- Carbonylation of methyl acetate in the presence of polymeric rhodium-containing catalysts
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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.
- Kolesnichenko, N. V.,Batov, A. E.,Markova, N. A.,Slivinsky, E. V.
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- Concerted General Acid Catalysis in the Reaction of Acetate Ion with Water-soluble Carbodi-imide
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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.
- Ibrahim, Ibrahim T.,Williams, Andrew
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- Selectivity Behavior in Hydrocarbonylation of Methyl Acetate Using Homogeneous Rh Complex Catalyst
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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.
- Kelkar, A. A.,Chaudhari, R. V.
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- Degradation of a veterinary pharmaceutical product in water by electro-oxidation using a BDD anode
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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.
- Espinoza, C.,Contreras, N.,Berros, C.,Salazar, R.
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- The atmospheric oxidation of ethyl formate and ethyl acetate over a range of temperatures and oxygen partial pressures
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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.
- Orlando, John J.,Tyndall, Geoffrey S.
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- TRIOXABICYCLO PENTANE IH PHOTOSENSITIZED OXYGENATION OF 2-DIAZO-3-BUTANONE
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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.
- Ando, Wataru,Miyazaki, Hajime,Ito, Kenji,Auchi, Daikan
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- Infrared Study of the Surface Reaction of Gaseous Sulphuryl Chloride with Metal Carboxylates
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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
- Nakamura, Shigeaki
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- Adsorption of ethanoic acid on zeolites NaY and HY
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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.
- Pope, Christopher G.
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- ELECTROPHILIC ADDITION REACTIONS TO PHENYLACETYLENE CATALYZED BY HETEROPOLY ACID
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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.
- Matsuo, Kazuhiro,Urabe, Kazuo,Izumi, Yusuke
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- Mass Spectra and Pyrolyses of Some Vinylene Carbonates
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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.
- Breitbeil, Fred W.,Skrobot, Angeline A.
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- Ctc-[Pt(NH3)2(cinnamate)(valproate)Cl2] is a highly potent and low-toxic triple action anticancer prodrug
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Pt(iv) prodrugs have gained tremendous attention due to their indisputable advantages compared to cisplatin. Herein, new Pt(iv) derivatives with cinnamic acid at the first axial position, and inhibitor of matrix metalloproteinases-2 and-9, histone deacetylase, cyclooxygenase or pyruvate dehydrogenase at the second axial position are constructed to develop multi-action prodrugs. We demonstrate that Pt(iv) prodrugs are reducible and have superior antiproliferative activity with IC50 values at submicromolar concentrations. Notably, Pt(iv) prodrugs exhibit highly potent anti-tumour activity in an in vivo breast cancer model. Our results support the view that a triple-action Pt(iv) prodrug acts via a synergistic mechanism, which involves the effects of CDDP and the effects of axial moieties, thus jointly leading to the death of tumour cells. These findings provide a practical strategy for the rational design of more effective Pt(iv) prodrugs to efficiently kill tumour cells by enhancing their cellular accumulation and tuning their canonical mechanism.
- Li, Yang,Shi, Shan,Zhang, Shurong,Gan, Zongjie,Wang, Xin,Zhao, Xudong,Zhu, Yijian,Cao, Meiting,Wang, Xiaoyue,Li, Wei
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- SYNTHESIS OF ACETIC ANHYDRIDE BY VAPOR PHASE CARBONYLATION OF METHYL ACETATE WITH A NICKEL-ACTIVE CARBON CATALYST
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Vapor phase carbonylation of methyl acetate on nickel-active carbon catalyst was studied under pressurized conditions in the presence of methyl iodide as a promoter.High pressure was essential for the acetic anhydride formation.A fairly large amount of acetic acid, by-product, was also formed under the water-free reaction condition.
- Fujimoto, Kaoru,Shikada, Tsutomu,Miyauchi, Michiharu,Tominaga, Hiro-o
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- Dicarboxylic Acids Link Proton Transfer Across a Liquid Membrane to the Synthesis of Acyl Phosphates. A Model for P-Type H(+)-ATPases
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H(+)-ATPases are ion pumps that link proton transfer across cell membranes to the synthesis or hydrolysis of ATP.A current research goal is to understand the molecular-level mechanism of this linking.We present a chemical model that mimics some features of H(+)-ATPases by linking proton transfer across a liquid membrane to the synthesis of acyl phosphates using carboxylic acid anhydride intermediates.Citraconic acid (cis-2-methyl-2-butenedioic acid) accelerated the transfer of protons from a pH 0.3 solution across a chloroform liquid membrane to a pH 10 solution.The mechanism involved spontaneous formation of a small amount of citraconic anhydride (0.6percent) in the pH 0.3 layer.This anhydride partitioned into the chloroform layer and diffused to the pH 10 layer, where it hydrolyzed, generating two protons.When the pH 10 layer contained phosphate (1.0 M), some of the citraconic anhydride reacted with phosphate to form citraconyl phosphate, 5.0percent yield.In separate experiments, we confirmed that citraconyl phosphate had high phosphoryl donor potential by reacting it with morpholine to form a phosphoramidate (11.5percent yield) or with fluoride to form fluorophosphonate (32percent yield).To demonstrate the link between an acyl phosphate and a proton gradient in the reverse direction, we used succinyl phosphate, whose hydrolysis occurs in two steps: formation of succinic anhydride, which consumes protons, followed by hydrolysis of succinic anhydride, which releases protons.We generated a pH gradient by carrying out these two steps in separate solutions.Hydrolysis of succinyl phosphate (3.9 mmol) at pH 6.00 started with a increase in pH to 6.16 (0.59 mmol of H(+) consumed) caused by the formation of succinic anhydride.We extracted this anhydride with dichloromethane and transferred it to a separate solution at pH 6.05.Hydrolysis of the anhydride released protons (0.36 mmol), decreasing the pH to 5.23.Our model suggests that H(+)-ATPases could use acyl phosphates and carboxylic acid anhydride intermediates to link proton transfer to ATP synthesis or hydrolysis.
- Colton, Ian J.,Kazlauskas, Romas J.
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- Electrophilic Substitution of Polycyclic Fluoranthene Hydrocarbons
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The first systematic study of the sites of electrophilic substitution (acylation and/or bromination) of polycyclic fluoranthene hydrocarbons is described.The hydrocarbons studied include indenopyrene (1), benzaceanthrylene (2), benzacephenanthrylene (3), and indenochrysene (4).Compounds 1-4 all undergo bromination regioselectively in a single site.The latter are determined by conversion of the bromo derivatives to monodeuterio analogues by metal exchange with butyllithium and analysis of their high-resolution 1H and 13C NMR spectra in comparison with those of the parent hydrocarbons.This method is potentially generally applicable to determination of the sites of substitution of other complex polycyclic hydrocarbon ring systems.Acylation of 1 is shown to take place in the same site as bromination, i.e., the 12-position.For 2 and 4, substitution occurs in the 8- and 5-positions, respectively, in good agreement with theoretical prediction by the DEWAR-PI method based on the relative energies of the Wheland intermediates for substitution at various ring positions.However, for 1 and 3 the principal sites of bromination observed experimentally are the 12- and 1-positions, respectively, which do not accord with theoretical prediction of the 3,5- and 8-positions, respectively.In the latter cases, the observed sites of bromination are only slightly less favorable energetically than the theoretically calculated sites and are probably within the limit of accuracy of the calculations.
- Minabe, Masahiro,Cho, Bongsup P.,Harvey, Ronald G.
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- Diozonides from coozonolyses of suitable O-methyl oximes and ketones
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Ozonolyses of the O-methyl oximes of cyclic ketones 5a - c in the presence of 1,4-cyclohexanedione (6) and ozonolyses of the O-methylated dioxime 8 of 1,4-cyclohexanedione in the presence of cycloketones 7a - c afforded the corresponding diozonides 11. Ozonolysis of the O-methyl oxime of acetone gave diozonide 18 in the presence of 6 and diozonide 21 in the presence of butanedione. Ozonolysis of the O-methyl oxime of cyclohexanone in the presence of butanedione gave diozonide 22. In addition, representatives of the hitherto unknown types of dispiro ozonides 12 having a lactam ring system have been obtained from the ozonolyses of 8 and 7.
- Griesbaum, Karl,Liu, Xuejun,Dong, Yuxiang
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- Detection of Elusive Chloro- and Bromo Substituted Ozonides by Nucleophilic Substitution Reactions
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Ozonolyses of 2,3-dichloro-2-butene (4), 4,5-dichloro-4-octene (9) and 2,3-dibromo-1,4-dichloro-2-butene (12) on polyethylene gave the corresponding ozonides 5,10 and 13a, respectively, which could not be isolated or unequivocally identified. Their identity could be proven, however, via substitution of the chloro- or bromo substituents at the ozonide rings by stabilizing substituents and subsequent isolation of the substituted ozonides 6, 11, 13b and 13c. Ozonolysis of 2,3-diacetoxy-2-butene (14) on polyethylene, in dichloro methane and in pentane gave mixtures of 16 and 17 but not ozonide 6.
- Griesbaum, Karl,Schlindwein, Konrad,Bettinger, Herbert
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- Linear-reactor-infrared-matrix and Microwave Spectroscopy of the cis-2-Butene Gas-phase Ozonolysis
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Investigation of the formation of complex products in the gas-phase ozonolysis of cis-2-butene by linear-reactor-infrared-matrix and linear-reactor-microwave spectroscopy is reported.The following species have been unequivocally detected: secondary 2-butene ozonide, acetic acid, peracetic acid, glycolaldehyde, dimethyl ketene, the simple mixed anhydrides of formic and acetic acid, 2,3-epoxy-butane and 2-butanone, besides polyatomic products alredy known.In contrast, the primery ozonide has been detectable neither by LR.-MW. nor by LR.-IR.Observation of both stereoisomeric epoxides and kinetic modelling are used to support the intermediate formation of the O'Neal-Blumstein radical CH3CH(O2)CH(O)CH3 and the existence of a reaction channel in which the two carbon atoms of the C,C double bond of the olefin remain connected.As the dominant reaction path a mechanism with a Criegee type split into methyldioxirane (ethylidene peroxide) and acetaldehyde is considered and subsequently proposed to explain formation of many complex products by either unimolecular or bimolecular processes of the peroxide.For the reactions considered, thermochemical estimates of reaction enthalpies and activation data are included.Kinetic modelling for a partial reaction mechanism involving at least two different paths of decay of the O'Neal-Blumstein biradical into Criegee-type intermediates and the 2,3-epoxy-butanes is discussed.
- Kuehne, Heinz,Forster, Martin,Hulliger, Juerg,Ruprecht, Heidi,Bauder, Alfred,Guenthard, Hans-Heinrich
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- Oxidation of ethyl ether on borate glass: Chemiluminescence, mechanism, and development of a sensitive gas sensor
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A gas sensor was developed by using the chemiluminescence (CL) emission from the oxidation of ethyl ether by oxygen in the air on the surface of borate glass. Theoretical calculation, together with experimental investigation, revealed the main CL reactions: ethyl ether is first oxidized to acetaldehyde and then to acetic acid, during which main luminous intermediates such as CH3CO? are generated and emit light with a peak at 493 nm. At a reaction temperature of 245°C, the overall maximal emission was found at around 460 nm, and the linear range of the CL intensity versus the concentration of ethyl ether was 0.12-51.7 μg mL-1 (R = 0.999, n = 7) with a limit of detection (3σ) of 0.04 μg mL-1. Interference from foreign substances including alcohol (methanol, ethanol and isopropanol), acetone, ethyl acetate, n-hexane, cyclohexane, dichloromethane, or ether (n-butyl ether, tetrahydrofuran, propylene oxide, isopropyl ether and methyl tert-butyl ether) was not significant except a minimal signal from n-butyl ether (a simple, sensitive and selective gas sensor for the determination of trace ethyl ether.
- Hu, Jing,Xu, Kailai,Jia, Yunzhen,Lv, Yi,Li, Yubao,Hou, Xiandeng
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- Atmospheric chemistry of two biodiesel model compounds: Methyl propionate and ethyl acetate
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The atmospheric chemistry of two C4H8O2 isomers (methyl propionate and ethyl acetate) was investigated. With relative rate techniques in 980 mbar of air at 293 K the following rate constants were determined: k(C2H5C(O)OCH3 + Cl) = (1.57 ± 0.23) × 10-11, k(C2H5C(O) OCH3 + OH) = (9.25 ± 1.27) × 10-13, k(CH 3C(O)OC2H5 + Cl) = (1.76 ± 0.22) × 10-11, and k(CH3C(O)OC2H5 + OH) = (1.54 ± 0.22) × 10-12 cm3 molecule -1 s-1. The chlorine atom initiated oxidation of methyl propionate in 930 mbar of N2/O2 diluent (with, and without, NOx) gave methyl pyruvate, propionic acid, acetaldehyde, formic acid, and formaldehyde as products. In experiments conducted in N 2 diluent the formation of CH3CHClC(O)OCH3 and CH3CCl2C(O)OCH3 was observed. From the observed product yields we conclude that the branching ratios for reaction of chlorine atoms with the CH3-, -CH2-, and -OCH3 groups are 9 ± 2%, respectively. The chlorine atom initiated oxidation of ethyl acetate in N2/O 2 diluent gave acetic acid, acetic acid anhydride, acetic formic anhydride, formaldehyde, and, in the presence of NOx, PAN. From the yield of these products we conclude that at least 41 ± 6% of the reaction of chlorine atoms with ethyl acetate occurs at the -CH2- group. The rate constants and branching ratios for reactions of OH radicals with methyl propionate and ethyl acetate were investigated theoretically using transition state theory. The stationary points along the oxidation pathways were optimized at the CCSD(T)/cc-pVTZ//BHandHLYP/aug-cc-pVTZ level of theory. The reaction of OH radicals with ethyl acetate was computed to occur essentially exclusively (~99%) at the -CH2- group. In contrast, both methyl groups and the -CH2- group contribute appreciably in the reaction of OH with methyl propionate. Decomposition via the α-ester rearrangement (to give C2H5C(O)OH and a HCO radical) and reaction with O 2 (to give CH3CH2C(O)OC(O)H) are competing atmospheric fates of the alkoxy radical CH3CH2C(O)OCH 2O. Chemical activation of CH3CH2C(O)OCH 2O radicals formed in the reaction of the corresponding peroxy radical with NO favors the α-ester rearrangement.
- Andersen, Vibeke F.,Berhanu, Tesfaye A.,Nilsson, Elna J. K.,Jorgensen, Solvejg,Nielsen, Ole John,Wallington, Timothy J.,Johnson, Matthew S.
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- Acyl iodides in organic synthesis: V. Reactions with carboxylic acid esters
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Acyl iodides react with alkyl, alkenyl, and aralkyl esters derived from saturated, unsaturated, and aromatic mono- and dicarboxylic acids in the absence of a catalyst. The reaction involves cleavage of the OR bond and formation of organic iodide RI (including CH2=CHI) and one or two symmetric carboxylic acid anhydrides. Phenyl acetate reacts with benzoyl iodide to give acetyl iodide and phenyl benzoate as a result of cleavage of the (O=)C-O bond. The reaction of diethyl fumarate with acetyl iodide is accompanied by cis- trans isomerization to afford maleic anhydride. In the reactions of acetyl iodide with diethyl oxalate and diethyl malonate, CO and CO2 and CO 2 and polyketene are formed, respectively, in addition to ethyl iodide and acetic anhydride. Ethyl esters of strong organic acids, e.g., ethyl trihaloacetates, failed to react with acyl iodides under analogous conditions.
- Voronkov,Trukhina,Vlasova
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- MECANISME DE CETONISATION DU PHENYLACETYLENE ACIDO-CATALYSEE PAR H2SO4, HSO3CH3 et BF3 (CH3COOH)2. MISE EN EVIDENCE DE L'INTERMEDIARE ACETOXYSTYRENE
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Acetic acid reacts with phenylacetylene in acid catalysis to give an intermediate product: α-acetoxystyrene, which reacts fastly to give acetophenone.A kinetical study is shown.
- Montheard, Jean-Pierre,Camps, Marcel,Benzaid, Ahmed
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- PROCESS FOR GENERATING ACID ANHYDRIDES
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Provided is a method of producing an anhydride of an organic mono-acid comprising contacting an organic mono-acid and a thermally regenerable anhydride to produce the anhydride of the organic mono-acid, and either a diacid of the regenerable anhydride, a partially hydrolyzed regenerable anhydride, or both. In a particular example, acetic acid and glutaric anhydride can be reacted to form acetic anhydride.
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Paragraph 0087-0088; 0089-0092
(2021/11/13)
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- A transesterification-acetalization catalytic tandem process for the functionalization of glycerol: The pivotal role of isopropenyl acetate
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At 30 °C, in the presence of Amberlyst-15 as a catalyst, a tandem sequence was implemented by which a pool of innocuous reactants (isopropenyl acetate, acetic acid and acetone) allowed upgrading of glycerol through selective acetylation and acetalization processes. The study provided evidence for the occurrence of multiple concomitant reactions. Isopropenyl acetate acted as a transesterification agent to provide glyceryl esters, and it was concurrently subjected to an acidolysis reaction promoted by AcOH. Both these transformations co-generated acetone which converted glycerol into the corresponding acetals, while acidolysis sourced also acetic anhydride that acted as an acetylation reactant. However, tuning of conditions, mostly by changing the reactant molar ratio and optimizing the reaction time, was successful to steer the set of all reactions towards the synthesis of either a 1?:?1 mixture of acetal acetates (97% of which was solketal acetate) and triacetin, or acetal acetates in up to 91% yield, at complete conversion of glycerol. To the best of our knowledge, a one-pot protocol with such a degree of control on the functionalization of glycerol via transesterification and acetalization reactions has not been previously reported. The procedure was also easily reproduced on a gram scale, thereby proving its efficiency for preparative purposes. Finally, the design of experiments with isotopically labelled reagents, particularly d4-acetic acid and d6-acetone, helped to estimate the contribution of different reaction partners (iPAc/AcOH/acetone) to the formation of final products. This journal is
- Calmanti, Roberto,Perosa, Alvise,Rigo, Davide,Selva, Maurizio
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supporting information
p. 5487 - 5496
(2020/09/23)
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- PHTHALAZINE DERIVATIVES, AND PREPARATION METHOD, PHARMACEUTICAL COMPOSITION AND USE THEREOF
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The present invention provides a compound of formula I, a cis-trans isomer, an enantiomer, a diastereoisomer, a racemate, a solvate, a hydrate, or a pharmaceutical acceptable salt and ester thereof, a preparation method for preparing the same, a pharmaceutical composition comprising the same and a use of the compound as an α5-GABAA receptor regulator, wherein T, Z, A and Y are as defined in the description.
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Paragraph 0194; 0261
(2018/11/21)
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- Production of acetic anhydride
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An object is to provide a method for producing a ketene derivative that decreases the consumption quantity of phosphorus compounds, and the discharge quantity of the phosphorus compounds into the environment. A method for producing a ketene derivative includes a step (i) of conducting thermal decomposition reaction of acetic acid in a presence of a phosphorus-containing catalyst in a reactor to produce a thermal decomposition gas containing ketene, a step (ii) of cooling the thermal decomposition gas to be separated into a gaseous component containing ketene, and a condensed liquid containing a phosphorus compound (a), and a step (iii) of causing the ketene to react with a different organic compound to produce a ketene derivative. The step (i) includes conducting the thermal decomposition reaction while supplying, into the reactor, the condensed liquid containing the phosphorus compound (a) or a concentrated liquid of the condensed liquid.
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Paragraph 0067-0069
(2017/06/27)
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- Anhydrides from aldehydes or alcohols via oxidative cross-coupling
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A novel type of metal-free oxidative cross-coupling for the synthesis of symmetrical and mixed anhydrides from aldehydes or benzylic alcohols has been developed. The aldehydes or alcohols were converted in situ into their corresponding acyl chlorides, which were then reacted with an array of carboxylic acids. The methodology has a general applicability, and was successfully employed to prepare either aromatic or aliphatic symmetrical anhydrides and mixed anhydrides, which are very unstable compounds.
- Gaspa, Silvia,Amura, Ida,Porcheddu, Andrea,De Luca, Lidia
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supporting information
p. 931 - 939
(2017/02/10)
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- One-step synthesis of pyruvic acid from glycerol oxidation over Pb promoted Pt/activated carbon catalysts
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One-step production of pyruvic acid through selective oxidation of glycerol was investigated using lead promoted platinum/activated carbon (Pb-Pt/AC) catalysts under mild conditions. The results of N2 physisorption, X-ray diffraction, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy revealed that the alloy phases of PtPb and PtxPb were favorable for pyruvic acid production from glycerol oxidation, whereas the Pb3(CO3)2(OH)2 and surface Pb0 species inhibited the glycerol conversion. The loading of Pb and the catalyst preparation method (including impregnation and deposition precipitation) affected the formation of different metal species. Pyruvic acid was obtained at a yield of 18.4% on a 5.0 wt% Pb-5.0 wt% Pt/AC catalyst prepared by co-deposition precipitation method and 500 °C argon treatment.
- Zhang, Chen,Wang, Tao,Ding, Yunjie
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p. 928 - 937
(2017/05/22)
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- Acetic anhydride preparation method
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The invention relates to a preparation method of acetic anhydride. The method employs acetic acid and thionyl chloride as raw materials, the steps of synthesis, tail gas recovery, and condensation collection are carried out on the above raw materials according to certain proportion; mass ratio of acetic acid to thionyl chloride is 1:1-2; synthesis temperature is 130-140 DEG C; the condensation collection step is carried out after 30-60 minutes of the reaction, a reactor is heated to the temperature of 135-145 DEG C, when no gas escapes from a condenser tube, condensed liquid is collected; the tail gas recovery step is characterized in that a sodium hydroxide solution with mass concentration being 25-35% is used for recovery. The method has the advantages of reasonable design and strong operationality, acetic anhydride with extremely high purity can be prepared by only one step, equipment investment is saved, production cost for acetic anhydride is reduced, and product yield is high.
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Paragraph 0017
(2016/11/24)
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- An anhydride producing method
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An anhydride producing method is disclosed. The method includes oxidizing a C2-C7 alcohol or a C2-C7 aldehyde under the existence of a catalyst and an oxidant to obtain an anhydride, wherein the reaction pressure is atmospheric pressure, the temperature is 50-200 DEG C, the hourly space velocity is 0.5-100 h, the catalyst is a supported type Pd catalyst and the oxidant is oxygen or air. The method adopts the oxygen as the oxidant, and achieves high-selectivity conversion of the alcohol or the aldehyde to the anhydride through an oxidizing manner. Anhydride selectivity is 10-85%. A substrate conversion rate is 10-100%. The yield of the anhydride is 10-85%. The method does not need a high reaction temperature and can be performed at room temperature or a temperature close to room temperature, thus saving a large amount of energy. The method is low in equipment requirement, low in investment, simple in reaction system and easy in industrialization. The catalyst is long in service lifetime and free of loss.
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Paragraph 0033; 0034
(2017/06/24)
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- HIV INTEGRASE INHIBITORS
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The present invention features compounds that are HIV integrase inhibitors and therefore are useful in the inhibition of HIV replication, the prevention and/or treatment of infection by HIV, and in the treatment of AIDS and/or ARC.
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- Resin, optical material, and optical device
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The purpose of the invention is to provide a resin, which has a high refractive index, excellent heat resistance and moldability, and high transparency, and is useful as a material for configuring optical devices, etc. The invention provides a resin comprising acyl hydrazone bonds and having a number average molecular weight of 500-500,000, wherein the acyl hydrazone bond equivalent is 100-4000.
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- Efficient hydration of alkynes through acid-assisted Bronsted acid catalysis
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The combined acid catalyzed hydration of alkynes is an efficient one-step synthesis of carbonyl compounds. This atom-economical method is effective with a wide range of substrates, and the products are obtained in very good yields with low catalyst loading (0.2%). Furthermore, solid acids like Nafion were also efficient and could be easily recycled multiple times without loss of reactivity.
- Liang, Shengzong,Hammond, Gerald B.,Xu, Bo
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p. 903 - 906
(2015/01/09)
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- Alcohol cross-coupling for the kinetic resolution of diols via oxidative esterification
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We present an organocatalytic C-O-bond cross-coupling strategy to kinetically resolve racemic diols with aromatic and aliphatic alcohols, yielding enantioenriched esters. This one-pot protocol utilizes an oligopeptide multicatalyst, m-CPBA as the oxidant, and N,N-diisopropylcarbodiimide as the activating agent. Racemic acyclic diols as well as trans-cycloalkane-1,2-diols were kinetically resolved, achieving high selectivities and good yields for the products and recovered diols.
- Hofmann, Christine,Schümann, Jan M.,Schreiner, Peter R.
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p. 1972 - 1978
(2015/02/19)
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- METHODS AND COMPOSITIONS FOR MAKING ANTIBODIES AND ANTIBODY DERIVATIVES WITH REDUCED CORE FUCOSYLATION
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The invention provides methods and compositions for preparing antibodies and antibody derivatives with reduced core fucosylation.
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Page/Page column
(2014/01/23)
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- PROCESS
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A continuous process for the co-production of acetic acid and acetic anhydride by (a) contacting carbon monoxide with a liquid reaction composition comprising methyl acetate, dimethyl ether or a mixture thereof, a Group VIII metal catalyst, methyl iodide, acetic acid, acetic anhydride, water in a concentration of 0.1 wt% or less, (b) withdrawing liquid reaction composition from the reaction zone and introducing at least a portion of the withdrawn liquid reaction composition into a flash separation zone, and (c) removing from the flash separation zone a vapour fraction comprising acetic anhydride, acetic acid and methyl iodide and a liquid fraction comprising acetic anhydride, and Group VIII metal catalyst in which at least one of the liquid reaction composition and the withdrawn liquid reaction composition introduced into the flash separation zone comprises at least one metal salt selected from salts of Group IA and Group IIA metals and the molar ratio of acetic acid to acetic anhydride in the vapour fraction removed from the flash separation zone is maintained at greater than or equal to 1, preferably greater than or equal to 1.2.
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Page/Page column 14-15
(2014/09/29)
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- SYNTHESIS OF HIGH CALORIC FUELS AND CHEMICALS
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In one embodiment, the present application discloses methods to selectively synthesize higher alcohols and hydrocarbons useful as fuels and industrial chemicals from syngas and biomass. Ketene and ketonization chemistry along with hydrogenation reactions are used to synthesize fuels and chemicals. In another embodiment, ketene used to form fuels and chemicals may be manufactured from acetic acid which in turn can be synthesized from synthesis gas which is produced from coal, biomass, natural gas, etc.
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-
Paragraph 0070
(2013/05/23)
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- Process for Producing Carboxylic Acid Anhydrides
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The present invention relates to a process for producing carboxylic acid anhydrides by the carbonylation reaction of a carboxylic acid ester, derived from an alcohol and a carboxylic acid, with carbon monoxide containing a small amount of hydrogen in a liquid reaction medium in the presence of a Group VIII B catalyst to produce a carboxylic acid anhydride. The liquid reaction medium comprises the Group VIII B catalyst, an organic halide, the carboxylic acid ester, an alkali metal salt, the carboxylic acid anhydride, the carboxylic acid, N-acetylimidazole as a protecting agent, and ethylidene diacetate (EDA) as an organic promoter. By making use of the protecting agent of N-acetylimidazole, metal ions in the reactor can be prevented from reacting with EDA so as to reduce the formation of hardly-soluble tars during the reaction. Also, the EDA organic promoter is kept at a certain content in the system to promote the overall carbonylation reaction rate.
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Page/Page column 4
(2012/03/12)
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- Methods and compositions for making antibodies and antibody derivatives with reduced core fucosylation
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The invention provides methods and compositions for preparing antibodies and antibody derivatives with reduced core fucosylation.
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- METHOD FOR PREPARING ACETYLATED DERIVATIVES OF AN AMYLACEOUS MATERIAL
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The present invention relates to a continuous method for preparing acetylated derivatives of an amylaceous material. The invention also relates to a solid composition of at least one acetylated derivative of an amylaceous material obtained by means of said method. The invention finally relates to the use of such a composition to prepare thermoplastic, elastomeric, adhesive, pharmaceutical and/or ink compositions.
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- Cleavage of α-dicarbonyl compounds by terpene hydroperoxide
-
The highly reactive α-dicarbonyl compounds, glyoxal, methylglyoxal (MGO), and 3-deoxyglucosone, react with the amino groups of proteins to form advanced glycation end-products (AGEs) which have been implicated in diabetic complications, aging, and Alzheimer's disease. We found that a test sample of terpinen-4-ol (T4) containing hydroperoxides showed cleaving activity toward an α-dicarbonyl compound, but that the freshly isolated pure sample did not. Prepared terpinen-4-ol hydroperoxide (T4-H) also efficiently cleaved the C-C bond of the α-dicarbonyl compounds via Baeyer-Villiger-like rearrangement and subsequent hydrolysis of an acid anhydride moiety in the rearranged product to give carboxylic acids. Other terpene hydroperoxides, as well as T4-H, showed significant cleaving activities, and all these hydroperoxides protected RNase A from the lowering of enzyme activity induced by MGO. The cleaving mechanism via Baeyer-Villiger-like rearrangement was confirmed by time-interval NMR measurements of the reaction mixture of the symmetrical α-dicarbonyl compound, diacetyl with T4-H.
- Nagamatsu, Ryu-Ichiro,Mitsuhashi, Shinya,Shigetomi, Kengo,Ubukata, Makoto
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p. 1904 - 1908
(2013/01/15)
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- Efficient and convenient synthesis of symmetrical carboxylic anhydrides from carboxylic acids with sulfated zirconia by phase transfer catalysis
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An efficient and convenient procedure for the synthesis of symmetrical carboxylic anhydrides from carboxylic acids with sulfated zirconia by PEG-1000 phase transfer catalysis has been developed. The reactions proceeded under mild and solvent-free conditions to provide the carboxylic anhydrides in good to excellent yields. The product can be isolated by a simple extraction with organic solvent, and the catalyst system can be recycled or reused without any significant loss of catalytic activity.
- Hu, Yu Lin,Zhao, Xing E.,Lu, Ming
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experimental part
p. 255 - 262
(2012/04/17)
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- CONTROLLED-RELEASE IMMUNOGENIC FORMULATIONS TO MODULATE IMMUNE RESPONSE
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Single-dose controlled-release immunogenic formulations, such as vaccines, based on bioerodible polyanhydride copolymer or homopolymer microparticles for the control of immune response mechanisms are provided. The copolymer or homopolymer microparticles degrade by surface-erosion from in vivo hydrolysis of anhydride linkages at the surface of the microparticle, which results in controlled release of immunogen(s) to a patient.
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- PROCESS FOR PRODUCING CARBOXYLIC ACID ANHYDRIDES
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A process for producing carboxylic acid anhydrides by the carbonylation reaction of a carboxylic acid ester, derived from an alcohol and a carboxylic acid, with carbon monoxide containing a small amount of hydrogen in a liquid reaction medium in the presence of a Group VIII B catalyst to produce a carboxylic acid anhydride. The reaction medium comprises the Group VIII B catalyst, an organic halide, the carboxylic acid ester, an alkali metal salt, the carboxylic acid anhydride, the carboxylic acid, and at least one ionic liquid consisting of a cation and an anion where the cation of the ionic liquid has a nitrogen-containing heterocyclic structure. The ionic liquid has at least one of the following structural forms: The reaction rate of the carbonylation reaction is increased by the use of the specified ionic liquid promoters.
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Page/Page column 5
(2010/06/19)
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- Solvent free catalytic synthesis of 2-methylallylidene diacetate using cation-exchange resin
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2-Methylallylidene diacetate (DMA) was synthesis between methacrolein (MAL) and acetic anhydride using a mesoporous strong acidic cation-exchange resin as the catalyst. The effects of the molar ratio of the reactants, catalyst loading and stirring rate were investigated. The reaction kinetic equations were established under conditions that eliminated both internal and external diffusions. Kinetic constants such as the pre-exponential factor and the activation energy were also determined. The mechanism is proposed according to the kinetic study.
- Wang, Baohe,Zhang, Haojian,Jing, Xin,Zhu, Jing
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experimental part
p. 753 - 757
(2010/07/06)
-
- Process for producing carboxylic acid anhydrides
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The present invention relates to a process for producing carboxylic acid anhydrides, in which a carboxylic acid ester, derived from an alcohol and a carboxylic acid, and carbon monoxide containing a small amount of hydrogen are used as raw materials and subjected to a carbonylation reaction in a liquid reaction medium in the presence of a Group VIII B catalyst to produce a carboxylic acid anhydride. The reaction medium comprises the Group VIII B catalyst, an organic halide, the carboxylic acid ester, an alkali metal salt, at least one organic promoter, the carboxylic acid anhydride and the carboxylic acid, wherein the organic promoter is selected from at least one of the following structural forms (I), (II) and (III). According to the process of the present invention, the reaction rate of the carbonylation reaction is increased by the use of the specified organic promoters.
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Page/Page column 7-8; 10
(2009/07/10)
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- CARBONYLATION PROCESS
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Disclosed is an improved carbonylation process for the production of carboxylic acids, carboxylic acid esters, and/or carboxylic acid anhydrides wherein a carbonylation feedstock compound selected from one or more organic oxygenates such as alcohols, ethers, and esters is contacted with carbon monoxide in the presence of a carbonylation catalyst and one or more onium compounds. The carbonylation process differs from known carbonylation processes in that a halide compound, other than the onium salt, such as a hydrogen halide (typically, hydrogen iodide) and/or an alkyl halide (typically, methyl iodide), extraneous or exogenous to the carbonylation process is not fed or supplied to the process. The process can be improved by using a bidentate ligand comprising two functional groups selected from tertiary amines and tertiary phosphines, such as 2,2′-bipyridine and diphosphine derivatives.
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Page/Page column 9
(2009/10/06)
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- BENZOXAZINE DERIVATIVES AND USES THEREOF
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Compounds of formula (I) or pharmaceutically acceptable salts thereof are provided, wherein each of Z, X, R1, R2, R3, R4, y, n, and Ar are as defined, and described in classes and subclasses herein, which are agonists or partial agonists of the 2C subtype of brain serotonin receptors. The compounds, and compositions thereof, are useful for treating a variety of central nervous system disorders such as schizophrenia.
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Page/Page column 84
(2008/12/05)
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- The process of 4-hydroxybiphenyl synthesis from 4-isopropylbiphenyl
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The kinetics of the oxidation of 4-isopropylbiphenyl (1) in the liquid phase by oxygen to 1 -(1,1′-biphenyl-4-yl)-1 -methylethyl hydroperoxide (2) was investigated. The oxidizability of 1 in the temperature range from 60°C to 120°C and the overall energy activation of oxidation were determined. Long-term oxidation of 1 to 2 in the temperature range of 80-120°C was investigated, and the yield and selectivity of the process were determined. Pure 2 was obtained, and its properties were defined. 4-Hydroxybiphenyl was obtained as a result of the acidic decomposition of 2.
- Stec, Zbigniew,Orlinska, Beata,Jakubowski, BartLomiej,Zawadiak, Jan
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p. 527 - 532
(2008/12/22)
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- Highly efficient Bronsted acid-catalyzed cycloisomerizations of alkynes bearing bis(acetoxy) groups to indenyl ketones
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A Bronsted acid-catalyzed cycloisomerization of functionalized alkynes is described, which is assumed to be initiated through the formation of a benzylic cation intermediate. The reaction offers a highly efficient and straightforward route to indenyl ketones with a wide range of substituents under mild conditions.
- Liu, Yuanhong,Zhou, Shaolin,Li, Guijie,Yan, Bin,Guo, Shenghai,Zhou, Yebing,Zhang, Hao,Wang, Peng George
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supporting information; body text
p. 797 - 801
(2009/04/08)
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- Kinetic model of acylation of diacetylethylenediamine
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Descriptive kinetics of synthesis of tetraacetylethylenediamine by acylation of diacetylethylenediamine with acetic acid anhydride was examined. The apparent rate constants of the process were obtained, and a mathematical model adequately describing the process was constructed.
- Platonova,Akhmetshin,Kossoi,Vdovets,Laskin,Malin,Sitdikov
-
experimental part
p. 1808 - 1812
(2009/09/25)
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- CARBONYLATION PROCESS
-
Disclosed is a carbonylation process for the production of carboxylic acids, carboxylic acid esters and/or carboxylic acid anhydrides wherein a carbonylation feedstock compound selected from one or more organic oxygenates such as alcohols, ethers, and esters is contacted with carbon monoxide in the presence of a carbonylation catalyst and one or more onium compounds. The carbonylation process differs from known carbonylation processes in that a halide compound such as a hydrogen halide, typically hydrogen iodide, and/or alkyl halide, typically methyl iodide, extraneous or exogenous to the carbonylation process is not fed or supplied separately to the process.
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Page/Page column 8
(2008/06/13)
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- Secondary deuterium isotope effects on the acidity of carboxylic acids and phenols
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Secondary deuterium isotope effects (IEs) on acidities have been accurately measured by an NMR titration method applicable to a mixture of isotopologues. Deuteration definitely decreases the acidity of carboxylic acids and phenols, by up to 0.031 in the ΔpK per D. For aliphatic acids, the IEs decrease as the site of deuteration becomes more distant from the OH, as expected, but a surprising result is that IEs in both phenol and benzoic acid do not decrease as the site of deuteration moves from ortho to meta to para. The experimental data are supported by ab initio computations, which, however, substantially overestimate the IEs. The discrepancy does not seem to be due to solvation. The IEs originate in isotope-sensitive vibrations whose frequencies and zero-point energies are lowered upon deprotonation. In the simplest case, formate, the key vibration can be recognized as the C-H stretch, which is weakened by delocalization of the oxygen lone pairs. For the aromatic acids, delocalization cannot account for the near constancy of IEs from ortho, meta, and para deuteriums, but the observed IEs are consistent with calculated vibrational frequencies and electron densities. Moreover, the ability of the frequency analysis to account for the IEs is evidence against an inductive origin.
- Perrin, Charles L.,Dong, Yanmei
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p. 4490 - 4497
(2008/02/04)
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- Carbonylation process
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Disclosed is a carbonylation process wherein a mixture of a dialkyl carbonate and halide compound is contacted with carbon monoxide in the presence of a metal selected from Group VIII of the Periodic Table to co-produce carbon dioxide and a carbonyl compound selected from a carboxylic acid, an alkyl carboxylate ester, a carboxylic acid anhydride or a mixture of any two or more thereof. The carbon dioxide co-product of the process may be recovered, and sold or further reacted with a suitable substrate to produce useful chemicals such as urea or cyclic carbonates.
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Page/Page column 10-11
(2008/06/13)
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- Acetic anhydride and acetate ester co-production
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A method of co-producing acetic anhydride and an acetate ester includes pyrolizing acetic acid at elevated temperature to produce a first ketene stream, the first ketene stream being a vapor phase stream comprising ketene, acetic acid and water; cooling the first ketene stream to condense acetic acid and water therefrom, thereby generating (i) a weak acid aqueous stream and (ii) a ketene feed stream; feeding the ketene feed stream to an acetic anhydride reactor where the ketene is reacted with acetic acid to produce acetic anhydride; concurrently with step (c), feeding the weak acid aqueous stream to an esterification reactor wherein acetic acid in the weak acid stream is reacted with an organic alcohol to produce an acetate ester. Preferably, the organic alcohol is selected from organic alcohols which (i) form acetate esters which esters and optionally alcohols provide azeotropic mixtures with water and (ii) wherein the azeotropic mixtures have a water content greater than the amount of water generated by reaction of the alcohol with acetic acid to facilitate azeotropically separating the acetate ester from the reaction mixture.
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Page/Page column 3
(2008/06/13)
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- HETEROCYCLIC SUBSTITUTED INDANE DERIVATIVES AND RELATED COMPOUNDS FOR THE TREATMENT OF SCHIZOPHRENIA
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This invention relates to compounds of the formula (I) wherein J, M, G, m, X, R', R2, R4, R5, R6, R7, R8, R9, Y, n, z, and R" are defined as in the specification, pharmaceutical compositions containing them and their use in the treatment of central nervous system and other disorders.
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Page/Page column 85-86
(2010/02/12)
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- Method of phenol and carbonyl production
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The present invention describes a high yield and simplified method of preparing phenols and carbonyl compounds, such as acetaldehyde, through the catalytic decomposition of aromatic hydroperoxides. The synthetic process generally consists of decomposing hydroperoxides under a positive gas atmosphere and at an elevated temperature (80 to 100° C.) in the presence of a catalytic amount (0.01-0.8 mass percent (%)) of an anionic surface-active agent of the formula R—OSO3M or R—OP3Z2, where “M” is Na or K, where “Z” is Na, K or an alkyl groups containing between ten and fourteen carbons (C10-C14) and where “R” is an alkyl group consisting of between ten and fourteen carbons (C10-C14).
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- BLEACH ACTIVATOR BASED ON INULIN
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The invention relates to the use of a partially acylated fructan, in particular a partially acylated inulin, having a degree of substitution with acyl groups of 0.4-2.5 and a degree of substitution of at most 0.2 with other substituents, as a bleach activator. The solubility and efficiency of these derivatives is better than that of comparable products such as completely acylated derivatives and carboxylated derivatives. The derivatives are prepared by acylation in an aqueous medium under controlled pH.
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- Processes for the preparation of 6-11 bicyclic erythromycin derivatives
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The present invention relates to processes and intermediates for the preparation of 6-11 bicyclic erythromycin derivatives. In particular, the present invention relates to processes and intermediates for the preparation of a compound of formula (IX-c):
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- FLEXIBLE METHOD FOR THE JOINT PRODUCTION OF (I) FORMIC ACID, (II) A CARBOXYLIC ACID COMPRISING AT LEAST TWO CARBON ATOMS AND/OR THE DERIVATIVES THEREOF, AND (III) A CARBOXYLIC ACID ANHYDRIDE
-
Disclosed is a method for jointly producing (i) formic acid (III); (ii) a carboxylic acid comprising at least two carbon atoms (II) and/or the derivatives thereof; and (iii) a carboxylic acid anhydride (VII). According to said method, (a) a formic acid ester (I) is transesterified to formic acid (III) and the corresponding carboxylic acid ester (IV) by means of a carboxylic acid comprising at least two carbon atoms (II); (b) at least one portion of the carboxylic acid ester (IV) formed in step (a) is carbonylated in order to obtain the carboxylic acid anhydride (V); and (c) at least one portion of the carboxylic acid anhydride (V) formed in step (b) is further dehydrated by means of a carboxylic acid (VI) so as to form a carboxylic acid anhydride (VII) and the carboxylic acid (II).
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Page/Page column 24-28
(2008/06/13)
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- PROCESS FOR THE CARBONYLATION OF A CONJUGATED DIENE
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A process for the carbonylation of a conjugated diene, comprising reacting the conjugated diene with carbon monoxide and a co-reactant having a mobile hydrogen atom in the presence of a catalyst system including: (a) a source of palladium; and (b) a bidentate diphosphine ligand of formula (II): R1R2 > p1R3m-R-R4n-p2 5R6 wherein p1 and p2 represent phosphorus atoms; R1, R2, R5, and R6 independently represent the same or different optionally substituted organic radical containing a tertiary carbon atom through which each radical is linked to the phosphorus atom; R3 and R4 independently represent the same or different optionally substituted methylene groups; R represents an organic group comprising the bivalent bridging group C1-C2 through which R is connected to R3 and R4; m and n independently represent a natural number in the range of from 0 to 4, wherein the rotation about the bond between the carbon atoms C1 and C2 of the bridging group is restricted a temperature in the range of from 0 °C to 250 °C, and wherein the dihedral angle between the plane occupied by the three atom sequence composed of C1, C2 and the atom directly bonded to C1 in the direction of p1, and the plane occupied by the three atom sequence C1, C2 and the atom directly bonded to C2 in the direction of p2, is in the range of from 0 to 120°; and (c) a source of an anion.
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- 13-substituted milbemycin derivatives, their preparation and their use against insects and other pests
-
Compounds of formula (I) and salts thereof: Wherein R1 represents methyl, ethyl, isopropyl or s-butyl; and R2 represents hydrogen or alkyl. R3 represents hydrogen, optionally substituted alkanoyl, optionally substituted alkenoyl, optionally substituted alkynoyl, alkylsulfonyl, or alkoxycarbonyl, or R2 and R3 together with the nitrogen atom to which they are attached form a saturated, optionally substituted 4- to 6-membered heterocyclic ring group. The moiety -a- together with the carbon atom to which it is attached forms a 3- to 6-membered cycloalkyl group. These compounds have anthelmintic, acaricidal and insecticidal activity.
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- Continuous carbonylation process
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Disclosed is a continuous process wherein carbon monoxide, a carbonylatable reactant, and a halide in the gas phase are contacted with a non-volatile catalyst solution comprising an ionic liquid and a Group VIII metal to produce a carbonylation product in the gas phase. The process is useful for the continuous preparation of acetic acid by the carbonylation of methanol.
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Page/Page column 9-10
(2008/06/13)
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- Sulfonamide-containing heterocyclic compounds
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The present invention provides a sulfonamide- or sulfonylurea-containing heterocyclic compounds. Specifically, it provides a heterocyclic compound represented by the formula (I), a pharmacologically acceptable salt thereof or a hydrate of them. In the formula, A is hydrogen atom, a halogen atom, a C1-C4 alkyl or alkoxy group which may be substituted with a halogen atom, or cyano group; B is an optionally substituted aryl group or monocyclic heteroaryl group, or: (wherein, the ring Q is an aromatic ring which may have nitrogen atom; and the ring M is a ring sharing a double bond with the ring Q, which ring may have a heteroatom; and the rings Q and M may share nitrogen atom); K is a single bond; T, W, X and Y are the same as or different from each other and each is ═C(D)— (wherein, D is hydrogen or a halogen atom) or nitrogen atom; U and V are the same as or different from each other and each is ═C(D)—, nitrogen atom, —CH2—, oxygen atom or —CO—; Z is a single bond or —CO—NH—; and R1 is hydrogen atom, etc.
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- Polyoxyalkylene derivative and process of producing the same
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A polyoxyalkylene derivative is represented by formula (I) : wherein Z represents a residue of a compound having 2 to 8 hydroxyl groups; AO represents an oxyalkylene group having 2 to 18 carbon atoms; n and m each represent an integer of 0 to 2000 provided that both n and m do not represent 0; a and b each represent an integer satisfying the relationships; 2≤a+b≤8 and 1≤b; R represents a hydrocarbon group having 1 to 30 carbon atoms; and X represents a divalent hydrocarbon group having 3 to 10 carbon atoms.
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