna
, p. 9469 - 9475 (2019)
Herein, a series of Fe-based catalysts have been designed and prepared by grinding a mixture of MIL-88d and melamine, and then the mixture was followed by pyrolysis. An unusual Fe/Fe3C-activated site is uniformly encapsulated in the N-doped carbon tubes obtained by pyrolysis of the film-like nanocrystals of MIL-88d. Experimental characterizations and theoretical calculations demonstrate that the surface N sites can effectively trap the nitrobenzene and aniline by their phenyl groups with the formation of three C-N bonds that made the catalyst exhibit excellent catalytic activity (turnover frequencies of ≤11268 h-1 calculated on the basis of nitrobenzene) and chemoselectivity for the reduction of nitro derivatives under facile conditions.
ELECTROCATALYTIC HYDROGENATION OF ORGANIC COMPOUNDS ON DEVARDA COPPER AND RANEY NICKEL ELECTRODES IN BASIC MEDIA
Belot, Gerard,Desjardins, Sylvie,Lessard, Jean
, p. 5347 - 5350 (1984)
Using Devarda copper and Raney nickel electrodes, nitrobenzene, nitrocyclohexane, p-nitroacetophenone, N-methyl-p-anisaldehyde imine, benzophenone, and phenanthrene have been electrocatalytically hydrogenated with high chemical and current efficiency.
Post-functionalized iridium-Zr-MOF as a promising recyclable catalyst for the hydrogenation of aromatics
Rasero-Almansa, Antonia M.,Corma, Avelino,Iglesias, Marta,Sanchez, Felix
, p. 3522 - 3527 (2014)
The multifunctional heterogeneous catalyst iridium-Zr-based MOF is able to effectively catalyze the hydrogenation of aromatic compounds in high yields under mild conditions. The catalyst was found to be highly active and reusable, giving similar reactivity and selectivity after at least five catalytic uses. This journal is the Partner Organisations 2014.
A simple and reproducible method for the synthesis of silica-supported rhodium nanoparticles and their investigation in the hydrogenation of aromatic compounds
Mevellec, Vincent,Nowicki, Audrey,Roucoux, Alain,Dujardin, Christophe,Granger, Pascal,Payen, Edmond,Philippot, Karine
, p. 1214 - 1219 (2006)
Colloidal suspensions of rhodium nanoparticles have been easily prepared in aqueous solution by chemical reduction of the precursor RhCl 3·3H2O in the presence of the surfactant N,N-dimethyl-N-cetyl-N-(2-hydroxyethyl)ammonium chloride (HEA16Cl) and further used to immobilize rhodium nanoparticles on silica by simple impregnation. The obtained silica-supported rhodium nanoparticles have been investigated by adapted characterization methods such as transmission electron microscopy and X-ray photoelectron spectroscopy. A particle size increase from 2.4 to 5 nm after the silica immobilization step and total elimination of the surfactant has been observed. This "heterogeneous" catalyst displayed good activities for the hydrogenation of mono-, di- alkylsubstituted and/or functionalized aromatic derivatives in water under atmospheric hydrogen pressure and at room temperature. In all cases, the catalyst could be recovered several times after a simple decantation or filtration and reused without any significant loss in catalytic activity. This supported catalyst has also been tested under higher hydrogen pressure giving rise to TOFs reaching 6430 h -1 at 30 bar and in terms of catalytic lifetime 30 000 TTO in 8.5 h for pure anisole hydrogenation at 40 bar. the Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2006.
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Kirchhoff
, p. 2533 (1976)
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Green Synthesis of Rhodium Nanoparticles that are Catalytically Active in Benzene Hydrogenation and 1-Hexene Hydroformylation
Alsalahi, Waleed,Tylus, Wlodzimierz,Trzeciak, Anna M.
, p. 2051 - 2058 (2018)
Rhodium nanoparticles (Rh NPs) were prepared according to a green method based on the reduction of (acetylacetonato)dicarbonylrhodium(I), Rh(acac)(CO)2, in water at 80 °C. The nanoparticles, which were obtained without the addition of a reducing agent, were stabilized by polyvinylpyrrolidone (PVP) or polyvinyl alcohol (PVA) polymers and characterized by TEM (transmission electron microscopy), XPS (X-ray photoelectron spectroscopy), and XRD (X-ray powder diffraction) methods. The excellent catalytic activity of these Rh NPs was evidenced in the hydrogenation of benzene to cyclohexane. In the presence of PPh3, Rh NPs formed a highly active system in the hydroformylation of 1-hexene. In this system, they acted as a source of soluble rhodium species. Rh NPs were also synthesized in water using rhodium(II) acetate, Rh2(OAc)4, and rhodium(III) chloride, RhCl3, as rhodium sources, and their catalytic activity was compared with that of the rhodium precursors.
N,N-Chelate nickel(II) complexes bearing Schiff base ligands as efficient hydrogenation catalysts for amine synthesis
Xu, Mengyin,Wang, Yang,Zhou, Yifeng,Yao, Zi-Jian
, (2021/12/09)
Five N, N-chelate nickel (II) complexes bearing N-(2-pyridinylmethylene)-benzylamine ligands with different substituent groups were synthesized in good yields. The nickel complexes exhibited prominent catalytic efficiency toward amine synthesis from nitro compounds by using NaBH4 or H2 as hydrogen source through two catalytic systems. Various amines with different substituents were obtained in moderate to excellent yields. All substrates with electron-donating and electron-withdrawing properties were tolerated in the two reduction systems. Given the efficient catalytic activity, broad substance scope, and mild reduction conditions, the nickel catalysts have potential applications in industrial production.
One-pot synthesis of cyclohexylamine and: N -aryl pyrroles via hydrogenation of nitroarenes over the Pd0.5Ru0.5-PVP catalyst
Chaudhari, Chandan,Sato, Katsutoshi,Ikeda, Yasuyuki,Terada, Kenji,Abe, Naoya,Nagaoka, Katsutoshi
supporting information, p. 9743 - 9746 (2021/06/15)
The direct synthesis of cyclohexylamine via the hydrogenation of nitrobenzene over monometallic (Pd, Ru or Rh) and bimetallic (PdxRu1-x) catalysts was studied. The Pd0.5Ru0.5-PVP catalyst was the most effective catalyst for this reaction. The catalyst can be reused and applied for the synthesis of N-aryl pyrroles and quinoxalines from nitrobenzenes.
Development and Application of Efficient Ag-based Hydrogenation Catalysts Prepared from Rice Husk Waste
Unglaube, Felix,Kreyenschulte, Carsten Robert,Mejía, Esteban
, p. 2583 - 2591 (2021/04/09)
The development of strategies for the sustainable management and valorization of agricultural waste is of outmost importance. With this in mind, we report the use of rice husk (RH) as feedstock for the preparation of heterogeneous catalysts for hydrogenation reactions. The catalysts were prepared by impregnating the milled RH with a silver nitrate solution followed by carbothermal reduction. The composition and morphology of the prepared catalysts were fully assessed by IR, AAS, ICP-MS, XPS, XRD and STEM techniques. This novel bio-genic silver-based catalysts showed excellent activity and remarkable selectivity in the hydrogenation of nitro groups in both aromatic and aliphatic substrates, even in the presence of reactive functionalities like halogens, carbonyls, borate esters or nitriles. Recycling experiments showed that the catalysts can be easily recovered and reused multiple times without significant drop in performance and without requiring re-activation.
