- Ethylene carbonate production by cyclocondensation of ethylene glycol and urea in the presence of metal oxides and metal acetylacetonates
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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.
- Lyadov,Kochubeev,Markova,Khadzhiev
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- Ni@Pd nanoparticles supported on ionic liquid-functionalized KCC-1 as robust and recyclable nanocatalysts for cycloaddition of propargylic amines and CO2
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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.
- Sadeghzadeh, Seyed Mohsen,Zhiani, Rahele,Emrani, Shokufe
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- 1H and 2H NMR spectroscopic studies on the metabolism and biochemical effects of 2-bromoethanamine in the rat
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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.
- Holmes,Caddick,Lindon,Wilson,Kryvawych,Nicholson
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- 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
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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.
- Anthony, Maria L.,Holmes, Elaine,McDowell, Peter C. R.,Gray, Tim J. B.,Blackmore, Melanie,Nicholson, Jeremy K.
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- Gold (III) phosphorus complex immobilized on fibrous nano-silica as a catalyst for the cyclization of propargylic amines with CO2
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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.
- Sadeghzadeh, Seyed Mohsen
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- SBA-15 Supported Dendritic ILs as a Green Catalysts for Synthesis of 2-Imidazolidinone from Ethylenediamine and Carbon Dioxide
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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.]
- Liu, Jinghan,Ma, Jianjun,Miao, Penghua,Min, Qingwang,Qi, Meijuan,Shamsa, Farzaneh
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- PROCESS SULFONATION OF AMINOETHYLENE SULFONIC ESTER WITH CARBON DIOXIDE ADDITION TO PRODUCE TAURINE
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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.
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Paragraph 47-49
(2021/10/02)
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- Highly synergistic effect of ionic liquids and Zn-based catalysts for synthesis of cyclic carbonates from urea and diols
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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.
- Cheng, Weiguo,Deng, Lili,Dong, Li,He, Hongyan,Li, Zengxi,Qian, Wei,Shi, Zijie,Su, Qian,Sun, Wenzhong
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- Rational design of bifunctional catalyst from KF and ZnO combination on alumina for cyclic urea synthesis from CO2 and diamine
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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.
- John, Crowny,Kulal, Nagendra,Shanbhag, Ganapati V.
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- β-Amino Phosphine Mn Catalysts for 1,4-Transfer Hydrogenation of Chalcones and Allylic Alcohol Isomerization
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Mn complexes with amino acid derived PN ligands were used in the catalytic transfer hydrogenation (TH) of ketone and chalcone substrates in 2-propanol with mild heating. Moreover, chalcones are reduced selectively to the saturated ketone at short times and can be fully converted to the alcohol when reactions are prolonged. The mechanism of chalcone reduction was briefly considered. Allylic alcohols are not reactive in 2-propanol, but quantitative isomerization occurs in toluene. Thus, we suspect that the allylic alcohols are dehydrogenated and the resulting ketone is formed through a direct 1,4-hydrogenation of the chalcone. Finally, several other related ligands that have been used in Mn-based TH reactions were explored to test the viability of ligand design in favoring chemoselectivity. The β-amino phosphine ligands proved most effective in this regard.
- Vigneswaran, Vipulan,MacMillan, Samantha N.,Lacy, David C.
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p. 4387 - 4391
(2019/11/14)
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- Concise and Additive-Free Click Reactions between Amines and CF3SO3CF3
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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.
- Song, Hai-Xia,Han, Zhou-Zhou,Zhang, Cheng-Pan
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supporting information
p. 10907 - 10912
(2019/08/02)
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- Visible-Light-Mediated Liberation and In Situ Conversion of Fluorophosgene
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The first example for the photocatalytic generation of a highly electrophilic intermediate that is not based on radical reactivity is reported. The single-electron reduction of bench-stable and commercially available 4-(trifluoromethoxy)benzonitrile by an organic photosensitizer leads to its fragmentation into fluorophosgene and benzonitrile. The in situ generated fluorophosgene was used for the preparation of carbonates, carbamates, and urea derivatives in moderate to excellent yields via an intramolecular cyclization reaction. Transient spectroscopic investigations suggest the formation of a catalyst charge-transfer complex-dimer as the catalytic active species. Fluorophosgene as a highly reactive intermediate, was indirectly detected via its next downstream carbonyl fluoride intermediate by NMR. Furthermore, detailed NMR analyses provided a comprehensive reaction mechanism including a water dependent off-cycle equilibrium.
- Petzold, Daniel,Nitschke, Philipp,Brandl, Fabian,Scheidler, Veronica,Dick, Bernhard,Gschwind, Ruth M.,K?nig, Burkhard
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supporting information
p. 361 - 366
(2018/11/23)
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- Synthesis, spectroscopic characterization, and in vitro antibacterial evaluation of novel functionalized sulfamidocarbonyloxyphosphonates
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Several new sulfamidocarbonyloxyphosphonates were prepared in two steps, namely carbamoylation and sulfamoylation, by using chlorosulfonyl isocyanate (CSI), α-hydroxyphosphonates, and various amino derivatives and related (primary or secondary amines, β-amino esters, and oxazolidin-2-ones). All structures were confirmed by 1H, 13C, and 31P NMR spectroscopy, IR spectroscopy, and mass spectroscopy, as well as elemental analysis. Eight compounds were evaluated for their in vitro antibacterial activity against four reference bacteria including Gram-positive Staphylococcus aureus (ATCC 25923), and Gram-negative Escherichia coli (ATCC 25922), Klebsiella pneumonia (ATCC 700603), Pseudomonas aeruginosa (ATCC 27853), in addition to three clinical strains of each studied bacterial species. Compounds 1a–7a and 1b showed significant antibacterial activity compared to sulfamethoxazole/trimethoprim, the reference drug used in this study.
- Bouzina, Abdeslem,Bechlem, Khaoula,Berredjem, Hajira,Belhani, Billel,Becheker, Imène,Lebreton, Jacques,Le Borgne, Marc,Bouaziz, Zouhair,Marminon, Christelle,Berredjem, Malika
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- Synthesis and kinetics of disassembly for silyl-containing ethoxycarbonyls using fluoride ions
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In this study, a series of silyl-containing ethoxycarbonates and ethoxycarbamates on electron poor anilines and phenols were synthesized and their kinetics of disassembly determined in real-time upon exposure to fluoride ion sources at room temperature. The results provide a greater understanding of stability and kinetics for silyl-containing protecting groups that eliminate volatile molecules upon removal, which will allow for simplification of orthogonal protection in complex organic molecules.
- Camerino, Eugene,Daniels, Grant C.,Wynne, James H.,Iezzi, Erick B.
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p. 1884 - 1888
(2018/02/06)
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- Trimethylphosphine-Promoted Alcoholysis of α,β-Unsaturated Imides and α,β-Unsaturated Esters
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α,β-Unsaturated imides and α,β-unsaturated esters were found to undergo alcoholysis in the presence of trimethylphosphine. The reaction is initiated by nucleophilic addition of trimethylphosphine to the double bond of the α,β-unsaturated carbonyl compound. Saturated imides also undergo the alcoholysis in the presence of the corresponding α,β-unsaturated imide.
- Sato, Haruka,Hosokawa, Seijiro
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supporting information
p. 1343 - 1349
(2018/01/27)
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- KCC-1 Supported Ruthenium-Salen-Bridged Ionic Networks as a Reusable Catalyst for the Cycloaddition of Propargylic Amines and CO2
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Abstract: This study investigates the potential application of an efficient, easily recoverable and reusable KCC-1 nanoparticle-supported Salen/Ru(II) catalyst in the synthesis of 2-oxazolidinones from CO2, and propargylic amines. The KCC-1/Salen/Ru(II) NPs were thoroughly characterized by using TEM, SEM, TGA, FT-IR, ICP-MS, and BET. This observation was exploited in the direct and selective chemical fixation of CO2, affording high degrees of CO2 capture and conversion. The recycled catalyst has been analyzed by ICP-MS showing only minor changes in the morphology after the reaction, thus confirming the robustness of the catalyst.
- Saadati, Seyed Mahdi,Sadeghzadeh, Seyed Mohsen
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p. 1692 - 1702
(2018/04/02)
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- The ethylenically unsaturated group-containing isocyanate compound
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PROBLEM TO BE SOLVED: To provide a production method capable of obtaining an ethylenically unsaturated group-containing isocyanate compound with high yield, which is excellent in safety to human bodies or environments without using phosgene and in which the production processes and production facilities are simplified.SOLUTION: There is a method for producing an ethylenically unsaturated group-containing isocyanate compound which produces a compound having an ethylenically unsaturated bond and an isocyanate group in the molecule using an amino alcohol as a raw material, wherein the method has a step of producing a cyclic compound having a urethane bond in the molecule as an intermediate.
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Paragraph 0138
(2019/01/04)
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- Converting urea into high value-added 2-oxazolidinones under solvent-free conditions
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Zn-modified mesoporous Mg-Al nanoplates oxides were prepared by co-precipitation and further characterized and used in the synthesis of 2-oxazolidinones from urea and epoxides under solvent-free conditions. The characterization results suggested that Zn1.1Mg2.0AlO4.6, which featured more accessible active medium basic sites, were favorable for obtaining superior catalytic activity. This synthetic process is mild, convenient, simple and gives good yields up to 80%.
- Wang, Peixue,Li, Qinghe,Liu, Shimin,Deng, Youquan
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p. 94382 - 94386
(2016/10/21)
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- Imidazolium and Potassium Hydrogen Carbonate Salts as Ecofriendly Organocatalysts for Oxazolidinone Synthesis
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Although oxazolidinones are valuable intermediate compounds for industrial applications, no synthetic method is suitable for their production on a large scale owing to the use of reagents/catalysts that are hazardous or toxic to human health or ecotoxic for the environment. In this manuscript, we describe new and efficient catalysts, that is, the nontoxic hydrogen carbonate anion in combination with a potassium or diisobutylimidazolium ([iBu2IM]) countercation, for the conversion of β-amino alcohols into cyclic oxazolidinones in high yields of 69 to 90 %. Depending on the catalytic conditions, both catalysts could be easily recovered from the crude reaction products and reused several times without a decrease in their catalytic performance. Furthermore, the imidazolium cation is a renewable catalyst, because its preparation requires less than 10 % of carbon fossil sources.
- Fournier, Antoine H.,de Robillard, Guillaume,Devillers, Charles H.,Plasseraud, Laurent,Andrieu, Jacques
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p. 3514 - 3518
(2016/07/28)
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- Efficient synthesis of 2-oxazolidinones from epoxides and carbamates catalyzed by amine-functionalized ionic liquids
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A series of amine-functionalized ionic liquids were prepared and their catalytic performance was tested in the synthesis of 2-oxazolidinones from epoxides and carbamates. Under optimized reaction conditions, good to excellent yields of various 2-oxazolidinones were achieved with different epoxides and carbamates. Moreover, the amine-functionalized ionic liquid catalyst could be easily recovered and reused without significant loss in activity.
- Shang, Jianpeng,Li, Zuopeng,Su, Caina,Guo, Yong,Deng, Youquan
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p. 71765 - 71769
(2015/09/08)
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- Combining Low-Pressure CO2 Capture and Hydrogenation to Form Methanol
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This paper describes a novel approach to CO2 hydrogenation, in which CO2 capture with aminoethanols at low pressure is coupled with hydrogenation of the captured product, oxazolidinone, directly to MeOH. In particular, (2-methylamino)ethanol or valinol captures CO2 at 1-3 bar in the presence of catalytic Cs2CO3 to give the corresponding oxazolidinones in up to 65-70 and 90-95% yields, respectively. Efficient hydrogenation of oxazolidinones was achieved using PNN pincer Ru catalysts to give the corresponding aminoethanol (up to 95-100% yield) and MeOH (up to 78-92% yield). We also have shown that both CO2 capture and oxazolidinone hydrogenation can be performed in the same reaction mixture using a simple protocol that avoids intermediate isolation or purification steps. For example, CO2 can be captured by valinol at 1 bar with Cs2CO3 catalyst followed by 4-isopropyl-2-oxazolidinone hydrogenation in the presence of a bipy-based pincer Ru catalyst to produce MeOH in 50% yield after two steps.
- Khusnutdinova, Julia R.,Garg, Jai Anand,Milstein, David
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p. 2416 - 2422
(2015/04/14)
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- Copper(II)-catalysed oxidative carbonylation of aminols and amines in water: A direct access to oxazolidinones, ureas and carbamates
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Copper(II) chloride catalyses the oxidative carbonylation of aminols, amine and alcohols to give 2-oxazolidinones, ureas and carbamates. Reaction proceeds smoothly in water under homogeneous conditions (Ptot = 4 MPa; PO2 = 0.6 MPa, PCO), at 100°C in relatively short reaction times (4 h) and without using bases or any other additives. This methodology represents an economic and environmentally benign non-phosgene alternative for the preparation of these three important N-containing carbonyl compounds.
- Casiello, Michele,Iannone, Francesco,Cotugno, Pietro,Monopoli, Antonio,Cioffi, Nicola,Ciminale, Francesco,Trzeciak, Anna M.,Nacci, Angelo
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- Catalytic fluoride triggers dehydrative oxazolidinone synthesis from CO2
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Herein, catalytic fluoride (F-) is demonstrated to be a trigger for dehydrative immobilization of atmospheric pressure CO2, such that reaction of CO2 with β-amino alcohols derived from natural amino acids gives optically pure oxazolidinones in high yields. A synergistic combination of fluoride and organosilicon agents (e.g., Bu4NF + Ph3SiF or siloxanes) enhances the catalytic activity and functional group compatibility. This system lies at the interface between homogenous and heterogeneous catalysis, and may prove useful for the development of recoverable/reusable siloxane-based CO2 immobilization materials. This journal is
- Takada, Yuki,Foo, Siong Wan,Yamazaki, Yusuke,Saito, Susumu
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p. 50851 - 50857
(2015/02/19)
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- Direct assembly of 2-oxazolidinones by chemical fixation of carbon dioxide
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The reaction of β- and γ-haloamines with carbon dioxide to give pharmaceutically relevant 2-oxazolidinones and 1,3-dioxazin-2-ones, was found to proceed efficiently in the presence of a base and in the absence of catalyst. After optimization of reaction conditions, the system was successfully expanded to a variety of haloamines, even at multigram scale. The reaction was further studied in silico by DFT calculations. The reaction of β- and γ-haloamines with carbon dioxide to give pharmaceutically relevant cyclic urethanes was found to proceed efficiently in the presence of a base and in the absence of catalyst (see figure). After optimization of reaction conditions, the system was expanded to a variety of haloamines, even at a multigram scale. The reaction was further studied in silico by DFT calculations.
- Niemi, Teemu,Perea-Buceta, Jesus E.,Fernandez, Israel,Alakurtti, Sami,Rantala, Erika,Repo, Timo
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supporting information
p. 8867 - 8871
(2014/07/22)
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- Amidation of esters with amino alcohols using organobase catalysis
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A catalytic protocol for the base-mediated amidation of unactivated esters with amino alcohol derivatives is reported. Investigations into mechanistic aspects of the process indicate that the reaction involves an initial transesterification, followed by an intramolecular rearrangement. The reaction is highly general in nature and can be extended to include the synthesis of oxazolidinone systems through use of dimethyl carbonate.
- Caldwell, Nicola,Campbell, Peter S.,Jamieson, Craig,Potjewyd, Frances,Simpson, Iain,Watson, Allan J. B.
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p. 9347 - 9354
(2014/12/11)
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- Novelty of immobilized enzymatic synthesis of 3-ethyl-1,3-oxazolidin-2-one using 2-aminoalcohol and dimethyl carbonate: Mechanism and kinetic modeling of consecutive reactions
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Oxazolidinones are multifunctional compounds possessing diverse biological and pharmacological activity. Enzymatic synthesis of oxazolidin-2-one was studied using 2-aminoalochol and dimethyl carbonate and synthesis of 3-ethyl-1,3-oxazolidin-2-one was chosen as the model reaction using a variety of immobilized lipases; among which Candida antarctica lipase B (Novozyme 435) was the best catalyst. The reaction leads to the final product oxazolidin-2-one via methyl ethyl (2-hydroxyethyl) carbamate as the intermediate. The parameters affecting rate of reaction and the conversion of both steps were studied systematically and covered effects of agitation speed, solvent, catalyst loading and reaction temperature. A reaction mechanism was proposed wherein the coproduct methanol is generated in the first step leading to the formation of methyl ethyl (2-hydroxyethyl) carbamate as the intermediate which rearranges itself leading to the final products 3-ethyl-1,3-oxazolidin-2-one and methanol. The kinetic constant and activation energy were determined for each step of the reaction. The study was further extended to other 2-aminoalochols under optimized reaction conditions to prepare different oxazolidinones. This is a first report of its kind describing kinetics and mechanism of bimolecular consecutive enzyme catalyzed reactions.
- Yadav, Ganapati D.,Pawar, Sandip V.
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- Novelty of immobilized enzymatic synthesis of 3-ethyl-1,3-oxazolidin-2-one using 2-aminoalcohol and dimethyl carbonate: Mechanism and kinetic modeling of consecutive reactions
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Oxazolidinones are multifunctional compounds possessing diverse biological and pharmacological activity. Enzymatic synthesis of oxazolidin-2-one was studied using 2-aminoalochol and dimethyl carbonate and synthesis of 3-ethyl-1,3-oxazolidin-2-one was chosen as the model reaction using a variety of immobilized lipases; among which Candida antarctica lipase B (Novozyme 435) was the best catalyst. The reaction leads to the final product oxazolidin-2-one via methyl ethyl (2-hydroxyethyl) carbamate as the intermediate. The parameters affecting rate of reaction and the conversion of both steps were studied systematically and covered effects of agitation speed, solvent, catalyst loading and reaction temperature. A reaction mechanism was proposed wherein the coproduct methanol is generated in the first step leading to the formation of methyl ethyl (2-hydroxyethyl) carbamate as the intermediate which rearranges itself leading to the final products 3-ethyl-1,3-oxazolidin-2-one and methanol. The kinetic constant and activation energy were determined for each step of the reaction. The study was further extended to other 2-aminoalochols under optimized reaction conditions to prepare different oxazolidinones. This is a first report of its kind describing kinetics and mechanism of bimolecular consecutive enzyme catalyzed reactions.
- Yadav, Ganapati D.,Pawar, Sandip V.
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- Ethyl imidazole-1-carboxylate (EImC) as a carbonylating agent: Efficient synthesis of oxazolidin-2-ones from amino alcohols
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Various substituted oxazolidin-2-ones were synthesized from the corresponding amino alcohols using ethyl imidazole- 1-carboxylate (EImC). Highly substituted and sterically hindered amino alcohols and amino alcohols having a free hydroxy group were cyclized to oxazolidin-2-ones efficiently. This method is simple and produces oxazolidin-2-ones in very good yield.
- Veeraswamy,Reddy, K. Indrasena,Ragavan, R. Venkat,Yennam, Satyanarayana,Jayashree
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p. 109 - 111
(2013/03/14)
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- Cycloaddition of styrene oxide and CO2 mediated by pyrolysis of urea
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This paper reports the effectiveness of carrying out the cycloaddition reaction of styrene oxide (SO) and CO2 without the use of any catalysts. A naturally abundant and cheap material, urea, was utilized in promoting the reaction by controlling the reaction conditions. The influence of reaction temperature, carbon dioxide (CO2) pressure, amount of urea, and the reaction time on the selectivity of styrene carbonate (SC) was investigated. The Royal Society of Chemistry 2013.
- Tharun, Jose,Kim, Dong Woo,Roshan, Roshith,Kathalikkattil, Amal Cherian,Selvaraj, Manickam,Park, Dae-Won
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p. 14290 - 14293
(2013/09/02)
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- Enantioselective organocatalytic michael addition of nitroalkanes and other nucleophiles to β-trifluoromethylated acrylamides
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An organocatalytic asymmetric Michael addition of nitroalkanes to trifluoromethylated acrylamides in good yields and with good to excellent diastereoselectivities and excellent enantioselectivities is described. The Michael adducts could be readily transf
- Wen, Lele,Yin, Liang,Shen, Qilong,Lu, Long
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supporting information
p. 502 - 506
(2013/05/22)
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- Efficient synthesis of 2-oxazolidinone from epoxides and carbamates with binary MgFe oxides as a magnetic solid base catalyst
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Magnetic binary MgFe oxides were prepared by co-precipitation method, characterized and tested in the synthesis of 2-oxazolidinones from epoxides and carbamates. The catalytic results showed that the catalyst with Mg/Fe molar ratio of 1 and calcined at 400°C exhibited superior catalytic activity. The catalyst could be magnetically separated, recycled and reused for five runs without noticeable deactivation. Under the optimized conditions, various 2-oxazolidinones derivatives were successfully synthesized with good to excellent isolated yields.
- Shang, Jianpeng,Liu, Shimin,Lu, Liujin,Ma, Xiangyuan,He, Yude,Deng, Youquan
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- Synthesis of cyclic N-nitrourethanes by the simultaneous oxidative desulfurization and nitration of cyclic thiourethanes
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The reaction of five- and six-membered cyclic thiourethanes with acetyl nitrate results in a vigorous reaction that generates copious amounts of red-brown nitrogen oxide fumes and produces the corresponding cyclic N-nitrourethanes in high yields (>95%). The overall yield of the cyclic N-nitrourethanes starting from an aminoalcohol using the " thiourethane" route is superior to the conventional route going through the cyclic urethane. Copyright
- Willer, Rodney L.,Campbell, Christopher G.,Storey, Robson F.
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scheme or table
p. 421 - 423
(2012/06/18)
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- Switchable palladium-catalyst reaction of bromomethyl sulfoxides, CO, and N-nucleophiles: Aminocarbonylation at Csp3 versus oxidative carbonylation of amines
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The palladium-catalyzed reaction of α-bromomethyl sulfoxides, carbon monoxide, and N-nucleophiles follows different reaction pathways according to the catalytic system and the reaction conditions. The Pd-xantphos catalyst affords high yields of α-sulfinyl amides by an aminocarbonylation process and is the first example of this type of transformation for a nonbenzylic sp3-hybridized carbon. On the other hand, the oxidative carbonylation of amines occurs with α-bromomethyl sulfoxides, carbon monoxide, and catalytic Pd(PPh3)4 under aerobic conditions, yielding ureas and oxalamides from either primary or secondary amines. The reaction with ambident nucleophiles such as amino alcohols was highly selective and took place exclusively at the amino group despite the presence of the alcohol functionality. In parallel to the reaction paths for simple amines, amino alcohols were converted into hydroxy sulfinyl amides when the reaction was catalyzed by Pd-xantphos, while Pd(PPh3)4 catalyst afforded cyclic carbamates. The alkoxycarbonylation reaction of bromomethyl sulfoxides with simple alcohols and CO leading to the corresponding sulfinyl esters is also described.
- Mollar, Cristian,Ramirez De Arellano, Carmen,Medio-Simon, Mercedes,Asensio, Gregorio
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p. 9693 - 9701,9
(2012/12/12)
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- Switchable palladium-catalyst reaction of bromomethyl sulfoxides, CO, and N-nucleophiles: Aminocarbonylation at Csp3 versus oxidative carbonylation of amines
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The palladium-catalyzed reaction of α-bromomethyl sulfoxides, carbon monoxide, and N-nucleophiles follows different reaction pathways according to the catalytic system and the reaction conditions. The Pd-xantphos catalyst affords high yields of α-sulfinyl amides by an aminocarbonylation process and is the first example of this type of transformation for a nonbenzylic sp3-hybridized carbon. On the other hand, the oxidative carbonylation of amines occurs with α-bromomethyl sulfoxides, carbon monoxide, and catalytic Pd(PPh3)4 under aerobic conditions, yielding ureas and oxalamides from either primary or secondary amines. The reaction with ambident nucleophiles such as amino alcohols was highly selective and took place exclusively at the amino group despite the presence of the alcohol functionality. In parallel to the reaction paths for simple amines, amino alcohols were converted into hydroxy sulfinyl amides when the reaction was catalyzed by Pd-xantphos, while Pd(PPh3)4 catalyst afforded cyclic carbamates. The alkoxycarbonylation reaction of bromomethyl sulfoxides with simple alcohols and CO leading to the corresponding sulfinyl esters is also described.
- Mollar, Cristian,Ramirez De Arellano, Carmen,Medio-Simón, Mercedes,Asensio, Gregorio
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p. 9693 - 9701
(2013/01/15)
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- Interaction of substrate and catalyst during the formation of oxazolidinones from 2-aminoalcohols and diethyl carbonate using recyclable 1,3-dichlorodistannoxanes
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An efficient synthesis of oxazolidinone (OXZ) using 2-aminoalcohols (2AAs) and diethyl carbonate (DEC) as reagents in the presence of recyclable catalyst 1,3-dichloro-1,1,3,3-tetraalkyldistannoxane, [(RR′SnCl)2O] 2 (1) is reported. 0.5 mol% (with respect to 2AA) of 1 provides OXZ quantitatively within 1 h at 80 °C with turnover frequency (TOF) of 200 h-1. The observed TOF is much higher than the reported value (4 h-1) of the most convenient and commercially feasible K 2CO3 catalyst. Chiral 2AAs produce OXZs with 99% ee. Molar dependency of 1, DEC and 2AA is found to be 1:2:2. Molar conductivities (Ω-1 cm2 mol-1) in DMSO at 25 °C are 6.41 for 1a (R = R′ = Bu), 5.25 for 1b (R = Bu, R′ = Ph), 2.87 for 1c (R = Ph, R′ = Bu), and 2.21 for 1d (R = R′ = Ph) which reveal the mobility of bridged Cl in 1 during reaction. The study of a broad range of substrates and reaction parameters supports a reaction pathway that begins with initial attack by -OH of the pre-formed 2-ethylcarbamato aminoalcohol (2ECA) of 2AA on Snb of 1 displacing the bridged Cl. Change in the reaction rates resulted due to various alkyl and aryl substituents on Sn provides better understanding of the distannoxane catalysis, which has not been attempted before for the said reaction.
- Pulla, Sharon,Unnikrishnan, Vineed,Ramidi, Punnamchandar,Sullivan, Shane Z.,Ghosh, Anindya,Dallas, Jerry L.,Munshi, Pradip
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experimental part
p. 33 - 43
(2011/05/02)
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- Synthesis of some 2-Oxazolidinones in mild conditions
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One step efficient protocol for the synthesis of 2-oxazolidinones in paste chemical medium is described under microwave activation with 80 % yield.
- Bratulescu, George
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experimental part
p. 929 - 930
(2011/12/15)
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- Synthesis of urea derivatives from amines and CO2 in the absence of catalyst and solvent
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Urea derivatives are obtained in mild to good yield from the reactions of primary aliphatic amines with CO2 in the absence of any catalysts, organic solvents or other additives. To optimize reaction conditions, experimental variables including temperature, pressure, the concentration of amine, reaction time etc. were studied. Satisfactory yields were obtained at the optimized conditions that are comparable to the presence of catalyst and solvent. The preliminary investigation of the reaction mechanism showed that alkyl ammonium alkyl carbamate was quickly formed as the intermediate, and then the final product was formed by the intramolecular dehydration.
- Wu, Chaoyong,Cheng, Haiyang,Liu, Ruixia,Wang, Qiang,Hao, Yufen,Yu, Yancun,Zhao, Fengyu
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experimental part
p. 1811 - 1816
(2011/02/22)
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- Ceria nanoparticles as heterogeneous catalyst for CO2 fixation by ω-aminoalcohols
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In contrast to γ-Al2O3, TiO2, ZrO2, MgO and Y2O3, CeO2 is a reusable catalyst for the reaction of CO2 with ω-aminoalcohols to form cyclic carbamates; the highest yield (68%) was obtained for the preparation of N-alkyl 1,3-oxazolidin-2-ones from N-alkyl ethanolamines.
- Juarez, Raquel,Concepcion, Patricia,Corma, Avelino,Garcia, Hermenegildo
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experimental part
p. 4181 - 4183
(2010/08/22)
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- Method for Making Carbamates, Ureas and Isocyanates
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The present invention provides methods of forming carbamates, ureas, and isocyanates. In certain embodiments these methods include the step of reacting an amine with an ester-substituted diaryl carbonate to form an activated carbamate which can be further derivitized to form non-activated carbamate or a urea. The urea or carbamate can be subjected to a pyrolysis reaction to form isocyanate.
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Page/Page column 8
(2010/05/13)
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- Novel routes to aminophosphonic acids: Interaction of dimethyl H-phosphonate with hydroxyalkyl carbamates
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It was found that the reaction of dimethyl H-phosphonate (1) with 2-hydroxyalkyl-N-2′-hydroxyalkyl carbamates at 135°C includes several chemical reaction steps: (i) chemical transforma-tions of 1-methyl-2- hydroxyethyl-N-2′-hydroxyethyl carbamate (2) and 2-methyl-2-hydroxyethyl- N-2′-hydroxyethyl carbamate (3); (ii) transesterification of dimethyl H-phosphonate with 2 and 3, and with secondary hydroxyl-containing compounds that are formed during the course of the chemical transformation of 2-hydroxyalkyl-N-2′-hydroxyalkyl carbamates; (iii) hydrolysis of 1 and dialkyl H-phosphonates, formed via transesterification of 1 with secondary hydroxyl-containing compounds. The interaction was studied by means of 1H, 13C, 31P NMR, and FAB mass spectroscopy.
- Troev,Koseva,Haegele
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p. 119 - 124
(2008/09/18)
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- Samarium diiodide as an efficient catalyst for the conversion of N-acyloxazolidinones into esters
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The transformation of N-acyloxazolidinones into esters is readily performed using catalytic amounts of samarium diiodide in tetrahydrofuran at room temperature. This method allows the isolation of various esters without racemization in the case of scalemi
- Magnier-Bouvier, Caroline,Reboule, Iréna,Gil, Richard,Collin, Jacqueline
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scheme or table
p. 1211 - 1215
(2009/04/06)
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- An excellent procedure for the synthesis of oxazolidin-2-ones
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Synthesis of oxazolidin-2-ones derivatives was carried out starting from urea and ethanolamine reagents using microwave irradiation in a chemical paste medium. Georg Thieme Verlag Stuttgart.
- Bratulescu, George
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p. 3111 - 3112
(2008/09/16)
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- A novel way to chiral 2-oxazolidinones: selenium-catalyzed cyclocarbonylation of 2-aminoethanols
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Selenium-catalyzed cyclocarbonylation of 2-aminoethanols with CO under atmospheric pressure at 30 °C afforded 2-oxazolidinones in excellent yields without any other co-catalyst. The method was then applied to the syntheses of chiral 2-oxazolidinones and no racemization was detected.
- Li, Peng,Yuan, Xiaohua,Wang, Shudong,Lu, Shiwei
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p. 12419 - 12423
(2008/03/13)
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- Synthesis of 2-oxazolidinones by salen-Co-complexes catalyzed oxidative carbonylation of β-amino alcohols
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2-Oxazolidinones are synthesized in high yield by oxidative carbonylation of β-amino alcohols using salen-Co(II)/NaI or salen-Co(III)-I as a catalyst and using CO as the carbonyl source. Studies of functional group compatibility using a series of substituted salen-Co(II) or salen-Co(III)-I complexes demonstrate a broad tolerance of functionality during the carbonylation reaction.
- Liu, Jian-Ming,Peng, Xin-Gao,Liu, Jian-Hua,Zheng, Shu-Zhan,Sun, Wei,Xia, Chun-Gu
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p. 929 - 932
(2008/02/04)
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- A novel and efficient (NHC)CuI (NHC = N-heterocyclic carbene) catalyst for the oxidative carbonylation of amino compounds
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Oxidative carbonylation of amino compounds to prepare corresponding 2-oxazolidinones, ureas, and carbamates selectively in the presence of (NHC)CuI without any additives was firstly achieved in good yields and selectivities.
- Zheng, Shuzhan,Li, Fuwei,Liu, Jianming,Xia, Chungu
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p. 5883 - 5886
(2008/02/09)
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- Efficient synthesis of oxazolidin-2-one via (chitosan-Schiff base)cobalt(II)-catalyzed oxidative carbonylation of 2-aminoalkan-1-ols
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The (chitosan-Schiff base)cobalt(II) complex was found to be an efficient catalyst for the oxidative carbonylation (CO/O2) of 2-aminoalkan-1-ols 1 to give oxazolidin-2-ones 2, in the presence of NaI. The effects of promoters, temperature, solvents, and other reaction conditions were investigated in this study.
- Liu, Jianming,Sun, Wei,Zheng, Shuzhan,Xia, Chungu
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p. 1593 - 1598
(2008/02/09)
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- Pd(Phen)Cl2 stabilized by ionic liquid: an efficient and reusable catalyst for biphasic oxidative cyclocarbonylation of β-aminoalcohols and 2-aminophenol
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Biphasic oxidative cyclocarbonylation of β-aminoalcohols and 2-aminophenol to synthesize corresponding 2-oxazolidinones were investigated in the presence of ionic liquid stabilized Pd(phen)Cl2 complex. Catalytic comparison results showed that, 1-butyl-3-methyl-imidazolium iodide salts (BMImI) can serve simultaneously as a specific stabilizer to protect the transition metal complex against deactivation, a promoter to increase the catalytic performance and a reaction medium to recycle the catalyst with unprecedented TOF value.
- Li, Fuwei,Xia, Chungu
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p. 4845 - 4848
(2008/02/05)
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- 2,3,4,5-TETRAHYDRO-1H-1,5-BENZODIAZEPINE DERIVATIVE AND MEDICINAL COMPOSITION
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The present invention has its object to provide a 2,3,4,5-tetrahydro-1H-1,5-benzodiazepine derivative represented with the Formula (1) , or the pharmaceutically acceptable salt, which is effective as a therapeutic and prophylactic agent for diabetes, diabetic nephropathy, or glomerulosclerosis.
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- A general, facile, and safe procedure for the preparation of S-methyl N-alkylthiocarbamates by methylthiocarbonylation of primary aliphatic amines with S,S-dimethyl dithiocarbonate
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A general procedure is reported for the selective preparation of S-methyl N-alkylthiocarbamates by methylthiocarbonylation of primary aliphatic amines, employing S,S-dimethyl dithiocarbonate as a phosgene substitute. The reactions are carried out in water at room temperature (20-25°C), with S,S-dimethyl dithiocarbonate/amine ratios varying between 1:1.2 and 1:2, and with quantitative recovery of the excess amine. The target products are obtained in exceptionally high yields (generally >95%) and with very high purity (generally >99.5%). Also to be noted is the complete chemoselectivity of the reactions, which can be carried out in the presence of hydroxy or aminophenyl groups. Georg Thieme Verlag Stuttgart.
- Artuso, Emma,Carvoli, Gianni,Degani, Iacopo,Fochi, Rita,Magistris, Claudio
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p. 1096 - 1102
(2008/02/04)
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- A highly efficient sulfur-catalyzed oxidative carbonylation of primary amines and β-amino alcohols
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A highly efficient sulfur-catalyzed oxidative carbonylation of aliphatic amines and aliphatic β-amino alcohols to ureas and 2-oxazolidinones, respectively, was developed. Sodium nitrite was involved in the reoxidation of hydrogen sulfide to sulfur in the catalytic oxidative carbonylation cycle. Georg Thieme Verlag Stuttgart.
- Peng, Xingao,Li, Fuwei,Xia, Chungu
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p. 1161 - 1164
(2007/10/03)
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- A practical ruthenium-catalyzed cleavage of the allyl protecting group in amides, lactams, imides, and congeners
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A convenient methodology for the deprotection of N-allylic amide-like moieties was developed. The first examples accounting for the ruthenium-catalyzed deallylation of amides, lactams, imides, pyrazolidones, hydantoins, and oxazolidinones have been achieved by the sequential use of Grubbs carbene (isomerization step) and RuCl3 (oxidation step). A variety of substrates, including enantiopure multifunctional β- and γ-lactams, can be employed.
- Alcaide, Benito,Almendros, Pedro,Alonso, Jose M.
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p. 2874 - 2879
(2008/02/03)
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- Modified Mg: Al hydrotalcite in the synthesis of oxazolidin-2-ones
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The modified Mg: Al (3: 1) hydrotalcite has been found to be an efficient catalyst in the conversion of carbamates into oxazolidin-2-ones under mild reaction conditions. A wide variety of oxazolidin-2-ones were obtained with excellent chemical yield. The Royal Society of Chemistry 2005.
- Cwik, Agnieszka,Fuchs, Aliz,Hell, Zoltan,Boejtoes, Ildiko,Halmai, Dora,Bombicz, Petra
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p. 967 - 969
(2007/10/03)
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