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108-24-7Relevant articles and documents
Carbonylation of methyl acetate in the presence of polymeric rhodium-containing catalysts
Kolesnichenko, N. V.,Batov, A. E.,Markova, N. A.,Slivinsky, E. V.
, p. 259 - 262 (2002)
New catalytic systems based on RhCL3 and polymeric nitrogen- and oxygen-containing supports were proposed for the carbonylation of methyl acetate to acetic anhydride. The catalytic systems possess a high activity typical of homogeneous catalysts. The high activity is retained upon the repeated use of the catalyst separated from the reaction products. The nitrogen-containing polymers of the chitosan type serve as cocatalysts. In their presence, the induction period disappears, and the catalytically active species are stabilized, thus enabling the replacement of expensive LiI for cheaper salts of this metal.
Concerted General Acid Catalysis in the Reaction of Acetate Ion with Water-soluble Carbodi-imide
Ibrahim, Ibrahim T.,Williams, Andrew
, p. 25 - 27 (1980)
An intermediate, identified as an O-acetylisourea, is observed spectroscopically in the reaction of a water-soluble carbodi-imide with acetate buffers; a stepwise mechanism for intermediate formation as currently accepted is excluded by the observation of general acid catalysis, while acetate ion attack on carbodi-imide is concerted with proton transfer, and monoanions of dicarboxylic acids react with carbodi-imide with intramolecular concerted proton transfer.
Selectivity Behavior in Hydrocarbonylation of Methyl Acetate Using Homogeneous Rh Complex Catalyst
Kelkar, A. A.,Chaudhari, R. V.
, p. 334 - 343 (1995)
Hydrocarbonylation of methyl acetate using various homogeneous transition metal complex catalysts has been studied.It was observed that Rh(CO)Cl(PPh3)2 was the most active and selective catalyst for ethylidene diacetate synthesis.The effect of the catalyst, methyl acetate, and methyl iodide concentrations; temperature; and partial pressures of CO, H2, and various transition metal complexes as co-catalysts on the selectivity behavior has been studied.Palladium complexes were found to enhance the selectivity of ethylidene diacetate substantially.Catalyst concentration, partial pressures of CO and H2, and temperature also influence the selectivity pattern substantially.On the basis of these results, a possible reaction mechanism is discussed.
Degradation of a veterinary pharmaceutical product in water by electro-oxidation using a BDD anode
Espinoza, C.,Contreras, N.,Berros, C.,Salazar, R.
, p. 2507 - 2511 (2014)
The electrochemical oxidation (EO) treatment in water of Fantetra, a veterinary drug widely used in Chile, and its components: oxytetracycline hydrochloride, phtalylsulfathiazole and diphenhydramine, has been carried out at constant current using a BDD/Stainless steel system. First, solutions of each drug were electrolyzed following the decay of the absorbance of each compound and total organic carbon abatement. The mineralization of the Fantetra commercial formulation was also studied. An analysis of the degradation by-products was made by high performance liquid chromatography. Thus, during the degradation of each pharmaceutical by the electrochemical oxidation process, aliphatic carboxylic acids were detected prior to their complete mineralization to CO2 and nitrogen ions, while NO3- and NH4+ remain in the treated solution. This is an essential preliminary step towards the applicability of the EO processes for the treatment of wastewater containing pharmaceutical compounds.
The atmospheric oxidation of ethyl formate and ethyl acetate over a range of temperatures and oxygen partial pressures
Orlando, John J.,Tyndall, Geoffrey S.
, p. 397 - 413 (2010)
The Cl-atom-initiated oxidation of two esters, ethyl formate [HC(O)OCH 2CH3] and ethyl acetate [CH3C(O)OCH 2CH3], has been studied at pressures close to 1 atm as a function of temperature (249-325 K) and O2 partial pressure (50-700 Torr), using an environmental chamber technique. In both cases, Cl-atom attack at the CH2 group is most important, leading in part to the formation of radicals of the type RC(O)OCH(O?)CH3 [R = H, CH3]. The atmospheric fate of these radicals involves competition between reaction with O2 to produce an anhydride compound, RC(O)OC(O)CH3, and the so-called α-ester rearrangement that produces an organic acid, RC(O)OH, and an acetyl radical, CH3C(O). For both species studied, the α-ester rearrangement is found to dominate in air at 1 atm and 298 K. Barriers to the rearrangement of 7.7 ± 1.5 and 8.4 ± 1.5 kcal/mole are estimated for CH3C(O)OCH(O?)CH3 and HC(O)OCH(O?)CH3, respectively, leading to increased occurrence of the O2 reaction at reduced temperature. The data are combined with those obtained from similar studies of other simple esters to provide a correlation between the rate of occurrence of the α-ester rearrangement and the structure of the reacting radical.
TRIOXABICYCLO PENTANE IH PHOTOSENSITIZED OXYGENATION OF 2-DIAZO-3-BUTANONE
Ando, Wataru,Miyazaki, Hajime,Ito, Kenji,Auchi, Daikan
, p. 555 - 556 (1982)
Photosensitized oxygenation of 2-diazo-3-butanone at -78 deg C in CH2Cl2 gave trioxabicyclo pentane which has a long enough life time to allow chemical and spectroscopic characterization.
Infrared Study of the Surface Reaction of Gaseous Sulphuryl Chloride with Metal Carboxylates
Nakamura, Shigeaki
, p. 1 - 4 (1983)
The surface reaction of metal carboxylates RCO2M (R=H, Me, Et, Prn, and Pri; M=Li, Na, and K) with gaseous sulphuryl chloride has been monitored by i.r. spectroscopy.Reactions (I) and (II) take place. 2RCO2M+SO2Cl2RCOMSO4+RCOCl+MC
Adsorption of ethanoic acid on zeolites NaY and HY
Pope, Christopher G.
, p. 3647 - 3651 (1996)
The enthalpy and entropy of adsorption of ethanoic acid by the zeolite HY do not appear to be strongly influenced by the geometric constraints of the pore system. These results, which were predicted previously, contrast with those on H-ZSM-5. A companion examination of adsorption by NaY was complicated by chemical reactions which produced small amounts of ethanoate ions, water, ethanoic anhydride and methane. These products were not observed on HY. The intensity of FTIR absorption bands in the frequency range 1850-1250 cm-1, which resulted from adsorption of ethanoic acid on NaY, depended strongly on adsorbed molecule concentration and were time dependent. Spectra were simpler, and less intense at the same surface concentration on HY.
ELECTROPHILIC ADDITION REACTIONS TO PHENYLACETYLENE CATALYZED BY HETEROPOLY ACID
Matsuo, Kazuhiro,Urabe, Kazuo,Izumi, Yusuke
, p. 1315 - 1316 (1981)
Heteropoly acid efficiently catalyzed the addition reactions of water and carboxylic acid to phenylacetylene to form acetophenone at 60 deg C in the liquid phase.The higher catalytic activity of heteropoly acid compared with H2SO4 and HClO4 is due to the cooperative action of heteropoly anion.
Mass Spectra and Pyrolyses of Some Vinylene Carbonates
Breitbeil, Fred W.,Skrobot, Angeline A.
, p. 702 - 704 (1982)
The mass spectra of a series of 1,3-dioxol-2-ones were examined for evidence of oxirenes in the fragmentation process.The M-cation radical-CO2 (oxirene or isomers) fragment was observed in six of eight samples.Four major pathways explain the mass spectra: M-cation radical-CO2-CO, M-cation radical-C2O3, M-cation radical-C2O2R and M-cation radical-CO-CO2.Metastable peaks support this.Similar pathways on pyrolysis were sought and observed.At 800 deg C and pressure of 1.5-4 mm, 1,3-dioxol-2-ones 1-3 and 5-7 were pyrolyzed in a stream of helium.The major products were, respectively, ketene (R1=R2=H), propene (R1=R2=CH3), fluorene (R1=R2=C6H5), ethene (R1=H, R2=CH3), stilbene (R1=H, R2=C6H5), and styrene (R1=CH3, R2=C6H5).Apparently the 1,3-dioxol-2-ones lose CO2 and CO successively to produce a carbene which either rearranges or dimerizes.