5279-58-3Relevant articles and documents
Facile N-Formylation of Amines on Magnetic Fe3O4?CuO Nanocomposites
Datta Khanal, Hari,Mishra, Kanchan,Rok Lee, Yong
, p. 4477 - 4484 (2021/08/30)
A facile, eco-friendly, efficient, and recyclable heterogeneous catalyst is synthesized by immobilizing copper impregnated on mesoporous magnetic nanoparticles. The surface chemistry analysis of Fe3O4?CuO nanocomposites (NCs) by XRD and XPS demonstrates the synergistic effect between Fe3O4 and CuO nanoparticles, providing mass-transfer channels for the catalytic reaction. TEM images clearly indicate the impregnation of CuO onto mesoporous Fe3O4. This hydrothermally synthesized eco-friendly and highly efficient Fe3O4?CuO NCs are applied as a magnetically retrievable heterogeneous catalyst for the N-formylation of wide range of aliphatic, aromatic, polyaromatic and heteroaromatic amines using formic acid as a formylating agent at room temperature. The catalytic activity of the NCs for N-formylation is attributable to the synergistic effect between Fe3O4 and CuO nanoparticles. The N-formylated product is further employed for the synthesis of biologically active quinolone moieties.
Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
Du, Chen-Xia,Huang, Zijun,Jiang, Xiaolin,Li, Yuehui,Makha, Mohamed,Wang, Fang,Zhao, Dongmei
supporting information, p. 5317 - 5324 (2020/09/17)
We report sodium trihydroxyaryl borates as the first robust tetracoordinate organoboron catalysts for reductive functionalization of CO2. These catalysts, easily synthesized from condensing boronic acids with metal hydroxides, activate main group element-hydrogen (E-H) bonds efficiently. In contrast to BX3 type boranes, boronic acids and metal-BAr4 salts, under transition metal-free conditions, sodium trihydroxyaryl borates exhibit high reactivity of reductive N-formylation toward a variety of amines (106 examples), including those with functional groups such as ester, olefin, hydroxyl, cyano, nitro, halogen, MeS-, ether groups, etc. The over-performance to catalyze formylation of challenging pyridyl amines affords a promising alternative method to the use of traditional formylation reagents. Mechanistic investigation supports electrostatic interactions as the key for Si/B-H activation, enabling alkali metal borates as versatile catalysts for hydroborylation, hydrosilylation, and reductive formylation/methylation of CO2.
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
, (2017/10/05)
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.
Method of N-formylating amines with a phosphonic anhydride
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Page/Page column 21; 22; 23; 24; 31; 32, (2018/02/28)
A method for N-formylating an amine that includes reacting the amine and a formamide compound in the presence of a phosphonic anhydride to form an N-formylated amine. The phosphonic anhydride is present in an amount of 5-100 mol % relative to a total number of moles of the amine, and the reacting is performed for 1-24 hours at a temperature of 45-100° C.
Rational design and synthesis of 1,5-disubstituted tetrazoles as potent inhibitors of the MDM2-p53 interaction
Surmiak, Ewa,Neochoritis, Constantinos G.,Musielak, Bogdan,Twarda-Clapa, Aleksandra,Kurpiewska, Katarzyna,Dubin, Grzegorz,Camacho, Carlos,Holak, Tad A.,D?mling, Alexander
, p. 384 - 407 (2016/12/22)
Using the computational pharmacophore-based ANCHOR.QUERY platform a new scaffold was discovered. Potent compounds evolved inhibiting the protein-protein interaction p53-MDM2. An extensive SAR study was performed based on our four-point pharmacophore model
A process for preparing N - aryl amide compound
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Paragraph 0052-0055, (2017/08/02)
The method discloses a method used for preparing an N-aryl amide compound from amides and aniline compounds. According to the method, a palladium salt and a ligand are taken as catalysts; an N,N-dimethyl formamide compound, an aniline compound, a protonic acid, a Lewis acid, and an organic solvent are mixed; and an obtained mixture is subjected to heating reaction so as to obtain the N-aryl amide compound. Advantages of the method are that: preparation route is short, substrate universality is excellent, reaction conditions are mild, synthesis yield is high, and used raw materials and catalysts are simple and easily available.
Carbon Dioxide Based N-Formylation of Amines Catalyzed by Fluoride and Hydroxide Anions
Hulla, Martin,Bobbink, Felix D.,Das, Shoubhik,Dyson, Paul J.
, p. 3338 - 3342 (2016/11/16)
We described herein a simple approach for N-formylation with CO2 and hydrosilane reducing agents. Fluoride and hydroxide salts efficiently catalyzed the reaction, principally through activation of the hydrosilanes, which led to hydrosilane reactivities comparable to those of NaBH4/LiAlH4. Consequently, the N-formylation of amines with CO2 could be achieved at room temperature and atmospheric pressure. The mechanism of these anionic catalysts contrasts that of the currently reported systems, for which activation of CO2 is the key mechanistic step. Using tetrabutylammonium fluoride as a simple ammonium salt catalyst, the N-formylated products of both aliphatic and aromatic amines could be obtained in excellent yields with high selectivities.
The ortho effect on the acidic and alkaline hydrolysis of substituted formanilides
Desai, Salil Dileep,Kirsch, Lee E.
, p. 471 - 488 (2015/06/30)
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.
Synthesis of N-arylcarboxamides by the efficient transamidation of DMF and derivatives with anilines
Gu, Da-Wei,Guo, Xun-Xiang
, p. 9117 - 9122 (2015/11/09)
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.
Deep eutectic solvent promoted highly efficient synthesis of N, N'-diarylamidines and formamides
Azizi, Najmadin,Gholibeglo, Elham,Babapour, Mahbobe,Ghafuri, Hossein,Bolourtchian, Seyed Mohammad
, p. 768 - 773 (2012/10/30)
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.
