103-70-8Relevant articles and documents
Mesoporous silica SBA-15 functionalized with acidic deep eutectic solvent: A highly active heterogeneous N-formylation catalyst under solvent-free conditions
Azizi, Najmedin,Edrisi, Mahtab,Abbasi, Faezeh
, (2018)
Mesoporous silica SBA-15 functionalized with N-methylpyrrolidonium-zinc chloride based deep eutectic solvent (DES) is found to be a more efficient and reusable catalyst for a convenient N-formylation of a variety of amines at room temperature. N-Formylation of primary, secondary as well as heterocyclic amines have been carried out in good to excellent yields by treatment with formic acid in low loading of DES/SBA-15 an environmentally benign catalyst for the first time. The DES/SBA-15 catalyst, which possesses both Br?nsted and Lewis acidities as well as an active SBA-15 support, makes this procedure quite simple, reusable, more convenient and practical. This catalyst was tolerant of a wide range of functional groups, and it can be reused for four runs without obvious deactivation.
N-Formylbenzotriazole: A stable and convenient N- and O-formylating agent
Katritzky,Chang,Yang
, p. 503 - 505 (1995)
N-Formylbenzotriazole, prepared by the reaction of benzotriazole and formic acid in the presence of dicyclohexylcarbodiimide, is demonstrated to be a superior N- and O-formylating agent.
Mild and convenient N-formylation protocol in water-containing solvents
Aleiwi, Bilal A.,Mitachi, Katsuhiko,Kurosu, Michio
, p. 2077 - 2081 (2013)
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.
Synthesis of Substituted Thioamides from gem-Dibromoalkenes and Sodiumsulfide
Morri, Ashok K.,Thummala, Yadagiri,Adepu, Ramesh,Sharma, Gangavaram V. M.,Ghosh, Subhash,Doddi, Venkata Ramana
, p. 7159 - 7163 (2019)
A three-component reaction of 1,1-dibromoalkenes, sodium sulfide, and N-substituted formamide for the synthesis of disubstituted thioamides has been developed. Various dibromoalkenes were found to be compatible under these conditions and gave corresponding thioamides in good to excellent yields.
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
Alinezhad, Heshmatollah,Salehian, Fatemeh
, p. 532 - 538 (2013)
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.
Highly efficient rhodium-catalyzed transfer hydrogenation of nitroarenes into amines and formanilides
Wei, Yawen,Wu, Jianjun,Xue, Dong,Wang, Chao,Liu, Zhaotie,Zhang, Zhuozhuo,Chen, Guangfu,Xiao, Jianliang
, p. 1295 - 1298 (2014)
An efficient and selective rhodium-catalyzed transfer hydrogenation of nitroarenes with formic acid as the hydrogen source to give amines or formanilides has been developed. The addition of iodide ion accelerates the reaction, which can take place at room temperature. Georg Thieme Verlag Stuttgart New York.
Copper promoted aerobic oxidative c(sp3)-c(sp3) bond cleavage of n-(2-(pyridin-2-yl)-ethyl)anilines
Yu, Yang,Zhang, Yong,Sun, Chengyu,Shi, Lei,Wang, Wei,Li, Hao
, p. 2725 - 2732 (2020)
A strategy of aerobic oxidative C(sp3)-C(sp3) bond cleavage of N-ethylaniline derivatives bearing azaarenes for the synthesis of N-aryl formamides has been developed. This approach was carried out smoothly with the CuI/TEMPO/air system to give N-aryl formamides in yields of 50-90%. With this methodology, a mutagenically active compound was constructed in 90% yield. Moreover, the reaction also provided a one-pot synthetic tool for accessing a promoter of hematopoietic stem cells by difunctionalization in 61% yield.
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Kleine
, p. 327 (1896)
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Barnett,Roberts
, p. 758 (1972)
Thermal and microwave-assisted N-formylation using solid-supported reagents
Desai, Bimbisar,Danks, Timothy N.,Wagner, Gabriele
, p. 955 - 957 (2005)
A rapid and easy route to formamides by microwave assisted N-formylation of primary and secondary amines is described. Using an insoluble polymer or an inorganic solid-supported reagent as a formylating agent, microwave irradiation furnished the corresponding formamides in high yields, with reduced reaction time and solvent volume over the conventional approach.
Mesoporous Sn(IV) Doping DFNS Supported BaMnO3 Nanoparticles for Formylation of Amines Using Carbon Dioxide
Yang, Jie,Wang, Liujie,Sun, Aili,Zhiani, Rahele
, p. 573 - 581 (2021)
Abstract: In the present paper, Sn(IV) doping DFNS (SnD) supported nanoparticles of BaMnO3 (BaMnO3/SnD) and using as a catalyst for the N-formylation of amines by CO2 hydrogenation. In this catalyst, the SnD with the ratios of Si/Sn in the range of from 6 to 50 were obtained with method of direct hydrothermal synthesis (DHS) as well as the nanoparticles of BaMnO3 were on the surfaces of SnD in situ reduced. Scanning electron microscope (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray energy dispersive spectroscopy (EDS), and transmission electron microscopy (TEM) were utilized for characterizing the nanostructures BaMnO3/SnD. It is found that the nanostructures of BaMnO3/SnD can be a nominate due to its effective and novel catalytic behavior in N-formylation of amines through hydrogenation of CO2. Graphic Abstract: [Figure not available: see fulltext.]
Synthesis, characterization, antibacterial and catalytic activity of a nanopolymer supported copper(ii) complex as a highly active and recyclable catalyst for the formamidation of arylboronic acids under aerobic conditions
Nasrollahzadeh, Mahmoud,Zahraei, Ali,Ehsani, Ali,Khalaj, Mehdi
, p. 20351 - 20357 (2014)
This paper reports on the synthesis and use of a nanopolymer supported copper(ii) complex, as a separable catalyst for the formamidation of arylboronic acids under aerobic conditions. The catalyst was characterized using powder XRD, SEM, EDS, TGA-DTG and FT-IR spectroscopy. This method has the advantages of high yields, elimination of homogeneous catalysts, simple methodology and easy work up. Catalytic efficiency remains unaltered even after several repeated cycles. The synthesized catalyst is found to be more highly toxic towards Gram-positive bacteria than Gram-negative bacteria. This journal is the Partner Organisations 2014.
Catalyst freeN-formylation of aromatic and aliphatic amines exploiting reductive formylation of CO2using NaBH4
Kumar, Arun,Kumar, Yashwant,Mahajan, Dinesh,Sharma, Nidhi,Sharma, Pankaj
, p. 25777 - 25787 (2021)
Herein, we report a sustainable approach forN-formylation of aromatic as well as aliphatic amines using sodium borohydride and carbon dioxide gas. The developed approach is catalyst free, and does not need pressure or a specialized reaction assembly. The reductive formylation of CO2with sodium borohydride generates formoxy borohydride speciesin situ, as confirmed by1H and11B NMR spectroscopy. Thein situformation of formoxy borohydride species is prominent in formamide based solvents and is critical for the success of theN-formylation reactions. The formoxy borohydride is also found to promote transamidation reactions as a competitive pathway along with reductive functionalization of CO2with amine leading toN-formylation of amines.
Atomically Dispersed Zn-Nx Sites in N-Doped Carbon for Reductive N-formylation of Nitroarenes with Formic Acid
Li, Jinlei,Li, Cunyao,Feng, Siquan,Zhao, Ziang,Zhu, Hejun,Ding, Yunjie
, p. 1546 - 1550 (2020)
Replacement of noble metal catalysts with low-cost, non-noble heterogeneous catalysts is highly desirable. Herein, we prepared a reactive, inexpensive and stable isolated single-atom Zn/N-doped porous carbon (ZnNC) catalyst derived from a versatile zeolitic imidazolate framework precursor. The optimized ZnNC-1000 with Zn-Nx species possesses high zinc loading (5.2 wtpercent) and nitrogen content (6.73 wtpercent), exhibits efficient catalytic performance in the one-pot N-formylation of nitroarene to the corresponding formamides by using formic acid as the hydrogen donor and formylation agent. H2-D2 exchange reaction and HCOOH-chemisorption experiments demonstrated that atomically dispersed Zn-Nx species are essential for the activation of hydrogen and HCOOH molecules, which finally contributed to the highest catalytic activity of ZnNC-1000 for the reductive N-formylation reaction.
Ruthenium-cluster-catalysed Reductive Carbonylation of Nitrobenzene: X-Rsay Structure of , a Catalytic Intermediate
Bhaduri, Sumit,Khwaja, Hanif,Sharma, Krishna,Jones, Peter G.
, p. 515 - 516 (1989)
The ruthenium cluster has been structurally characterised and shown to play an important role, along with its precursor , in the hydroxyde- or methoxide-promoted reductive carbonylation of nitrobenzene.
Formylation of amines and alcohols using aminopropylated mesoporous SBA-15 silica (APMS) as an efficient and recyclable catalyst
Malakooti, Reihaneh,Sobhani, Sara,Razavi, Nasrin,Shafiei, Soheila,Mokhtari, Rezvan
, p. 1979 - 1990 (2011)
Aminopropylated mesoporous SBA-15 silica (APMS) is introduced as a new, recyclable and efficient catalyst for the formylation of a variety of amines and alcohols by using readily available formic acid under solvent-free conditions.
Immobilized Zn(OAc)2on bipyridine-based periodic mesoporous organosilica for N -formylation of amines with CO2and hydrosilanes
Lin, Xiao-Tao,Matsumoto, Kazuhiro,Maegawa, Yoshifumi,Takeuchi, Katsuhiko,Fukaya, Norihisa,Sato, Kazuhiko,Inagaki, Shinji,Choi, Jun-Chul
, p. 9501 - 9505 (2021)
Zinc acetate (Zn(OAc)2) was successfully immobilized on a bipyridine-based periodic mesoporous organosilica (BPy-PMO-TMS), as confirmed by solid-state NMR and energy-dispersive X-ray spectroscopies, X-ray diffractometry, and nitrogen adsorption/desorption isotherm analyses. The immobilized Zn complex, Zn(OAc)2(BPy-PMO-TMS), exhibited good catalytic activity during the N-formylations of amines and amides with CO2 and PhSiH3 to produce the corresponding formamides. Zn(OAc)2(BPy-PMO-TMS) with a lower Zn loading was found to exhibit higher catalytic activity.
Catalysis and reaction mechanisms of N-formylation of amines using Fe(III)-exchanged sepiolite
Eren, Bilge,Aydin, Reyhan,Eren, Erdal
, p. 584 - 590 (2014)
This study presents a rapid, economical and "green" N-formylation of anilines with formic acid (FA) using Fe(III)-exchanged sepiolite (IES) as a catalyst. The IES exhibited excellent catalytic properties and the reactions were complete within 20-90 min to afford products with high yields. The adsorption mechanism of FA on the IES sample was studied by infrared (IR) spectroscopy at a temperature range of 120-400°C. The thermal desorption of pyridine was detected by the IR technique to estimate the acidity of IES. Lewis acid-bound pyridine bands at 1618-1631 cm-1 and 1443-1445 cm -1 were observed even after the IES sample was heated above 400°C.
Synthesis of N-arylcarboxamides by the efficient transamidation of DMF and derivatives with anilines
Gu, Da-Wei,Guo, Xun-Xiang
, p. 9117 - 9122 (2015)
A novel protocol for the transamidation of DMF and derivatives with weakly nucleophilic anilines has been developed, utilizing a catalytic amount of Pd(OAc)2 and 2,2′-bipyridine, and with PivOH and BF3·Et2O as additives. This methodology has a broad substrate scope, and various corresponding transamidation products were prepared in good to excellent yields from commercially available DMF derivatives and anilines. The synthetic utility of the reported protocol was further demonstrated with a gram-scale experiment. Control experiments suggested the efficient transformation of DMF and derivatives with anilines might owe to the synergistic effect of palladium complex, PivOH, and BF3·Et2O.
Catalysis of amide hydrolysis and formation under neutral conditions by a zwitterionic imidazolium thiolate
Keillor,Neverov,Brown
, p. 4669 - 4673 (1994)
As a simple model for the hydrolysis of peptides mediated by the cysteine proteases, 2-(mercaptomethyl)-1-methylimidazole (1) was used to catalyze the hydrolysis of four nonactivated amides, namely, formamide, dimethylformamide, N-formylmorpholine, and formanilide (3a-d), at 98 °C, pD 7.6-8.0, μ = 1.0 (KC1). Progress of the hydrolysis reactions was followed by 1H NMR, and the kinetics as a function of added [1] were used to determine the second-order catalytic rate constants (kcat). A putative intermediate 5-formyl thiolester of 1 (4) was not observed to build up during the course of the hydrolysis: the partitioning of authentic 4 between H2O and morpholine and between H2O and aniline was determined (98 °C, pD 8.0). The hydrolysis of N-formylmorpholine was observed to be catalyzed by added phosphate buffer under the same conditions. When the hydrolysis of a 200 mM D2O solution of N-formylmorpholine was allowed to proceed to completion, an equilibrium position of 33 mM amide, 167 mM HCO2H, and 167 mM morpholine was attained: that same equilibrium position was obtained starting with a solution 200 mM in each of HCO2H and morpholine. The conditional equilibrium constant, K′eq = [NFM]/([HCO2H]tot-[morpholine]tot), was found to be 1.2 M-1.
Amine modified mesoporous Al2O3@MCM-41: An efficient, synergetic and recyclable catalyst for the formylation of amines using carbon dioxide and DMAB under mild reaction conditions
Nale, Deepak B.,Rath, Dharitri,Parida,Gajengi, Aravind,Bhanage, Bhalchandra M.
, p. 4872 - 4881 (2016)
This work reports an amine modified meso Al2O3@MCM-41, particularly the ordered mesoporous silica, as a catalyst for the formylation of amines with carbon dioxide (CO2) and with dimethylamine-borane (DMAB) as a green reducing source. This newly developed catalytic system represents a heterogeneous and environmentally benign protocol. Besides this, the catalyst could be reused for five consecutive cycles without any significant loss in its catalytic activity towards the synthesis of formamides. The amine modified meso Al2O3@MCM-41 catalysts were well characterized by high and low angle XRD, temperature programmed desorption (TPD), BET-surface area, TGA/DTA and FT-IR analysis techniques. The effect of various reaction parameters such as temperature, CO2 pressure, time and the ratio of substrates to DMAB for the synthesis of formamides has been investigated. The developed protocol can be applicable for the synthesis of most important key intermediates like formoterol, orlistat, leucovarin and iguratimod in biologically active compounds.
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Hurd,Roe
, p. 3355,3357 (1939)
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Copper-Catalyzed N-Formylation of Amines through Tandem Amination/Hydrolysis/Decarboxylation Reaction of Ethyl Bromodifluoroacetate
Li, Xiao-Fang,Zhang, Xing-Guo,Chen, Fan,Zhang, Xiao-Hong
, p. 12815 - 12821 (2018)
Ethyl bromodifluoroacetate (BrCF2COOEt) was first used as the N-formylating reagent in the copper-catalyzed N-formylation of amines. A range of primary, secondary, cyclic arylamines, and aliphatic amines underwent the N-formylation smoothly to furnish the N-formamides in moderate-to-excellent yields.
An efficient method for the N-formylation of amines under catalyst- and additive-free conditions
Xu, Zhuo-Wei,Xu, Wen-Yi,Pei, Xiao-Jun,Tang, Fei,Feng, Yi-Si
, p. 1254 - 1258 (2019)
A simple catalyst- and additive-free method for the N-formylation of amines has been developed. The advantages of this protocol include a wide range of functional group tolerance, high efficiency and a lack of required extra promoters under mild conditions. This convenient strategy will provide a facile synthesis towards N-formamide natural products and pharmaceutical derivatives. A mechanism that involves difluorocarbene is proposed for this reaction.
Mechanistic Study of the N-Formylation of Amines with Carbon Dioxide and Hydrosilanes
Hulla, Martin,Laurenczy, Gabor,Dyson, Paul J.
, p. 10619 - 10630 (2018)
N-formylation of amines with CO2 and hydrosilane reducing agents proceeds via fast and complex chemical equilibria, which hinder easy analysis of the reaction pathways. In situ reaction monitoring and kinetic studies reveal that three proposed pathways, via direct- and amine-assisted formoxysilane formation (pathways 1 and 2, respectively) and via a silylcarbamate intermediate (pathway 3), are possible depending on the reaction conditions and the substrates. While pathway 1 is favored for non-nucleophilic amines in the absence of a catalyst, a base catalyst results in noninnocent behavior of the amine in the CO2 reduction step toward the formoxysilane intermediate. The reaction pathway is altered by strongly nucleophilic amines, which form stable adducts with CO2. Silylcarbamate intermediates form, which can be directly reduced to the N-formylated products by excess hydrosilane. Nevertheless, without excess hydrosilane, the silylcarbamate is an additional intermediate en route to formoxysilanes along pathway 2. Exchange NMR spectroscopy (EXSY) revealed extensive substituent exchange around the hydrosilane silicon center, which confirms its activation during the reaction and supports the proposed reaction mechanisms. Numerous side reactions were also identified, which help to establish the reaction equilibria in the N-formylation reactions.
Additive-free selective methylation of secondary amines with formic acid over a Pd/In2O3 catalyst
Benaissa, Idir,Cantat, Thibault,Genre, Caroline,Godou, Timothé,Pinault, Mathieu
, p. 57 - 61 (2022/01/19)
Formic acid is used as the sole carbon and hydrogen source in the methylation of aromatic and aliphatic amines to methylamines. The reaction proceeds via a formylation/transfer hydrogenation pathway over a solid Pd/In2O3 catalyst without the need for any additive.
Olefin functionalized IPr.HCl monomer as well as preparation method and application thereof
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Paragraph 0069-0073; 0078, (2021/06/21)
The invention relates to an olefin functionalized IPr.HCl monomer, a preparation method thereof, a method for preparing an N-heterocyclic carbene functionalized organic polymer (PS-IPr-x) by using the olefin functionalized IPr.HCl monomer, and application of the N-heterocyclic carbene functionalized organic polymer as a heterogeneous catalyst for catalyzing reduction N-formylation of carbon dioxide and amine. A heterogeneous catalyst is prepared by using cheap and easily available DVB as a polymerization cross-linking agent through an AIBN-initiated olefin polymerization method, and has the advantages of low preparation cost and simple preparation method. Meanwhile, the catalytic activity of the catalyst is obviously higher than that of reported catalysts, and the catalyst has a wide practical application prospect.
