- Mesoporous Sn(IV) Doping DFNS Supported BaMnO3 Nanoparticles for Formylation of Amines Using Carbon Dioxide
-
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.]
- Yang, Jie,Wang, Liujie,Sun, Aili,Zhiani, Rahele
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p. 573 - 581
(2020/07/27)
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- Choline-based ionic liquids for CO2 capture and conversion
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Choline-based ionic liquids (Ch-ILs) with anions possessing interacting sites to attract CO2 were designed, which could capture CO2 with capacity >1.0 mol CO2 per molar IL under ambient conditions. Moreover, this kind of ILs combining with CuCl could catalyze the formylation of amines with CO2/H2 at 120 °C. Especially, choline imidazolate showed the best performance, affording a series of N-formamides in excellent yields. It was demonstrated that the IL activated CO2 and the synergistic effect between the IL and CuCl resulted in the high activity for catalysing the formylation of amines with CO2/H2.
- Li, Ruipeng,Zhao, Yanfei,Li, Zhiyong,Wu, Yunyan,Wang, Jianji,Liu, Zhimin
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p. 256 - 261
(2018/11/23)
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- The synthesis of cyanoformamides via a CsF-promoted decyanation/oxidation cascade of 2-dialkylamino-malononitriles
-
A mild and efficient method for the synthesis of cyanoformamides from N,N-disubstituted aminomalononitriles with CsF as the promoter has been developed. This method features a wide substrate scope and high reaction efficiency, and will facilitate corresponding cyanoformamide-based biological studies and synthetic methodology development.
- Lei, Lin-Sheng,Xue, Cao-Gen,Xu, Xue-Tao,Jin, Da-Ping,Wang, Shao-Hua,Bao, Wen,Liang, Huan,Zhang, Kun,Asiri, Abdullah M.
-
supporting information
p. 3723 - 3726
(2019/04/17)
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- Practical Catalytic Cleavage of C(sp3)?C(sp3) Bonds in Amines
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The selective cleavage of thermodynamically stable C(sp3)?C(sp3) single bonds is rare compared to their ubiquitous formation. Herein, we describe a general methodology for such transformations using homogeneous copper-based catalysts in the presence of air. The utility of this novel methodology is demonstrated for Cα?Cβ bond scission in >70 amines with excellent functional group tolerance. This transformation establishes tertiary amines as a general synthon for amides and provides valuable possibilities for their scalable functionalization in, for example, natural products and bioactive molecules.
- Li, Wu,Liu, Weiping,Leonard, David K.,Rabeah, Jabor,Junge, Kathrin,Brückner, Angelika,Beller, Matthias
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supporting information
p. 10693 - 10697
(2019/07/09)
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- Ethanol-mediated N-formylation of amines with CO2/H2 over cobalt catalysts
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The CO2-involved synthesis of chemicals is of great significance from a green and sustainable point of view. Herein, we present an efficient Co-based catalytic system composed of a commercially available Co salt, the tetradentate phosphine ligand P-(CH2CH2PPh2)3, and a base, denoted as [Co]/PP3/base, for the synthesis of formamides via the formylation of amines with CO2/H2. It was indicated that the selectivity of products (i.e., formamide or methylamine) could be tuned to some extent via changing the solvent and the base. Using ethanol as the solvent, the Co(ClO4)2·6H2O/PP3/K2CO3 system showed high activity for the production of formamides, affording product yields of 82-95%, together with its broad substrate scope. Exploration of the reaction mechanism indicated that formamide was formed with HCOOH as the intermediate, while the methylamine byproduct was produced with HCHO as the intermediate via the hydrogenolysis of dialkylaminomethane.
- Liu, Zhenghui,Yang, Zhenzhen,Ke, Zhengang,Yu, Xiaoxiao,Zhang, Hongye,Yu, Bo,Zhao, Yanfei,Liu, Zhimin
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p. 13933 - 13937
(2018/08/21)
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- N-doped carbon supported Pd catalysts for N-formylation of amines with CO2/H2
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Using mesoporous N-doped carbons (NCs) derived from glucose and melamine as the supports, a series of Pd/NC catalysts were prepared, in which Pd nanoparticles with average size2 and H2 in ethanol without any additives. Especially, the catalyst Pd/NC-800-6.9% containing quaternary N showed the best performance, affording a series of formylamides in good or even excellent yields. Further investigation reveals that the interaction between the Pd nanoparticles and quaternary nitrogen in the NC support was responsible for the good performance of the catalyst.
- Luo, Xiaoying,Zhang, Hongye,Ke, Zhengang,Wu, Cailing,Guo, Shien,Wu, Yunyan,Yu, Bo,Liu, Zhimin
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p. 725 - 731
(2018/04/02)
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- Synthesis of New Class of Copper(II) Complex-Based FeNi3/KCC-1 for the N-Formylation of Amines Using Dihydrogen and Carbon Dioxide
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This study investigated the potential application of an efficient, easily recoverable, and reusable copper(II)-based catalyst bearing polyvinyl alcohol (PVA) immobilized on FeNi3/KCC-1/APTPOSS [FeNi3/KCC-1/APTPOSS/TCT/PVA/Cu(II)] magnetic nano-particles (MNPs) for the N-formylation of amines via CO2 hydrogenation. FeNi3/KCC-1/TCT/PVA/Cu(II) MNPs were thoroughly characterized by transmission electron microscopy, field emission-scanning electron microscopy, vibrating sample magnetometry, thermo-gravimetric analysis, inductively coupled plasma-mass spectrometry (ICP-MS), and the Brunauer, Emmett, and Teller method. After the reaction, only minor changes to the morphology of the catalyst recycled by the ICP-MS were evidenced, thus corroborating its robustness. Graphical Abstract: [Figure not available: see fulltext.]
- Zhiani, Rahele,Saadati, Seyed Mahdi,Zahedifar, Mahboobeh,Sadeghzadeh, Seyed Mohsen
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p. 2487 - 2500
(2018/07/05)
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- Mesoporous imine-based organic polymer: catalyst-free synthesis in water and application in CO2 conversion
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A mesoporous imine-functionalized organic polymer (Imine-POP) was prepared based on the reaction of an aryl ammonium salt with an aromatic aldehyde in water without any catalyst and template. The Pd coordinated Imine-POP exhibited high catalytic activity for the N-formylation of amines with CO2/H2 at 100 °C, affording a series of formamides in high yields.
- Yu, Xiaoxiao,Yang, Zhenzhen,Guo, Shien,Liu, Zhenghui,Zhang, Hongye,Yu, Bo,Zhao, Yanfei,Liu, Zhimin
-
supporting information
p. 7633 - 7636
(2018/07/15)
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- Method for preparing N-formylated amine compounds
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The invention discloses a method for preparation N-formylated amine compounds. In the method, the amine compounds and 1,3-dihydroxy acetone are taken as reaction raw materials reacting in a reactor for 2-48 hours at the reaction temperature of 0-100DEG C in a reaction medium in the presence of composite catalysts and oxidants, and the N-formylated amine compounds are obtained. The method is simpleand moderate in reaction conditions, cost can be reduced, target products can be obtained with high yield, and the catalysts used have high catalytic activity and are easy to be separated from a reaction system and reuses; the method is environment friendly during the whole process, the reaction raw materials are easy to be converted from biodiesel by-product propylene glycol, and use of glycerolis facilitated.
- -
-
Paragraph 0040; 0048; 0049
(2018/11/03)
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- An efficient reduction of N-substituted carbonylimidazolides into formamides by NaBH4
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A novel, simple and versatile protocol was investigated for highly efficient synthesis of formamides through reducing N-substituted carbonylimidazolides by NaBH4 under mild reaction conditions. By this method, not only carboxylic acids or isocyanates, but also amines can readily access formamides with high yields.
- Chen, Zhiyong,Cao, Yiming,Tian, Zeyu,Zhou, Xuan,Xu, Wenjin,Yang, Jia,Teng, Hanbing
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p. 2166 - 2170
(2017/05/10)
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- Method for synthesizing formamide compound
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The invention discloses a method for synthesizing a formamide compound. The synthetic method comprises the following steps: taking carbamyl imidazole compound as a raw material, preparing the formamide compound in a mixed solution of tetrahydrofuran and water by taking hydroboron as a reducing agent. The catalyst hydroboron used in the method disclosed by the invention has the advantages of environment friendliness, stable performance, high conversion rate and the like. Moreover, the initial raw material and used reagents are simple and readily available, the cost is low, and the operation is simple and feasible. Therefore, the route is a route which is low in cost, simple in operation and suitable for industrial production.
- -
-
Paragraph 0056-0058
(2017/09/01)
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- Pyridine-functionalized organic porous polymers: applications in efficient CO2 adsorption and conversion
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Pyridine-functionalized porous organic polymers showed excellent CO2 uptake capacity (up to 63 and 171 mg g-1 at 0.1 and 1 bar at 273 K), and performed well as supports for Ru(0) nanoparticles. The resultant CarPy-CMP@Ru served as an efficient catalyst for the formylation of amines with CO2/H2, together with high product yields (89-93%), high stability and easy recyclability.
- Yang, Zhenzhen,Wang, Huan,Ji, Guipeng,Yu, Xiaoxiao,Chen, Yu,Liu, Xinwei,Wu, Cailing,Liu, Zhimin
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supporting information
p. 2869 - 2872
(2017/04/14)
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- Catalyst-free: N -formylation of amines using BH3NH3 and CO2 under mild conditions
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The catalyst-free N-formylation of amines using CO2 as the C1 source and BH3NH3 as the reductant has been developed for the first time. The corresponding formylated products of both primary and secondary amines are obtained in good to excellent yields (up to 96% of isolated yield) under mild conditions.
- Zhao, Tian-Xiang,Zhai, Gao-Wen,Liang, Jian,Li, Ping,Hu, Xing-Bang,Wu, You-Ting
-
supporting information
p. 8046 - 8049
(2017/07/22)
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- Highly productive CO2 hydrogenation to methanol-a tandem catalytic approach: Via amide intermediates
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A new system for CO2 reduction to methanol has been demonstrated using homogeneous ruthenium catalysts with a range of amine auxiliaries. Modification of this amine has a profound effect on the yield and selectivity of the reaction. A TON of 8900 and TOF of 4500 h-1 is achieved using a [RuCl2(Ph2PCH2CH2NHMe)2] catalyst with a diisopropylamine auxiliary.
- Everett,Wass
-
supporting information
p. 9502 - 9504
(2017/09/01)
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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
-
-
- Preparation method for methanamide
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The invention relates to a method for preparing methanamide compounds through carbonylation of amine. The method employs primary amine or secondary amine and carbon monoxide (CO) as reactants and prepares the methanamide compounds through a CO-inserted carbonylation reaction under the catalysis of ruthenium-loaded hydroxyapatite (Ru/HAP). Reaction conditions are that the reaction is carried out in a tank reactor under stirring; CO pouring pressure is 0.5 to 5.0 MPa; and reaction temperature is 100 to 200 DEG C. The method has the characteristics that (1) the reaction has 100% atom economy and is free of generation of any by-product; (2) the ruthenium-loaded hydroxyapatite is used as a catalyst, the catalyst is simple to prepare and efficiently catalyzes the reaction, and the yield of the methanamide compounds can reach 80% or above; and (3) the catalyst has good stability and can be cyclically used four times or more.
- -
-
Paragraph 0031; 0032
(2017/05/26)
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- Preparation method of formamide compound
-
The invention provides a preparation method of a formamide compound. A preparation process of the preparation method comprises the following steps: uniformly mixing formic acid and an amine compound raw material selected from primary amine or secondary amine to prepare a homogeneous reaction system; raising the temperature of the homogeneous reaction system to 160 DEG C to 230 DEG C; decomposing the homogeneous reaction system to obtain carbon monoxide and enabling the carbon monoxide to participate in reaction; collecting a reaction product to obtain the formamide compound. The invention provides a novel technology for synthesizing the formamide compound through a heterogeneous method; a catalyst does not need to be used in a reaction process and an operation process is simple and controllable; the selectivity of the amine compound raw material is high.
- -
-
Paragraph 0066-0070
(2018/03/24)
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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.
- -
-
Paragraph 0014; 0023
(2017/08/26)
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- Formyloxyacetoxyphenylmethane as an N-Formylating Reagent for Amines, Amino Acids, and Peptides
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Formyloxyacetoxyphenylmethane is a stable, water-tolerant, N-formylating reagent for primary and secondary amines that can be used under solvent-free conditions at room temperature to prepare a range of N-formamides, N-formylanilines, N-formyl-α-amino acids, N-formylpeptides, and an isocyanide.
- Chapman, Robert S. L.,Lawrence, Ruth,Williams, Jonathan M. J.,Bull, Steven D.
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supporting information
p. 4908 - 4911
(2017/09/23)
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- Supported nano-gold-catalyzed N-formylation of amines with paraformaldehyde in water under ambient conditions
-
A simple and efficient Au/Al2O3 catalyst was prepared by the co-precipitation method for the oxidative N-formylation of amines with paraformaldehyde. Under the optimized reaction conditions, excellent amine conversion and N-formamide selectivity can be obtained with up to 97% yield with water as the solvent under ambient conditions. This catalyst tolerated a wide range of primary amines and second amines, and it can be reused for at least five runs without obvious deactivation.
- Ke, Zhengang,Zhang, Yan,Cui, Xinjiang,Shi, Feng
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p. 808 - 816
(2016/02/12)
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- An Efficient Protocol for Formylation of Amines Using Carbon Dioxide and PMHS under Transition-Metal-Free Conditions
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A highly efficient, green and simple base catalytic system was investigated for the formylation of amines using CO2 and PMHS [poly(methylhydrosiloxane)] under mild reaction conditions. This reaction proceeds smoothly without additives and furnishes the corresponding N-formylated products from both the 1° and the 2° aliphatic as well as aromatic amines in good to excellent yields.
- Nale, Deepak B.,Bhanage, Bhalchandra M.
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p. 1413 - 1417
(2016/05/24)
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- 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
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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.
- Nale, Deepak B.,Rath, Dharitri,Parida,Gajengi, Aravind,Bhanage, Bhalchandra M.
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p. 4872 - 4881
(2016/07/07)
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- Biomass-derived γ-valerolactone as an efficient solvent and catalyst for the transformation of CO2 to formamides
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Efficient conversion of carbon dioxide (CO2) into valuable chemicals is a very attractive topic. Herein, we conducted the first work on the utilization of biomass-derived γ-valerolactone (GVL) as the solvent and catalyst for transformation of CO2 with various primary and secondary amines in the presence of phenylsilane (PhSiH3), and the corresponding desired formamides were produced with high yields without any additional catalyst. Systematic studies indicated that the lactone structure of GVL played a key role in the formation of the active silyl formates and the activation of N-H bonds in amines, thus leading to the excellent performance of GVL for the catalytic reactions.
- Song, Jinliang,Zhou, Baowen,Liu, Huizhen,Xie, Chao,Meng, Qinglei,Zhang, Zhanrong,Han, Buxing
-
supporting information
p. 3956 - 3961
(2016/07/21)
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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.
- -
-
Paragraph 0040; 0041
(2017/03/14)
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- Imidazolium-Based Ionic Liquids Catalyzed Formylation of Amines Using Carbon Dioxide and Phenylsilane at Room Temperature
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The CO2-involved synthesis of chemicals is of significance. In this work, we found that 1-alkyl-3-methylimidazolium ionic liquids (ILs) had high efficiency for catalyzing the formylation of amines using CO2 and phenylsilane at room temperature, producing the corresponding formylated products in excellent yields under the metal-free condition. The ILs acted as bifunctional catalysts, which activated the Si-H bond of phenylsilane to react with CO2 to form the formoxysilane intermediate and simultaneously activated the amine substrate through the hydrogen bond. Moreover, the imidazolium cation and the anions of the ILs showed an excellent synergistic effect on catalyzing the formylation of amines.
- Hao, Leiduan,Zhao, Yanfei,Yu, Bo,Yang, Zhenzhen,Zhang, Hongye,Han, Buxing,Gao, Xiang,Liu, Zhimin
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p. 4989 - 4993
(2015/09/15)
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- A green protocol for the N-formylation of amines using molybdate sulfuric acid as a reusable solid catalyst
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A novel and efficient method for the N-formylation of amines via the reaction of orthoformates and amines is developed. The reactions are mediated by a catalytic amount of molybdate sulfuric acid as a heterogeneous solid acid.
- Karami, Bahador,Farahi, Mahnaz,Pam, Fariba
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p. 6292 - 6296
(2015/02/19)
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- Transformylating amine with DMF to formamide over CeO2 catalyst
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We here report a new protocol for the formylation of various amines, primary or secondary, aromatic or alkyl, cyclic or linear, mono- or di-amine, with dimethylformamide (DMF) as the formylation reagent to obtain the corresponding formamides in good to excellent yields over CeO2 catalyst. The reaction requires no homogeneous acidic or basic additives and is tolerant to water.
- Wang, Yehong,Wang, Feng,Zhang, Chaofeng,Zhang, Jian,Li, Mingrun,Xu, Jie
-
supporting information
p. 2438 - 2441
(2014/03/21)
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- Copper-diphosphine complex catalysts for N-formylation of amines under 1 atm of carbon dioxide with polymethylhydrosiloxane
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N-formylation of a wide range of amines proceeded using copper-diphosphine complexes as homogeneous catalysts with polymethylhydrosiloxane (PMHS) under 1 atm of CO2. In the reaction of piperidine, for example, the turnover number (TON) reached 11700 in 23 h with 90% yield of the formylated product. This TON value is much higher than those of the reported catalysts for the formylation of amines under 1 atm of CO2 with hydrosilanes. The Cu complexes with phosphines having ortho-phenylene structures acted as good ligands for the formylation, as compared to a bidentate ligand connected with a propyl chain and a monodentate ligand. Among these diphosphines, ligands with alkyl functionalities, such as isopropyl and cyclohexyl groups, produced better results than the phenyl group. Not only cyclic secondary amines, but also linear secondary amines and aromatic and aliphatic primary amines were found to be reactive substrates. In the case of 2,2,6,6-tetramethylpiperidin-4-amine, the formylation proceeded regioselectively. A catalytic reaction pathway was proposed from a separate experiment using [Me2NCO2] [Me2NH2]. The Royal Society of Chemistry 2013.
- Motokura, Ken,Takahashi, Naoki,Kashiwame, Daiki,Yamaguchi, Sho,Miyaji, Akimitsu,Baba, Toshihide
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p. 2392 - 2396
(2013/09/02)
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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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- Iridium-catalyzed formylation of amines with paraformaldehyde
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Amines have been formylated using aqueous formaldehyde or paraformaldehyde and the iridium catalyst [CpIrI2]2. Paraformaldehyde acts as both a formylating agent and an oxidant.
- Saidi, Ourida,Bamford, Mark J.,Blacker, A. John,Lynch, James,Marsden, Stephen P.,Plucinski, Pawel,Watson, Robert J.,Williams, Jonathan M.J.
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supporting information; experimental part
p. 5804 - 5806
(2010/11/05)
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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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- Phase-separable catalysis using room temperature ionic liquids and supercritical carbon dioxide
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A new phase-separable catalysis concept is demonstrated using supercritical carbon dioxide and the room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate for hydrogenation of alkenes and carbon dioxide.
- Liu,Abrams,Baker,Tumas
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p. 433 - 434
(2007/10/03)
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- Protected aminothiazolylacetic acid derivatives
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Described is a protected aminothiazolylacetic acid derivative represented by the following formula (I): STR1 wherein A represents a nitrogen atom or a methine group, R1 and R2 may be the same or different and individually represent a hydrogen atom, a lower alkyl group or a substituted or unsubstituted aryl group, R3 represents a lower alkoxy group, a halogenated lower alkoxy group, a triphenylmethoxy group, a lower alkyl group or an acyloxy group, and R4 represents a halogen atom, a hydroxy group, a lower alkoxy group or a substituted or unsubstituted amino group; and salts thereof; as well as processes for the preparation thereof. The protected aminothaizolylacetic acid derivative according to the present invention is an useful intermediate for introducing a 2-(2-aminothiazol-4-yl)-2-alkoxyiminoacetyl group or a 2-(2-aminotiazol-4-yl)-2-alkenoyl group into a cephem skeleton.
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- Solvent effect in the ruthenium catalyzed carbonylation of amines. Selective synthesis of dialkylformamides
-
Formamides are selectively produced in the ruthenium-catalyzed carbonylation of amines in alcoholic solvents.The process is shown to occur sequentially via initial carbonylation of the alcohol to yield the corresponding formate, which then reacts with the amine to yield the formamide.The method is of interest for the carbonylation of unreactive amines (aniline, t-butylamine).
- Bitsi, G.,Jenner, G.
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p. 429 - 436
(2007/10/02)
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- Enthalpic Interaction Coefficient of Formamides Dissolved in N,N-Dimethylformamide
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Enthalpies of dilution of formamide, N-methylformamide, N-ethylformamide, N-propylformamide, N-butylformamide, N-pentylformamide, N,N-diethyl-formamide, N,N-dipropylformamide, N,N-dibutylformamide, and N,N-dipentyl-formamide dissolved in N,N-dimethylformamide as solvent have been measured calorimetrically at 25 deg C.The results are interpreted in terms of the McMillan-Mayer theory.Enthalpic interaction parameters are obtained for pairs, triplets, and in some cases, quadruplets of solute molecules.In general, the enthalpic pair interaction coefficients are negative, whereas the triplet coefficients are positive.The interaction enthalpies are positive only for N-methylformamide and formamide.The magnitudes of the enthalpic pair and triplet interaction coefficients increase with increasing number of C atoms in the N-alkyl groups.The results for the formamides presented in this paper are compared with those for corresponding acetamides published earlier.Although the trends are comparable, distinct differences are observed.The contribution of the α-CH3 group at the CO side of the dialkylacetamides to the enthalpic interaction coefficient appears to be negligible.The same is true for α-CH2 groups at the NH side of a number of amides and related compounds.The enthalpic pair interaction coefficients of the mono-N-alkylsubstituted formamides show a shift of about 100 J-kg-mol-2 as compared with isomeric N-alkylacetamides.This is discussed in terms of the difference in proton donating and accepting ability of several types of amide molecules.It is concluded that substitution effects should be incorporated in additivity models for these type of systems.
- Bloemendal, M.,Sijpkes, A. H.,Somsen, G.
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-
- Application of the Water-gas Shift Reaction. III. Reduction of Oxidized Nitrogen Compounds with CO and H2O Catalyzed by (BPh4)2
-
The ruthenium(II) complex, 4>(BPh4)2 (cod=1,5-cyclooctadiene, py=pyridine) has been shown to catalyze the reduction of oxidized nitrogen compounds with CO and H2O.In this reaction, primary, secondary, and tertiary nitroalkanes are converted into amides, ketones, and amines, respectively.Nitrosobenzene and picoline N-oxides are also reduciable to amines in good yields.
- Okano, Tamon,Fujiwara, Kensuke,Konishi, Hisatoshi,Kiji, Jitsuo
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p. 1975 - 1976
(2007/10/02)
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