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.
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Campbell
, p. 4019 (1951)
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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.
Electrophilic amination of methylbenzenes with sodium azide in trifluoromethanesulfonic acid
Borodkin,Elanov,Shubin
, p. 934 - 935 (2009)
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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.
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Keller,Smith
, p. 1122 (1944)
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Brown,Etzel,Henke
, p. 635 (1928)
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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.
Metal-assisted lossen rearrangement
Jasikova, Lucie,Hanikyrova, Eva,Skriba, Anton,Jasik, Juraj,Roithova, Jana
, p. 2829 - 2836 (2012)
A new reaction mechanism for the Lossen rearrangement of hydroxamic acids catalyzed by basic salts is presented. It is shown that the rearrangement proceeds in metal complexes of deprotonated hydroxamic acids. The deprotonation can occur either at the oxygen atom (observed for the zinc complexes) or at the nitrogen atom (observed for the potassium complexes). Both anionic forms are characterized by infrared multiphoton dissociation spectroscopy. The rearrangements proceed from the reactive N-deprotonated metal hydroxamates and lead to metal carbamates. The mechanism is elucidated by computational chemistry, mass-spectrometric studies, and preparative experiments.
Rearrangement of N-Methylaniline over H-ZSM-5, H-Theta-1, and H-Y Zeolites
Mordi, Raphael C.,Dwyer, John,Fields, Roy
, p. 627 - 630 (1993)
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Nickel oxide nanoparticles grafted on reduced graphene oxide (rGO/NiO) as efficient photocatalyst for reduction of nitroaromatics under visible light irradiation
Al-Nafiey, Amer,Kumar, Anurag,Kumar, Malika,Addad, Ahmed,Sieber, Brigitte,Szunerits, Sabine,Boukherroub, Rabah,Jain, Suman L.
, p. 198 - 207 (2017)
Nickel oxide nanoparticles were grafted on reduced graphene oxide via simultaneous reduction of graphene oxide and nickel salt in a single step reaction. The synthesized material (rGO/NiO) was found to be efficient visible light active photocatalyst for the reduction of nitroaromatic derivatives to their corresponding amino compounds. Hydrazine monohydrate provided necessary protons and electrons for the targeted reaction. After completion of the reaction, the photocatalyst could readily be recovered by simple external magnet and could be reused for six runs without any significant loss of its activity. More importantly, the photocatalyst did not show any leaching during the reaction as confirmed by ICP-AES analysis of the recovered catalyst.
Photocatalytic formation of a carbamate through ethanol-assisted carbonylation of p-nitrotoluene
Maldotti, Andrea,Amadelli, Rossano,Samiolo, Luca,Molinari, Alessandra,Penoni, Andrea,Tollari, Stefano,Cenini, Sergio
, p. 1749 - 1751 (2005)
The nitroarene p-nitrotoluene is converted with a selectivity higher than 85% to the corresponding carbamate at room temperature and atmospheric pressure, using photoexcited particles of TiO2 as catalyst and EtOH as carbonylating species. The Royal Society of Chemistry 2005.
Nanocrystalline Pt-CeO2 as an efficient catalyst for a room temperature selective reduction of nitroarenes
Shukla, Astha,Singha, Rajib Kumar,Sasaki, Takehiko,Bal, Rajaram
, p. 785 - 790 (2015)
We have developed a new synthesis strategy to prepare Pt nanoparticles with size between 2 and 5 nm supported on CeO2 nanoparticles with size between 30 and 60 nm by the hydrothermal method in the presence of the surfactant cetyltrimethyl ammonium bromide (CTAB) and a polymer (PVP). It was found that the catalyst is highly active for the chemoselective hydrogenation of nitro compounds in aqueous medium in the presence of molecular hydrogen at room temperature (25 °C). The catalyst was characterized by XRD, ICP-AES, XPS, BET-surface area measurements, SEM, TEM and EXAFS. Different reaction parameters like reaction time, catalyst ratio, Pt loading etc. were studied in detail. The investigation revealed that the site of Pt plays a crucial role in the activity by favouring the reduction of nitro-compounds. The catalyst shows >99.9% conversion of nitro-compounds with 99% selectivity of amino compounds. The reusability of the catalyst was tested by conducting the experiment with the same catalyst and it was found that the catalyst does not change its activity and selectivity even after five reuses. This journal is
SYNTHESIS OF METHYL-N-ARYLCARBAMATES BY THE CARBONYLATION OF AZOXY, AZO, AND NITRO COMPOUNDS
Manov-Yuvenskii, V. I.,Petrovskii, K. B.,Lapidus, A. L.
, p. 543 - 545 (1984)
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Gilman,Sternbach
, p. 465 (1971)
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Magnetically Recyclable Metal–Organic Framework@Fe3O4 Composite-Catalyzed Facile Reduction of Nitroarene Compounds in Aqueous Medium
Yang, Sen,Zhang, Zhi-Hui,Chen, Qun,He, Ming-Yang,Wang, Liang
, (2018)
A kind of Metal–organic framework (MOF) composite namely Cu-BTC@Fe3O4 (BTC?=?1,3,5-benzenetricarboxylate) was prepared and showed good catalytic activity toward the reduction of nitroarenes. This reaction proceeded smoothly under mild reaction conditions in aqueous medium using sodium borohydride as the reduction agent, affording the corresponding anilines in good to excellent yields. In addition, the catalyst could be easily recovered with an external permanent magnet and be reused for successive six runs with slight decrease in its activity.
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Albisetti et al.
, p. 1489,1492 (1959)
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Pd Nanoparticles Assembled on Metalporphyrin-Based Microporous Organic Polymer as Efficient Catalyst for Tandem Dehydrogenation of Ammonia Borane and Hydrogenation of Nitro Compounds
Zou, Zhijuan,Jiang, Yaya,Song, Kunpeng
, p. 1277 - 1286 (2020)
Abstract: Metalporphyrin-based porous polymers supporting high dispersed Pd nanoparticle (NP) catalysts (HUST-1-Pd) were prepared with a novel solvent-knitting hyper-crosslinked polymer method using 5-, 10-, 15-, and 20-tetraphenylporphyrin (TPP) as building blocks. The N2 sorption isotherms of the catalysts show that the HUST-1-Pd possesses many ultra-micropores and continuous mesopores. The NPs are assembled on tetraphenylporphyrin structures and show Pd-N4 composition-dependent catalysis for methanolysis of ammonia borane (AB) and hydrogenation of aromatic nitro compounds to primary amines in methanol solutions at room temperature. The nano-palladium reduced by NaBH4 has efficient catalytic activity for AB methanolysis. A variety of R-NO2 derivatives were reduced selectively into R-NH2 via palladium catalyzed tandem reactions with 5–30?min of reaction time with conversion yields reaching up to 90%. The derivatives also give excellent recycling performance (more than 10 times). Furthermore, the turnover frequency (TOF) can reach 87,209?h?1. The HUST-1-Pd compounds represent a unique metal catalyst for hydrogenation reactions in a green environment without using pure hydrogen. Graphic Abstract: A monodisperse Pd NPs embed in porphyrin-based microporous organic polymer was reported to catalyse the tandem dehydrogenation of ammonia borane and hydrogenation of R-NO2 to R-NH2 at room temperature. The catalyst is efficient and reusable in an environment-friendly process with short reaction times and high yields.[Figure not available: see fulltext.]
One-pot tandem catalysis over Pd@MIL-101: boosting the efficiency of nitro compound hydrogenation by coupling with ammonia borane dehydrogenation
Yang, Qihao,Chen, Yu-Zhen,Wang, Zhiyong U.,Xu, Qiang,Jiang, Hai-Long
, p. 10419 - 10422 (2015)
The hydrogenation efficiency of nitro compounds was found to be greatly boosted by coupling with dehydrogenation of ammonia borane. The Pd@MIL-101 with tiny Pd NPs is exceptionally efficient and recyclable in the tandem reactions and diverse nitro compounds can be selectively reduced to the corresponding amines in 1.5-5 min with quantitative yields.
Sulfamide chemistry applied to the functionalization of self-assembled monolayers on gold surfaces
Pantaine, Lo?c,Humblot, Vincent,Coeffard, Vincent,Vallée, Anne
, p. 648 - 658 (2017)
Aniline-terminated self-assembled monolayers (SAMs) on gold surfaces have successfully reacted with ArSO2NHOSO2Ar (Ar = 4-MeC6H4 or 4-FC6H4) resulting in monolayers with sulfamide moieties
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Micewicz
, (1928)
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Transition metal imide/organic imine metathesis reactions: Unexpected observations
McInnes, Jacqueline M.,Mountford, Philip
, p. 1669 - 1670 (1998)
Mixtures of [Ti(NBut)Cl2(py)3] 1 and PhC(NAr)H (Ar = C6H3Me2-2,6 or C6H4Me-4) gave quantitative conversion to [Ti(NAr)Cl2(py)3] and PhC(NBut)H, the products of Ti=N-But/C=NAr transition metal imide/organic imine metathesis; examination of the kinetics for Ar = C6H4Me-4 showed that the rate limiting step for this process is zero order in [1], demonstrating that these reactions do not involve metal imide particiption in the rate limiting step.
PROTONATION OF REAGENTS AND ACID-BASE CATALYSIS IN ACYLATION
Kalnin'sh, K. K.
, p. 822 - 828 (1992)
The kinetic characteristics of the model reaction of electron transfer and the reaction of acylation of aromatic amines by aromatic acid anhydrides were investigated as a function of the concentration of acid catalyst and a correlation was established between the type of this function and the characteristics of protonation of the amines.The rate constants of the catalytic and noncatalytic flows of the forward and reverse reactions in the phthalic anhydride-p-toluidine system were determined as a function of the molarity and proton-acceptor properties of the solvent.The mechanism of acid-base catalysis was examined as a sequence of proton and electron transfer processes. Keywords: catalysis, kinetics, protonation.
Iodide Reduction of Sulfilimines. 2. Evidence for Concurrent Stepwise and Concerted Mechanisms for the Decomposition of Sulfurane Intermediates
Young, Paul R.,Huang, H. C.
, p. 1805 - 1809 (1987)
The iodide reduction of N-(substituted ethyl or phenyl)-S,S-dimethylsulfilimmonium salts (aqueous solution, 25 deg C, μ = 1.0 with KCl) is first order in proton activity and iodide concentration in the pH range 0.5-5.The solvent deuterium isotope effects for the reduction reaction vary in the range kH/kD = 0.26-0.48 as the nitrogen substituent is changed from ethyl- to trifluoroethylamine.Electron-withdrawing groups in the leaving group decrease the rate of the reaction and give βl.g. values of ca. 0.7 for cyanoethyl- and trifluoroethylamine leaving groups and ca. 0.1 for the more basic ethylamine derivatives; a βl.g. of 0.58 is observed for aniline derivatives.General acid catalysis is observed in the reduction of the acidic ethylamine and aniline derivatives with Broensted α values of 0.59 and 0.39 for cyanoethyl- and trifluoroethylamine leaving groups, respectively; for anilines, the Broensted α values decreased from 0.67 to 0.50 as the leaving group is changed from 4-methyl- to 3-nitroaniline.The value of βl.g. decreases with decreasing strength of the catalyzing acid and the term pxy = (δβl.g./δpKaHA) = (δα/δKal.g.) ca. -0.06 to -0.1.The solvent deuterium isotope effect on the general catalyzed reduction reaction increases with increasing acid strength; for the cyanoethylamine derivative, kBH/kBD = 1.47-2.32 for acetic and chloroacetic acids, respectively.A mechanism is suggested involving concurrent stepwise and concerted mechanisms for the reduction reaction; the mechanism observed seems to depend on the nature of the catalyzing acid.
Recyclable aluminium oxy-hydroxide supported Pd nanoparticles for selective hydrogenation of nitro compounds via sodium borohydride hydrolysis
G?ksu, Haydar
, p. 8498 - 8504 (2015)
The reduction of aromatic/aliphatic nitro compounds to primary amines with high yields was easily realized by transfer hydrogenation comprising commercially available aluminium oxy-hydroxide-supported Pd nanoparticles (0.5 wt% Pd, Pd/AlO(OH)) as catalysts and NaBH4 as the hydrogen reservoir at room temperature in a water/methanol mixture (v/v = 7/3). The presented catalytic methodology is highly efficient for the reduction of various nitro compounds as well as reusable. A variety of R-NO2 derivatives were tested by performing the Pd/AlO(OH) catalysed reduction reaction and all the nitro compounds were selectively reduced to their corresponding primary amines in reaction times ranging from 0.75 to 13 min with yields reaching up to 99%. This process can be assessed as an eco-friendly method involving both reusable catalysts (Pd/AlO(OH) NPs) and hydrogen sources (NaBH4).
Palladium Immobilized on a Polyimide Covalent Organic Framework: An Efficient and Recyclable Heterogeneous Catalyst for the Suzuki–Miyaura Coupling Reaction and Nitroarene Reduction in Water
Dong, Zhenhua,Pan, Hongguo,Gao, Pengwei,Xiao, Yongmei,Fan, Lulu,Chen, Jing,Wang, Wentao
, p. 299 - 306 (2021/05/10)
An efficient and recyclable Pd nano-catalyst was developed via immobilization of Pd nanoparticles on polyimide linked covalent organic frameworks (PCOFs) that was facilely prepared through condensation of melamine and 3,3′,4,4′-biphenyltetracarboxylic dianhydride. The Pd nanoparticles (Pd NPs) catalyst was thoroughly characterized by FT-IR, XRD, SEM, TEM. Furthermore, the catalytic activity of Pd NPs catalyst was evaluated by Suzuki–Miyaura coupling reaction and nitroarene reduction in water, respectively. The excellent yields of corresponding products revealing revealed that the Pd NPs catalyst could be applied as an efficient and reusable heterogeneous catalyst for above two reactions. Graphical Abstract: [Figure not available: see fulltext.]
Synthesis and characterization of chitosan pyridyl imine palladium (CPIP) complex as green catalyst for organic transformations
Chundawat, Narendra Singh,Pathan, Sultan,Singh, Girdhar Pal,Deuri, Arup Saha,Zarrintaj, Payam,Chauhan, Narendra Pal Singh
, p. 2835 - 2850 (2021/02/11)
In this work, the modification of chitosan using 2-acetyl pyridine has been used to prepare an intermediate, chitosan pyridyl imine (CPI), in first step and then in second step it is further reacted with Pd(OAc)2 to develop chitosan pyridyl imine palladium (CPIP) complex catalyst in a very simplistic way. The formed CPIP has been extensively characterized with respect to raw chitosan utilizing methods including FT-IR, pyrolysis GC–MS, XRD, XPS, FE-SEM, EDS, TGA-DTG and DSC. TG-DSC study suggested that the catalyst is thermally stable up to 300?°C. This catalyst shows an excellent activity in the reduction of toxic pollutant nitrobenzene to less toxic aniline. CPIP complex has also been found to give magnificent results in Suzuki–Miyaura and Heck cross-coupling reactions, and therefore, using this green catalyst, the toxic phosphine ligand can be excluded from cross-coupling reactions. This study furnishes an economic and eco-friendly catalyst for organic transformation in sustainable chemistry.