- N-formylation of amines using phenylsilane and CO2 over ZnO catalyst under mild condition
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Several research studies have been conducted on N-formylation of amines using phenylsilane and CO2. However, most of these studies involved tedious processes of catalyst preparation or complex procedures. In the present study, we describe the use of a simple and commercially available ZnO catalyst for selective N-formylation of amines under mild condition. High-yielding N-formylation products with good recyclability and wide substrate scope were obtained, which can promote fine chemical synthesis and CO2 capture.
- Cheng, Yujie,Gan, Tao,He, Qian,He, Xiaohui,Ji, Hongbing,Sun, Qingdi,Wang, Pengbo,Zhang, Hao
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- Mesoporous Sn(IV) Doping DFNS Supported BaMnO3 Nanoparticles for Formylation of Amines Using Carbon Dioxide
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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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- Bifunctional Ru-loaded Porous Organic Polymers with Pyridine Functionality: Recyclable Catalysts for N-Formylation of Amines with CO2 and H2
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A series of pyridine functionalized porous organic polymers (POPs-Py&PPh3) have been synthesized by polymerizing tris(4-vinylphenyl)phosphane and 4-vinylpyridine. The pyridine moieties in the copolymer materials contribute to CO2 adsorption and promote the subsequent conversion of CO2. The POP supported Ru catalyst (Ru/POP3-Py&PPh3) shows a high catalytic activity (TON up to 710) in the N-formylation of various primary and secondary amines with CO2/H2, affording the corresponding formamides in good yields (55–95%) under mild reaction conditions. The heterogeneous catalyst can be easily separated from the reaction system and reused for at least eight cycles in the N-formylation of morpholine. (Figure presented.).
- Zhang, Kai,Zong, Lingbo,Jia, Xiaofei
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p. 1335 - 1340
(2021/02/05)
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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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- Solvate sponge crystals of (DMF)3NaClO4: reversible pressure/temperature controlled juicing in a melt/press-castable sodium-ion conductor
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A new type of crystalline solid, termed “solvate sponge crystal”, is presented, and the chemical basis of its properties are explained for a melt- and press-castable solid sodium ion conductor. X-ray crystallography and atomistic simulations reveal details of atomic interactions and clustering in (DMF)3NaClO4and (DMF)2NaClO4(DMF =N-N′-dimethylformamide). External pressure or heating results in reversible expulsion of liquid DMF from (DMF)3NaClO4to generate (DMF)2NaClO4. The process reverses upon the release of pressure or cooling. Simulations reveal the mechanism of crystal “juicing,” as well as melting. In particular, cation-solvent clusters form a chain of octahedrally coordinated Na+-DMF networks, which have perchlorate ions present in a separate sublattice space in 3?:?1 stoichiometry. Upon heating and/or pressing, the Na+?DMF chains break and the replacement of a DMF molecule with a ClO4?anion per Na+ion leads to the conversion of the 3?:?1 stoichiometry to a 2?:?1 stoichiometry. The simulations reveal the anisotropic nature of pressure induced stoichiometric conversion. The results provide molecular level understanding of a solvate sponge crystal with novel and desirable physical castability properties for device fabrication.
- Prakash, Prabhat,Ardhra, Shylendran,Fall, Birane,Zdilla, Michael J.,Wunder, Stephanie L.,Venkatnathan, Arun
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p. 5574 - 5581
(2021/04/30)
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- Erratum: Thermodynamic Analysis of Metal-Ligand Cooperativity of PNP Ru Complexes: Implications for CO2Hydrogenation to Methanol and Catalyst Inhibition (J. Am. Chem. Soc. (2019) 141:36 (14317-14328) DOI: 10.1021/jacs.9b06760)
-
Equation 13 in the Supporting Information contained a sign error, resulting in the incorrect pKa values reported for (PNP)Ru-CO2and PNP. The pKa of (PNP)Ru-CO2should be 26.1 ± 0.4 (not 24.6 ± 0.4). The pKa of PNP should be 29.0 ± 0.4 (not 28.6 ± 0.4). The same incorrect pKa values are reported on page 14322, in the left column, last paragraph for PNP, and in the right column, first paragraph for (PNP)Ru-CO2), and on page 14323, in Table 2, as well as in the SI (Table S3 and Figure S12 caption). Also in the Supporting Information, Figures S15 and S17 have the wrong functions plotted. The slope of the correct function was used in extrapolating thermochemical parameters derived from Figure S17. The slope of Figure S15 was used to extrapolate thermochemical parameters, which resulted in our reporting incorrect values. The value of K8,Cl should be 0.004 ± 0.0016 (not 2.5 × 10-7). The value of K5,Cl should be 2.0(±0.8) × 10-31(not 1.3 × 10-34), and hence the corresponding pKa should be >29.7 ± 0.2 (not >33.9 ± 0.4). The value of K6,Clshould be 1.0(±0.6) × 10-7(not 6.3 × 10-12), and hence the corresponding ΔG6,Cl should be 9.5 ± 0.3 kcalmol-1(not 15.3 ± 0.5 kcalmol-1). A corrected Supporting Information file is provided that has revised versions of eq 13, Figure S12 caption, Figure S15, Figure S17, and Table S3. The corrected Table 2 is shown below. None of these errors impact the discussion and conclusions drawn. We regret these errors and apologize for any confusion that may have resulted.
- Ardon, Yotam,Geary, Jackson,Mathis, Cheryl L.,Philliber, Mallory A.,Reese, Maxwell S.,Saouma, Caroline T.,Vanderlinden, Ryan T.
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supporting information
p. 11274 - 11274
(2021/08/03)
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- Method for preparing N, N-dimethylformamide
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The invention relates to a method for preparing N, N-dimethylformamide (DMF). According to the method, dimethylamine and carbon monoxide (CO) are used as reactants, and the DMF is prepared through CO-inserted carbonylation reaction under the catalytic action, wherein the reaction conditions are as follows: the reaction is carried out in a fixed bed reactor, the reaction pressure is 1.0-8.0 MPa, the reaction temperature is 150-250 DEG C, the feeding volume space velocity of dimethylamine is 50-800 h, and the volume space velocity of CO is 50-800 h. The method is characterized in that (1) the reaction has 100% atom economy and no by-product is generated, and (2) the oxide A-metal-oxide B composite material is used as the catalyst, the catalyst catalyzes the reaction with high selectivity, the selectivity of DMF reaches 99% or above, and the catalyst is high in stability and can be continuously operated for 500 h.
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Paragraph 0009-0052
(2021/06/06)
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- Preparation method of N, N-dimethylformamide
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The invention relates to a preparation method of N, N-dimethylformamide (DMF). According to the method, dimethylamine and carbon monoxide (CO) are adopted as reactants, and the DMF is prepared through CO-inserted carbonylation reaction under the catalytic action, wherein the reaction conditions are as follows: the reaction is carried out in a fixed bed reactor, the reaction pressure is 1.0-8.0 MPa, the reaction temperature is 150-250 DEG C, the feeding space velocity of dimethylamine is 50-800 h, and the flow velocity of the raw material CO is 5-25 mL.min. The method is characterized in that (1) the reaction has 100% atom economy and no by-product is generated, and (2) the Ru-loaded HAP is used as the catalyst, the catalyst is simple to prepare and efficiently catalyzes the reaction, the optimal yield of DMF can reach 95%, the catalyst is high in stability, and continuous operation can be performed for 500 h.
- -
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Paragraph 0011-0080
(2021/06/06)
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- Catalysis of Positively Charged Ru Species Stabilized by Hydroxyapatite in Amine Formylation
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Formamide is an important solvent and synthetic intermediate. Herein, we designed a hydroxyapatite (HAP)-stabilized, positively charged Ru-based catalysts which can efficiently catalyze the formylation reaction of amines with CO for the synthesis of formamide. The Ru-HAP showed excellent catalytic performance in N,N-Dimethylformamide (DMF) synthesis, with about 75 % dimethylamine conversion and >99 % DMF selectivity at 300 h of continuous reaction. The combination of characterization results and control experiments showed that positively charged Ru species, including hydrated RuOx and Ru3+ species, were catalytically active. In particular, the surface RuOx species were more active than the Ru3+ species located within the HAP framework.
- Jiao, Dongxia,Wang, Yehong,Zhang, Zhixin,Zhang, Jian,Lei, Lijun,Wang, Feng
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p. 4159 - 4163
(2021/08/20)
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- Chromium-catalysed efficient: N -formylation of amines with a recyclable polyoxometalate-supported green catalyst
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A simple and efficient protocol for the formylation of amines with formic acid, catalyzed by a polyoxometalate-based chromium catalyst, is described. Notably, this method shows excellent activity and chemoselectivity for the formylation of primary amines; diamines have also been successfully employed. Importantly, the chromium catalyst is potentially non-toxic, environmentally benign and safer than the widely used high valence chromium catalysts such as CrO3 and K2Cr2O7. The catalyst can be recycled several times with a negligible impact on activity. Finally, a plausible mechanism is provided based on the observation of intermediate and control experiments.
- Dan, Demin,Chen, Fubo,Zhao, Whenshu,Yu, Han,Han, Sheng,Wei, Yongge
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supporting information
p. 90 - 94
(2021/01/11)
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- An Efficient and Practical System for the Synthesis of N,N-Dimethylformamide by CO2 Hydrogenation using a Heterogeneous Ru Catalyst: From Batch to Continuous Flow
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In the context of CO2 utilization, a number of CO2 conversion methods have been identified in laboratory-scale research; however, only a very few transformations have been successfully scaled up and implemented industrially. The main bottleneck in realizing industrial application of these CO2 conversions is the lack of industrially viable catalytic systems and the need for practically implementable process developments. In this study, a simple, highly efficient and recyclable ruthenium-grafted bisphosphine-based porous organic polymer (Ru@PP-POP) catalyst has been developed for the hydrogenation of CO2 to N,N-dimethylformamide, which affords a highest ever turnover number of 160 000 and an initial turnover frequency of 29 000 h?1 in a batch process. The catalyst is successfully applied in a trickle-bed reactor and utilized in an industrially feasible continuous-flow process with an excellent durability and productivity of 915 mmol h?1 gRu?1.
- Gunasekar, Gunniya Hariyanandam,Padmanaban, Sudakar,Park, Kwangho,Jung, Kwang-Deog,Yoon, Sungho
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p. 1735 - 1739
(2020/02/11)
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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 0076-0122
(2020/06/16)
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- Formylation of Amines by CO2Hydrogenation Using Preformed Co(II)/Nickel(II) Complexes
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Preparation of formamides by CO2 hydrogenation requires an efficient catalyst and temperatures around 100 °C or higher, but most catalysts reported so far incorporate rare and toxic precious metals. Five cobalt(II) or nickel(II) complexes with dmpe or PNN (dmpe = 1,2-bis(dimethylphosphino)ethane; PNN = [(2-(di-tert-butylphosphinomethyl)-6-diethylaminomethyl)pyridine) have been evaluated as precatalysts for the hydrogenation of CO2 to prepare formamides from the corresponding secondary amines. The most active catalyst for these reactions was found to be [NiCl2(dmpe)] in DMSO, producing dimethylformamide (DMF) from CO2, H2, and dimethylamine in up to 6300 TON, the highest activity reported for this reaction with an abundant metal-phosphine complex.
- Affan, Mohammad A.,Jessop, Philip G.,Schatte, Gabriele
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supporting information
p. 14275 - 14279
(2020/10/09)
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- A scalable continuous photochemical process for the generation of aminopropylsulfones
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An efficient continuous photochemical process is presented that delivers a series of novel γ-aminopropylsulfones via a tetrabutylammonium decatungstate (TBADT) catalysed HAT-process. Crucial to this success is the exploitation of a new high-power LED emitting at 365 nm that was found to be superior to an alternative medium-pressure Hg lamp. The resulting flow process enabled the scale-up of this transformation reaching throughputs of 20 mmol h-1 at substrate concentrations up to 500 mM. Additionally, the substrate scope of this transformation was evaluated demonstrating the straightforward incorporation of different amine substituents as well as alkyl appendages next to the sulfone moiety. It is anticipated that this methodology will allow for further exploitations of these underrepresented γ-aminopropylsulfone scaffolds in the future. This journal is
- Baumann, Marcus,Bonciolini, Stefano,Di Filippo, Mara
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supporting information
p. 9428 - 9432
(2020/12/15)
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- Unprecedented Formation of 2,5-Diaminoquinones from the Reaction of Vanillin with Secondary Amines in Aerobic Conditions
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Vanillin is widely used as a flavoring agent in foods, perfumes and in several other applications. Even if huge amounts of vanillin are annually employed in these manufacturing processes, its reactivity is underexplored, especially for the formation of potentially toxic substances. In this context, we observed the formation of orange to red crystalline compounds in the reaction of vanillin with secondary amines in aerobic conditions. NMR and HRMS allowed identifying the products as 2,5-diamino-1,4-benzoquinones. Preliminary investigations of this reaction led to a proposed mechanism involving an oxidative fragmentation of vanillin as the key step. MTT tests did not show any toxic effect up to 0.1 mm.
- Barbero, Mauro,Papillo, Valentina A.,Grolla, Ambra A.,Negri, Roberto,Travaglia, Fabiano,Bordiga, Matteo,Condorelli, Fabrizio,Arlorio, Marco,Giovenzana, Giovanni B.
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supporting information
p. 136 - 139
(2019/12/27)
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- Method for preparing N, N-dimethylformamide (DMF)
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The present invention relates to a process for preparing N, N-dimethylformamide (DMF). According to the method, dimethylamine and carbon monoxide (CO) are used as reactants, and DMF is prepared through carbonylation reaction of CO insertion under the catalytic action. The reaction conditions are as follows: the reaction is carried out in a fixed bed reactor, the reaction pressure is 1.0-8.0 MPa, the reaction temperature is 150-250 DEG C, and the dimethylamine feeding space velocity is 50-800 h . The method is characterized in that (1) the reaction has 100% atom economy, and no by-productis generated, (2) the bimetallic loaded metal oxide is used as a catalyst, the catalyst is simple to prepare and efficiently catalyzes the reaction, the yield of the DMF can reach 85% or above, and the stability is good.
- -
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Paragraph 0011-0028; 0039-0044
(2020/06/20)
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- Preparation method of N, N-dimethylformamide
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The invention relates to a preparation method of N, N-dimethylformamide (DMF). According to the method, dimethylamine and carbon monoxide (CO) are adopted as reactants, and DMF is prepared through a carbonylation reaction of CO insertion under the catalytic action of bimetallic loaded hydroxyapatite. The reaction conditions are as follows: the reaction is carried out in a fixed bed reactor, the reaction pressure is 1.0-8.0 MPa, the reaction temperature is 150-250 DEG C, the dimethylamine feeding space velocity is 50-800 h , and the flow rate of a raw material CO is 5-25 mL * min . The method is characterized in that (1) the reaction has 100% atom economy, and no by-product is generated, (2) the bimetallic loaded HAP is used as a catalyst, the catalyst is simple to prepare and efficiently catalyzes the reaction, the optimal yield of the DMF can reach 90%, and the catalyst is good in stability.
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Paragraph 0010-0049
(2020/06/20)
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- An efficient way for the: N -formylation of amines by inorganic-ligand supported iron catalysis
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The first example of an inorganic-ligand supported iron(iii) catalysed coupling of formic acid and amines to form formamides is reported. The pure inorganic catalyst (NH4)3[FeMo6O18(OH)6] (1), which consists of a central FeIII single-atomic core supported within a cycle-shaped inorganic ligand consisting of six MoVIO6 octahedra, shows excellent activity and selectivity, and avoids the use of complicated/commercially unavailable organic ligands. Various primary amines and secondary amines have been successfully transformed into the corresponding formamides under mild conditions, and the formylation of primary diamines has also been achieved for the first time. The Fe catalyst 1 can be reused several times without appreciable loss of activity.
- Wu, Zhikang,Zhai, Yongyan,Zhao, Wenshu,Wei, Zheyu,Yu, Han,Han, Sheng,Wei, Yongge
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supporting information
p. 737 - 741
(2020/02/25)
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- The synthesis of cyanoformamides via a CsF-promoted decyanation/oxidation cascade of 2-dialkylamino-malononitriles
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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.
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supporting information
p. 3723 - 3726
(2019/04/17)
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- Electrocatalytic reduction of low concentration CO2
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Utilization of low concentration CO2 contained in the exhaust gases from various industries and thermal power stations without the need for energy-consuming concentration processes should be an important technology for solving global warming and the shortage of fossil resources. Here we report the direct electrocatalytic reduction of low concentration CO2 by a Re(i)-complex catalyst that possesses CO2-capturing ability in the presence of triethanolamine. The reaction rate and faradaic efficiency of CO2 reduction were almost the same when using Ar gas containing 10% CO2 or when using pure CO2 gas, and the selectivity of CO formation was very high (98% at 10% CO2). At a concentration of 1% CO2, the Re(i) complex still behaved as a good electrocatalyst; 94% selectivity of CO formation and 85% faradaic efficiency were achieved, and the rate of CO formation was 67% compared to that when using pure CO2 gas. The electrocatalysis was due to the efficient insertion of CO2 into the Re(i)-O bond in fac-[Re(dmb)(CO)3{OC2H4N(C2H4OH)2}] (dmb = 4,4′-dimethyl-2,2′-bipyridine).
- Kumagai, Hiromu,Nishikawa, Tetsuya,Koizumi, Hiroki,Yatsu, Taiki,Sahara, Go,Yamazaki, Yasuomi,Tamaki, Yusuke,Ishitani, Osamu
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p. 1597 - 1606
(2019/02/12)
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- Synthesis of Zn(NH3) (CO3) inorganic helical framework and its use for selective separation of carbon dioxide
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A novel one-pot solvothermal reaction based on urea hydrolysis to synthesize single crystals of the Zn(NH3)(CO3) inorganic helical framework and its applications in selective CO2 separation.
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- Amine formylation with CO2 and H2 catalyzed by heterogeneous Pd/PAL catalyst
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For the first time, Pd supported on natural palygorskite was developed for amine formylation with CO2 and H2. Both secondary and primary amines with diverse structures could be converted into the desired formamides at 100 °C, and good to excellent yields were obtained.
- Dai, Xingchao,Wang, Bin,Wang,Shi, Feng
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p. 1141 - 1146
(2019/07/09)
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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 0246-0249
(2019/04/26)
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- Thermodynamic Analysis of Metal-Ligand Cooperativity of PNP Ru Complexes: Implications for CO2 Hydrogenation to Methanol and Catalyst Inhibition
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The hydrogenation of CO2 in the presence of amines to formate, formamides, and methanol (MeOH) is a promising approach to streamlining carbon capture and recycling. To achieve this, understanding how catalyst design impacts selectivity and performance is critical. Herein we describe a thorough thermochemical analysis of the (de)hydrogenation catalyst, (PNP)Ru-Cl (PNP = 2,6-bis(di-tert-butylphosphinomethyl)pyridine; Ru = Ru(CO)(H)) and correlate our findings to catalyst performance. Although this catalyst is known to hydrogenate CO2 to formate with a mild base, we show that MeOH is produced when using a strong base. Consistent with pKa measurements, the requirement for a strong base suggests that the deprotonation of a six-coordinate Ru species is integral to the catalytic cycle that produces MeOH. Our studies also indicate that the concentration of MeOH produced is independent of catalyst concentration, consistent with a deactivation pathway that is dependent on methanol concentration, not equivalency. Our temperature-dependent equilibrium studies of the dearomatized congener, (*PNP)Ru, with various H-X species (to give (PNP)Ru-X; X = H, OH, OMe, OCHO, OC(O)NMe2) reveal that formic acid equilibrium is approximately temperature-independent; relative to H2, it is more favored at elevated temperatures. We also measure the hydricity of (PNP)Ru-H in THF and show how subsequent coordination of the substrate can impact the apparent hydricity. The implications of this work are broadly applicable to hydrogenation and dehydrogenation catalysis and, in particular, to those that can undergo metal-ligand cooperativity (MLC) at the catalyst. These results serve to benchmark future studies by allowing comparisons to be made among catalysts and will positively impact rational catalyst design.
- Mathis, Cheryl L.,Geary, Jackson,Ardon, Yotam,Reese, Maxwell S.,Philliber, Mallory A.,Vanderlinden, Ryan T.,Saouma, Caroline T.
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supporting information
p. 14317 - 14328
(2019/10/11)
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- α-Methylation of 2-Arylacetonitrile by a Trimethylamine-Borane/CO2 System
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A highly selective monomethylation of 2-arylacetonitrile using CO2 is described. The utilization of trimethylamine-borane facilitates the six-electron reduction of CO2. This reaction is the first selective six-electron reductive functionalization of CO2 faciliated by C(sp3)-H bonds. A variety of 2-arylpropionitrile was obtained in good yields. The reaction could also be applied at the gram scale.
- Zhang, Xiaowei,Wang, Sheng,Xi, Chanjuan
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p. 9744 - 9749
(2019/08/16)
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- Stimulus-responsive supramolecular glasses
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Supramolecular polymers or materials that exhibit high stiffness and can efficiently be healed. The supramolecular materials polymer is based on monomers having three or more same or different binding sites that permit non-covalent, directional interactions between multiple monomer molecules. The properties of the supramolecular networks formed from the monomers are governed by cross-linked architecture and the large weight-fraction of the binding motif. The material in one embodiment forms a disordered glass, which in spite of the low-molecular weight of the building block, displays typical polymeric behavior. The material exhibits high stiffness and offers excellent coating and adhesive properties. On account of reversible dissociation and the formation of a low-viscosity liquid upon application of an optical stimulus or thermal stimulus or both, rapid healing as well as (de)bonding are possible.
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- Sustainable Co-Synthesis of Glycolic Acid, Formamides and Formates from 1,3-Dihydroxyacetone by a Cu/Al2O3 Catalyst with a Single Active Sites
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Glycolic acid (GA), as important building block of biodegradable polymers, has been synthesized for the first time in excellent yields at room temperature by selective oxidation of 1,3-dihyroxyacetone (DHA) using a cheap supported Cu/Al2O3 catalyst with single active CuII species. By combining EPR spin-trapping and operando ATR-IR experiments, different mechanisms for the co-synthesis of GA, formates, and formamides have been derived, in which .OH radicals formed from H2O2 by a Fenton-like reaction play a key role.
- Dai, Xingchao,Adomeit, Sven,Rabeah, Jabor,Kreyenschulte, Carsten,Brückner, Angelika,Wang, Hongli,Shi, Feng
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supporting information
p. 5251 - 5255
(2019/03/07)
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- Thermal behavior of ammonium dinitramide and amine nitrate mixtures
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This paper focuses on the thermal behavior of mixtures of ammonium dinitramide (ADN) and amine nitrates. Because some mixtures of ADN and amine nitrate exhibit low melting points and high-energy content, they represent potential liquid propellants for spacecraft. This study focused on the melting behavior and thermal-decomposition mechanisms in the condensed phase of ADN/amine nitrate mixtures during heating. We measured the melting point and exothermal behavior during constant-rate heating using differential scanning calorimetry and performed thermogravimetry–differential thermal analysis–mass spectrometry (TG–DTA–MS) to analyze the thermal behavior and evolved gases of ADN/amine nitrate mixtures during simultaneous heating to investigate their reaction mechanisms. Results showed that the melting point of ADN was significantly lowered upon the addition of amine nitrate with relatively low molecular volume and low melting point. TG–DTA–MS results showed that the onset temperature of the thermal decomposition of ADN/amine nitrates was similar to that of pure ADN. Furthermore, during thermal decomposition in the condensed phase, ADN produced highly acidic products that promoted exothermic reactions, and we observed the nitration and nitrosation of amines from the dissociation of amine nitrates.
- Matsunaga, Hiroki,Katoh, Katsumi,Habu, Hiroto,Noda, Masaru,Miyake, Atsumi
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p. 2677 - 2685
(2018/11/23)
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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.
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Paragraph 0040; 0048; 0049
(2018/11/03)
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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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- Ru@PsIL-Catalyzed Synthesis of N-Formamides and Benzimidazole by using Carbon Dioxide and Dimethylamine Borane
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This work reports the synthesis and characterization of ruthenium nanoparticles (Ru NPs) supported on polymeric ionic liquids (PILs). This catalyst shows high catalytic activity towards the N-formylation of amines and synthesis of benzimidazoles from 1,2-diamines and carbon dioxide (CO2) by reductive dehydrogenation of dimethylamine borane. This methodology shows excellent functional group tolerance with broad substrate scope towards the synthesis of N-formamides and benzimidazoles. Interestingly, this protocol also provides the tandem reduction of 2-nitroamines and CO2 to synthesize benzimidazoles. It was proposed that the ionic liquid phase of the polymer plays pivotal roles such as assisting the stabilization of nanoparticles electrostatically, providing an ionic environment, and controlling the easy access of the substrates/reagents to the active sites. The developed methodology utilizes CO2 as a C1 source and water/ethanol as a green solvent system. Additionally, the catalyst was found to be recyclable in nature and shows five consecutive recycling runs without significant loss in its activity.
- Saptal, Vitthal B.,Sasaki, Takehiko,Bhanage, Bhalchandra M.
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p. 2593 - 2600
(2018/04/30)
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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 0180-0181
(2018/02/28)
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- B(C6F5)3: a robust catalyst for the activation of CO2 and dimethylamine borane for the N-formylation reactions
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In this work, B(C6F5)3 is utilized as an organocatalyst for the transition-metal-free N-formylation of amines using carbon dioxide (CO2) as a C1 source and dimethylamine borane (Me2NH·BH3) as a green hydrogen transfer source at 80 °C. Most reported works utilize silane and hydrogen for the N-formylation reactions using CO2 which have thus far been limited by low atom economy, high cost or the use of harsh reaction conditions. This catalytic protocol affords a broad range of formylated products in moderate to excellent yields under mild reaction conditions with a high TON and TOF. The bulky boron (B(C6F5)3) catalyst reacts with amines and forms a Frustrated Lewis Pair (FLP) and activates CO2 and Me2NH·BH3 molecules. Additionally, this boron catalyst shows high catalytic activity for the cyclization of o-phenylenediamines using CO2 and Me2NH·BH3 to synthesize benzimidazoles.
- Saptal, Vitthal B.,Juneja, Gaurav,Bhanage, Bhalchandra M.
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supporting information
p. 15847 - 15851
(2018/10/04)
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- An Efficient Ruthenium Catalyst Bearing Tetradentate Ligand for Hydrogenations of Carbon Dioxide
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A ruthenium complex with a tetradentate bipyridine ligand was proved to be a highly efficient catalyst for the conversions of CO2. Turnover numbers up to 300 000, 9800, and 2100 were achieved for the hydrogenations of CO2 to formamides, formamides to methanol and amines, and the direct hydrogenation of CO2 to methanol, respectively.
- Zhang, Feng-Hua,Liu, Chong,Li, Wei,Tian, Gui-Long,Xie, Jian-Hua,Zhou, Qi-Lin
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supporting information
p. 1000 - 1002
(2018/09/21)
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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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- Production of Formamides from CO and Amines Induced by Porphyrin Rhodium(II) Metalloradical
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It is of fundamental importance to transform carbon monoxide (CO) to petrochemical feedstocks and fine chemicals. Many strategies built on the activation of C≡O bond by π-back bonding from the transition metal center were developed during the past decades. Herein, a new CO activation method, in which the CO was converted to the active acyl-like metalloradical, [(por)Rh(CO)]? (por = porphyrin), was reported. The reactivity of [(por)Rh(CO)]? and other rhodium porphyrin compounds, such as (por)RhCHO and (por)RhC(O)NHnPr, and corresponding mechanism studies were conducted experimentally and computationally and inspired the design of a new conversion system featuring 100% atom economy that promotes carbonylation of amines to formamides using porphyrin rhodium(II) metalloradical. Following this radical based pathway, the carbonylations of a series of primary and secondary aliphatic amines were examined, and turnover numbers up to 224 were obtained.
- Zhang, Jiajing,Zhang, Wentao,Xu, Minghui,Zhang, Yang,Fu, Xuefeng,Fang, Huayi
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supporting information
p. 6656 - 6660
(2018/05/24)
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- Low-Temperature Reductive Aminolysis of Carbohydrates to Diamines and Aminoalcohols by Heterogeneous Catalysis
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Short amines, such as ethanolamines and ethylenediamines, are important compounds in today's bulk and fine chemicals industry. Unfortunately, current industrial manufacture of these chemicals relies on fossil resources and requires rigorous safety measures when handling explosive or toxic intermediates. Inspired by the elegant working mechanism of aldolase enzymes, a novel heterogeneously catalyzed process—reductive aminolysis—was developed for the efficient production of short amines from carbohydrates at low temperature. High-value bio-based amines containing a bio-derived C2 carbon backbone were synthesized in one step with yields up to 87 C%, in the absence of a solvent and at a temperature below 405 K. A wide variety of available primary and secondary alkyl- and alkanolamines can be reacted with the carbohydrate to form the corresponding C2-diamine. The presented reductive aminolysis is therefore a promising strategy for sustainable synthesis of short, acyclic, bio-based amines.
- Pelckmans, Michiel,Vermandel, Walter,Van Waes, Frederik,Moonen, Kristof,Sels, Bert F.
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supporting information
p. 14540 - 14544
(2017/10/23)
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- Synthesis of N,N-dimethylformamide from carbon dioxide in aqueous biphasic solvent systems
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This paper presents the homogeneous catalyzed hydrogenation of carbon dioxide to N,N-dimethylformamide (DMF) with an in-situ generated ruthenium catalyst based on RuCl3?×?H2O and the phosphine ligand 2,2′-bis(diphenylphosphinomethyl)-1,1′-biphenyl (BISBI). Investigations showed that the complex formation of an active species requires the presence of an amine. The catalyst was recycled by immobilization in a nonpolar alcoholic solvent while the formed product was extracted in-situ into the aqueous phase. The self-assembling reaction system showed stability for 10 recycling runs without a significant loss of activity resulting in an average yield of 31% DMF at 40?bar and 140?°C without the occurrence of any byproducts. Furthermore, a combination of the developed reaction system with ternary amines enables the application of wash amine solutions as carbon dioxide carrier.
- Kuhlmann,Schmitz,Ha?mann,Prüllage,Behr
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- Catalytic Formylation of Primary and Secondary Amines with CO2 and H2 Using Abundant-Metal Catalysts
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Catalytic hydrogenation of CO2 is an efficient and selective way to prepare formic acid derivatives, but most of the highly active catalysts used for this purpose require precious metals. In this study, in situ abundant-metal complexes have been evaluated as potential catalysts for CO2 hydrogenation to prepare formamides, including N-formylmorpholine, 2-ethylhexylformamide, and dimethylformamide, from the corresponding amines. From these initial screening results, the most active catalysts for these reactions were found to be MX2/dmpe in situ catalysts (M = Fe(II), Ni(II); X = Cl-, CH3CO2-, acac- dmpe = 1,2-bis(dimethylphosphino)ethane) in DMSO. The optimal reaction conditions were found to be 100-135 °C and a total pressure of 100 bar. Morpholine was formylated with a TON value of up to 18000, which is the highest TON for the hydrogenation of CO2 to formamides using any abundant-metal-phosphine complex. With an appropriate selection of catalyst and reaction conditions, >90-98% conversion of amine to formamide could be achieved.
- Affan, Mohammad A.,Jessop, Philip G.
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supporting information
p. 7301 - 7305
(2017/06/23)
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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
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supporting information
p. 9502 - 9504
(2017/09/01)
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- Selective N-Formylation of Amines with H2 and CO2 Catalyzed by Cobalt Pincer Complexes
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N-formylation of amines utilizing CO2 in the presence of reducing agents constitute an important methodology in organic synthesis. Presented herein is a selective N-formylation of amines with CO2 and H2 catalyzed by complexes of Earth-abundant cobalt. A wide range of amines were converted to their corresponding formamides under CO2 and H2 pressure, catalyzed by Co-PNP pincer complex, generating water as the sole byproduct.
- Daw, Prosenjit,Chakraborty, Subrata,Leitus, Gregory,Diskin-Posner, Yael,Ben-David, Yehoshoa,Milstein, David
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p. 2500 - 2504
(2017/05/31)
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- Method for preparing methallyl alcohol and amide simultaneously
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A method for preparing methallyl alcohol and amide simultaneously is characterized in that methylallyl carboxylate taken as a raw material and an amine compound taken as an ammonolysis agent react under the action of a catalyst to produce methallyl alcohol and an amide compound. The methylallyl carboxylate and the amine compound taken as the ammonolysis agent are firstly adopted, and the methallyl alcohol and the amide compound are obtained under the action of the catalyst. The reaction process is a bulk reaction, no solvents are added, almost no wastewater or salt are produced, and byproduct methyl allyl ether is not produced; the defect that a large number of wastewater is produced through hydrolysis is overcome due to adoption of ammonolysis, the methallyl alcohol and the amide compound are coproduced directly by use of ammonoysis, coupling production is realized, and the cost is reduced.
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Paragraph 0028-0029
(2017/11/29)
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- Aqueous Biphasic Systems for the Synthesis of Formates by Catalytic CO2 Hydrogenation: Integrated Reaction and Catalyst Separation for CO2-Scrubbing Solutions
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Aqueous biphasic systems were investigated for the production of formate–amine adducts by metal-catalyzed CO2 hydrogenation, including typical scrubbing solutions as feedstocks. Different hydrophobic organic solvents and ionic liquids could be employed as the stationary phase for cis-[Ru(dppm)2Cl2] (dppm=bis-diphenylphosphinomethane) as prototypical catalyst without any modification or tagging of the complex. The amines were found to partition between the two phases depending on their structure, whereas the formate–amine adducts were nearly quantitatively extracted into the aqueous phase, providing a favorable phase behavior for the envisaged integrated reaction/separation sequence. The solvent pair of methyl isobutyl carbinol (MIBC) and water led to the most practical and productive system and repeated use of the catalyst phase was demonstrated. The highest single batch activity with a TOFav of approximately 35 000 h?1 and an initial TOF of approximately 180 000 h?1 was achieved in the presence of NEt3. Owing to higher stability, the highest productivities were obtained with methyl diethanolamine (Aminosol CST 115) and monoethanolamine (MEA), which are used in commercial scale CO2-scrubbing processes. Saturated aqueous solutions (CO2 overpressure 5–10 bar) of MEA could be converted into the corresponding formate adducts with average turnover frequencies up to 14×103 h?1 with an overall yield of 70 % based on the amine, corresponding to a total turnover number of 150 000 over eleven recycling experiments. This opens the possibility for integrated approaches to carbon capture and utilization.
- Scott, Martin,Blas Molinos, Beatriz,Westhues, Christian,Franciò, Giancarlo,Leitner, Walter
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p. 1085 - 1093
(2017/03/29)
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- A dimethylamine carbonylation preparation N, N - dimethyl formamide
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The present invention relates to a method for preparing N, N-dimethylformamide (DMF) through dimethylamine carbonylation, wherein dimethylamine and carbon monoxide (CO) are adopted as reactants, and a CO inserted carbonylation reaction is performed under the catalysis effect to prepare DMF. The reaction conditions are that: the reaction is performed in a fixed bed reactor, the reaction pressure is 1.0-8.0 MPa, the reaction temperature is 150-250 DEG C, and the feeding space velocity of dimethylamine is 50-800 h. The method is characterized in that (1) the reaction has 100% atom economy, and does not produce the by-product, and (2) the noble metal supported metal oxide or molecular sieve is adopted as the catalyst, the catalyst preparation is simple, the reaction is efficiently catalyzed, and the DMF yield can achieve more than or equal to 80%.
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Paragraph 0012; 0013; 0014; 0015; 0016; 0017; 0018-0033
(2017/06/22)
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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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- Selective Synthesis of Trimethylamine by Catalytic N-Methylation of Ammonia and Ammonium Chloride by utilizing Carbon Dioxide and Molecular Hydrogen
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The synthesis of trimethylamine (TMA) through a multicomponent combination of ammonia with carbon dioxide and molecular hydrogen by using a homogeneous ruthenium catalyst was explored. The use of [Ru(triphos)(tmm)] [triphos: 1,1,1-tris(diphenylphosphinomethyl)ethane, tmm: trimethylene methane] together with aluminum trifluoromethanesulfonate as a co-catalyst resulted in high ammonia conversion and excellent selectivity for TMA in organic solvents. Aqueous solutions of ammonium chloride were methylated almost quantitatively to the corresponding hydrochloride salt (i.e., TMA·HCl) in a biphasic solvent system by using the same Ru complex without the need for any co-catalyst.
- Beydoun, Kassem,Thenert, Katharina,Streng, Emilia S.,Brosinski, Sandra,Leitner, Walter,Klankermayer, Jürgen
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p. 135 - 138
(2016/01/26)
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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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- 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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- N-heterocyclic olefins as robust organocatalyst for the chemical conversion of carbon dioxide to value-added chemicals
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In this report, the activity of N-heterocyclic olefins (NHOs) as a newly emerging class of organocatalyst is investigated for the chemical fixation of carbon dioxide through reactions with aziridines to form oxazolidinones and the N-formylation of amines with polymethylhydrosiloxane (PMHS) or 9-borabicy-clo[3.3.1]nonane (9-BBN) as the reducing agent under mild conditions. The exocyclic carbon atoms of NHOs are highly nucleophilic owing to the electron-donating ability of the two nitrogen atoms. This high nucleophilicity of the NHOs activates CO2 molecules to form zwitterionic NHO–carboxylate (NHO– CO2) adducts, which are active in formylation reactions as well as the carboxylation of aziridines to oxazolidinones.
- Saptal, Vitthal B.,Bhanage, Bhalchandra M.
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p. 1980 - 1985
(2017/07/13)
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