- Magnetically‐recoverable Schiff base complex of Pd(II) immobilized on Fe3O4@SiO2 nanoparticles: an efficient catalyst for the reduction of aromatic nitro compounds to aniline derivatives
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Fe3O4@SiO2/Schiff base/Pd(II) is reported as a magnetically recoverable heterogeneous catalyst for the chemoselective reduction of aromatic nitro compounds to the corresponding amines through catalytic transfer hydrogenation (CTH). In this regard, a small amount of the nanocatalyst (0.52?mol% Pd) and hydrazine hydrate, showing safe characteristics and perfect ability as the hydrogen donor, were added to the nitro substrates. The experiments described the successful reduction of aromatic nitro compounds with good to excellent yields and short reaction times. The catalyst, due to its magnetic property, could be simply separated from the reaction mixture by a permanent magnet and reused in seven consecutive reactions without considerable loss in its activity. Moreover, the leaching of Pd was only 3.6% after the seventh run. Thus, the most striking feature of this method is to use a small amount of the magnetic nanocatalyst along with a cheap and safe hydrogen source to produce the important amine substances selectively, which makes the method economical, cheap, environmentally friendly, and simple. Graphic abstract: [Figure not available: see fulltext.]
- Azadi, Sedigheh,Esmaeilpour, Mohsen,Sardarian, Ali Reza
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p. 809 - 821
(2021/07/20)
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- A mild and selective Cu(II) salts-catalyzed reduction of nitro, azo, azoxy, N-aryl hydroxylamine, nitroso, acid halide, ester, and azide compounds using hydrogen surrogacy of sodium borohydride
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The first mild, in situ, single-pot, high-yielding well-screened copper (II) salt-based catalyst system utilizing the hydrogen surrogacy of sodium borohydride for selective hydrogenation of a broad range of nitro substrates into the corresponding amine under habitancy of water or methanol like green solvents have been described. Moreover, this catalytic system can also activate various functional groups for hydride reduction within prompted time, with low catalyst-loading, without any requirement of high pressure or molecular hydrogen supply. Notably, this system explores a great potential to substitute expensive traditional hydrogenation methodologies and thus offers a greener and simple hydrogenative strategy in the field of organic synthesis.
- Kalola, Anirudhdha G.,Prasad, Pratibha,Mokariya, Jaydeep A.,Patel, Manish P.
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supporting information
p. 3565 - 3589
(2021/10/12)
-
- Discovery and development of 2-aminobenzimidazoles as potent antimalarials
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The emergence of Plasmodium falciparum resistance to frontline antimalarials, including artemisinin combination therapies, highlights the need for new molecules that act via novel mechanisms of action. Herein, we report the design, synthesis and antimalarial activity of a series of 2-aminobenzimidazoles, featuring a phenol moiety that is crucial to the pharmacophore. Two potent molecules exhibited IC50 values against P. falciparum 3D7 strain of 42 ± 4 (3c) and 43 ± 2 nM (3g), and high potency against strains resistant to chloroquine (Dd2), artemisinin (Cam3.IIC580Y) and PfATP4 inhibitors (SJ557733), while demonstrating no cytotoxicity against human cells (HEK293, IC50 > 50 μM). The most potent molecule, possessing a 4,5-dimethyl substituted phenol (3r) displayed an IC50 value of 6.4 ± 0.5 nM against P. falciparum 3D7, representing a 12-fold increase in activity from the parent molecule. The 2-aminobenzimidazoles containing a N1-substituted phenol represent a new class of molecules that have high potency in vitro against P. falciparum malaria and low cytotoxicity. They possessed attractive pharmaceutical properties, including low molecular weight, high ligand efficiency, high solubility, synthetic tractability and low in vitro clearance in human liver microsomes.
- Avery, Vicky M.,Challis, Matthew P.,Creek, Darren J.,De Paoli, Amanda,Devine, Shane M.,Kigotho, Jomo K.,MacRaild, Christopher A.,Norton, Raymond S.,Scammells, Peter J.,Siddiqui, Ghizal
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-
- Yeast supported gold nanoparticles: an efficient catalyst for the synthesis of commercially important aryl amines
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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.
- Krishnan, Saravanan,Patel, Paresh N.,Balasubramanian, Kalpattu K.,Chadha, Anju
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supporting information
p. 1915 - 1923
(2021/02/06)
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- Copper catalyzed reduction of azides with diboron under mild conditions
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We report herein the first Cu catalyzed reduction of azides with B2pin2 (pin = pinacolato) as the reductant under very mild conditions. A series of primary amines and amides were obtained in moderate to excellent yields with high chemoselectivity and good functional group tolerance. This reaction can be performed with a cheap copper salt, a simple NHC ligand and a diboron reagent.
- Chen, Yang,Deng, Shengqi,Gao, Yihua,Liu, Liwen,Liu, Yu,Lu, Da,Wang, Qianwen,Zhang, Xiao
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supporting information
(2020/02/27)
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- CuIBiOI is an efficient novel catalyst in Ullmann-type CN– couplings with wide scope—A rare non-photocatalyic application
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Preparation of a new, mixed-cationic layered CuIBiOI was prepared and its non-photocatalytic catalytic properties were explored. This solid substance had BiOI-like, lamellar and deflected structure resulting from CuI ion incorporation in the Bi2O2 layers. The as-prepared substance was fully characterized by XRD, Raman, far IR, UV–DR, XP spectroscopies, thermal (TG-DTG) and analytical (ICP-MS, SEM-EDX) methods, electron microscopies (SEM, TEM) as well as BET surface area measurements. By performing Ullmann-type CN– coupling reactions between aryl halides and aqueous ammonia, its catalytic capabilities were tested. The effects of solvents, added base and catalyst loading as well as reaction time and reaction temperature were scrutinized, and a green way for the reaction was identified. The recyclability of the catalyst without the loss of activity and its general applicability for a wide range of aryl halides were also demonstrated.
- Djerdj, Igor,Kónya, Zoltán,Kocsis, Marianna,Kukovecz, ákos,Pálinkó, István,Sipos, Pál,Varga, Gábor
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- Preparation method of 2-nitro-aniline
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The invention discloses a preparation method of 2-nitro-aniline. The method comprises the steps: under conditions of a high-boiling-point high-polarity solvent used as a reaction solvent and the presence of an inorganic acid, controlling the temperature to be 100 to 140 DEG C and carrying out normal-pressure desulfonation reaction on the 2-nitro-4-sulfonic aniline; and after the reaction is finished, carrying out vacuum concentration to remove the high-boiling-point high-polarity solvent, adding water, uniformly mixing, regulating the pH value to 8-10, sequentially extracting, washing, concentrating and drying to obtain the 2-nitro-aniline, and recycling the high-boiling-point high-polarity solvent after the reaction for reuse. According to the preparation method, a normal-pressure desulfonation reaction is carried out within a relatively low temperature range, the energy consumption in the preparation process is low, meanwhile, less waste salt is generated, only 2.7-3.3 tons of sodiumsulfate is generated according to 2-nitro-aniline per ton, the purity (HPLC) of the finally obtained 2-nitro-aniline product is greater than 97%, and the highest yield can reach 91%.
- -
-
Paragraph 0014-0068
(2020/11/12)
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- Flow hydrodediazoniation of aromatic heterocycles
-
Continuous flow processing was applied for the rapid replacement of an aromatic amino group with a hydride. The approach was applied to a range of aromatic heterocycles, confirming the wide scope and substituent-tolerance of the processes. Flow equipment was utilized and the process optimised to overcome the problematically-unstable intermediates that have restricted yields in previous studies relying on batch procedures. Various common organic solvents were investigated as potential hydride sources. The approach has allowed key structures, such as amino-pyrazoles and aminopyridines, to be deaminated in good yield using a purely organic-soluble system.
- R?der, Liesa,Nicholls, Alexander J.,Baxendale, Ian R.
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- Divergent Late-Stage (Hetero)aryl C?H Amination by the Pyridinium Radical Cation
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(Hetero)arylamines constitute some of the most prevalent functional molecules, especially as pharmaceuticals. However, structurally complex aromatics currently cannot be converted into arylamines, so instead, each product isomer must be assembled through a multistep synthesis from simpler building blocks. Herein, we describe a late-stage aryl C?H amination reaction for the synthesis of complex primary arylamines that other reactions cannot access directly. We show and rationalize through a mechanistic analysis the reasons for the wide substrate scope and the constitutional diversity of the reaction, which gives access to molecules that would not have been readily available otherwise.
- Ham, Won Seok,Hillenbrand, Julius,Jacq, Jér?me,Genicot, Christophe,Ritter, Tobias
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supporting information
p. 532 - 536
(2019/01/04)
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- Base promoted peroxide systems for the efficient synthesis of nitroarenes and benzamides
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A useful and efficient approach for the synthesis of nitroarenes from several aromatic amines (including heterocycles) using peroxide and base has been developed. This oxidative reaction is very easy to handle and afforded the products in good yields. Formation of benzamides from benzylamine was also successfully carried out with this metal-free catalytic system in good to excellent yields.
- Gupta, Sampa,Ansari, Alisha,Sashidhara, Koneni V.
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supporting information
(2019/09/07)
-
- Preparing method of ultraviolet absorber UV-234
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The invention provides a preparing method of an ultraviolet absorber UV-234. The preparing method comprises the steps of conducting ammoniation, diazotization, coupling, first-step reduction, second-step reduction reaction and post-treatment on ortho-nitrochlorobenzene to prepare 2-[2'-hydroxy-3',5'-di(alpha,alpha-dimethyl benzyl)phenyl]benzotriazole. According to the preparing method, ortho-nitrochlorobenzene is ammonified by adopting ammonium hydroxide with the concentration of 10-25%, then is subjected to diazotization with nitrite to produce diazonium salt, no diazotization needs to occurunder a strong acid medium, by-product ammonium hydroxide of existing products of a company is comprehensively utilized, low emission of three wastes is achieved, and the required cost is low; a two-step reduction method is adopted in a reduction ring closing process of intermediate azo products, the situation is avoided that a strong reduction agent directly reduces azo double bonds into amine, impurity production is reduced, and not only is the purity of the products increased but also the product yield is increased.
- -
-
Paragraph 0028; 0030; 0035; 0037; 0042; 0044
(2019/08/26)
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- Preparation method of ultraviolet absorbent UV - 329 (by machine translation)
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The invention provides a preparation method, UV - 329, of an ultraviolet absorber. The method comprises the following steps: performing ammonification, diazotization, coupling, one-step reduction, two-step reduction reaction and post-treatment to prepare 2 - (2 '- hydroxyl -5' - t-octylphenyl) benzotriazole product by o-nitrochlorobenzene. To the method, by ammonia water with a concentration 10%~25%, o-nitrochlorobenzene is subjected to diazotization reaction with nitrite to generate a diazonium salt, the diazotization reaction does not need to be carried out in a strong acid medium, and byproduct ammonia water of the product in the company is comprehensively utilized. The reduction closed-loop process of the intermediate azo product adopts 2-step reduction method, the strong reducing agent is prevented from directly reducing the azo double bond to the amine, impurity generation, product purity, and yield. (by machine translation)
- -
-
Paragraph 0032; 0034; 0039; 0041; 0046; 0048
(2019/08/26)
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- A green and recyclable ligand-free copper (I) catalysis system for amination of halonitrobenzenes in aqueous ammonia solution
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The amination of halonitrobenzenes is an important reaction to produce the corresponding nitroanilines. Direct amination of p-chloronitrobenzene (p-CNB) to p-nitroaniline (p-NAN) with aqueous NH3 solution was investigated over various transition metal salts in the absence of ligand, inorganic base and organic solvent. It was found that CuI is the most effective catalyst with respect to p-CNB conversion, p-NAN selectivity (≈ 100%) and the post-reaction separation and recycling. A high p-NAN yield of 97% could be obtained at 200 °C in 6.5 h with molar ratios of NH3/p-CNB and CuI/p-CNB of 21 and 0.1, respectively. A possible reaction mechanism was proposed, in which NH3 was not only a substrate but also a ligand to coordinate with CuI and formed a water-soluble Cu complex, and then it started the catalytic cycle. The influence of reaction variables such as NH3 concentration, CuI concentration, temperature and time on the p-CNB conversion and the p-NAN selectivity was examined. At room temperature the desired product of p-NAN is insoluble in water but the Cu complex catalyst is water-soluble and so the aqueous phase including the catalyst and NH3 can be easily separated and reused for the subsequent reaction runs. The green and sustainable system is effective for the conversion of diverse halonitrobenzenes to nitroanilines.
- Li, Yan,Shi, Ruhui,Lin, Weiwei,Cheng, Haiyang,Zhang, Chao,Arai, Masahiko,Zhao, Fengyu
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- Preparation method of ultraviolet absorber UV-328
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A preparation method of an ultraviolet absorber UV-328 is provided. The method includes o-nitrochlorobenzene ammoniation, diazotization, coupling, a first reduction step, a second reduction reaction and after-treatment to prepare a 2-(2'-hydroxyl-3',5'-di-tert-amyl phenyl) benzotriazole product. Ammonia water having a concentration of 10-25% is adopted for o-nitrochlorobenzene ammoniation, then diazotization is performed with nitrite to generate a diazonium salt, the diazotization does not need a strong acidic medium, and the ammonia water which is a byproduct of products of the company is comprehensively utilized, thus achieving low emission of three wastes and a low cost. Reduction for ring closing of an intermediate azo product adopts a two-step reduction process, avoiding a situation that a strong reductant directly reduces azo double bonds into amine, reducing impurity generation, increasing product purity and increasing the product yield.
- -
-
Paragraph 0031; 0033; 0038; 0040; 0045; 0047; 0057; 0062
(2019/10/01)
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- Benzimidazolium-based high temperature ionic liquid-in-oil microemulsion for regioselective nitration reaction
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Owing to the fascinating applications of ionic liquids (ILs) based non-aqueous microemulsions (MEs) in the field of chemical reactions due to their high thermal stability compared to that of aqueous MEs and requirement of water-free environment, we design
- Kar, Barnali,Ghosh, Prasanjit,Kundu, Kaushik,Bardhan, Soumik,Paul, Bidyut K.,Das, Sajal
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p. 122 - 130
(2018/07/25)
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- Silica-supported perchloric acid and potassium bisulfate as reusable green catalysts for nitration of aromatics under solvent-free microwave conditions
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Silica-supported perchloric acid and bisulfate (SiO2/HClO4 and SiO2/KHSO4) have been developed as reusable green catalysts for nitration of aromatic compounds using NaNO2 in acetonitrile medium under conventional and solvent-free microwave conditions. The reaction times under microwave irradiation are significantly shorter than conventional method even though the yields obtained in microwave-assisted reactions are comparable with those obtained under reflux conditions.
- Kumar, M. Satish,Sriram, Y. Hemanth,Venkateswarlu,Rajanna,Sudhakar, M. Sai,Venkanna, Purugula,Saiprakash
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supporting information
p. 59 - 67
(2017/12/26)
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- Sodium perborate/NaNO2/KHSO4-triggered synthesis and kinetics of nitration of aromatic compounds
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Sodium perborate (SPB) was used as efficient green catalyst for NaNO2/KHSO4-mediated nitration of aromatic compounds in aqueous acetonitrile medium. Synthesis of nitroaromatic compounds was achieved under both conventional and solvent-free microwave conditions. Reaction times were comparatively shorter in the microwave-assisted than conventional reaction. The reaction kinetics for nitration of phenols in aqueous bisulfate and acetonitrile medium indicated first-order dependence on [Phenol], [NaNO2], and [SPB]. Reaction rates accelerated with introduction of electron-donating groups but retarded with electron-withdrawing groups. Kinetic results did not fit well quantitatively with Hammett’s equation. Observed deviations from linearity were addressed in terms of exalted Hammett’s constants (σˉ or σeff), para resonance interaction energy (ΔΔGp) parameter, and Yukawa–Tsuno parameter (r). This term provides a measure of the extent of resonance stabilization for a reactive structure that builds up charge (positive) in its transition state. The observed negative entropy of activation (?ΔS#) suggests greater solvation and/or cyclic transition state before yielding products.
- Rajanna,Muppidi, Suresh,Pasnoori, Srinivas,Saiprakash
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p. 6023 - 6038
(2018/09/21)
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- Preparation and characterization of Fe3O4/SiO2/CdS nanocomposites as efficient magnetic photocatalysts for the reduction of nitro compounds under visible LED irradiation
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A series of magnetic Fe3O4/SiO2/CdS nanocomposites were synthesized through a facile and convenient method. The characterization of the prepared nanocomposites was performed by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), vibrating sample magnetometer (VSM), UV–Vis spectroscopy, and UV–vis diffuse reflectance spectroscopy (DRS). The prepared magnetic photocatalysts were first utilized for the photocatalytic reduction of nitro compounds under visible LED irradiation. The Fe3O4/SiO2/CdS nanocomposites exhibited enhanced photoactivity compared with the bare CdS and commercial CdS (Aldrich). The results demonstrated that Fe3O4/SiO2/CdS nanocomposites have potential to provide a promising visible light driven photocatalyst for the selective reduction of nitro compounds to corresponding amines under mild conditions. The prepared photocatalyst can be recovered by magnetic separation and successfully reused for 3 cycles.
- Eskandari, Parvin,Kazemi, Foad
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p. 233 - 239
(2018/06/15)
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- Thermal azide-Alkene cycloaddition reactions: straightforward multi-gram access to Δ2-1,2,3-Triazolines in deep eutectic solvents
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The multi-gram synthesis of a wide range of 1,2,3-Triazolines via azide-Alkene cycloaddition reactions in a Deep Eutectic Solvent (DES) is reported. The role of DES in this transformation as well as the origin of the full product distribution was studied with an experimental/computational-DFT approach.
- Sebest, Filip,Casarrubios, Luis,Rzepa, Henry S.,White, Andrew J. P.,Díez-González, Silvia
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p. 4023 - 4035
(2018/09/11)
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- Visible-light-driven Efficient Photocatalytic Reduction of Organic Azides to Amines over CdS Sheet–rGO Nanocomposite
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CdS sheet–rGO nanocomposite as a heterogeneous photocatalyst enables visible-light-induced photocatalytic reduction of aromatic, heteroaromatic, aliphatic and sulfonyl azides to the corresponding amines using hydrazine hydrate as a reductant. The reaction shows excellent conversion and chemoselectivity towards the formation of the amine without self-photoactivated azo compounds. In the adopted strategy, CdS not only accelerates the formation of nitrene through photoactivation of azide but also enhances the decomposition of azide to a certain extent, which entirely suppressed formation of the azo compound. The developed CdS sheet-rGO nanocomposite catalyst is very active, providing excellent results under irradiation with a 40 W simple household CFL lamp.
- Singha, Krishnadipti,Mondal, Aniruddha,Ghosh, Subhash Chandra,Panda, Asit Baran
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supporting information
p. 255 - 260
(2018/01/15)
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- Regioselective nitration of anilines with Fe(NO3)3·9H2O as a promoter and a nitro source
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An efficient Fe(NO3)3·9H2O promoted ortho-nitration reaction of aniline derivatives has been developed. This reaction may go through a nitrogen dioxide radical (NO2) intermediate, which is generated by the thermal decomposition of iron(iii) nitrate. The practicality of the present method using nontoxic and inexpensive iron reagents has been shown by the broad substrate scope and applications.
- Gao, Yang,Mao, Yuanyou,Zhang, Biwei,Zhan, Yingying,Huo, Yanping
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p. 3881 - 3884
(2018/06/08)
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- Potassium Periodate/NaNO2/KHSO4-Mediated Nitration of Aromatic Compounds and Kinetic Study of Nitration of Phenols in Aqueous Acetonitrile
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Synthesis and kinetics of potassium periodate(KIO4)/NaNO2/KHSO4)-initiated nitration of aromatic compounds have been studied in aqueous acetonitrile medium. Synthesis of nitroaromatic compounds is achieved under conventional and solvent-free microwave conditions. Reaction times in microwave-assisted reaction are comparatively less than in conventional reaction. The reaction kinetics for the nitration of phenols in aqueous bisulfate and acetonitrile medium indicated first-order dependence on [phenol], [NaNO2], and [KIO4]. An increase in [KHSO4] accelerated the rate of nitration under otherwise similar conditions. The rate of nitration increased in the solvent of high dielectric media (solvents with high dielectric constant (D)). Observed results were in accordance with Amis and Kirkwood plots [log k′ vs. (1/D) and [(D ? 1)/(2D + 1)]. These observations probably indicate the participation of anionic species and molecular or (dipolar) species in the rate-determining step. In addition, the plots of (log k′) versus volume% of organic solvent were also linear, which probably indicate the importance of both electrostatic and nonelectrostatic forces, solvent–solute interactions during nitration of phenols. Reaction rates accelerated with the introduction of electron-donating groups and retarded with electron-withdrawing groups, but results could not be quantitatively correlated with Hammett's equation and depicted deviations from linearity. These deviations could probably be attributed to cumulative effects arising inductive, resonance, and steric effects. Leffler's plot (ΔH# vs. ΔS#) was found linear indicating the compensation (cumulative) effect of both enthalpy and entropy parameters in controlling the mechanism of nitration.
- Sriram, Y. Hemanth,Fatima, Touheeth,Rajanna,Kumar, M. Satish,Raju, R. Madhusudan
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supporting information
p. 622 - 632
(2017/06/30)
-
- A photocatalytic green system for chemoselective reduction of nitroarenes
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A highly efficient photocatalytic reduction of nitroarenes using TiO2/polyethylene glycol 400-water (TiO2/PEG-H2O) is reported. This system at deoxygenated and illuminated (sunlight or violet LED) conditions efficiently reduced nitroarenes using oxalic acid or ammonium formate as a sacrificial electron donor. Reducible functional groups such as chloro, hydroxy, flouro, bromo and carbonyl were intact under the optimized reaction conditions. The 0.1 and 0.5-1 mmol amount of nitroarenes was used under sunlight and violet LED (400 nm) irradiation, respectively. Reusability of the nanotitania was successfully carried out four times. The analyses of the recovered catalyst after five runs including TEM, XRD, TGA and CHN were done and results showed that PEG is located on TiO2; no change in morphology, crystallinity and particle sizes was observed.
- Ramdar, Moosa,Kazemi, Foad,Kaboudin, Babak
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p. 1155 - 1163
(2017/05/17)
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- Magnetically Recoverable Gold Nanorods as a Novel Catalyst for the Facile Reduction of Nitroarenes Under Aqueous Conditions
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Abstract: In this work, cysteine-functionalized Fe3O4@Carbon magnetic nanoparticles were used for the synthesis of gold nanorods. Fe3O4@C nanoparticles were first prepared by synthesis of Fe3O4magnetic nanoparticles (MNPs), and then carbon-coated MNPs (Fe3O4@C) were synthesized by glucose carbonization using a hydrothermal method. Finally, the gold NRs were loaded on the modified surface of Fe3O4@C MNPs. The designed magnetically recoverable gold nanorods, after full characterization by FTIR, SEM, TEM, TGA, VSM, XRD, and ICP-OES, were applied to the reduction of nitroarenes. The Fe3O4@C@Cys–Au nanorods showed higher performance than Fe3O4@C@Cys–Au nanospheres in a selective facile reduction of nitroarenes to the corresponding aminoarenes in aqueous medium at room temperature using NaBH4. Graphical Abstract: [Figure not available: see fulltext.]
- Lamei, Kamran,Eshghi, Hossein,Bakavoli, Mehdi,Rostamnia, Sadegh
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p. 491 - 501
(2017/02/18)
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- Chemoselective Deprotection of Sulfonamides under Acidic Conditions: Scope, Sulfonyl Group Migration, and Synthetic Applications
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Chemoselective acidic hydrolysis of sulfonamides with trifluoromethanesulfonic acid has been evaluated as a deprotection method and further extended to more complex synthetic applications. In contrast to conventional troublesome sulfonamide hydrolysis, a near-stoichiometric amount of acid was found to be sufficient to bring about efficient deprotection of various neutral or electron-deficient N-arylsulfonamides, whereas electron-rich substrates provided sulfonyl group migration products. The deprotection method developed is fully selective for N-arylsulfonamides, and the possibility to discriminate among various different sulfonamides is demonstrated.
- Javorskis, Tomas,Orentas, Edvinas
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p. 13423 - 13439
(2017/12/26)
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- Dibenzothiophene Sulfoximine as an NH3 Surrogate in the Synthesis of Primary Amines by Copper-Catalyzed C?X and C?H Bond Amination
-
Readily accessible dibenzothiophene sulfoximine is an NH3 surrogate allowing the preparation of free anilines by copper-catalyzed cross-coupling reactions with aryl iodides or amides followed by radical S?N bond cleavage. The one-pot/two-step r
- Li, Zhen,Yu, Hao,Bolm, Carsten
-
supporting information
p. 9532 - 9535
(2017/08/01)
-
- Cobalt-Catalyzed Regioselective Ortho C(sp2)-H Bond Nitration of Aromatics through Proton-Coupled Electron Transfer Assistance
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A cobalt-catalyzed proton-coupled electron transfer (PCET) mediated regioselective ortho-specific nitration of aromatic C(sp2)-H bonds using chelation-assisted removable vicinal diamine directing groups was developed. The reaction proceeded under mild conditions in the presence of Co(OAc)2·4H2O as the catalyst with AgNO2 utilized as the nitro source as well as terminal oxidant in the presence of O2 as an external oxidant. No external base or additives were required for this process. Controlled experiments and mechanistic investigations with DFT calculations revealed that the reaction proceeds through a PCET promoted nitro functional group transfer pathway. Moreover, the produced compounds are valuable and pharmaceutically quite relevant.
- Nageswar Rao, Desaboini,Rasheed, Sk.,Raina, Gaurav,Ahmed, Qazi Naveed,Jaladanki, Chaitanya Kumar,Bharatam, Prasad V.,Das, Parthasarathi
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p. 7234 - 7244
(2017/07/26)
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- Organocatalytic oxidation of substituted anilines to azoxybenzenes and nitro compounds: Mechanistic studies excluding the involvement of a dioxirane intermediate
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An organocatalytic and environmentally friendly approach for the selective oxidation of substituted anilines was developed. Utilizing a 2,2,2-trifluoroacetophenone-mediated oxidation process, substituted anilines can be transformed into azoxybenzenes, while a simple treatment with MeCN and H2O2 leads to the corresponding nitro compounds, providing user-friendly protocols that can be easily scaled up. Various substitution patterns and functional groups were tolerated leading to products in high to excellent yields. Mechanistic studies utilizing HRMS provide clear evidence for the distinct mechanistic intermediates that are involved. This study constitutes an indirect proof excluding the involvement of a dioxirane intermediate in the green organocatalytic oxidation, utilizing 2,2,2-trifluoroacetophenone as the catalyst.
- Voutyritsa, Errika,Theodorou, Alexis,Kokotou, Maroula G.,Kokotos, Christoforos G.
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supporting information
p. 1291 - 1298
(2017/06/06)
-
- A highly efficient heterogeneous copper-catalysed cascade reaction of aryl iodides with acetamidine hydrochloride leading to primary arylamines
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A highly efficient heterogeneous copper-catalysed cascade reaction of aryl iodides with acetamidine hydrochloride was achieved in DMF in the presence of 10 mol% of an MCM-41-immobilised L-proline-copper(I) complex (MCM-41-L-proline-CuI) with Cs2CO3 as base, yielding a variety of primary arylamines in good to excellent yields. The new heterogeneous copper complex can be easily prepared from commercially readily available and inexpensive reagents, recovered by a simple filtration of the reaction solution and used at least seven more times without any decrease in activity.
- Huang, Xue,Xiao, Ruian,You, Chongren,Yan, Tao,Cai, Mingzhong
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p. 315 - 320
(2017/06/19)
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- Chemoselective transfer hydrogenation of nitroarenes by highly dispersed Ni-Co BMNPs
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Highly dispread Ni-Co bimetallic nanoparticles (Ni-Co BMNPs) are synthesized and applied as an efficient catalyst in the chemoselective transfer hydrogenation of nitroarenes (CTH) using hydrazine hydrate as the hydrogen donor. The BMNPs can efficiently catalyze the reduction reaction without any additives under mild conditions with high TOF. Significantly higher activity is achieved when compared with corresponding single-component catalysts, optimal composition of the Ni-Co BMNPs was screened which was proved to be crucial in both the selectivity and yields. Excellent performance of Ni-Co BMNPs can be ascribed to the improved dispersion of active sites on the BMNPs surface (compared with Ni NPs) and the electron transfer from cobalt to nickel.
- Zhang, Jia-Wei,Lu, Guo-Ping,Cai, Chun
-
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- Palladium(II)-catalyzed, heteroatom-directed, regioselective C-H nitration of anilines using pyrimidine as a removable directing group
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A new palladium-catalyzed, heteroatom-directed strategy for C-H nitration of anilines is described. This C-H functionalization reaction is highly ortho-selective and results in very good yields. The highlight of the work is the use of pyrimidine as the removable directing group. This approach constitutes one of the rare methods of ortho-nitration of anilines, a reaction that is normally very difficult to achieve via traditional approaches.
- Pawar, Govind Goroba,Brahmanandan, Abhilashamole,Kapur, Manmohan
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supporting information
p. 448 - 451
(2016/02/18)
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- Mequindox of tritium or deuterium-labeled preparation method
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The invention belongs to the technical field of veterinary drug preparation, and particularly relates to a preparation method for a tritium and deuterium labeled veterinary drug mequindox. The method comprises the following steps: adopting a trace synthesis method to allow tritium gas or deuterium gas and 4-bromine-2-nitroaniline or 4-iodine-2-nitroaniline to be subjected to dehalogenation reaction under the action of a catalyst and an acid acceptor, and meanwhile, introducing tritium gas or deuterium gas alternatively to generate 4-3H-2-nitroaniline or 4-2H-2-nitroaniline; performing the oxidation reaction and the Beirut reaction to prepare the C-6 tritium labeled or deuterium labeled mequindox, wherein the obtained product is clear in labeling point, high in specific activity (12.63 Ci/mmol), high in radiochemical purity (more than 98 percent) and high in chemical purity (more than 99.5 percent). The prepared tritium labeled mequindox provides a material foundation for the research of absorption, distribution, metabolism and residue elimination rules of the mequindox in an animal body; the prepared deuterium labeled mequindox can serve as an internal standard substance for the quantitative analysis of a mequindox trace amount.
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Paragraph 0053
(2017/02/09)
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- Highly efficient reduction of carbonyls, azides, and benzyl halides by NaBH4 in water catalyzed by PANF-immobilized quaternary ammonium salts
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A series of polyacrylonitrile fiber-supported quaternary ammonium salts (PANF-QAS) were prepared and applied to the catalytic reduction of aldehydes, ketones, azides, and benzyl halides in water using NaBH4 as the reducing reagent in a highly efficient, economic, and environmentally benign way. The structure-activity relationships were investigated, which showed that the catalysts made up of quaternary ammonium salts with longer alkyl chains, larger cationic radii and better lipophilicity speed up the reduction reaction to afford the products in excellent yield. Moreover, the optimized catalyst can be applied to the reduction of 1-naphthaldehyde in a continuous flow process with outstanding reactivity and recyclability.
- Du, Jianguo,Xu, Gang,Lin, Huikun,Wang, Guangwei,Tao, Minli,Zhang, Wenqin
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supporting information
p. 2726 - 2735
(2016/05/24)
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- Harnessing the pyrroloquinoxaline scaffold for FAAH and MAGL interaction: Definition of the structural determinants for enzyme inhibition
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This paper describes the development of piperazine and 4-aminopiperidine carboxamides/carbamates supported on a pharmacogenic pyrroloquinoxaline scaffold as inhibitors of the endocannabinoid catabolizing enzymes fatty acid amide hydrolase (FAAH) and monoacylglycerol lipase (MAGL). Structure-activity relationships and molecular modelling studies allowed the definition of the structural requirements for dual FAAH/MAGL inhibition and led to the identification of a small set of derivatives (compounds 5e, i, k, m) displaying a balanced inhibitory profile against both enzymes, with compound 5m being the frontrunner of the subset. Favorable calculated physico-chemical properties suggest further investigation for specific analogues.
- Brindisi, Margherita,Brogi, Simone,Maramai, Samuele,Grillo, Alessandro,Borrelli, Giuseppe,Butini, Stefania,Novellino, Ettore,Allarà, Marco,Ligresti, Alessia,Campiani, Giuseppe,Di Marzo, Vincenzo,Gemma, Sandra
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p. 64651 - 64664
(2016/07/23)
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- Nitration of arenes by 1-sulfopyridinium nitrate as an ionic liquid and reagent by in situ generation of NO2
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1-Sulfopyridinium nitrate was synthesized as a potent nitrating agent for the nitration of arenes without the need for any co-catalysts. A variety of nitro compounds were synthesized and fully characterized by IR, 1H NMR, 13C NMR, thermal gravimetric analysis (TGA), differential thermal gravimetry (DTG), CHN analysis and mass spectroscopy. Mechanistically, in situ generated nitrogen dioxide as a radical from the reagent is proposed for the presented nitration protocol.
- Moosavi-Zare, Ahmad Reza,Zolfigol, Mohammad Ali,Zarei, Mahmoud,Noroozizadeh, Ehsan,Beyzavi, M. Hassan
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p. 89572 - 89577
(2016/10/03)
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- A triazine-phosphite polymeric ligand bearing cage-like P,N-ligation sites: An efficient ligand in the nickel-catalyzed amination of aryl chlorides and phenols
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A novel P,N-ligand was introduced for efficient Ni-catalyzed amination of aryl chlorides. Reaction of cyanuric acid (1,3,5-triazine-2,4,6-triol) and trichlorophosphine (PCl3) resulted in the production of a new porous material (TPPM) containing triazine rings with phosphite moieties in a sheet morphology. Cavities in the prepared compound create sites on the surface of the material with appropriate ligation character to coordinate with metals for catalytic purposes. The nickel-catalyzed amination of aryl chlorides and of phenols in their 2,4,6-triaryloxy-1,3,5-triazine (TAT) protected form were efficiently accomplished in the presence of this easily prepared and reusable P,N-ligand under mild reaction conditions. More importantly, TPPM was reusable for 5 iterations following this protocol without significantly decreasing in its activity.
- Panahi, Farhad,Roozbin, Fatemeh,Rahimi, Sajjad,Moayyed, Mohammadesmaeil,Valaei, Aria,Iranpoor, Nasser
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supporting information
p. 80670 - 80678
(2016/10/12)
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- Simple and convenient copper-catalyzed amination of aryl halides to primary arylamines using NH4OH
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In this study, we investigated the direct synthesis of primary arylamines from aryl iodides and bromides by Cu-catalyzed amination using ammonium hydroxide (27% NH3in H2O) as nucleophile. In this article, two protocols are described: (1) a variety of aryl halides were treated with CuI (10?mol?%) and DMEDA (15?mol?%) in NH4OH/DMSO, or (2) with only CuI (10?mol?%) in NH4OH/PEG300. In each case, the desired primary arylamines were obtained in excellent yields. Although DMEDA and PEG have previously been employed as a ligand or solvent, respectively, the substrates were limited or additional ligands were required for successful conversion. Notably, our new protocols do not require additional inorganic bases, whereas previous methods have used a base. As such, these new protocols are one of the most simple, convenient, and efficient methods that have been reported, to date.
- Jung, Hee Seon,Yun, Taeil,Cho, Yungyeong,Jeon, Heung Bae
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p. 5988 - 5993
(2016/09/16)
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- A circulating aqueous phase system method of synthesizing aromatic primary amine
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The invention discloses a method for synthesizing an aromatic primary amine in a circulating water phase system. According to the method, an aryl halide and ammonia water are taken as raw materials, water is taken as a solvent, a carbonate, a fluoride, a phosphate or a hydroxide of an alkali metal or an alkaline-earth metal or a compound which can be converted to a corresponding alkali in water is taken as the alkali, polyamine carboxylic acid and a salt type compound thereof are taken as ligands, and a copper source catalyst is adopted for catalyzing the formation of the aromatic primary amine from the aryl halide and the ammonia water. According to the method disclosed by the invention, the water is used as the solvent, any phase transfer of the catalyst is not required, and the catalyst, the ligands and the reaction solvent, namely the water, can be recycled, so that the environment-friendly property of reaction is effectively improved, the method is more in line with requirements of green chemical development, a substrate particularly has a wide range of applications, and the method further has broad prospects in the aspects of preparation of natural products, medicaments and pesticides.
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Paragraph 0058; 0059
(2016/10/20)
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- A Highly Water-Dispersible/Magnetically Separable Palladium Catalyst: Selective Transfer Hydrogenation or Direct Reductive N-Formylation of Nitroarenes in Water
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Simple ion exchange of the chloride anion of an ionic-liquid-functionalized magnetic nanoparticle with [PdCl4]2- provided a highly water-dispersible and magnetically separable palladium catalyst that exhibited excellent activity toward transfer hydrogenation reactions in water as a solvent. The catalyst demonstrated outstanding performance in aqueous-phase transfer hydrogenation of various nitroarenes in a highly chemo- and regioselective manner by using HCOONH4 as a low-cost, green, and easily available hydrogen donor. Also, by using only 0.25 mol % of the catalyst and formic acid as both a hydrogen donor and formylating agent, the catalyst showed excellent activity in the one-pot, direct synthesis of N-arylformamides from nitroarenes in water as a solvent. Notably, owing to the presence of a hydrophilic ionic liquid on the surface of silica-coated iron oxide nanoparticles, the catalyst showed highly stable dispersion in water, as evidenced by the zeta potential and extremely low affinity to the organic phase. These features make this catalyst system suitable for an efficient double-separation strategy (successive extraction/final magnetic separation). The recovered aqueous phase containing the catalyst can be simply and efficiently reused in eight runs without a decrease in activity and can be easily separated from the aqueous phase at the end of the process by applying an external magnetic field.
- Karimi, Babak,Mansouri, Fariborz,Vali, Hojatollah
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p. 1750 - 1759
(2016/01/25)
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- Metal-free oxidative decarbonylative coupling of aromatic aldehydes with arenes: Direct access to biaryls
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A metal-free oxidative decarbonylative coupling of aromatic aldehydes with electron-rich or electron-deficient arenes to produce biaryl compounds was developed. This novel coupling was proposed to proceed via a non-chain radical homolytic aromatic substitution (HAS) type mechanism, based on the substrate scope, ortho-regioselectivity, radical trapping experiments and DFT calculation studies. With the ready availability of aromatic aldehydes and arenes, metal-free conditions should make this coupling attractive for the biaryl synthesis.
- Tang, Ren-Jin,He, Qing,Yang, Luo
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supporting information
p. 5925 - 5928
(2015/03/30)
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- Room-Temperature Cu(II)-Catalyzed Chemo- and Regioselective Ortho-Nitration of Arenes via C-H Functionalization
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An efficient Cu-catalyzed chemo- and regioselective ortho-nitration of N,1-diaryl-5-aminotetrazoles and N,4-diaryl-3-amino-1,2,4-triazoles have been described with good functional group compatibility. The procedure features the use of operationally simple protocol utilizing the commercially available less toxic CuCl2·2H2O as catalyst and Fe(NO3)3·9H2O as nitration source at room temperature. Removal of the 5-aminotetrazole directing group has been demonstrated using base hydrolysis to afford substituted 2-nitroanilines.
- Sadhu, Pradeep,Alla, Santhosh Kumar,Punniyamurthy, Tharmalingam
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p. 8245 - 8253
(2015/09/01)
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- Preparation of aniline derivatives
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In the present invention, provided is a novel manufacturing method of aniline derivative, which is more simple and eco-friendly and takes less cost compared with an existing synthesizing aniline method, comprising a step of manufacturing chemical formula 1 by making chemical formula 2 react with chemical formula 3 under catalyst, bases and solvents wherein the manufacturing method aniline derivative is manufactured through one pot in a simple manner and accordingly easily removes the solvent with use of distillation under reduced pressure after reaction.
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Paragraph 0087-0092
(2016/10/08)
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- Steric-Hindrance-Induced Regio- and Chemoselective Oxidation of Aromatic Amines
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Unusual regio- and chemoselective oxidation of aromatic amines hindered with ortho substituents (except -NH2, -NHCH3, and -OH) to the corresponding nitro compounds is described by use of nonanebis(peroxoic acid). The mechanistic investigation for selective oxidation of amines ortho-substituted with -NH2 or -OH showed the involvement of H-bonding between the ortho hydrogen of the adjacent -XH group (where X = NH, NR, or O) and an oxygen atom from the diperoxy acid. Various mono- and diamines are oxidized into corresponding mononitro derivatives in high yield and purity without employing any protection strategies. The protocol was also found to successful on the gram scale.
- Patil, Vilas Venunath,Shankarling, Ganapati Subray
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p. 7876 - 7883
(2015/09/01)
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- The ortho effect on the acidic and alkaline hydrolysis of substituted formanilides
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The kinetics of formanilides hydrolysis were determined under first-order conditions in hydrochloric acid (0.01-8 M, 20-60°C) and in hydroxide solutions (0.01-3 M, 25 and 40°C). Under acidic conditions, second-order specific acid catalytic constants were used to construct Hammett plots. The ortho effect was analyzed using the Fujita-Nishioka method. In alkaline solutions, hydrolysis displayed both first- and second-order dependence in the hydroxide concentration. The specific base catalytic constants were used to construct Hammett plots. Ortho effects were evaluated for the first-order dependence on the hydroxide concentration. Formanilide hydrolyzes in acidic solutions by specific acid catalysis, and the kinetic study results were consistent with the AAC2 mechanism. Ortho substitution led to a decrease in the rates of reaction due to steric inhibition of resonance, retardation due to steric bulk, and through space interactions. The primary hydrolytic pathway in alkaline solutions was consistent with a modified BAC2 mechanism. The Hammett plots for hydrolysis of meta- and para-substituted formanilides in 0.10 M sodium hydroxide solutions did not show substituent effects; however, ortho substitution led to a decrease in rate constants proportional to the steric bulk of the substituent.
- Desai, Salil Dileep,Kirsch, Lee E.
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p. 471 - 488
(2015/06/30)
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- Self-propagated Lossen rearrangement induced by a catalytic amount of activating agents under mild conditions
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A mild self-propagated Lossen rearrangement induced by a catalytic amount of activating agents in medium to high polar organic solvents has been developed. The rearrangement of aromatic and aliphatic hydroxamic acids in the presence of a catalytic amount (0.01 equiv) of acetic anhydride and an equimolar amount of base such as well-dried potassium carbonate afforded the corresponding amines in high yields. This alternative to traditional Lossen rearrangement provides a simple and mild method for the synthesis of amines from free hydroxamic acids.
- Hoshino, Yujiro,Shimbo, Yuki,Ohtsuka, Naoya,Honda, Kiyoshi
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supporting information
p. 710 - 712
(2015/01/30)
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- Phosphoric acid modified montmorillonite clay: A new heterogeneous catalyst for nitration of arenes
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The easily available montmorillonite clay is treated with phosphoric acid and 10 wt.% is found to be the optimum concentration of phosphoric acid that can be adsorbed chemically on the surface of the clay. Acidity of this phosphoric acid treated montmorillonite clay (PAM) is determined by volumetric as well as potentiometric titration and characterized. Catalytic efficacy of PAM in nitration of various aromatic compounds is reported.
- Bharadwaj, Saitanya K.,Boruah, Purna K.,Gogoi, Pradip K.
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p. 124 - 128
(2014/12/11)
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- Polymethylhydrosiloxane derived palladium nanoparticles for chemo- and regioselective hydrogenation of aliphatic and aromatic nitro compounds in water
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Chemo- and regioselective hydrogenation of a wide range of aliphatic, unsaturated, aromatic and heteroaromatic nitro compounds into their corresponding amines has been achieved with highly efficient polysiloxane-stabilised "Pd" nanoparticles on NAP-magnesium oxide supports using an environmentally friendly hydrogenating agent, polymethylhydrosiloxane [PMHS] in water. Highly stable and active Pd nanoparticles were prepared by the reduction of NAP-Mg-PdCl4 with PMHS, which serves as a reducing agent as well as a capping agent. The well-dispersed palladium nanoparticles on NAP-MgO catalysts also exhibit excellent regioselectivity in the hydrogenation of dinitrobenzenes to the corresponding nitroanilines. The catalyst has high durability against sintering during the hydrogenation reaction and can be reused with no loss in its activity. This journal is the Partner Organisations 2014.
- Damodara, Dandu,Arundhathi, Racha,Ramesh Babu, T. Venkata,Legan, Margaret K.,Kumpaty, Hephzibah J.,Likhar, Pravin R.
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p. 22567 - 22574
(2014/06/23)
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- Metal-free transfer hydrogenation of nitroarenes in water with vasicine: Revelation of organocatalytic facet of an abundant alkaloid
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Vasicine, an abundantly available quinazoline alkaloid from the leaves of Adhatoda vasica, has been successfully employed for metal- and base-free reduction of nitroarenes to the corresponding anilines in water. The method is chemoselective and tolerates a wide range of reducible functional groups, such as ketones, nitriles, esters, halogens, and heterocyclic rings. Dinitroarenes reduced selectively to the corresponding nitroanilines under the present reaction conditions.
- Sharma, Sushila,Kumar, Manoranjan,Kumar, Vishal,Kumar, Neeraj
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p. 9433 - 9439
(2014/12/11)
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- Iron and palladium(II) phthalocyanines as recyclable catalysts for reduction of nitroarenes
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Iron(II) and palladium(II) phthalocyanines have been established as recyclable heterogeneous catalysts for the reduction of aromatic nitro compounds to corresponding amines using diphenylsilane/sodium borohydride as hydrogen sources in ethanol. Various reducible functional groups, such as acetyl, ester, cyano, amide, sulphonamide and carboxylic acid etc. were well tolerated, and the methods were applicable up to gram scale. Mechanistic studies showed that reduction of nitro group proceed through direct (nitroso) pathway and possibly iron or palladium phthalocyanines activates nitro group for reduction. FePc and PdPc also catalyzed the generation of hydrogen from the combination of diphenylsilane/sodium borohydride and ethanol.
- Verma, Praveen Kumar,Bala, Manju,Thakur, Kavita,Sharma, Upendra,Kumar, Neeraj,Singh, Bikram
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p. 1258 - 1267
(2014/07/21)
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- Solid supported rhodium(0) nanoparticles: An efficient catalyst for chemo- and regio-selective transfer hydrogenation of nitroarenes to anilines under microwave irradiation
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A Solid-supported rhodium(0) (SS-Rh) catalyst has been developed and applied for the chemo- and regio-selective reduction of nitroarenes functionalized with CC multiple bonds and dinitroarenes to their corresponding amines respectively using hydrazine hydrate (N2H4· H2O) as a reducing source under mild microwave irradiation (MWI) conditions. The present methodology also shows excellent compatibility with a broad range of structurally diverse reducible functional groups. The catalyst can be recovered by simple filtration and reused for 13 cycles with consistent activity hence reduces the cost of the catalyst assertively.
- Guha, Nitul Ranjan,Bhattacherjee, Dhananjay,Das, Pralay
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supporting information
p. 2912 - 2916
(2014/05/06)
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