- Metal-free N-formylation of 2-aminophenols using dimethylformamide and CSA
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DMF has been proved to be an efficient formylation reagent for 2-aminophenols in the presence of (±) camphorsulfonic acid (CSA) in this work. CSA works as an acid catalyst and a neutralizer of dimethyl amine which is kicked off from DMF. Both electron-wit
- Yang, Yuanyong,Li, Yingxian,Zhang, Zhenhua,Zhao, Yonglong,Feng, Wei
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- An Environmentally Benign, Catalyst-Free N?C Bond Cleavage/Formation of Primary, Secondary, and Tertiary Unactivated Amides
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Herein, we report an operationally simple, cheap, and catalyst-free method for the transamidation of a diverse range of unactivated amides furnishing the desired products in excellent yields. This protocol is environmentally friendly and operates under extremely mild conditions without using any promoter or additives. Significantly, this strategy has been implied in the chemoselective synthesis of a pharmaceutical molecule, paracetamol, on a gram-scale with excellent yield. We anticipate that this universally applicable strategy will be of great interest in drug discovery, biochemistry, and organic synthesis.
- Kumar, Vishal,Dhawan, Sanjeev,Girase, Pankaj Sanjay,Singh, Parvesh,Karpoormath, Rajshekhar
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p. 5627 - 5639
(2021/11/11)
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- Palladium supported on MRGO@CoAl-LDH catalyzed reductive carbonylation of nitroarenes and carbonylative Suzuki coupling reactions using formic acid as liquid CO and H2 source
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In the present study, a heterogeneous palladium catalyst system, Pd nanoparticles supported on MRGO@CoAl-LDH, was synthesized and employed in reductive carbonylation of nitroarenes and carbonylative Suzuki coupling reactions using formic acid as CO and H2 source. The as-obtained heterogeneous catalyst was characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDAX), thermal gravimetric analysis (TGA), and vibrating sample magnetometer (VSM). The nanocatalyst was reused for 5 cycles with a negligible reduction in the yield of products. All reactions were carried out with high yields and under suitable and safe conditions. Also, we have successfully applied formic acid as a good and safe alternative to CO and H2 gases.
- Jadidi Nejad, Masoumeh,Heydari, Akbar
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- N-Formylation of amines using arylhydrazones of malononitrile and a Cu(II) complex under eco-friendly conditions at room temperature
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In this work, we report the synthesis of formamides via solvent free N-formylation of amines using known arylhydrazones of malononitrile including sodium 2-(2-(dicyanomethylene)hydrazinyl)benzenesulfonate (I), 2-(2-(dicyanomethylene)hydrazinyl) benzoic acid (II) and its Cu(II) complex (III) as catalysts at room temperature. These catalysts are highly active and the scope of the method was investigated using several heterocyclic, aromatic and aliphatic amines as substrates, which produced the corresponding formamides in high yields. The remarkable advantages of this method are the elimination of toxic solvents, operational simplicity, easy workup procedure, excellent yields and avoidance of column chromatography.
- Nasrollahzadeh, Mahmoud,Bidgoli, Nayyereh Sadat Soheili,Rocha, Bruno G.M.,Pombeiro, Armando J.L.,Mahmudov, Kamran T.
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- Effective and selective direct aminoformylation of nitroarenes utilizing palladium nanoparticles assisted by fibrous-structured silica nanospheres
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Abstract: Palladium nanoparticles (~ 1–3?nm, 0.4?wtpercent Pd) were uniformly distributed over the surface of fibrous silica nanospheres (KCC-1) modified via aminopropyltriethoxysilane using a fast and cost-effective palladium (II) chloride reduction process. The Pd nanoparticles (Pd NPs) distribution over the ensuing catalyst Pd/KCC-1-NH2 showed much more uniform distribution, and smaller size compared with the tedious hydrothermal reduction method. The morphological, chemical, and size analyses of Pd/KCC-1-NH2 by BET, UV–Vis spectra, XRD, HR-TEM, EDS and XPS analysis revealed that the succeeding material consist of a distinct fibrous silica nanospheres support adorn with Pd NPs. The resultant nanocatalyst was tested for the one-step reductive aminoformylation of aromatic nitro compounds using formic acid. A wide range of substituted nitroarenes including electron withdrawing, releasing, sterically hindered and multifunctional groups have been converted to corresponding aryl formamide in quantitative yields (yields up to 98percent) at moderate temperature (70?°C). Optimization study has proved that the 6 equivalent of formic acid is required and toluene was found to be the better solvent. The established practice is beneficial due to the use of formic acid as H2 source and formylating agent, easiness in handling of the catalyst and simple workup procedure with efficient catalyst reusability. Graphic abstract: [Figure not available: see fulltext.].
- Jaseer, E. A.,Qureshi, Ziyauddin S.
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- METHOD OF CARBON MONOXIDE FIXATION AND METHOD OF AMINE FORMYLATION
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The present invention relates to a method for fixing carbon monoxide in a metal-free condition and a method for formating amine using the same.
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Paragraph 0078; 0081-0085; 0100-0102
(2021/02/19)
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- Metal-free Carbon Monoxide (CO) Capture and Utilization: Formylation of Amines
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The capture and utilization of CO by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were performed in the absence of transition-metal complexes. The reaction of TBD with CO afforded TBD-CO adducts, which were converted to formylated TBD (TBD-CHO). TBD-CO adducts may include an interaction of CO with positively charged species based on NMR and IR analysis. In the presence of amines, CO was transferred from TBD-CO to amines, producing formylated amines with good yields. The reaction mechanism involving TBD-CO adducts is presented based on theoretical calculations. (Figure presented.).
- Noh, Hyeong-Wan,An, Youngjoon,Lee, Seulchan,Jung, Jaehoon,Son, Seung Uk,Jang, Hye-Young
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- Graphene Oxide: A Metal-Free Carbocatalyst for the Synthesis of Diverse Amides under Solvent-Free Conditions
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An environmentally friendly, inexpensive, carbocatalyst, graphene oxide (GO) promoted efficient, metal-free transamidation of various carboxamides with aliphatic, cyclic, and aromatic amines is demonstrated. The protocol is equally applicable to phthalimide, urea, and thioamide determining its adaptability. The oxygenated functionalities such as carbonyl (?C=O), epoxy (?O?), carboxyl (?COOH) and hydroxyl (?OH), present on graphene oxide surface impart acidic properties to the catalyst. The graphene oxide being heterogeneous in nature, work efficiently under solvent-free reaction conditions providing desired products in good to excellent yields. The one-pot synthesis of 2,3-Dihydro-5H-benzo[b]-1,4-thiazepin-4-one moiety by GO catalyzed Aza Michael addition followed by intramolecular transamidation is also described. A plausible reaction mechanistic pathway involving H-bonding is discussed. The graphene oxide can be recycled and reused up to five cycles without much loss in catalytic activity. (Figure presented.).
- Patel, Khushbu P.,Gayakwad, Eknath M.,Patil, Vilas V.,Shankarling, Ganapati S.
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supporting information
p. 2107 - 2116
(2019/03/26)
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- NH4I-promoted N-acylation of amines via the transamidation of DMF and DMA under metal-free conditions
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An unprecedented NH4I-promoted N-formylation and N-acetylization of various amines with dimethylformamide (DMF)and dimethylacetamide (DMA)has been developed. This protocol shows broad substrate scope for aromatic, aliphatic, and heterocyclic amines, which provides a metal-free strategy for N-acylation featuring mild reaction conditions, as well as inexpensive and readily available starting materials.
- Chen, Jiahui,Jia, Jing,Guo, Ziyi,Zhang, Jitan,Xie, Meihua
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supporting information
p. 1426 - 1429
(2019/05/06)
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- KOtBu-Promoted Transition-Metal-Free Transamidation of Primary and Tertiary Amides with Amines
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This work discloses transamidation of primary and tertiary amides with a range of aryl, heteroaryl, and aliphatic amines using potassium tert-butoxide. The reaction proceeds at room temperature under transition-metal-free conditions providing secondary amides in high yields. Moreover, reaction of cyclopropyl amine with tertiary amides proceeds with ring-opening to provide a rapid access to enamides.
- Ghosh, Tridev,Jana, Snehasish,Dash, Jyotirmayee
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supporting information
p. 6690 - 6694
(2019/09/12)
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- One-pot selective N-formylation of nitroarenes to formamides catalyzed by core-shell structured cobalt nanoparticles
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One-pot direct N-formylation of readily available nitroarenes with ammonium formate catalyzed by core-shell structured cobalt nanoparticles has been developed. A broad set of nitroarenes was successfully converted to their corresponding formamides in good to high yields with various functional group tolerance. This heterogeneous catalyst can be easily removed from the reaction medium and can be reused several times without a significant loss of reaction efficiency.
- Dong, Xiaosu,Wang, Zhaozhan,Duan, Yanan,Yang, Yong
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supporting information
p. 8913 - 8916
(2018/08/17)
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- Consecutive Lossen rearrangement/transamidation reaction of hydroxamic acids under catalyst- and additive-free conditions
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The Lossen rearrangement is a classic process for transforming activated hydroxamic acids into isocyanate under basic or thermal conditions. In the current report we disclosed a consecutive Lossen rearrangement/transamidation reaction in which unactivated hydroxamic acids were converted into N-substituted formamides in a one-pot manner under catalyst- and additive-free conditions. One feature of this novel transformation is that the formamide plays triple roles in the reaction by acting as a readily available solvent, a promoter for additive-free Lossen rearrangement, and a source of the formyl group in the final products. Acyl groups other than formyl could also be introduced into the product when changing the solvent to other low molecular weight aliphatic amide derivatives. The solvent-promoted Lossen rearrangement was better understood by DFT calculations, and the intermediacy of isocyanate and amine was supported well by experiments, in which the desired products were obtained in excellent yields under similar conditions. Not only monosubstituted formamides were synthesized from hydroxamic acids, but also N,N-disubstituted formamides were obtained when secondary amines were used as precursors.
- Jia, Mengmeng,Zhang, Heng,Lin, Yongjia,Chen, Dimei,Chen, Yanmei,Xia, Yuanzhi
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p. 3615 - 3624
(2018/05/26)
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- Supported Palladium Nanoparticles Catalyzed Reductive Carbonylation of Nitroarenes to N-Arylformamides
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A facile reductive carbonylation reaction of nitroarenes to N-arylformamide synthesis was investigated under polymer supported palladium (Pd@PS) nanoparticles catalyzed conditions. Dual role of oxalic acid dihydrate ((CO2H)2 ? 2H2O) as H2 source for hydrogenation and CO source for carbonylation reaction for desired products synthesis was critically investigated under favorable DMF solvent conditions. Several cross experiments were performed to establish the best possible hypothesis for the proposed mechanism and understanding about the involvement of CO in the reaction pathway. Further, ortho-substituted nitroarenes were found to be highly specific for facile para-hydroxylation to give corresponding para-hydroxy N-aryl formamides. (Figure presented.).
- Thakur, Vandna,Kumar, Ajay,Sharma, Nishtha,Shil, Arun K.,Das, Pralay
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supporting information
p. 432 - 437
(2017/12/26)
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- MARINE SESSILE ORGANISM-REPELLING COMPOSITION
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A compound represented by the formula below: wherein R is selected from the group consisting of benzyl, C3-11 alkyl, C3-11 alkenyl, C2-9 branched alkenyl, C3-9 branched alkyl, and —CH2OAc.
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Paragraph 0064-0067
(2018/05/03)
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- Sulfated polyborate-catalyzed N-formylation of amines: a rapid, green and efficient protocol
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Abstract: A rapid, green and efficient method for N-formylation reaction of various amines with formic acid in the presence of sulfated polyborate catalyst under solvent-free conditions has been described. The catalyst has the advantage of mild Bronsted as well as Lewis acid character. The catalyst is recyclable with no significant loss in catalytic activity. The present protocol is advantageous due to its solvent-free condition, short reaction time, high yields, easy workup and ability to tolerate a variety of functional groups.
- Khatri, Chetan K.,Chaturbhuj, Ganesh U.
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p. 2513 - 2519
(2017/11/06)
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- NaY zeolite functionalized by sulfamic acid/Cu(OAc)2 as a new and reusable heterogeneous hybrid catalyst for efficient solvent-free formylation of amines
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NaY zeolite functionalized by sulfamic acid/Cu(OAc)2 [NaY/SA/Cu(II)] was synthesized and used as a new, efficient and recyclable catalyst for preparation of formamides. This novel organic-inorganic hybrid catalyst was characterized by several techniques such as FT-IR, XRD, SEM, EDX and TG analysis. Chemoselectivity, easy procedure, excellent yields, very short reaction times, solvent-free and mild reaction conditions are some benefits of this new protocol.
- Kazemi, Samira,Mobinikhaledi, Akbar,Zendehdel, Mojgan
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p. 1767 - 1772
(2017/07/27)
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- New catalytic performance of immobilized sulfuric acid on activated charcoal for n-formylation of amines with ethyl formate
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Summary: Simple and highly efficient procedure for N-formylation of various amines was carried out in the presence of the immobilized sufuric acid on activated charcoal as an efficient promoter system. All reactions were taken place in refluxing ethyl formate (54 °C) under mild reaction conditions. The product formamides were obtained in high to excellent yields (83-95%) within 4-80 min.
- Abdollahi, Mohammad,Zeynizadeh, Behzad,Sadighnia, Leila
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p. 619 - 627
(2017/11/06)
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- Synthesis of pyrrolidones and quinolines from the known biomass feedstock levulinic acid and amines
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The catalytic conversion of biomass-derived compounds into value-added products such as food additives, agrochemical components, and pharmaceutical formulations, is a promising and cost effective synthetic strategy. Here, we describe the synthesis of a variety of N-(alkyl, aryl)-5-methyl-2-pyrrolidones through the reductive amination of levulinic acid using formic acid as the hydrogen source. This system is catalyzed by 3.8 nm ruthenium nanoparticles that were prepared by thermal decomposition of [Ru3(CO)12] in solvent-free conditions. When the reactions were carried out without the catalyst, the pyrrolidones were obtained with low yield and poor selectivity. In addition, the reaction between levulinic acid and 2-ethynylaniline produced 2-(2,4-dimethylquinolin-3-yl) acetic acid (8) in mild and metal-free conditions with good yield. Furthermore, the synthesis of substituted quinolines was achieved through a condensation reaction between levulinic acid and different 2-alkynylanilines promoted by p-toluenesulfonic acid, this method is highlighted as a novel procedure for the preparation of quinolines.
- Ortiz-Cervantes, Carmen,Flores-Alamo, Marcos,García, Juventino J.
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supporting information
p. 766 - 771
(2016/02/05)
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- A photoactive bimetallic framework for direct aminoformylation of nitroarenes
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A bimetallic catalyst, AgPd@g-C3N4, synthesized by reducing silver and palladium salts over graphitic carbon nitride (g-C3N4), enables the concerted reductive formylation of aromatic nitro compounds under photo-chemical conditions using formic acid, which serves the dual role of a hydrogen source and a formylating agent.
- Nasir Baig,Verma, Sanny,Nadagouda, Mallikarjuna N.,Varma, Rajender S.
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p. 1019 - 1022
(2016/02/27)
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- An efficient method for the synthesis of formamidine and formamide derivatives promoted by sulfonated rice husk ash (RHA-SO3H)
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A mild, simple and efficient method has been developed for the promotion of the preparation of N,N′-diphenylformamidines from various aromatic amines and ethyl orthoformate using sulfonated rice husk ash (RHA-SO3H) solid acid catalyst. This reagent has also been used for the N-formylation of a variety of amines using formic acid under solvent-free conditions. The procedures gave the products in very short reaction times and good-to-high yields. Also this catalyst can be reused for five times without loss of its catalytic activity.
- Seddighi, Mohadeseh,Shirini, Farhad,Mamaghani, Manouchehr
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p. 433 - 439
(2015/02/05)
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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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- 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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- An eco-friendly n-formylation of amines using nano cerium oxide as a recyclable catalyst under solvent-free and ultrasound irradiation conditions at room temperature
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A new method for the synthesis of formamides has been developed by the N-formylation of amines with formic acid in the presence of nano cerium oxide as an efficient and recyclable catalyst under ultrasound irradiation. The reaction system is remarkably simple and environmentally benign.
- Sajadi, S. Mohammad,Maham, Mehdi,Rezaei, Akbar
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- Br?nsted acidic ionic liquid supported on rice husk ash (RHA-[pmim]HSO4): A highly efficient and reusable catalyst for the formylation of amines and alcohols
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In this work, rice husk ash (RHA), as a natural source of amorphous silica, was used as a support for the immobilization of 1-methyl-3-(trimethoxysilylpropyl)-imidazolium hydrogen sulfate. The immobilized acidic ionic liquid was characterized with a variety of techniques including infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and pH analysis. The catalytic performance of this heterogeneous ionic liquid was probed for the N-formylation of a variety of amines using formic acid under solvent free conditions. It is also useful for the formylation of benzylic alcohols. The procedure gave the products in excellent yields in very short reaction times. Also this catalyst can be reused ten times without loss of its catalytic activity.
- Shirini, Farhad,Seddighi, Mohadeseh,Mamaghani, Manouchehr
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p. 50631 - 50638
(2014/12/10)
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- Synthesis, structural characterization, and catalytic activity of flower like zno nanostructures
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Tageteserecta flower like zinc oxide nanostructures composed of hexagonal nanorods were synthesized via sonochemical method at room temperature. The synthesized nanomaterials exhibited wurtzite hexagonal phase structure with the single crystalline nature. The diameter of the individual nanorods that constitute the flower shaped zinc oxide structures is in the range of 120-160 nm. The sonication time effectively determined the morphological properties of the prepared materials. The catalytic activity of prepared zinc oxide nanostructures towards N-formylation reactions were evaluated without any surface modification and the nanostructures exhibited good reaction yield with the prompt recyclability behavior.
- Ramachandran,Gnana Kumar,Kim, Ae Rhan,Yoo, Dong Jin
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p. 1091 - 1097
(2014/05/06)
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- Carbon nanotube-gold nanohybrid catalyzed N-formylation of amines by using aqueous formaldehyde
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The N-formylation of a variety of primary and secondary amines by using aqueous formaldehyde at room temperature in open air affords the corresponding formamides in excellent yield under the catalytic influence of a gold-carbon nanotube nanohybrid. The reaction is also marked by excellent chemoselectivity, low catalyst loading, and recyclability of the catalyst.
- Shah, Nimesh,Gravel, Edmond,Jawale, Dhanaji V.,Doris, Eric,Namboothiri, Irishi N.N.
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p. 2201 - 2205
(2014/08/18)
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- Highly efficient N-formylation of amines with ammonium formate catalyzed by nano-Fe3O4 in PEG-400
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A simple and efficient protocol for the formylation of amines with ammonium formate with excellent yields catalyzed by Fe3O4 nanoparticles in PEG-400 is described. Notably, this method shows excellent activity and chemoselectivity for the formylation of primary and secondary arylamines. Moreover, the nano-Fe3O4 catalyst and PEG-400 could be easily recovered and reused.
- Wang, Zhao-Gang,Lu, Ming
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p. 1234 - 1240
(2014/01/06)
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- A simple method for preparation of ZnO nanoparticles as a highly efficient nanocatalyst for N-formylation of primary and secondary amines under solvent-free condition
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A convenient reaction between alky, aryl, and heteroalkyl amines and formic acid as a formylating agent in the presence of catalytic amount of mechanochemically synthesized zinc oxide nanoparticles under solvent-free condition for the synthesis of corresponding N-formyl derivatives is described. Copyright Taylor and Francis Group, LLC.
- Alinezhad, Heshmatollah,Salehian, Fatemeh
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p. 532 - 538
(2013/07/19)
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- Melamine trisulfonic acid-catalyzed N-formylation of amines under solvent-free conditions
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A highly convenient method for N-formylation of amines via treatment by formic acid in the presence of melamine trisulfonic acid as a catalyst has been developed. This method showed improvements over previous reports in terms of yield, reaction time and chemoselectivity.
- Yang, Xiao Juan,Zhang, Yong Sen
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p. 2843 - 2848
(2013/07/26)
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- An ultrasound-promoted green approach for the N-formylation of amines under solvent- and catalyst-free conditions at room temperature
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A new environmentally benign, convenient, and facile methodology for the N-formylation of amines is reported using ultrasound irradiation under solvent- and catalyst-free conditions at room temperature. Compared with conventional methods, the main advantages of the present procedure are milder, cleaner and greener conditions, shorter reaction time, higher purity and yields, simpler work-up, and lower generation of waste or pollutions.
- Habibi, Davood,Nasrollahzadeh, Mahmoud
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p. 1008 - 1016
(2013/11/06)
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- Nano CoFe2O4 as a magnetically separable catalyst for the solvent-free synthesis of formamides under ultrasound irradiation at room temperature
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Formamides were efficiently synthesized from N-formylation of amines using CoFe2O4 nanoparticles as a magnetically recoverable and reusable catalyst under ultrasound irradiation. The main advantages allocated to this method are chemoselectivity, reduced reaction times, high yields, magnetically recyclable catalyst, non-solvent green conditions and simple work-up procedure.
- Bahari, Siavash
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p. 532 - 537
(2013/08/23)
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- Mild and convenient N-formylation protocol in water-containing solvents
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We have realized that N-formylations of free amines of some drug leads can improve PK/PD property of parent molecules without decreasing their biological activities. In order to selectively formylate primary amines of polyfunctional molecules, we have sought a mild and convenient formylation reaction. In our screening of N-formylation of an α-amino acid, l-phenylalanine, none of formylation conditions reported to date yielded the desired HCO-l-Phe-OH with satisfactory yield. N-formylations of amino acids with HCO2H require a water-containing media and suppress polymerization reactions due to the competitive reactions among carboxylic acids. We found that N-formylations of α-amino acids could be achieved with a water-soluble peptide coupling additive, an Oxyma derivative, (2,2-dimethyl-1,3-dioxolan-4-yl)methyl-2-cyano-2- (hydroxyimino)acetate (2), EDCI, and NaHCO3 in water or a mixture of water and DMF system, yielding N-formylated α-amino acids with excellent yields. Moreover, these conditions could selectively formylate primary amines over secondary amines at a controlled temperature. A usefulness of these conditions was demonstrated by selective formylation of daptomycin antibiotic which contains three different amino groups.
- Aleiwi, Bilal A.,Mitachi, Katsuhiko,Kurosu, Michio
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p. 2077 - 2081
(2013/05/08)
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- A very simple, highly efficient and catalyst-free procedure for the N-formylation of amines using triethyl orthoformate in water under ultrasound-irradiation
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N-Formylation of amines has efficiently been carried out in excellent yields by treatment of amines with triethyl orthoformate in water under ultrasound irradiation. The process is remarkably simple and environmentally benign.
- Habibi, Davood,Sahebekhtiari, Hesam,Nasrollahzadeh, Mahmoud,Taghipour, Ahmad
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p. 209 - 212
(2013/07/26)
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- Sulfated tungstate catalyzed highly accelerated N-formylation
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Sulfated tungstate catalyzed, green, rapid, and practical method for N-formylation of amines using formic acid under solvent-free conditions is described. This method showed improvements over the reported in terms of yield, reaction time, and chemoselectivity.
- Pathare, Sagar P.,Sawant, Ravindra V.,Akamanchi, Krishnacharya G.
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experimental part
p. 3259 - 3263
(2012/07/30)
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- Deep eutectic solvent promoted highly efficient synthesis of N, N'-diarylamidines and formamides
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A deep eutectic solvent was used as a dual catalyst and reaction medium for the efficient N-formylation of aromatic amines without hazardous organic solvent and catalyst. Treatment of aromatic amines with trimethyl orthoformate and formic acid in deep eutectic solvent at 70 °C gives the corresponding N-formyl derivatives in good to excellent yields. This simple ammonium deep eutectic solvent, easily synthesized from choline chloride and SnCl2, with 100% atom economy and making it applicable to industry and laboratory. Furthermore, heating the trimethyl orthoformate and aromatic primary amines in the deep eutectic solvent results in formation of the corresponding N,N'-diarylamidines in high yields.
- Azizi, Najmadin,Gholibeglo, Elham,Babapour, Mahbobe,Ghafuri, Hossein,Bolourtchian, Seyed Mohammad
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p. 768 - 773
(2012/10/30)
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- An efficient method for N-formylation of amines using natural heu zeolite at room temperature under solvent-free conditions
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A rapid and practical green route for N-formylation of primary and secondary amines with formic acid at room temperature under the solvent-free conditions using HEU zeolite as a heterogeneous, reusable and highly efficient catalyst is described. The process is remarkably simple and environmentally benign. Excellent chemoselectivity was observed for the conversion of primary amines in the presence of secondary amines.
- Bahari, Siavash,Mohammadi-Aghdam, Babak,Sajadi, S. Mohammad,Zeidali, Fereshteh
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experimental part
p. 2251 - 2254
(2012/08/28)
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- Tandem migration - Carboalkoxylation of o-isocyanophenyl acetals leading to benzoxazoles
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An efficient approach to benzoxazoles via tandem migration - carboalkoxylation of o-isocyanophenyl acetals has been developed. Both a Lewis acid and base are essential for this reaction, and the BF3· OEt2/2,4,6-collidine combination
- Okitsu, Takashi,Nagase, Kenta,Nishio, Nobuhiko,Wada, Akimori
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supporting information; experimental part
p. 708 - 711
(2012/04/04)
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- Silica supported perchloric acid catalyzed rapid N-formylation under solvent-free conditions
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A rapid and chemoselective method for the N-formylation of structurally diverse amines with formic acid using silica supported perchloric acid (HClO4-SiO2) at room temperature and under solvent-free conditions has been developed. The catalyst was found to be compatible with different functional groups and the formylation proceeded smoothly with amines bearing electron withdrawing as well as electron donating substituents.
- Ansari, Mohd. Imran,Hussain, Mohd. Kamil,Yadav, Nisha,Gupta, Puneet K.,Hajela
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experimental part
p. 2063 - 2065
(2012/07/14)
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- N-Formylsaccharin: A new formylating agent
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N-Formylsaccharin, a very cheap reagent, has been revealed to be an efficient and chemoselective formylating agent of amines. Georg Thieme Verlag Stuttgart New York.
- Cochet, Thomas,Bellosta, Véronique,Greiner, Alfred,Roche, Didier,Cossy, Janine
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experimental part
p. 1920 - 1922
(2011/10/02)
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- Indium-catalyzed N -formylation of amines under solvent-free conditions
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We have developed a simple, mild method for N-formylation of a wide variety of amines in the presence of indium metal as a catalyst under solvent-free conditions. This reaction is applicable to the chemoselective N-formylation of amino groups and -amino acid esters without epimerization. Georg Thieme Verlag Stuttgart.
- Kim, Joong-Gon,Jang, Doo Ok
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experimental part
p. 1231 - 1234
(2010/07/08)
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- Sulfonic acid supported on hydroxyapatite-encapsulated-γ-Fe2O3 nanocrystallites as a magnetically Br?nsted acid for N-formylation of amines
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Treatment of aqueous formic acid (85%) with structurally diverse amines in the presence of a catalytic amount of sulfonic acid supported on hydroxyapatite-encapsulated-γ-Fe2O3 [HAp@-γ-Fe2O3] (0.9 mol.%) as a heterogeneous, reusable and highly efficient catalyst gave the corresponding formamides in good to excellent yields at room temperature. The magnetically catalytic system was recovered by-passing time consuming filtration operation by using an external magnet device. In addition to facility, this methodology, it also enhances product purity and promises economic as well as environmental benefits.
- Ma'mani, Leila,Sheykhan, Mehdi,Heydari, Akbar,Faraji, Mohammad,Yamini, Yadollah
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experimental part
p. 64 - 69
(2010/07/05)
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- A very simple and highly efficient procedure for N-formylation of primary and secondary amines at room temperature under solvent-free conditions
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N-Formylation of primary and secondary amines has efficiently been carried out at room temperature in excellent yields by using catalytic amount of sodium formate in formic acid under solvent-free conditions. The process is remarkably simple and environmentally benign.
- Brahmachari, Goutam,Laskar, Sujay
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experimental part
p. 2319 - 2322
(2010/05/19)
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- Nano-MgO: An efficient catalyst for the synthesis of formamides from amines and formic acid under MWI
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Nano-MgO a basic catalyst was prepared by solution combustion technique. It was characterized by powder XRD, SEM, BET and TEM analyses. It was used as a catalyst for the study of microwave-assisted N-formylation of various aromatic and alkyl amines with formic acid under solvent-free conditions. Nano-MgO showed excellent catalytic properties and the reactions went to completion, within 1-2 min to give products in high yield (90-98%). The catalyst is recoverable quantitatively and re-cycled with almost consistent activity. This new nano catalyst has the advantages of higher yield, lower cost, reduced environmental hazards, and the procedure is highly convenient. Graphical Abstract: Nano-MgO was prepared and characterized by PXRD, SEM, BET and TEM analyses. It was used for the study of microwave-assisted N-formylation of various amines with formic acid under solvent-free condition.
- Reddy, M. B. Madhusudana,Ashoka,Chandrappa,Pasha
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experimental part
p. 82 - 87
(2010/11/03)
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- Facile and highly efficient N-formylation of amines using a catalytic amount of iodine under solvent-free conditions
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We developed a simple, practical, and catalytic method for the N-formylation of a wide variety of amines in the presence of molecular iodine as a catalyst under solvent-free conditions. This reaction is applicable to the chemoselective N-formylation of amino groups and -amino acid esters without epimerization.
- Kim, Joong-Gon,Jang, Doo Ok
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experimental part
p. 2093 - 2096
(2010/10/03)
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- A convenient one-pot synthesis of formamide derivatives using thiamine hydrochloride as a novel catalyst
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Formamide derivatives have been synthesized in excellent yields from amine and formic acid in the presence of a catalytic amount of thiamine hydrochloride (VB1) at 80 °C. The advantages of this method are the use of a cheap, stable, non-toxic, and readily available catalyst, easy work-up, improved yields, and solvent-free conditions.
- Lei, Min,Ma, Lei,Hu, Lihong
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experimental part
p. 4186 - 4188
(2010/09/12)
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- ZnO as a new catalyst for N-formylation of amines under solvent-free conditions
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The treatment of amines with formic acid in the presence of ZnO under solvent-free conditions brings about highly and efficient N-formylation to give the corresponding formamides in excellent yields. The N-formylation reaction not only involves mild conditions, simple operation, and high yields but also high chemoselectivity.
- Hosseini-Sarvari, Mona,Sharghi, Hashem
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p. 6652 - 6654
(2007/10/03)
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- Microwave enhanced reduction of nitro and azido arenes to N-arylformamides employing Zn-HCOONH4: Synthesis of 4(3H)-quinazolinones and pyrrolo[2,1-c][1,4]benzodiazepines
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Microwave mediated reduction of nitro and azido arenes to N-arylformamides using Zn-HCOONH4 is described. In the absence of microwave conditions, this methodology affords amines. This protocol has been extended to the synthesis of pyrrolo[2,1-c][1,4]benzodiazepines and 4(3H)-quinazolinones.
- Kamal, Ahmed,Srinivasa Reddy,Rajendra Prasad,Hari Babu,Ramana, A. Venkata
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p. 6517 - 6521
(2007/10/03)
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- A chemoselective method for the reductive N-formylation of aryl azides under catalytic transfer hydrogenation conditions
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A highly facile and chemoselective method for the reductive N-formylation of aryl azides under catalytic transfer hydrogenation conditions is described.
- Reddy, P.Ganapati,Baskaran
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p. 1919 - 1922
(2007/10/03)
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- HYDROXYLATION DIRECTE D'ESTERS DE PHENYLE ET D'ANILIDES PAR LE PEROXYDE D'HYDROGENE EN MILIEU SUPERACIDE
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In SbF5-HF, hydrogen peroxide reacts on the aromatic ring of esters 1a-5a and anilides 11a-15a to give monohydroxylated derivatives in good yields.With compounds 2a, 4a and 5a, meta or para isomers are by far the major products, whereas with formate 1a and benzoate 3a, the proportion of the ortho isomer is more important.With anilides, the reaction is less selective, the three isomers being obtained in comparable amounts.Thus, the relative proportions of ortho, meta and para-hydroxylated derivatives obtained using 70 percent H2O2 with acetate 2a and acetanilide 12a are 6/51/43 and 36.5/30/33.5, respectively.The important proportion of meta hydroxylation is the result of the reaction of protonated hydrogen peroxide H3O2+ on the protonated substrate.
- Berrier, Christian,Jacquesy, Jean-Claude,Jouannetaud, Marie-Paule,Morellet, Guy
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p. 158 - 164
(2007/10/02)
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