693-06-1Relevant academic research and scientific papers
Towards environmentally benign capture and conversion: Heterogeneous metal catalyzed CO2 hydrogenation in CO2 capture solvents
Kothandaraman, Jotheeswari,Heldebrant, David J.
, p. 828 - 834 (2020)
The transformation of captured CO2 into value-added chemicals to mitigate increasing CO2 concentration in the atmosphere has gained significant attention recently. Though carbon capture and storage (CCS) is already being practiced in a few places, it suffers from energy-intensive CO2 desorption and compression steps involved, which can be avoided in the carbon capture and utilization (CCU) approach. Herein, a selection of carbon capture solvents were screened to assess the reactivity of condensed-phase heterogeneous metal catalyzed hydrogenation of CO2. Among the catalysts screened, the Cu/ZnO/Al2O3 catalyst was active for the one-pot CO2 capture and conversion process to methanol using post and pre-combustion carbon capture solvents comprised of various amines and alcohols. Our findings indicate that formamides are less-reactive under our conditions in comparison with formate ester intermediates and a combination of 1° alcohols and amines gives the highest methanol yield. Screening volatile organic compound (VOC)-free alcohols and amines led us to an environmentally benign system of bio-derived and biodegradable chitosan and polyethylene glycol (PEG200), which provide a moderate concentration of methanol (139.5 mmol L-1) with the facile separation of volatile products (water and methanol). The chitosan/PEG200 system was recycled three times, ultimately providing a promising VOC-free, biodegradable, bio-derived and recyclable CO2 capture and conversion pathway.
Catalytic N-diphosphonomethylation of amino alkanols and bisamino alkanes using tris(trimethylsilyl) phosphite as a convenient synthon
Prishchenko, Andrey A.,Alekseyev, Roman S.,Novikova, Olga P.,Livantsov, Mikhail V.,Livantsova, Ludmila I.,Petrosyan, Valery S.
supporting information, (2021/11/09)
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.
Highly Efficient and Selective N-Formylation of Amines with CO2 and H2 Catalyzed by Porous Organometallic Polymers
Shen, Yajing,Zheng, Qingshu,Chen, Zhe-Ning,Wen, Daheng,Clark, James H.,Xu, Xin,Tu, Tao
supporting information, p. 4125 - 4132 (2021/01/12)
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.
Facile access to: N-formyl imide as an N-formylating agent for the direct synthesis of N-formamides, benzimidazoles and quinazolinones
Huang, Hsin-Yi,Liang, Chien-Fu,Lin, Xiu-Yi,Yen, Shih-Yao
supporting information, p. 5726 - 5733 (2020/08/21)
N-Formamide synthesis using N-formyl imide with primary and secondary amines with catalytic amounts of p-toluenesulfonic acid monohydrate (TsOH·H2O) is described. This reaction is performed in water without the use of surfactants. Moreover, N-formyl imide is efficiently synthesized using acylamidines with TsOH·H2O in water. In addition, N-formyl imide was successfully used as a carbonyl source in the synthesis of benzimidazole and quinazolinone derivatives. Notable features of N-formylation of amines by using N-formyl imide include operational simplicity, oxidant- A nd metal-free conditions, structurally diverse products, and easy applicability to gram-scale operation.
METHOD OF CARBON MONOXIDE FIXATION AND METHOD OF AMINE FORMYLATION
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Paragraph 0078; 0081-0085; 0096-0098, (2021/02/19)
The present invention relates to a method for fixing carbon monoxide in a metal-free condition and a method for formating amine using the same.
Preparation method of N-vinyl alkylamide
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Paragraph 0065-0066; 0071-0072, (2020/12/29)
The invention relates to the technical field of vinyl compound production, in particular to a preparation method of Nvinyl alkyl amide. The preparation method comprises the following steps: A) under the action of a composite basic catalyst, reacting acetaldehyde with alkylamide to obtain Nhydroxyethyl alkylamide, and carrying out esterification reaction on the obtained Nhydroxyethyl alkylamide andacid anhydride to obtain an ester compound; wherein the composite basic catalyst comprises an inorganic base and an amine compound; and B) carrying out medium-temperature cracking on the ester compound, and carrying out vacuum distillation to obtain the Nvinyl alkylamide. Research finds that inorganic base and amine compounds are adopted as catalysts at the same time, so that the dosage of a basic catalyst required by reaction of Nhydroxyethyl alkylamide and anhydride can be remarkably reduced, the temperature required by subsequent cracking reaction is reduced, a reaction system tends to bemilder, and the reaction yield is improved. The yield and the purity of a reaction product can be remarkably improved while the energy consumption is reduced.
PHOTO-REDOX TITANIUM CONTAINING ORGANIC FRAMEWORKS AND METHODS OF MAKING AND USE THEREOF
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Paragraph 0165; 0172-0173, (2020/07/07)
Disclosed herein are metal-organic frameworks and methods of making and use thereof.
Metal-free Carbon Monoxide (CO) Capture and Utilization: Formylation of Amines
Noh, Hyeong-Wan,An, Youngjoon,Lee, Seulchan,Jung, Jaehoon,Son, Seung Uk,Jang, Hye-Young
supporting information, (2019/04/26)
The capture and utilization of CO by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were performed in the absence of transition-metal complexes. The reaction of TBD with CO afforded TBD-CO adducts, which were converted to formylated TBD (TBD-CHO). TBD-CO adducts may include an interaction of CO with positively charged species based on NMR and IR analysis. In the presence of amines, CO was transferred from TBD-CO to amines, producing formylated amines with good yields. The reaction mechanism involving TBD-CO adducts is presented based on theoretical calculations. (Figure presented.).
Organocatalytic Decarboxylation of Amino Acids as a Route to Bio-based Amines and Amides
Claes, Laurens,Janssen, Michiel,De Vos, Dirk E.
, p. 4297 - 4306 (2019/08/26)
Amino acids obtained by fermentation or recovered from protein waste hydrolysates represent an excellent renewable resource for the production of bio-based chemicals. In an attempt to recycle both carbon and nitrogen, we report here on a chemocatalytic, metal-free approach for decarboxylation of amino acids, thereby providing a direct access to primary amines. In the presence of a carbonyl compound the amino acid is temporarily trapped into a Schiff base, from which the elimination of CO2 may proceed more easily. After evaluating different types of aldehydes and ketones on their activity at low catalyst loadings (≤5 mol%), isophorone was identified as powerful organocatalyst under mild conditions. After optimisation many amino acids with a neutral side chain were converted in 28–99 % yield in 2-propanol at 150 °C. When the reaction is performed in DMF, the amine is susceptible to N-formylation. This consecutive reaction is catalysed by the acidity of the amino acid reactant itself. In this way, many amino acids were efficiently transformed to the corresponding formamides in a one-pot catalytic system.
N-formylation of amine using graphene oxide as a sole recyclable metal-free carbocatalyst
Ma, Juan,Zhang, Jingyu,Zhou, Xiao,Wang, Jiawei,Gong, Hang
, p. 2851 - 2860 (2018/10/31)
Abstract: Graphene oxide (GO), an inexpensive, environment-friendly, and metal-free carbocatalyst, used for the N-formylation of amines is developed. In this reaction, GO shows good activity, selectivity, and recyclability. This strategy has an array of advantages, such as being metal free, without additive, wide-scope protocol, scalable with a low catalyst loading of 3?wt%, use of readily available and recyclable carbocatalyst, and DMF as a readily available formyl source. Furthermore, this strategy provides an avenue for the convenient hydroformylation of various amines. Graphical abstract: [Figure not available: see fulltext.].
