- Chemoselective reduction of nitroarenes, N-acetylation of arylamines, and one-pot reductive acetylation of nitroarenes using carbon-supported palladium catalytic system in water
-
Developing and/or modifying fundamental chemical reactions using chemical industry-favorite heterogeneous recoverable catalytic systems in the water solvent is very important. In this paper, we developed convenient, green, and efficient approaches for the chemoselective reduction of nitroarenes, N-acetylation of arylamines, and one-pot reductive acetylation of nitroarenes in the presence of the recoverable heterogeneous carbon-supported palladium (Pd/C) catalytic system in water. The utilize of the simple, effective, and recoverable catalyst and also using of water as an entirely green solvent along with relatively short reaction times and good-to-excellent yields of the desired products are some of the noticeable features of the presented synthetic protocols. Graphic abstract: [Figure not available: see fulltext.].
- Zeynizadeh, Behzad,Mohammad Aminzadeh, Farkhondeh,Mousavi, Hossein
-
p. 3289 - 3312
(2021/05/11)
-
- Tin(ii) chloride dihydrate/choline chloride deep eutectic solvent: Redox properties in the fast synthesis of: N -arylacetamides and indolo(pyrrolo)[1,2- a] quinoxalines
-
In this contribution a physicochemical, IR and Raman characterization for the tin(ii) chloride dihydrate/choline chloride eutectic mixture is reported. The redox properties of this solvent were also studied by cyclic voltammetry finding that it can be successfully used as an electrochemical solvent for electrosynthesis and electroanalytical processes and does not require negative potentials as verified by the reduction of nitrobenzene. The potential use of this eutectic mixture as a redox solvent was further explored in obtaining aromatic amines and N-arylacetamides starting from a wide variety of nitroaromatic compounds. In addition, a fast synthetic strategy for the construction of a series of indolo(pyrrolo)[1,2-a]quinoxalines was developed by reacting 1-(2-nitrophenyl)-1H-indole(pyrrole) with aldehydes. This simple protocol offers a straightforward method for the construction of the target quinoxalines in short reaction times and high yields where the key step involves a tandem one-pot reductive cyclization-oxidation.
- Bejarano, Oscar Rodríguez,Ochoa-Puentes, Cristian,Pe?a-Solórzano, Diana,Trujillo, Sergio Alfonso
-
p. 40552 - 40561
(2020/11/18)
-
- The immobilized Cu nanoparticles on magnetic montmorillonite (MMT?Fe3O4?Cu): As an efficient and reusable nanocatalyst for reduction and reductive-acetylation of nitroarenes with NaBH4
-
In this study, the immobilization of copper nanoparticles on superparamagnetic montmorillonite, MMT?Fe3O4?Cu, was studied. Magnetically nanoparticles (MNPs) of iron oxide (Fe3O4) were primarily prepared by a chemical co-precipitation method. Next, the prepared Fe3O4 MNPs were intercalated within the interlamellar spaces and external surface of sodium-exchanged montmorillonite. Finally, Cu NPs were immobilized on magnetic montmorillonite by a simply mixing of an aqueous solution of CuCl2·2H2O with MMT?Fe3O4 followed by the reduction with NaBH4. Characterization of MMT?Fe3O4 clay system represented that through the immobilization of Fe3O4 MNPs, disordered-layers structure of MMT was easily reorganized to an ordered-layers arrangement. The synthesized composite systems were characterized using FT-IR, SEM, EDX, XRD, VSM, BET and ICP-OES analyses. SEM analysis exhibited that dispersion of Cu NPs, with the size distribution of 15–25 nm, on the surface of magnetic clay was taken place perfectly. BET surface analysis indicated that after the immobilization of Fe3O4 and Cu species, the surface area and total pore volume of MMT?Fe3O4?Cu system was decreased. Next, the Cu-clay nanocomposite system showed a perfect catalytic activity towards reduction of nitroarenes to anilines as well as reductive-acetylation of nitroarenes to acetanilides using NaBH4 and Ac2O in water as a green and economic solvent. The copper magnetic clay catalyst can be easily separated from the reaction mixture by an external magnetic field and reused for six consecutive cycles without the significant loss of its catalytic activity.
- Zeynizadeh, Behzad,Rahmani, Soleiman,Tizhoush, Hengameh
-
-
- 4-Imidazol-1-yl-butane-1-sulfonic acid ionic liquid: Synthesis, structural analysis, physical properties and catalytic application as dual solvent-catalyst
-
4-Imidazol-1-yl-butane-1-sulfonic acid (ImBu-SO3H) has been successfully synthetized and fully characterized by FT-IR and high-resolution NMR spectroscopy (1H, 13C). The “plausible” alternative structures of ImBu-SO3H were discussed on the basis of its NMR data. The ionic liquid showed interesting dual solvent-catalyst property, which was studied experimentally for the acetylation of a variety of functionalized alcohols, phenols, thiols, amines and α-tocopherol (α-CTP) as the most active form of vitamin E with acetic anhydride and which provided good yields within a short reaction time. ImBu-SO3H was successfully recycled by product extraction with an average recovered yield of 82% for 5 subsequent runs. The catalytic activity of the recycled ImBu-SO3H showed almost no loss even after five consecutive runs.
- Khaligh, Nader Ghaffari,Mihankhah, Taraneh,Johan, Mohd Rafie,Juan, Joon Ching
-
p. 866 - 878
(2019/07/12)
-
- The immobilized Ni(II)-thiourea complex on silica-layered copper ferrite: A novel and reusable nanocatalyst for one-pot reductive-acetylation of nitroarenes
-
In this study, magnetically nanoparticles of CuFe2O4@SiO2@PTMS@Tu@Ni(II) as novel and reusable catalyst were prepared. Synthesis of the Ni (II)-nanocatalyst was carried out through the complexation of Ni(OAc)2·4H2O with the immobilized thiourea on silica-layered CuFe2O4. The prepared nanocomposite system was then characterized using SEM, EDX, XRD, VSM, ICP-OES, Raman, UV–Vis and FT-IR analyses. Catalytic activity of the Ni(II)-CuFe2O4 system was investigated towards rapid reduction of aromatic nitro compounds to arylamines with sodium borohydride as well as one-pot reductive-acetylation of nitroarenes to acetanilides with NaBH4/Ac2O system without the isolation of intermediate arylamines. All reactions were carried out in H2O within 3–7?min to afford the products arylamines/acetanilides in high to excellent yields. Reusability of the Ni(II)-nanocatalyst was examined for seven consecutive cycles without the significant loss of the catalytic activity.
- Zeynizadeh, Behzad,Shokri, Zahra,Hasanpour Galehban, Morteza
-
-
- Ni2B@Cu2O and Ni2B@CuCl2: two new simple and efficient nanocatalysts for?the green one-pot reductive acetylation of nitroarenes and direct N-acetylation of arylamines using solvent-free mechanochemical grinding
-
Abstract: Ni2B@Cu2O and Ni2B@CuCl2 are introduced as simple and efficient earth-abundant transition-metal-based nanocomposites for the?green one-pot reductive acetylation of aromatic nitro compounds and direct N-acetylation of arylamines using a solvent-free mechanochemical grinding technique. The designed Ni2B-based nanocomposites were characterized by Fourier-transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) analysis, and scanning electron microscopy (SEM) with energy-dispersive X-ray (EDX) spectroscopy. Notable advantages of these methods include broad substrate scope, use of a solvent-free mechanochemical grinding technique, implementation of earth-abundant transition-metal-based nanocomposites as simple and practical catalysts, and short reaction time and high yield at ambient condition. The mentioned methods can also be successfully applied for the?synthesis of a broad range of other amides (especially substituted acetamides) using green chemistry protocols. Also, the recoverability and reusability of the mentioned new nanocomposites were investigated. Graphical abstract: [Figure not available: see fulltext.].
- Zeynizadeh, Behzad,Younesi, Reza,Mousavi, Hossein
-
p. 7331 - 7352
(2018/08/25)
-
- Novel preparation method of 3-amino-2-hydroxyacetophenone
-
The invention provides a novel preparation method of 3-amino-2-hydroxyacetophenone. The novel preparation method comprises the following steps of using 2-aminophenol as an initial raw material; enabling the 2-aminophenol and acetic anhydride to synthesize 2-acetamidophenol acetate in a polar solvent under the alkaline or acid catalyzing condition; then, performing Fries rearrangement on the 2-acetamidophenol acetate in an aprotic solvent under the catalyzing action of anhydrous titanium tetrachloride, and adopting an acid hydrolysis one-pot method, so as to synthesize the 3-amino-2-hydroxyacetophenone. The novel preparation method has the advantages that the price of the used raw materials is low, the obtaining is easy, and the selection of the raw materials is diversified; the implementing of the production technology is easy, the management and control are easy, the purity of a final product is high, the dangerous technology is avoided, the equipment is simple, the synthesizing route is novel and short, the production capacity is increased, and the production and processing cost is reduced.
- -
-
Paragraph 0016; 0018
(2017/08/31)
-
- Synthesis of 2-methylbenzoxazoles directly from: N -phenylacetamides catalyzed by palladium acetate
-
A method to synthesize 2-methylbenzoxazoles directly from N-phenylacetamides catalyzed by Pd(OAc)2 in the presence of K2S2O8 and TfOH has been developed. The desired products were obtained in moderate to excellent yields. This approach provides a facile procedure to prepare benzoxazoles with available substrates. It is found that TfOH is the key factor for this cyclization reaction. A plausible mechanism of the reaction is proposed according to the control reactions and the literature.
- Wang, Biying,Jiang, Chengfei,Qian, Jiasheng,Zhang, Shuwei,Jia, Xiaodong,Yuan, Yu
-
p. 101 - 107
(2017/12/27)
-
- Magnetically separable γ-Fe2O3 nanoparticles: An efficient catalyst for acylation of alcohols, phenols, and amines using sonication energy under solvent free condition
-
This paper reports a facile synthesis of magnetically separable iron oxide (γ-Fe2O3) nanoparticles using thermolysis method. The structural and morphological study of the synthesized γ-Fe2O3 nanoparticles was carried out using X-ray diffraction (XRD), field emission gun-scanning electron microscopy (FEG-SEM), energy dispersive X-ray spectrum (EDS), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS) techniques. The electron microscopy reveals that the γ-Fe2O3 nanoparticles have spherical morphology with a particle size in the range of 40-100 nm. The XPS study confirmed the Fe is in +3 oxidation state. The synthesized γ-Fe2O3 nanoparticles have been used as an efficient heterogeneous catalyst for the organic transformation between phenols, alcohols, and amines with acetic anhydride under sonication using mild reaction conditions. Various electrons withdrawing and electrons donating substrates show an excellent yield of desired products with the advantage of magnetic separation and reusability of γ-Fe2O3 nanocatalyst.
- Bhosale, Manohar A.,Ummineni, Divya,Sasaki, Takehiko,Nishio-Hamane, Daisuke,Bhanage, Bhalchandra M.
-
-
- A novel silver nanoparticle embedded mesoporous polyaniline (mPANI/Ag) nanocomposite as a recyclable catalyst in the acylation of amines and alcohols under solvent free conditions
-
A mesoporous polyaniline/silver (mPANI/Ag) nanocomposite has been prepared using mesoporous organic polymer polyaniline with silver nitrate via radical polymerization of aniline monomer in the presence of hydrochloric acid. The mPANI/Ag nanocomposite has been characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectra (EDX), Fourier transform infrared spectroscopy (FT-IR), and ultraviolet-visible absorption spectra (UV-vis). The XRD patterns indicated that the crystalline phase of Ag is cubic. TEM images show that the Ag nanoparticles are well dispersed in the mesoporous polyaniline matrix. The mPANI/Ag acts as an efficient heterogeneous nanocatalyst in the acylation of substituted amines and alcohols using acetic acid. The catalyst is air-stable, inexpensive, easy to prepare and can be reused several times without a significant decrease in activity and selectivity. This journal is
- Mandi, Usha,Roy, Anupam Singha,Banerjee, Biplab,Islam, Sk. Manirul
-
p. 42670 - 42681
(2015/02/19)
-
- Poly(N-vinylimidazole) as an efficient catalyst for acetylation of alcohols, phenols, thiols and amines under solvent-free conditions
-
Poly(N-vinylimidazole) is able to promote instantaneous quantitative acetylation of a variety of functionalized alcohols, phenols, thiols and amines with acetic anhydride at room temperature under solvent-free conditions. This new method consistently has excellent yields and the catalyst can be reused and recovered several times. Furthermore, the reaction can even be carried out on a larger scale. The Royal Society of Chemistry.
- Khaligh, Nader Ghaffari
-
-
- A succinimide-N-sulfonic acid catalyst for acetylation reactions in absence of a solvent
-
A small amount of succinimide-N-sulfonic acid efficiently catalyzed the acetylation of a variety alcohols, phenols, thiols, amines and aldehydes with acetic anhydride at room temperature under solvent free conditions. This catalyst has the advantages of excellent yields and short reaction times and the reaction can be carried out on a large scale, which makes it potentially useful for industrial applications.
- Shirini, Farhad,Khaligh, Nader Ghaffari
-
p. 695 - 703
(2013/08/25)
-
- Palladium-catalyzed C-H activation of anilides at room temperature: Ortho-arylation and acetoxylation
-
Room-temperature ortho-arylation and acetoxylation of anilides have been achieved using cationic palladium (Pd[TFA]+) as catalyst and (NH 4)2S2O8 as oxidant. Preliminary investigation of the mechanism
- Yang, Fan,Song, Feijie,Li, Wei,Lan, Jingbo,You, Jingsong
-
p. 9649 - 9652
(2013/09/02)
-
- Ruthenium-catalyzed oxidative ortho-benzoxylation of acetanilides with aromatic acids
-
Substituted acetanilides reacted with aromatic acids in the presence of [{RuCl2(p-cymene)}2], AgSbF6 and (NH 4)2S2O8 in ClCH2CH 2Cl at 100 °C for 24 h yielding ortho-benzoxylated acetanilides in good to excellent yields in a highly regioselective manner via C-H bond activation. The Royal Society of Chemistry 2013.
- Padala, Kishor,Jeganmohan, Masilamani
-
supporting information
p. 9651 - 9653
(2013/10/08)
-
- HF-Pyridine: A versatile promoter for monoacylation/sulfonylation of phenolic diols and for direct conversion of t-butyldimethylsilyl ethers to the corresponding acetates
-
Monoacylation and trifluoromethanesulfonylation of phenolic diols were achieved by the aid of HF-pyridine, whereas diacylation occurred with pyridine alone. Furthermore, HF-pyridine was found to promote the direct conversion of t-butyldimethylsilyl ethers to the corresponding acetates.
- Michigami, Kyosuke,Yoshimoto, Kazuya,Hayashi, Masahiko
-
scheme or table
p. 138 - 139
(2012/03/09)
-
- Preparation, characterization and use of poly(4-vinylpyridinium) perchlorate as a new, efficient, and versatile solid phase catalyst for acetylation of alcohols, phenols and amines
-
Poly(4-vinylpyridine) perchlorate, is a supported, recyclable, eco-benign catalyst for the reaction acetylation of structurally diverse alcohols, phenols and amines at room temperature under solvent-free conditions. The catalyst was studied by FT-IR, X-ray diffraction, Scanning Electron Microscope and Thermo-gravimetric Analyses. All the products were extensively characterized by 1H NMR, FT-IR, GC-MS and melting point analyses. The catalyst can be recovered and reused without loss of activity. The work-up of the reaction consists of a simple filtration, followed by concentration of the crude product and purification. It is important to point out that a large-scale reaction is possible using a same amount of catalyst.
- Khaligh, Nader Ghaffari
-
-
- Efficient iodine-mediated beckmann rearrangement of ketoximes to amides under mild neutral conditions
-
Aryl ketoximes readily underwent Beckmann rearrangement to give N-substituted amides in excellent yields on electrophilic activation by elemental iodine in anhydrous acetonitrile under reflux. The main advantages of this environmentally friendly protocol include a high selectivity as a result of the absence of any accompanying deprotection to form the parent ketones as byproducts, mild neutral conditions, procedural simplicity, and particularly ease of isolation of the products.
- Ganguly, Nemai C.,Mondal, Pallab
-
experimental part
p. 3705 - 3709
(2011/01/03)
-
- SbCl3 as a highly efficient catalyst for the acetylation of alcohols, phenols, and amines under solvent-free conditions
-
Antimony trichloride has been found to be an efficient and expedient catalyst for the acylation of alcohols, phenols, amines, and sugars with acetic anhydride in high yields and in a short reaction time under solvent-free conditions at room temperature. Also, racemization of chiral alcohols and epimerization of sugars were not observed in any of the substrates. Copyright Taylor & Francis Group, LLC.
- Bhattacharya, Asish K.,Diallo, Mamadou A.,Ganesh, Krishna N.
-
p. 1518 - 1526
(2008/09/20)
-
- Direct ortho-acetoxylation of anilides via palladium-catalyzed sp 2 C-H bond oxidative activation
-
(Chemical Equation Presented) Various anilides have been directly ortho-acetoxylated through a Pd(OAc)2-catalyzed C-H bond activation process. The amide group in anilides was found to functionalize as an elegant directing group to convert aromatic sp2 C-H bonds into C-O bonds in high regioselectivity with acetic acid as the acetate source and K 2S2O8 as the oxidant.
- Wang, Guan-Wu,Yuan, Ting-Ting,Wu, Xue-Liang
-
p. 4717 - 4720
(2008/09/21)
-
- Lithium chloride catalysed acetylation of alcohols, thiols, phenols and amines
-
Lithium Chloride is found to efficiently catalyse the acetylation of alcohols, thiols, phenols and amines with acetic anhydride in excellent yield.
- Sabitha, Gowravaram,Subba Reddy,Srividya,Yadav
-
p. 2311 - 2315
(2007/10/03)
-
- Montmorillonite clay catalysis. Part 10. K-10 and KSF-catalysed acylation of alcohols, phenols, thiols and amines: Scope and limitation
-
Montmorillonite K-10 and KSF are highly efficient catalysts for the acetylation of a variety of alcohols, thiols, phenols and amines with acetic anhydride. Amino groups can be selectively acetylated in the presence of hydroxy groups, while the hydroxy groups can be preferentially acetylated in the presence of thiol groups. No selectivity is observed between primary and secondary hydroxy groups in the presence of K-10 and KSF. The catalysts are found not to be efficient for acetylation of tertiary alcohols. This method is simple and convenient with minimum environmental impact. The catalysts are also effective for the acylation of alcohols, thiols, phenols and amines with acetyl chloride and benzoyl chloride. Cyclic anhydrides such as succinic anhydride, maleic anhydride and phthalic anhydride and p-toluene sulfonyl chloride show less reactivity than acetic anhydride and acyl chlorides.
- Li, Tong-Shuang,Li, Ai-Xiao
-
p. 1913 - 1917
(2007/10/03)
-
- Montmorillonite K-10 and KSF as remarkable acetylation catalysts
-
Montmorillonite K-10 and KSF catalyse the acetylation of alcohols, thiols, phenols and amines with acetic anhydride in excellent yield.
- Li, Ai-Xiao,Li, Tong-Shuang,Ding, Tian-Hui
-
p. 1389 - 1390
(2007/10/03)
-
- Reexamination of the Thermolytic Rearrangement of 4-Halophenyl Azides to 2-Aminophenols and other Products
-
The halogenation of derivatives of 2-aminophenol with N-chloro- and N-bromosuccinimides at ambient temperatures in acetic acid was studied.With the necessary compounds available, a reexamination of the thermolytic rearrangement of 2-halophenyl azides to 2-aminophenols and other products was undertaken.It is certain that the rearrangement of 4-halophenyl azides to 2-aminophenols occurs but the products identified in this study differ significantly from those reported previously by Suschitzky et al. (1963, 1966). Keywords: Acetylated-2-amino-5-halophenols; 2-Acetamido-5-haloanisoles; 6-Halo-2-methylbenzoxazoles; 6-Halobenzoxazolones; 6-Halotriacetylaminophenols; 1H-NMR spectra; Fungicidal activity.
- Gershon, H.,Clarke, D. D.,Gershon, M.
-
p. 367 - 380
(2007/10/02)
-
- Photolysis and Thermolysis of Phenyl Azide in Acetic Acid. Trapping of 1-Azacyclohepta-1,2,4,6-tetraene and Nucleophilic Aromatic Substitution
-
Photolysis and thermolysis of phenyl azide in acetic acid yielded 1H-azepin-2(3H)-one (4), 2-methylbenzoxazole (15), 2- and 4- acetamidophenyl acetates (16) and (12), 2- and 4- acetamidophenols (14) and (13), acetanilide, and azobenzene.Addition of ethanol to the system caused a linear decrease in the yield of (4) and a more remarkable decrease in total yield for the para-products than that for the ortho-products to give 2- and 4- acetamidophenyl ethyl ethers (9) and (8).Photolysis of the azide in ethanol in the presence of phenol afforded 2-phenoxy-3H-azepine (5) and aniline, but no 2- and 4-phenetidines.The yield of compounds (4) and (12)-(16) was independent of the presence of penta-1,3-diene(0.01 M), and somewhat decreased by an addition of bromobenzene.The rate of decomposition of azide in acetic acid was not accelerated as compared with that in 1,4-dioxan, and the activation parameters varied little in the two solvents.The results suggest that 1-azacyclohepta-1,2,4,6-tetraene (1) formed via singlet phenylnitrene or via singlet excited phenyl azide is trapped by acetic acid or phenol to give (4) or (5), and that a resonance-stabilized ion (3) neighbouring acetate anion is formed by an attack of the singlet nitrene on acetic acid to give aromatic nucleophilic substitution.
- Takeuchi, Hiroshi,Koyama, Kikuhiko
-
p. 1269 - 1274
(2007/10/02)
-
- Photolysis and Thermolysis of Phenyl Azide in Acetic Acid
-
The photolysis and thermolysis of phenyl azide in acetic acid gave 2,3-dihydro-1H-azepin-2-one via 1-azacyclohepta-1,2,4,6-tetraene, and ring-disubstituted products via a resonance-stabilized ion formed by attack of singlet phenylnitrene on acetic acid.
- Takeuchi, Hiroshi,Koyama, Kikuhiko
-
p. 202 - 204
(2007/10/02)
-