- Preparation and properties of starch-based film using N,N-bis(2-hydroxyethyl)formamide as a new plasticizer
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N,N-Bis(2-hydroxyethyl)formamide (BHF) was synthesized efficiently and used as a new plasticizer for corn starch to prepare flexible starch film. The hydrogen bond interaction between BHF and starch was proven by Fourier-transform infrared (FT-IR) spectroscopy. By scanning electron microscope (SEM), starch granules were completely disrupted and a continuous phase was obtained. The crystallinity of corn starch and BHF-plasticized starch film (BSF) was characterized by X-ray diffraction (XRD). The water resistance of BSF was better than that of glycerol-plasticized starch film (GSF). Water vapor permeability of BSF was lower than that of GSF. Tensile strengths of BSF were inferior to those of GSF, while the elongations at break of BSF were higher than those of GSF.
- Dai, Hongguang,Chang, Peter R.,Geng, Fengying,Yu, Jiugao,Ma, Xiaofei
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Read Online
- Catalytic N-diphosphonomethylation of amino alkanols and bisamino alkanes using tris(trimethylsilyl) phosphite as a convenient synthon
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The new mono- and bis(aminomethylenediphosphonic) acids are synthesized for the first time via unique reaction of tris(trimethylsilyl) phosphite and various N-formyl amino alkanols or bis(N-formyl amino) alkanes at the presence of effective catalyst – trimethylsilyl triflate under mild conditions. The further treatment of initially formed trimethylsilyl intermediates with the methanol excess resulted in the crystalline mono- and bis(aminomethylenediphosphonic) acids in high yields. The catalytic scheme of target substances formation is proposed and discussed in detail. The structures of target acids were confirmed by the 1H, 13C, 31P NMR spectra and high resolution mass spectra (HRMS). The resulting compounds are of great interest as perspective bioactive substances with versatile properties and effective polydentate ligands.
- Prishchenko, Andrey A.,Alekseyev, Roman S.,Novikova, Olga P.,Livantsov, Mikhail V.,Livantsova, Ludmila I.,Petrosyan, Valery S.
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supporting information
(2021/11/09)
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- Highly Efficient and Selective N-Formylation of Amines with CO2 and H2 Catalyzed by Porous Organometallic Polymers
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The valorization of carbon dioxide (CO2) to fine chemicals is one of the most promising approaches for CO2 capture and utilization. Herein we demonstrated a series of porous organometallic polymers could be employed as highly efficient and recyclable catalysts for this purpose. Synergetic effects of specific surface area, iridium content, and CO2 adsorption capability are crucial to achieve excellent selectivity and yields towards N-formylation of diverse amines with CO2 and H2 under mild reaction conditions even at 20 ppm catalyst loading. Density functional theory calculations revealed not only a redox-neutral catalytic pathway but also a new plausible mechanism with the incorporation of the key intermediate formic acid via a proton-relay process. Remarkably, a record turnover number (TON=1.58×106) was achieved in the synthesis of N,N-dimethylformamide (DMF), and the solid catalysts can be reused up to 12 runs, highlighting their practical potential in industry.
- Shen, Yajing,Zheng, Qingshu,Chen, Zhe-Ning,Wen, Daheng,Clark, James H.,Xu, Xin,Tu, Tao
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supporting information
p. 4125 - 4132
(2021/01/12)
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- PHOTO-REDOX TITANIUM CONTAINING ORGANIC FRAMEWORKS AND METHODS OF MAKING AND USE THEREOF
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Disclosed herein are metal-organic frameworks and methods of making and use thereof.
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Paragraph 0165; 0172-0173
(2020/07/07)
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- Method for preparing formamide compound by catalyzing carbon dioxide hydrogenation with porous material
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The invention belongs to the technical field of organic synthesis and heterogeneous catalysis, and particularly relates to a method for preparing a formamide compound by catalyzing carbon dioxide hydrogenation through a porous material. The method comprises the following steps: by taking a porous organic metal polymer as a catalyst, reacting an amine compound with carbon dioxide and hydrogen in anair atmosphere to prepare the formamide compound. The method has the advantages of high reaction efficiency, good selectivity, mild conditions, economy, environmental protection, simple operation andthe like; wherein a solid metal polymer material with large specific surface area, strong carbon dioxide adsorption, hierarchical pore channel distribution and highly dispersed metal centers is designed and synthesized as a reaction catalyst by changing a cross-linked copolymer proportion; the catalyst is especially used for catalytic synthesis of fine chemical N, N-dimethylformamide (DMF), doesnot need any additional solvent, alkali or other additives, and is convenient for separation and purification of DMF. The catalyst can be recycled; no special equipment is needed in the reaction, thereaction operation is simple, and further industrial application is facilitated.
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Paragraph 0140-0143
(2020/06/16)
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- Novel clamp metal complex and application thereof
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The invention discloses a method for preparing a novel clamp-shaped complex and application of the novel clamp-shaped complex in the reaction of catalytic hydrogenation of carboxylic acid ester compounds to produce corresponding alcohols and reaction of carbon dioxide catalytic hydrogenation to form formamide compounds. Carboxylic acid esters and hydrogen as raw materials or carbon dioxide, hydrogen and amine compounds as raw materials are reacted in an organic solvent condition or a solvent-free condition in the presence of a transition metal complex as a catalyst to respectively form the corresponding alcohol compounds and/or corresponding formamide compounds. The method has the advantages of being high in reaction efficiency, good in selectivity, mild in conditions, economical, environmentally-friendly, and simple in operation, and has good promotion and application prospects.
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Paragraph 0240; 0241; 0242; 0262-0266
(2019/04/26)
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- N-Formylation of Amines with CO2 and H2 by Using NHC–Iridium Coordination Assemblies as Solid Molecular Catalysts
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One of the NHC–iridium coordination assemblies containing 1,5-cyclooctadiene (COD) and iodide ion has been demonstrated as robust, efficient, recyclable solid molecular catalyst for N-formylation of diverse primary and secondary amines with CO2 and H2 under mild reaction conditions. Remarkably, in the case of N,N-dimethylformamide production, even at 0.1 mol % catalyst loading under solvent-free conditions, the solid catalyst can be readily recovered by simply filtration and reused more than 10 runs without noticeable loss of activity.
- Zhang, Yang,Wang, Jiaquan,Zhu, Haibo,Tu, Tao
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supporting information
p. 3018 - 3021
(2018/09/06)
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- Selective Iron-Catalyzed N-Formylation of Amines using Dihydrogen and Carbon Dioxide
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A family of iron(II) carbonyl hydride species supported by PNP pincer ligands was identified as highly productive catalysts for the N-formylation of amines via CO2 hydrogenation. Specifically, iron complexes supported by two different types of PNP ligands were examined for formamide production. Complexes containing a PNP ligand with a tertiary amine afforded superior turnover numbers in comparison to complexes containing a bifunctional PNP ligand with a secondary amine, indicating that bifunctional motifs are not required for catalysis. Systems incorporating a tertiary amine containing a PNP ligand were active for the N-formylation of a variety of amine substrates, achieving TONs up to 8900 and conversions as high as 92%. Mechanistic experiments suggest that N-formylation occurs via an initial, reversible reduction of CO2 to ammonium formate followed by dehydration to produce formamide. Several intermediates relevant to this reaction pathway, as well as iron-containing deactivation species, were isolated and characterized.
- Jayarathne, Upul,Hazari, Nilay,Bernskoetter, Wesley H.
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p. 1338 - 1345
(2018/02/14)
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- METHOD FOR PREPARING FORMAMIDE COMPOUND
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Disclosed is a method for preparing a formamide compound, the method uses carbon dioxide, hydrogen and an amine compound as raw materials and a transition metal complex as a catalyst, and the reaction is carried out in an organic solvent or in the absence of a solvent to form a formamide compound. The method of the present invention is an effective method of chemical utilization of carbon dioxide, which has the advantages of high reaction efficiency, a good selectivity, mild conditions, economic and environmental protection, being simple and convenient to operate and the like, and has a good popularization and application prospect.
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Paragraph 0197-0200
(2018/02/28)
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- Ru/ceria-catalyzed direct formylation of amines and CO to produce formamides
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We herein report a new strategy of directly converting amines and CO to formamides with 100% atom utilization efficiency. It is suitable for up to 25 amine substrates with no additives. Ru/ceria is found to be an excellent catalyst for this reaction due the efficient co-activation of CO and amine on Ru species.
- Wang, Yehong,Zhang, Jian,Chen, Haijun,Zhang, Zhixin,Zhang, Chaofeng,Li, Mingrun,Wang, Feng
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- Systematic variation of the optical bandgap in titanium based isoreticular metal-organic frameworks for photocatalytic reduction of CO2 under blue light
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A series of metal-organic frameworks isoreticular to MIL-125-NH2 were prepared, where the 2-amino-terephthalate organic links feature N-alkyl groups of increasing chain length (from methyl to heptyl) and varying connectivity (primary and secondary). The prepared materials display reduced optical bandgaps correlated with the inductive donor ability of the alkyl substituent as well as high photocatalytic activity towards the reduction of carbon dioxide under blue illumination operating over 120 h. Secondary N-alkyl substitution (isopropyl, cyclopentyl and cyclohexyl) exhibits larger apparent quantum yields than the primary N-alkyl analogs directly related to their longer lived excited-state lifetime. In particular, MIL-125-NHCyp (Cyp = cyclopentyl) exhibits a small bandgap (Eg = 2.30 eV), a long-lived excited-state (τ = 68.8 ns) and a larger apparent quantum yield (Φapp = 1.80%) compared to the parent MIL-125-NH2 (Eg = 2.56 eV, Φapp = 0.31%, τ = 12.8 ns), making it a promising candidate for the next generation of photocatalysts for solar fuel production based on earth-abundant elements.
- Logan, Matthew W.,Ayad, Suliman,Adamson, Jeremy D.,Dilbeck, Tristan,Hanson, Kenneth,Uribe-Romo, Fernando J.
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supporting information
p. 11854 - 11863
(2017/07/10)
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- A tertiary amine oxidation cracking method of preparing carboxamide
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The invention provides a method for preparing formamide through tertiary amine oxicracking. According to the method, tertiary amine serves as a substrate, air or oxygen serves as an oxygen source, and oxicracking occurs on the tertiary amine under the action of a catalyst to generate the formamide. The method is high in oxidation efficiency and product yield and economical and environmentally friendly by taking the air or oxygen as the oxygen source and has a very good application prospect.
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Paragraph 0014; 0023; 0024
(2017/08/26)
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- Method for preparation of formamide through carbonylation
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The invention relates to a method for preparation of formamide. The method adopts primary amine and/or secondary amine and carbon monoxide as reactants, and under the catalysis action, formamide is prepared by a carbon monoxide carbonylation reaction. The method is characterized in that a ruthenium loaded acidic compound metal oxide is used as a catalyst, and the reaction is carried out with high efficiency under milder conditions. The reaction process comprises the steps: putting primary amine and/or secondary amine with a certain concentration and a certain amount of the catalyst in a pressure vessel, introducing CO gas, sealing, and at the temperature of more than 100 DEG C and the reaction time of more than 2 h, carrying out a stirring reaction to obtain formamide. According to the method, the catalyst is simple to prepare and high in catalytic activity, the yield of the product formamide can reach 98%, and the separation process of the product and the catalyst is simple, the catalyst can be recycled for many times, and the reaction process has high controllability.
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Paragraph 0028; 0029
(2017/03/14)
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- Highly efficient ruthenium-catalyzed N-formylation of amines with H2 and CO2
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A highly efficient catalyst system based on ruthenium-pincer-type complexes has been discovered for N-formylation of various amines with CO2 and H2, thus affording the corresponding formamides with excellent productivity (turnover numbers of up to 1940000 in a single batch) and selectivity. Using a simple catalyst recycling protocol, the catalyst was reused for 12 runs in N,N-dimethylformamide production without significant loss of activity, thus demonstrating the potential for practical utilization of this cost-effective process.
- Zhang, Lei,Han, Zhaobin,Zhao, Xiaoyu,Wang, Zheng,Ding, Kuiling
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supporting information
p. 6186 - 6189
(2015/05/20)
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- C-N and N-H Bond Metathesis Reactions Mediated by Carbon Dioxide
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Herein, we report CO2-mediated metathesis reactions between amines and DMF to synthesize formamides. More than 20 amines, including primary, secondary, aromatic, and heterocyclic amines, diamines, and amino acids, are converted to the corresponding formamides with good-to-excellent conversions and selectivities under mild conditions. This strategy employs CO2 as a mediator to activate the amine under metal-free conditions. The experimental data and in situ NMR and attenuated total reflectance IR spectroscopy measurements support the formation of the N-carbamic acid as an intermediate through the weak acid-base interaction between CO2 and the amine. The metathesis reaction is driven by the formation of a stable carbamate, and a reaction mechanism is proposed.
- Wang, Yehong,Zhang, Jian,Liu, Jing,Zhang, Chaofeng,Zhang, Zhixin,Xu, Jie,Xu, Shutao,Wang, Fangjun,Wang, Feng
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p. 2066 - 2072
(2015/06/30)
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- Nanoceria-catalyzed highly efficient procedure for N-formylation of amines at room temperature under solvent-free conditions
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Nanoceria-catalyzed simple and efficient protocol for the N-formylation of amines using formic acid at room temperature under solvent-free conditions shows high yield of desired product chemoselectivity and improvement in reaction time.
- Patil, Umakant B.,Singh, Abhilash S.,Nagarkar, Jayashree M.
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supporting information
p. 524 - 526
(2013/06/05)
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- Convenient synthesis of analogs of aminomethylene gem-diphosphonic acid from amines without catalyst
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A simple, novel, and convenient synthesis of analogs of aminomethylene gem-diphosphonic acids in one-pot from primary and secondary amines in moderate yields was reported without catalyst.
- Wu, Mingshu,Chen, Ruyu,Huang, You
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p. 1393 - 1398
(2007/10/03)
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- A very convenient dimethylamination of activated aromatic halides using N,N-dimethylformamide and ethanolamines
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A very convenient dimethylamination of activated aromatic halides was achieved by using N,N-dimethylformamide(DMF) and ethanolamines. p- Nitrochlorobenzene, 2-halopyridines, 2-chloroquinoline and 2-chloropyrimidine gave the corresponding dimethylamino substituted products when treated with DMF and diethanolamine in 80-92% yield.
- Cho, Yoon Hwan,Park, Jae Chan
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p. 8331 - 8334
(2007/10/03)
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- A thermally curable mixture
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A thermally curable mixture contains 10-70% by weight of reactive compounds, 0.05-2% by weight of at least one basic catalyst, and at least one solvent. The reactive compounds are consisting essentially of a first reactive compound and a second reactive compound at a molar ratio between 1:1 and 1:10. The first reactive compound is at least one compound selected from polyfunctional amides, and the second reactive compound is at least one compound having an epoxy equivalent between 100 and 800 g KOH per mole epoxy group, selected from a group of aromatic diglycidylethers and aromatic poly-glycidylethers. The basic catalyst is at least one chemical agent selected from the group consisting of tertiary ammonium salts, tertiary aromatic amines, and tertiary heterocyclic amines. The solvent is at least one chemical compound selected from the group consisting of aliphatic alcohols, ether alcohols, diether, and tertiary amides.
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