497-25-6Relevant articles and documents
Ethylene carbonate production by cyclocondensation of ethylene glycol and urea in the presence of metal oxides and metal acetylacetonates
Lyadov,Kochubeev,Markova,Khadzhiev
, p. 852 - 856 (2016)
A promising method for the production of ethylene carbonate is the cyclocondensation of ethylene glycol and urea in the presence of a catalyst. In this study, the catalytic effect of oxides and acetylacetonates of various metals on the occurrence of this reaction has been examined. It has been shown that cobalt acetylacetonate is the most effective catalyst. The effect of reaction conditions (temperature, pressure, contact time, and catalyst concentration) on the main parameters of catalytic conversion has been studied.
Ni@Pd nanoparticles supported on ionic liquid-functionalized KCC-1 as robust and recyclable nanocatalysts for cycloaddition of propargylic amines and CO2
Sadeghzadeh, Seyed Mohsen,Zhiani, Rahele,Emrani, Shokufe
, (2018)
Novel heterogeneous catalyst systems comprised of a fibrous nanosilica-supported nano-Ni@Pd-based ionic liquid (KCC-1/IL/Ni@Pd) are described for the cyclization of propargylic amines with CO2 to provide 2-oxazolidinones. KCC-1 with high surface area was functionalized with IL acting as a robust anchor so that the nano-Ni@Pd was well dispersed on the fibres of the KCC-1 microspheres, without aggregation. Because of the amplification effect of IL, high loading capacities of the nanocatalysts were achieved. The reported synthesis includes several advantages like solvent-free conditions, operational simplicity, short reaction times, environmentally benign reaction conditions, cost effectiveness, high atom economy and excellent yields, making it a genuinely green protocol.
1H and 2H NMR spectroscopic studies on the metabolism and biochemical effects of 2-bromoethanamine in the rat
Holmes,Caddick,Lindon,Wilson,Kryvawych,Nicholson
, p. 1349 - 1359 (1995)
Male Fischer 344 rats were dosed with 2-bromoethanamine hydrobromide (BEA, N = 6) or [1,1,2,2,-2H4]-bromoethanamine hydrobromide (BEA-d4, N = 6) at 150 mg/kg i.p. and urine was collected -24 to 0 hr pre-dose and at 0-2 hr, 2-4 hr, 4-8 hr and 8-12 hr post-dose (p.d.). Urine samples were analysed directly using 500 and 600 MHz 1H NMR and 92.1 MHz 2H NMR spectroscopy. The major observed effect of BEA treatment was the induction of transient elevations in urinary glutaric acid (GTA) and adipic acid (ADA) excretion lasting up to 24 hr p.d. Most of the GTA was excreted in the 0-8 hr p.d. with maximal rates of 100-120 μM/hr for each rat occurring between 4 and 8 hr p.d. in animals treated with BEA or BEA-d4. GTA and ADA were shown to be of endogenous origin as there was no detectable incorporation of the 2H label into either compound following treatment of rats with BEA-d4. Following BEA-treatment there was an initial decrease in the levels of urinary citrate, succinate, 2-oxoglutarate and trimethylamine-N-oxide. A subsequent recovery of citrate and succinate was noted following the onset of medullary nephropathy. The abnormal urinary metabolite profiles were similar to that observed in the urine of humans with glutaric aciduria type II (an inborn error of metabolism) caused by a lack of mitochondrial fatty acyl coenzyme A dehydrogenases indicating that BEA or its metabolites have similar metabolic consequences. The BEA metabolite aziridine was detected by 1H and 2H NMR spectroscopy of the urine 8 hr p.d. together with BEA itself and two novel metabolites 2-oxazolidone (OX) and 5-hydroxy-2-oxazolidone (HOX). The formation of OX requires the reaction of BEA with endogenous bicarbonate followed by a cyclisation reaction eliminating HBr. Dosing rats with authentic OX resulted in the excretion of HOX but did not cause glutaric or adipic aciduria indicating that either aziridine or BEA itself was responsible for the presumed defect in mitochondrial metabolism.
1H NMR Spectroscopic Studies on the Reactions of Haloalkylamines with Bicarbonate Ions: Formation of N-Carbamates and 2-Oxazolidones in Cell Culture Media and Blood Plasma
Anthony, Maria L.,Holmes, Elaine,McDowell, Peter C. R.,Gray, Tim J. B.,Blackmore, Melanie,Nicholson, Jeremy K.
, p. 1046 - 1053 (1995)
1H NMR spectroscopic methods have been applied to compare the in vitro reactivity of the renal papillary nephrotoxin 2-bromoethanamine (BEA) with those of selected halide-substituted nephrotoxic analogues, 2-chloroethanamine (CEA), 2-fluoroethanamine (FEA), and 1-phenyl-2-iodoethanamine (PIEA). The primary 1H NMR-detectable transformation during a 24 h incubation of confluent Madin Darby canine kidney (MDCK) cells with BEA, CEA, and FEA (at concentrations up to the IC50 determined by neutral red uptake) was the appearance in cell culture media of 2-oxazolidone (OX). Additional novel signals assigned as FEA carbamate (N-carbanoyl-2-fluoroethanamine) were observed in media collected following incubation of cells with FEA. We propose that N-carbamate intermediates are formed from the spontaneous reaction of these haloalkylamines with HCO3--buffered growth media and that OX is formed from the carbamate via elimination of the hydrogen halide. Further 1H NMR experiments, conducted for up to 8 h at 25 deg C on 5 mM solutions of BEA, CEA, and FEA in (2)H2O containing a 20-fold excess of HCO3- at pH 7.6, demonstrated a time-dependent decrease in the concentration of the free haloalkylamines accompanied by the production of N-carbamate intermediates and OX. Under these pseudo-first-order reaction conditions, the formation of OX from BEA was complete within approximately 6 h. In similar reaction conditions OX formation from CEA (24 h after initiation) had reached 54 percent of its final equilibrium concentration. Equivalent experiments demonstrated that PIEA was almost completely converted to 4-phenyl-2-oxazolidinone (PHOX) within 2 h. These observations reveal the strong disposition of this series of haloalkylamines toward reaction with HCO3- and indicate that the compounds in this family may exist only transiently as free amines in vivo, where there will virtually always be excess HCO3-. The physiological relevance of the in vitro findings is further indicated by the NMR-detectable conversion of BEA to OX and also an alkylating aziridine (AZ) moiety in rat plasma containing BEA. The ability to form carbamoylated species and OX (or PHOX) may mediate the toxicity of this series of haloalkylamines and hence is potentially of considerable significance.
Gold (III) phosphorus complex immobilized on fibrous nano-silica as a catalyst for the cyclization of propargylic amines with CO2
Sadeghzadeh, Seyed Mohsen
, p. 216 - 223 (2016)
In this study, The HPG@KCC-1 NP was prepared through the ringopening polymerization of glycidol on the surface of KCC-1 to form HPG@KCC-1 and then HPG@KCC-1 NPs were functionalized using chlorodiphenylphosphine and phosphine-functionalized nanoparticles (HPG@KCC-1/PPh2) as a recyclable phosphorus ligand was obtained. Also, gold (III) complex of HPG@KCC-1/PPh2 ligand (HPG@KCC-1/PPh2/Au) was prepared which used for the cyclization of propargylic amines with CO2 to provide 2-oxazolidinones. High catalytic activity and ease of recovery from the reaction mixture using filtration, and several reuse times without significant losses in performance are additional eco-friendly attributes of this catalytic system.
SBA-15 Supported Dendritic ILs as a Green Catalysts for Synthesis of 2-Imidazolidinone from Ethylenediamine and Carbon Dioxide
Liu, Jinghan,Ma, Jianjun,Miao, Penghua,Min, Qingwang,Qi, Meijuan,Shamsa, Farzaneh
, (2021/07/26)
In this work, a simple and facile approach is conducted for preparing many new SBA-15 supported dendritic imidazolium ILs heterogeneous catalysts SBA-15/IL(1–3) having high ionic density from SBA-15. SBA-15/IL(3) as a green heterogeneous catalyst can be used for synthesis of 2-imidazolidinone from ethylenediamine and carbon dioxide and considering solvent-free condition. SBA-15/IL(3) showed to have the highest catalytic activity besides a positive dendritic influence on the yields of the synthesis of 2-imidazolidinone in the presence of CO2 is seen because of existing the high-density peripheral zwitterionic ionic liquid functional groups on the biobased SBA-15/IL(3) catalyst surfaces. Graphical Abstract: [Figure not available: see fulltext.]
PROCESS SULFONATION OF AMINOETHYLENE SULFONIC ESTER WITH CARBON DIOXIDE ADDITION TO PRODUCE TAURINE
-
Paragraph 47-49, (2021/10/02)
A process for producing taurine, comprising mixing aminoethanol sulfate ester (AES) and a carbon dioxide, thus producing a reaction mixture, and heating the reaction mixture in the presence of a sulfite or a bisulfite, or combination thereof, such that taurine is formed.
Highly synergistic effect of ionic liquids and Zn-based catalysts for synthesis of cyclic carbonates from urea and diols
Cheng, Weiguo,Deng, Lili,Dong, Li,He, Hongyan,Li, Zengxi,Qian, Wei,Shi, Zijie,Su, Qian,Sun, Wenzhong
, (2020/08/06)
The development of stable and efficient catalysts is an attractive topic for green chemistry reactions under mild reaction conditions. In order to improve solvent-free synthesis of cyclic carbonates from urea and diols, a binary catalyst systems of Zn-based and different ionic liquids (ILs) were developed and examined in this study. The yield of ethylene carbonate (EC) could reach to 92.2% in the presence of C16mimCl/ZnCl2 catalyst. Through exploring the structure-activity relationships of cation and anion, it was confirmed that a synergistic effect of cation and anion of catalyst had important influences on urea alcoholysis. Additionally, the controlling step of EC synthesis reaction involving the elimination of an ammonia molecule from intermediates had been revealed by in situ FT-IR. This could afford a guided insight for synthesizing cyclic carbonates with high yield. Furthermore, a possible mechanism for the catalytic process was proposed based on DFT and the experimental results via FT-IR, 1H-NMR and 13C NMR analysis, which revealed that not only a probable synergistic effects of cation-anion matters, but also C(2)-H of ILs and Zn2+ played a key role in accelerating the reaction of urea alcoholysis. This catalytic mechanism study is to provide a preliminary basis to develop novel catalysts for cyclic carbonates from urea and diols through a green synthetic pathway.
Rational design of bifunctional catalyst from KF and ZnO combination on alumina for cyclic urea synthesis from CO2 and diamine
John, Crowny,Kulal, Nagendra,Shanbhag, Ganapati V.
, (2020/04/22)
This study is mainly focused on the design of stable, active and selective catalyst for direct synthesis of 2-imidazolidinone (cyclic urea) from ethylenediamine and CO2. Based on the rationale for the catalyst properties needed for this reaction, KF, ZnO and Al2O3 combination was selected to design the catalyst. ZnO/KF/Al2O3 catalyst was prepared by stepwise wet-impregnation followed by the removal of physisorbed KF from the surface. High product yield could be achieved by tuning acid-base sites by varying the composition and calcination temperature. The catalysts were characterized by various techniques like XRD, N2-sorption, NH3-TPD, CO2-TPD, TEM, XPS and FT-IR measurements. It is shown that acidic and basic properties of the solvent can influence the activity and product selectivity for this reaction. Under optimized condition; 180 °C, 10 bar and 10 wt.% catalyst in batch mode, 96.3 % conversion and 89.6 % selectivity towards the 2-imidazolidinone were achieved.
Concise and Additive-Free Click Reactions between Amines and CF3SO3CF3
Song, Hai-Xia,Han, Zhou-Zhou,Zhang, Cheng-Pan
supporting information, p. 10907 - 10912 (2019/08/02)
Trifluoromethyl trifluoromethanesulfonate has proved to be an excellent reservoir of difluorophosgene and a promising click ligation for amines in the preparation of urea derivatives, heterocycles, and carbamoyl fluorides under metal- and additive-free conditions. The reactions are rapid, efficient, selective, and versatile, and can be performed in benign solvents, giving products in excellent yields with minimal efforts for purification. The characteristics of the reactions meet the requirements of a click reaction. The use of trifluoromethyl trifluoromethanesulfonate as a click reagent is advantageous over other “CO” sources (e.g., TsOCF3, PhCO2CF3, CsOCF3, AgOCF3, and triphosgene) because this reagent is readily accessible; easy to scale up; and highly reactive, even under metal- and additive-free conditions. It is anticipated that CF3SO3CF3 will be increasingly as important as SO2F2 as a click agent in future drug design and development.
