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Formation of a catalytically active intermediate for oxidation in H2O2/ionic liquid system: experimental and theoretical investigations
, Article Research on Chemical Intermediates ; Volume 43, Issue 4 , 2017 , Pages 2615-2625 ; 09226168 (ISSN) ; Vafaeezadeh, M ; Mahmoodi Hashemi, M ; Sharif University of Technology
Springer Netherlands
2017
Abstract
Abstract: A metal-free method for activation of hydrogen peroxide (H2O2) is introduced using piperidinium trifluoroacetate (PPHTFA) ionic liquid as catalyst. The catalyst has been used for selective oxidation of thioanisole to its corresponding sulfoxide at room temperature. It was found that the selectivities were reduced by increasing the reaction temperature. In this work, no organic solvents or metallic salts were used for activation of H2O2. Mechanistic studies suggested that the reaction proceeds via in situ formation of trifluoro hydroperoxy species as an active catalytic intermediate. Formation of the catalytic intermediate was screened by NMR, IR and Mass Spectroscopy analysis....
A novel phenolic ionic liquid for 1.5 molar CO2 capture: Combined experimental and DFT studies
,
Article
RSC Advances
;
Volume 5, Issue 71
,
Jun
,
2015
,
Pages 58005-58009
;
20462069 (ISSN)
; Aboudi, J
; Mahmoodi Hashemi, M
;
Sharif University of Technology
Royal Society of Chemistry
2015
Abstract
A phenolic-based ionic liquid (IL), 1-(2-hydroxyethyl)-2,3-dimethylimidazolium phenoxide has been introduced for 1.5 molar carbon dioxide (CO2 ) absorption at ambient conditions without using special methodologies or precautions. The structure of the IL was characterized by various methods such as FT-IR, 1H NMR, 13C NMR, elemental analysis (EA) and thermogravimetric analysis (TGA). The ability of this IL for CO2 uptake reaches to its maximum value after 2 h. The IL has been reused fr several times with constant efficiency. Density functional theory (DFT) calculations at the B3LYP/6-311++G∗∗ level of calculation have been carried out to gain more structural knowledge...
Synthesis of Conductive Magnetite Nanocomposite based on Polyaniline/Poly(maleic acid-co-acrylic acid) with Core-Shell Structure
, Article Advances in Polymer Technology ; 2016 ; 07306679 (ISSN) ; Najafi Moghadam, P ; Mahmoodi Hashemi, M ; Sharif University of Technology
John Wiley and Sons Inc
2016
Abstract
In this study, a new type of magnetite nanocomposite with a core-shell structure was synthesized using Fe3O4 nanoparticles as a core and polyaniline (PANI) as a shell. For this propose, the surface of Fe3O4 was chemically modified with hexamethylenediisocyanate (HMDI) to improve its compatibility and interphase interaction with the polymeric matrix. Thereafter, the PANI was reacted with modified Fe3O4 to anchor them to PANI by covalent bands which acted as a shell. In the second step, the poly (maleic acid-co-acrylic acid) (P(MAc-co-AA)) as polymeric dopant for the PANI was synthesized. Finally, the PANI anchored to Fe3O4 was immersed in an aqueous solution of poly (maleic...
Synthesis of conductive magnetite nanocomposite based on polyaniline/poly(maleic acid-co-acrylic acid) with core–shell structure
, Article Advances in Polymer Technology ; Volume 37, Issue 4 , 2018 , Pages 1041-1049 ; 07306679 (ISSN) ; Najafi moghadam, P ; Mahmoodi hashemi, M ; Sharif University of Technology
John Wiley and Sons Inc
2018
Abstract
In this study, a new type of magnetite nanocomposite with a core–shell structure was synthesized using Fe3O4 nanoparticles as a core and polyaniline (PANI) as a shell. For this propose, the surface of Fe3O4 was chemically modified with hexamethylenediisocyanate (HMDI) to improve its compatibility and interphase interaction with the polymeric matrix. Thereafter, the PANI was reacted with modified Fe3O4 to anchor them to PANI by covalent bands which acted as a shell. In the second step, the poly (maleic acid-co-acrylic acid) (P(MAc-co-AA)) as polymeric dopant for the PANI was synthesized. Finally, the PANI anchored to Fe3O4 was immersed in an aqueous solution of poly (maleic...
Oxidation of hantzsch 1,4- dihydropyridines to pyridines with thallium triacetate
, Article Iranian Journal of Chemistry and Chemical Engineering ; Volume 22, Issue 2 , 2003 , Pages 9-11 ; 10219986 (ISSN) ; Zakeri, M. S ; Arianfar, S ; Sharif University of Technology
2003
Abstract
Hantzsch 1, 4-dihydropyridines (1,4-DHPs) can be oxidized to the corresponding pyridine derivatives by thallium triacetate in high yields
Silver nanoparticles supported on silica-coated ferrite as magnetic and reusable catalysts for oxidant-free alcohol dehydrogenation
, Article RSC Advances ; Volume 5, Issue 29 , Jan , 2015 , Pages 22503-22509 ; 20462069 (ISSN) ; Shakourian Fard, M ; Ehyaei, N ; Mahmoodi Hashemi, M ; Sharif University of Technology
Royal Society of Chemistry
2015
Abstract
Silver (0) nanoparticles supported on silica-coated ferrite were synthesized to be used as an efficient and recyclable heterogeneous catalyst for oxidant-free dehydrogenation of alcohols to the corresponding carbonyl compounds. The catalyst can be easily recovered and reused for 8 reaction cycles without considerable loss of activity. The facile recovery of the catalyst is carried out by applying an external magnetic device. The catalyst was fully characterized by the techniques of TEM, SEM, XRD, EDS, ICP-AES, and VSM. This journal is
A green procedure for direct oxidation of organic halides to aldehydes and ketones catalyzed by a molybdate-based catalyst
, Article New Journal of Chemistry ; Volume 39, Issue 5 , Feb , 2015 , Pages 3845-3851 ; 11440546 (ISSN) ; Shakourian Fard, M ; Ramezanpour, S ; Mahmoodi Hashemi, M ; Sharif University of Technology
Royal Society of Chemistry
2015
Abstract
A molybdate-based heterogeneous magnetic catalyst was synthesized and used in direct oxidation of various primary and secondary organic halides to the corresponding aldehydes and ketones using 30% H2 O2 as an oxidant in ethanol. Various organic halides were oxidized to their corresponding aldehydes and ketones in good to excellent yields. The catalyst system can be easily separated by applying an external magnetic field and reused for 6 runs without any significant loss of catalytic activity. The catalyst was fully characterized by FT-IR, SEM, TEM, EDS, XRD, VSM, ICP-AES techniques, and elemental analysis (CHN)
A highly reactive and magnetic recyclable catalyst based on silver nanoparticles supported on ferrite for n-monoalkylation of amines with alcohols
, Article Applied Organometallic Chemistry ; Volume 31, Issue 10 , 2017 ; 02682605 (ISSN) ; Shakourian Fard, M ; Nouri, P ; Mahmoodi Hashemi, M ; Sharif University of Technology
2017
Abstract
Fe3O4@SiO2-Ag catalyst was found to be highly active and selective in the N-alkylation of amines with a variety of aromatic and linear alcohols. The heterogeneous nature of the Fe3O4@SiO2-Ag catalyst allows easy recovery and regeneration by applying an external magnet for six subsequent reaction cycles. The prepared catalyst was characterized using electron microscopy techniques, X-ray diffraction, vibrating sample magnetometry and atomic absorption spectroscopy. Copyright © 2017 John Wiley & Sons, Ltd
Silver nanoparticles immobilized onto poly(4-vinylpyridine)-functionalized magnetic nanoparticles: a robust magnetically recyclable catalyst for oxidant-free alcohol dehydrogenation
, Article Applied Organometallic Chemistry ; Volume 32, Issue 2 , February , 2018 ; 02682605 (ISSN) ; Shakourian Fard, M ; Talebloo, N ; Mahmoodi Hashemi, M ; Sharif University of Technology
John Wiley and Sons Ltd
2018
Abstract
A heterogeneous and recyclable catalyst with a high loading of silver nanoparticles was synthesized via the silver nanoparticles being supported onto the surface of magnetic nanoparticles coated with poly(4-vinylpyridine). The synthesized catalyst was used in the dehydrogenation of alcohols to corresponding carbonyl compounds. A broad diversity of alcohols was converted into their corresponding carbonyl compounds in excellent yields. The catalyst was easily recovered by applying an external magnetic field and reused for seven reaction cycles without considerable loss of activity. The catalyst was fully characterized using various techniques. Copyright © 2017 John Wiley & Sons, Ltd
Stereoselective synthesis of β-amino ketones via direct Mannich-type reactions, catalyzed with ZrOCl2·8H2O under solvent-free conditions
, Article European Journal of Organic Chemistry ; Issue 22 , 2006 , Pages 5152-5157 ; 1434193X (ISSN) ; Abdollahifar, A ; Mahmoodi Hashemi, M ; Zirak, M ; Sharif University of Technology
2006
Abstract
At room temperature, zirconium oxychloride (ZrOCl2· 8H2O) efficiently catalyzes the direct Mannich-type reaction of a variety of in situ generated aldimines using aldehydes and anilines with ketones in a three-component reaction under solvent-free conditions. The reaction proceeds rapidly and affords the corresponding β-amino ketones in good to high yields with good to excellent stereoselectivities. The catalyst can be recycled for subsequent reactions without any appreciable loss of efficiency. © Wiley-VCH Verlag GmbH & Co. KGaA, 2006
Facile, Efficient and Low Cost Synthesis of N-(1H-imidazoline-2-yl)-1H-Benzimidazol-2-Amine and its Derivatives
, M.Sc. Thesis Sharif University of Technology ; Mahmoodi Hashemi, Mohammed (Supervisor)
Abstract
Benzimidazoles are a bioactive family of chemicals which had been subject of many studies because of their valuable properties, and has a long history of production in chemical industries. Investigation on their properties and reactions with goal of achieving to new derivatives have drawn attention of many research teams. Recently, 2- Imidazolineaminobenzimidazole had been synthesized by microwave-assisted reaction of 2-Aminobenzimidazole with 2-Methylsulfanylimidazoline hydrogen iodide. But because of difficulties aroused by use of microwave system and expensive chemicals, we decided to utilized reaction procedures which could be facile, inexpensive with capability of high reaction scales....
Sodium hypochlorite-Dowex 1X8-200: A convenient oxidizing reagant
, Article Iranian Journal of Chemistry and Chemical Engineering ; Volume 21, Issue 2 , 2002 , Pages 71-73 ; 10219986 (ISSN) ; Ahmadibeni, Y ; Sharif University of Technology
2002
Abstract
The polymer supported hypochlorite ion is a facile selective oxidizing agent for the oxidation of various alcohols to aldehydes and ketones. Similarly it successfully oxidizes various Hantzsch type 1,4 - dihydropyridines to corresponding pyridines
Surfactant-Like brønsted acidic ionic liquid as an efficient catalyst for selective mannich reaction and biodiesel production in water
, Article Journal of the Iranian Chemical Society ; Volume 14, Issue 4 , 2017 , Pages 907-914 ; 1735207X (ISSN) ; Karbalaie Reza, M ; Mahmoodi Hashemi, M ; Qasempour Soleimany, K ; Sharif University of Technology
Springer Verlag
2017
Abstract
Abstract: The current study deals with the applications of a surfactant-like Brønsted acidic ionic liquid (IL) 1-dodecyl-3-methylimidazolium hydrogen sulfate ([DMIm]HSO4) for Mannich reaction at room temperature. The reaction was efficiently preceded in water as solvent without using any harmful and expensive organic additives. Our findings showed that the reaction is selective for cyclohexanone and no Mannich product was observed when cyclopentanone was used as starting material. Density functional theory (DFT) calculations were performed to provide an evidence about the nature of reactivity of the cyclohexanone/cyclopentanone. The activity of the catalyst was also tested for biodiesel...
Synthesis of Amines, Quinoxalines and New 1,4-Dihydropyridines in Water, Reactions of Indoles and Oxidation of 1,4-Dihydropyridines Using Sodium Nitrite
, Ph.D. Dissertation Sharif University of Technology ; Mahmoodi Hashemi, Mohammad (Supervisor)
Abstract
Briefly in this thesis, these subjects have been investigated: In recent years, water is used as a solvent instead of an organic solvents have become more and more important due to cheap and environmental consideration. In this context, preparation of quinoxaline, pyrrole, new 1,4-dihydropyridine and reduction of imine to amine with 1,4-dihydropyridine derivatives as the reducing agents with the use of one-pot multicomponent reaction have been reported. The existence of several hydrogen bonding groups (NH) in the new dihydropyridines they acts as biologically active compounds in the forthcoming years. In continuation, oxidation of thiols to disulfides in the presence of NBS and NCS and...
Designing of Magnetic Nanocatalyst and their Application in Oxidation of Alcohols and Other Functional Groups
, Ph.D. Dissertation Sharif University of Technology ; Mahmoodi Hashemi, Mohammad (Supervisor)
Abstract
In this thesis, heterogenous catalysts based on magnetic nanoparticles were synthesized. In these catalysts, magnetic nanoparticles were coated with defferent fuctional groups to produce a catalyst with magnetic properties which is easily separated from the reaction medium. The structure of synthesized catalyst was characterized using techniques such as transmission electron microscopy (TEM), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), and CHNS elemental analysis. Easy preparation, low cost, biodegradability and high thermal stability are advantages of these catalysts. At the end, the catalytic properties of resulted catalysts were investigated in many...
Design and Structural Study of Functionalized Nanoporous Catalysts Confined with Ionic Liquids and Their Applications in Some Organic Transformations
, M.Sc. Thesis Sharif University of Technology ; Mahmoodi Hashemi, Mohammad (Supervisor)
Abstract
The current thesis deals with designing of functionalized nanoporous catalysts modified with organic groups and ionic liquids and their applications for some challenging organic reactions such as synthesis of adipic acid and fatty acid esterifications. In this condition the catalysts show enhanced activity since the hydrophobicity of the surface can tune by applying organic groups. In this regard, oxidation of cyclohexene was performed using hydrogen peroxide as oxidant in the present of tungstate based task–specific ionic liquids and silica–functionalized ammonium tungstate as green catalysts. The results indicate that adipic acid achieves in high yield with excellent selectivity....
Preparation of Copper Salt of Para-amino Benzoic Acid Supported on Graphene Oxide as a Nanocatalyst and its Application in Some Organic Reactions
, M.Sc. Thesis Sharif University of Technology ; Mahmoodi Hashemi, Mohammad (Supervisor)
Abstract
The purpose of this study is to prepare a catalyst for copper nanoparticles that can be used in C-H activation processes in order to increase copper salt catalytic processes by converting it into a catalyst with characteristics of having recovery cycles, convenient separation and environmental friendliness and being in nano size. Consequently, copper nanoparticles are directly grafted onto graphene oxide, or using para-aminobenzoic acid grafted on graphene oxide. A copper nanoparticle catalyst was used in the reaction to activate the C(sp2)-H bonds of benzoxazole molecule and C-N bonds formation with secendary amines. Using the results of transition electron microscopy (TEM), scanning...
Synthesis and Application of Acidic and Hydrophobic Ionic Liquids in Mannich Reaction and Esterification of Fatty Acids
, M.Sc. Thesis Sharif University of Technology ; Mahmoodi Hashemi, Mohammed (Supervisor)
Abstract
The current study deals with application of a surfactant-like Brønsted acidic ionic liquid (IL) 1-dodecyl-3-methylimidazolium hydrogensulfate (catalys 1) for Mannich reaction at room temperature. The reaction has been efficiently proceeds in water as solvent without using any harmful and expensive organic additives. Our observation has been shown that the reaction is selective for cyclohexanone and no product was observed by using cyclopentanone at room temperature. Density functional theory (DFT) calculations were performed to provide evidence about the nature of reactivity of the cyclohexanone/cyclopentanone. The activity of the catalyst 2 (1-dodecyl-2,3-dimethylimidazolium...
Synthesis of Graphene-Based Magnetic Nanocatalyst Supported Ag Nanoparticles for Alcohols Oxidation
, M.Sc. Thesis Sharif University of Technology ; Mahmoodi Hashemi, Mohammad (Supervisor)
Abstract
In this thesis the graphene-based magnetic nanocatalyst was synthesized. The surface of this catalyst was cavered by silica and AgNPs. In addithion of simple sepration by magnetbar, yeild of reaction was promoted by surface modification. Catalyst structure was verified by transmission electron microscopy , scanning electron microscope, fourier transform infrared spectroscopy, X-ray diffraction and Energy dispersive spectroscopy.At the end catalytic activity was examined by oxidation reaction in persense of different alcohols. The oxidation of benzylic alcohol with electron withdrawing substituents was more difficult and the yield was lower, but electron donor substituents effect positively...
Preparation of Cobalt and Manganese Salts of Para-amino Benzoic Acid Supported on Graphene Oxide as an Oxidative Nanocatalysts
, M.Sc. Thesis Sharif University of Technology ; Mahmoodi Hashemi, Mohammad (Supervisor)
Abstract
In this thesis, a heterogeneous nanocatalyst based on graphene oxide was synthesized. To improve the graphene oxide, it was reacted with paraaminobenzoic acid and then metal salts (cobalt and manganese) were coated on it. The structure of the catalyst was confirmed by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), quantitative X-ray diffraction (EDS) and infrared (FT-IR) spectroscopy. Finally, the catalytic properties of the catalysts were evaluated in the oxidation reaction of different alcohols in the presence of oxygen. In the presence of benzyl alcohols with lethal electron groups, the oxidation conditions are stricter and the reaction efficiency is lower....