109-94-4Relevant articles and documents
Meakins,Morris
, p. 394 (1967)
Merger of Johnson-Claisen rearrangement and alkoxycarbonylation for atom efficient diester synthesis
Seidensticker, Thomas,M?ller, David,Vorholt, Andreas J.
, p. 371 - 374 (2016)
The orthoester Johnson-Claisen rearrangement of allyl alcohol with triethyl orthoacetate for the synthesis of ethyl 4-pentenoate has been optimized, in order to allow for a selective and efficient subsequent alkoxycarbonylation using formates in an atom efficient manner. Diethyl adipate was successfully yielded in up to 89% applying very low orthoester excess, formic acid and mild reaction conditions in an innovative, one-pot procedure.
Formic acid directly assisted solid-state synthesis of metallic catalysts without further reduction: As-prepared Cu/ZnO catalysts for low-temperature methanol synthesis
Shi, Lei,Shen, Wenzhong,Yang, Guohui,Fan, Xiaojing,Jin, Yuzhou,Zeng, Chunyang,Matsuda, Kenji,Tsubaki, Noritatsu
, p. 83 - 90 (2013)
Metallic catalysts (Cu/ZnO) and pure metals (Co, Ni, and Ag) without any impurities are directly prepared by a novel formic acid-assisted solid-state method without further reduction. During the decomposition of metal-formic acid precursors at 523 K under argon, H2 and CO are liberated and act in situ as reducing agents to obtain pure metals and metallic catalysts (C argon). X-ray diffraction, X-ray photoelectron spectroscopy, energy-dispersive spectroscopy, and temperature-programmed reduction analysis reveal that the as-prepared catalyst Cargon without further reduction is converted into metallic Cu0 and ZnO species. TPR analysis results, Fourier transform infrared analysis, and the thermal decomposition behavior in air illustrate that no amorphous carbon or carbonic residues are left in Cargon when formic acid is used as the chelating agent and reductant, because formic acid is the simplest organic acid. The as-prepared Cu/ZnO catalyst is tested for low-temperature methanol synthesis at 443 K from syngas containing CO2 and using ethanol as a solvent and catalyst; it exhibits much higher activity and methanol selectivity than catalysts prepared by conventional solid-state methods.
The products of the reaction of the hydroxyl radical with 2-ethoxyethyl acetate
Wells,Wiseman, Floyd L.,Williams, Dale C.,Baxley, J. Steven,Smith
, p. 475 - 480 (1996)
The gas-phase reaction products of the OH radical with 2-ethoxyethyl acetate (EEA, CH3C(O)OCH2CH2OCH2CH3) have been investigated. 1,2-Ethanediol acetate formate (EAF, CH3C(O)OCH2CH2OC(O)H)and ethyl formate (EF, HC(O)OCH2CH3) were identified as the two main products. A third product, ethylene glycol diacetate (EGD, CH3C(O)OCH2CH2OC(O)CH3), was also observed. EAF, EF, and EGD formation yields were determined to be 0.37 ±0.03 and 0.328 ± 0.018 and 0.040 ± 0.005. respectively. Proposed reaction mechanisms are discussed and compared with these data. 1996 John Wiley & Sons, inc.
The hydroxyl radical reaction rate constant and products of ethyl 3-ethoxypropionate
Steven Baxley,Henley, Michael V.,Wells
, p. 637 - 644 (1997)
The relative rate technique has been used to measure the hydroxyl radical (OH) reaction rate constant of ethyl 3-ethoxypropionate (EEP, CH3CH2-O-CH2CH2C(O)O-CH 2CH3). EEP reacts with OH with a bimolecular rate constant of (22.9 ± 7.4) × 10-12 cm3 molecule-1 s-1 at 297 ± 3 K and l atmosphere total pressure. In order to more clearly define EEP's atmospheric reaction mechanism, an investigation into the OH + EEP reaction products was also conducted. The OH + EEP reaction products and yields observed were: ethyl glyoxate (EG, 25 ± 1% HC(=O)C(=O)-O-CH2CH3), ethyl (2-formyl) acetate (EFA, 4.8 ± 0.2%, HC(=O)-CH2-C(=O)-O-CH2CH3), ethyl (3-formyloxy) propionate (EFP, 30 ± 1%, HC(=O)-O-CH2CH2-C(=O)-O-CH2CH3), ethyl formate (EF, 37 ± 1%, HC(=O)O-CH2CH3), and acetaldehyde (4.9 ± 0.2%, HC(=O)CH3). Neither the EEP's OH rate constant nor the OH/EEP reaction products have been previously reported. The products' formation pathways are discussed in light of current understanding of oxygenated hydrocarbon atmospheric chemistry.
The Reaction of Alkoxides with Dicobalt Octacarbonyl: Trapping of the Co(I) Intermediate in the Disproportionation ( Base Reaction ) with a Hard Lewis Base
Tasi, Miklos,Sisak, Attila,Ungvary, Ferenc,Palyi, Gyula
, p. 1103 - 1106 (1985)
Dicobalt octacarbonyl reacts with alcoholates (RO(-)) yielding alkoxycarbonylcobalt tetracarbonyls, ROC(O)Co(CO)4. - (Keywords: Alkoxides, reaction with dicobalt octacarbonyl; Alkoxycarbonylcobalt tetracarbonyls; Hydrocarbalkoxylation intermediates)
Hydrolysis of Imidazole-Containing Amide Acetals
Brown, R. S.,Ulan, J. G.
, p. 2382 - 2388 (1983)
N-(Dialkoxymethyl)imidazoles (amide acetals 1a-c) are shown to hydrolyze by a common mechanism between pH 1 and pH 11 that involves preequilibrium protonation of the imidazole distal N, followed by rate-llimiting C - N cleavage.The Broensted plot of the log C - N cleavage rate vs. pKa of the parent imidazole has a slope of -1.0 and suggest a transition sate in which (+) is nearly completely transferred to the departing dialkoxymethyl group.Throughout the pH range studied, C - N cleavage is the dominant process.The bicyclic amide acetal 2 formed from 4(5)-(hydroxyethyl)imidazole and triethyl orthoformate behaves similarly to the acyclic cases at pHs > 5 except that the observed rate of C - N cleavage for the former is depressed by (1 - 2) x 102-fold.This apparent reduction of C - N cleavage rate is analyzed in terms of reversibility of the ring opening.Such reversal is demonstrated by the ability of good nucleophiles such as N3- or H2NOH to trap the open ion, preventing reversal and hence increasing the apparent rate of loss of 2.From pH 0 to pH 5, an additional sigmoidal event in the pH/log kobsd profile for 2 is observed, which is analyzed as a protonation of the imidazole of the open ion.Such a protonation prevents the reversible reclosure and concomitantly increases the kobsd.Bicyclic 2 can be taken as a model for the tetrahedral intermediate formed during intramolecular alcoholysis of an N-acylimidazole or intramolecular attack of an imidazole on an ester.
Photocatalitic Decomposition of 2-Ethoxyethanol on Titanium Dioxide
Yamagata, Sadamu,Baba, Ryo,Fujishima, Akira
, p. 1004 - 1010 (1989)
The reaction mechanism of the photocatalytic oxidation of 2-etoxyethanol (Ethyl Cellosolve, EtOCH2CH2OH) on TiO2 powder was investigated by gas chromatography-mass spectrometry (GC-Ms) infrared (IR) spectroscopy, and electron spin resonance (ESR) with spin trapping technique.Irradiation of TiO2 powder with UV light in the presence of EtOCH2CH2OH under air led to the formation of ethyl formate, ethanol, acetaldehyde and carbon dioxide.The main product, ethyl formate was different from the product trough the reaction pathway proposed before for primary alcohols.It was also different from the product of electrolysis on Pt.Reaction mechanism is proposed based on Ir and ESR studies.
Kinetics of the Three Components Condensation of Triethoxymethane, Aniline and CH2-Acidic Compounds Forming Arylaminomethylene Compounds
Uray, Georg,Wolfbeis, Otto S.
, p. 627 - 642 (1981)
Condensation of triethoxymethane and aniline with dimedone gives 2-anilinomethylene dimedone as the main product.An 1H-NMR-spectroscopic investigation of the kinetics in chloroform-d1 and methanol-d4 shows different rate determining steps in these solvents.There are two predominant rate determining steps in a complicated multistep reaction sequence.The initial one involves condensation of aniline with triethoxymethane to form diphenyl formamidine via ethyl phenyl formimidate.The second step involves reaction of the intermediate diphenyl formamidine with dimedone.The rates are strongly dependent upon the nature of the solvent and the concentration of catalytic acid.In methanol the reaction of dimedone with the intermediate diphenyl formamidine is rate determining.For preparative purposes the isolation of the intermediate diphenyl formamidine and the subsequent use of less polar solvents offer an advantage, because the second step is found to be accelerated. - Keywords: Enaminones; Formimidate; Formamidine
The effect of oxygen pressure on the tropospheric oxidation of diethyl ether, H-atom elimination from the 1-ethoxyethoxy radical
Cheema,Holbrook,Oldershaw,Starkey,Walker
, p. 3243 - 3245 (1999)
The simulated tropospheric oxidation of diethyl ether gave yields of the products ethyl formate, acetaldehyde and ethyl acetate in broad agreement with previous studies. However the effect of variation of oxygen pressure on the relative yields of ethyl acetate and ethyl formate disagrees with the prediction of the mechanism previously proposed. It is suggested that ethyl acetate is produced by the reaction C2H5OCH(O)CH3 → CH3COOC2H5 + H as well as by the reaction of the 1-ethoxyethoxy radical with oxygen.
The atmospheric oxidation of diethyl ether: Chemistry of the C 2H5-O-CH(O?)CH3 radical between 218 and 335 K
Orlando, John J.
, p. 4189 - 4199 (2007)
The products of the Cl atom initiated oxidation of diethyl ether (DEE) were investigated at atmospheric pressure over a range of temperatures (218-335 K) and O2 partial pressures (50-700 Torr), both in the presence and absence of NOx. The major products observed at 298 K and below were ethyl formate and ethyl acetate, which accounted for ≈60-80% of the reacted diethyl ether. In general, the yield of ethyl formate increased with increasing temperature, with decreasing O2 partial pressure, and upon addition of NO to the reaction mixtures. The product yield data show that thermal decomposition reaction (3), CH3CH2-O-CH(O ?)CH3 → CH3CH2-O-CH=O + CH3, and reaction (6) with O2, CH3CH 2-O-CH(O?)CH3 + O2 → CH3CH2-O-C(=O)CH3 + HO2 are competing fates of the CH3CH2-O-CH(O?) CH3 radical, with a best estimate of k3/k6 ≈ 6.9 × 1024 exp(-3130/T). Thermal decomposition via C-H or C-O bond cleavage are at most minor contributors to the CH3CH 2-O-CH(O?)CH3 chemistry. The data also show that the CH3CH2-O-CH(O?)CH 3 radical is subject to a chemical activation effect. When produced from the exothermic reaction of the CH3CH2-O-CH(OO ?)CH3 radical with NO, prompt decomposition via both CH3- and probably H-elimination occur, with yields of about 40% and ≤15%, respectively. Finally, at temperatures slightly above ambient, evidence for a change in mechanism in the absence of NOx, possibly due to chemistry involving the peroxy radical CH3CH2-O-CH(OO ?)CH3, is presented. the Owner Societies.
Lisnyanskii et al.
, (1969)
Experimental Data on Chemical Equilibrium in the System with Ethyl Formate Synthesis Reaction at 298.15 K
Samarov, Artemiy,Trofimova, Maya,Toikka, Maria,Toikka, Alexander
, p. 2578 - 2582 (2020)
Chemical equilibrium (CE) in the quaternary reacting system formic acid-ethanol-ethyl formate-water was experimentally studied at 298.15 K and atmospheric pressure. The CE compositions were determined by gas chromatography analysis. The obtained data gave an opportunity to present the disposition of the surface of CE in a composition tetrahedron. The constants of CE ("concentration" and thermodynamic) were determined on the base of experimental data and UNIFAC model.
Introduction of a carboxyl group through an acetal as a new route to carboxylic acid derivatives of sugars
Carbonnel, Sylvie,Fayet, Catherine,Gelas, Jacques
, p. 63 - 73 (1999)
A new class of carboxylic acid derivatives of sugars is described. Acetalation of mono- and disaccharides with a functionalized vinylic ether or a diethoxybutanoate afforded mono- and diacetals bearing an ester group. Their saponification led to the corresponding carboxylic acid acetals in which the length of the acetal side chain can be modulated. Copyright (C) 1999 Elsevier Science Ltd.
Photooxidation Reactions of Ethyl 2-Methylpropionate (E2MP) and Ethyl 2,2-Dimethylpropionate (E22DMP) Initiated by OH Radicals: An Experimental and Computational Study
Kaipara, Revathy,Rajakumar, B.
, p. 2768 - 2784 (2020)
The relative rate (RR) technique was used for the measurement of OH-initiated photooxidation reactions of ethyl 2-methylpropionate (E2MP) and ethyl 2,2-dimethylpropionate (E22DMP) in the temperature range of 268-363 K at 760 Torr. In addition to this, the
Kinetics and mechanisms for the reactions of ozone with unsaturated oxygenated compounds
Al Mulla, Ismael,Viera, Lisa,Morris, Rebecca,Sidebottom, Howard,Treacy, Jack,Mellouki, Abdelwahid
, p. 4069 - 4078 (2010)
Rate coefficients for the reaction of ozone with a series of unsaturated oxygenated compounds are determined in air at atmospheric pressure and (298±3) K. Rate data are obtained using both relative and absolute rate techniques, and the measured rate coefficients are found to be in good agreement. The results show that the reactivity of the compounds with respect to addition of ozone to the double bond is a function of the nature of the oxygenated substituent. Product distribution studies on the reactions provide information on the decomposition pathways for the primary ozonides, and on the effect of the oxygenated group on the relative importance of the degradation pathways. The results are discussed in terms of their importance in the atmospheric oxidation of unsaturated oxygenated compounds.
Pleuromutilin derivative with 1, 3, 4-oxadiazole side chain and preparation and application thereof
-
Paragraph 0055-0056; 0070; 0090; 0092, (2021/07/24)
The invention belongs to the field of medicinal chemistry, and particularly relates to a pleuromutilin derivative with a 1, 3, 4-oxadiazole side chain and preparation and application thereof The pleuromutilin derivative with the 1, 3, 4-oxadiazole side chain is a compound shown in a formula 2 or a pharmaceutically acceptable salt thereof, and a solvent compound, an enantiomer, a diastereoisomer and a tautomer of the compound shown in the formula 2 or the pharmaceutically acceptable salt thereof or a mixture of the solvent compound, the enantiomer, the diastereoisomer and the tautomer in any proportion, including a racemic mixture. The pleuromutilin derivative has good antibacterial activity, is especially suitable for being used as a novel antibacterial agent for systemic system infection of animals or human beings, and has good water solubility.
Operando systems chemistry reaction catalysis (OSCR-Cat) for visible light driven CO2conversion
Das, Kousik,De, Ratnadip,Roy, Soumyajit,Verpoort, Francis
, p. 13355 - 13365 (2021/06/16)
A systems chemistry approach is taken for compartmentalization of a continuous reaction medium (water and CO2) with induced creation of micro-heterogeneity in the medium by using a SOM (soft-oxometalate) catalyst. The first step involves compartmentalization of an assembled catalyst-photosensitizer duo catalysing the reduction of CO2into formic acid in two reaction spaces: the interior of the compartment and the exterior of the compartment. The exterior compartment obeys typical surface activity driven nanocatalysis principles where the perturbation of the catalyst surface area inversely varies with product yield. The second step of disassembly to disrupt the SOM-catalyst, induced by addition of a base, releases the interior reaction product with total disappearance of the catalyst system. The assembly-disassembly cascade demonstrates the application of systems chemistry principles in perturbation, compartmentalization, catalysis and release of products with well-defined externally controlled stimuli such as concentration, light, and pH. The OSCR-catalyst reported here is an attempt to emulate Golgi bodies in the context of cellular chemistry on a functional level.
Alcohol-Activated Vanadium-Containing Polyoxometalate Complexes in Homogeneous Glucose Oxidation Identified with 51V-NMR and EPR Spectroscopy
Wesinger, Stefanie,Mendt, Matthias,Albert, Jakob
, p. 3662 - 3670 (2021/06/18)
Alcoholic solvents, especially methanol, show an activating affect for heteropolyacids in homogenously catalysed glucose transformation reactions. In detail, they manipulate the polyoxometalate-based catalyst in a way that thermodynamically favoured total oxidation to CO2 can be completely supressed. This allows a nearly 100 % carbon efficiency in the transformation reaction of glucose to methyl formate in methanolic solution at mild reaction conditions of 90 °C and 20 bar oxygen pressure. By using powerful spectroscopic tools like 51V-NMR and continuous wave EPR we could unambiguously prove that the vanadate-methanol-complex[VO(OMe)3]n is responsible for the selectivity shift in methanolic solution compared to the aqueous reference system.