- Utilization of Formic Acid as C1 Building Block for the Ruthenium-Catalyzed Synthesis of Formaldehyde Surrogates
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Dialkoxymethanes are becoming increasingly important as fuel additives, formaldehyde surrogates, and chemical intermediates, but the effective synthesis remains challenging. Herein, the catalytic synthesis of dialkoxymethane products using a molecular catalyst is reported. The catalytic system, comprising the [Ru(triphos)(tmm)] in combination with the Lewis acid Al(OTf)3, enables the direct synthesis of dialkoxymethane products with formic acid as C1 building block in high to excellent turnover numbers.
- Beydoun, Kassem,Thenert, Katharina,Wiesenthal, Jan,Hoppe, Corinna,Klankermayer, Jürgen
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p. 1944 - 1947
(2020/04/08)
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- Enhanced Hydrogenation of Carbon Dioxide to Methanol by a Ruthenium Complex with a Charged Outer-Coordination Sphere
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We report the hydrogenation of CO2 to MeOH by a Ru(triphos) catalyst containing a cationic tetraalkylammonium moiety in the outer coordination sphere. This catalyst affords higher TON and TOF values for MeOH than isostructural catalysts with neutral phosphine ligands. Kinetic data from operando NMR spectroscopy studies indicate the improvement in MeOH production arises from a 12-fold enhancement in the rate of hydrogenation of the transient formaldehyde intermediate. These results provide insight into the catalyst characteristics that promote MeOH formation.
- Erickson, Jeremy D.,Linehan, John C.,Preston, Andrew Z.,Wiedner, Eric S.
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p. 7419 - 7423
(2020/07/21)
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- Novel synthesis method of alkoxymethylamine compound
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The invention relates to a novel synthesis method of an alkoxymethylamine compound. The novel synthesis method comprises the steps: (1) dehydrating formaldehyde HCHO and alcohol R1OH by carrying out an aldolization under the action of an acid catalyst to obtain dialkoxymethane; and (2) carrying out a hydrocarbylation reaction on dialkoxymethane obtained in step (1) and substituted amine R2-NH2 toremove alcohol to obtain an alkoxymethyl substituent amine compound N-R1 oxymethyl-N-R2 amine. The synthesis method disclosed by the invention is simple in operation and high in yield reaching 92% orabove; and compared with the prior art, the novel synthesis method has the advantages that no acid wastewater, waste salts and chloromethyl alkyl ether serving as a cancerogen are greatly generated, the environment protection cost is favorably reduced, and the industrial prospect is higher.
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Paragraph 0043; 0044
(2019/10/01)
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- Effect of the Nature of the Catalyst on Catalytic Activity and Selectivity in the Formaldehyde Hydrogenation
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The effect the nature of the carrier and supported metal on the activity and selectivity of the catalyst in the reaction of formaldehyde hydrogenation to methanol is studied. The formation of such oxygenates as ethanol, formic acid, and diethyl formal is observed. It is found that ethanol forms on Fe-containing alloyed catalyst, while formic acid forms on the catalysts containing Au. Thermodynamic calculations are performed for a series of side reactions that confirm the formation of the resulting oxygenates.
- Tarasov
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p. 1670 - 1674
(2018/09/13)
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- Three Binary Azeotropic Systems for 1-(Methoxymethoxy)-propane, 1-(Ethoxymethoxy)-propane, and Methoxy(methoxymethoxy)methane with Three Alcohols at 101.33 kPa: Experimental Data, Correlation, and Purification
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The isobaric vapor-liquid equilibrium (VLE) data for three binary systems of 1-(methoxymethoxy)-propane and ethanol, 1-(ethoxymethoxy)-propane and 1-butanol, methoxy(methoxymethoxy)methane and 1-propanol at 101.33 kPa were measured using an improved Rose still. Three minimum boiling azeotropes were found for three binary systems containing ethanol, 1-butanol, and 1-propanol for which the azeotropic temperature and composition are 349.35 K and 70.95 mol % (ethanol), 384.02 K and 36.02 mol % (1-butanol), 368.68 K and 69.26 mol % (1-propanol), at 101.33 kPa, respectively. The VLE measurements were correlated by the Van Laar, Wilson, and nonrandom two-liquid models, and the results showed that the measurements had a good correlation by using thethree models for the three binary systems, respectively. The measurements of these three binary systems were thermodynamic as checked by the Herington semiempirical method.
- Song, Yu-He,Hou, Xing-Ming,Song, Juan,Zhang, Yue,Wang, Jie,Wei, Ping-He,Li, Cun-Fu
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p. 138 - 146
(2018/01/18)
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- Method for catalytically synthesizing diethoxymethane by ionic liquid
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The invention discloses a method for catalytically synthesizing diethoxymethane by ionic liquid. The method takes the ionic liquid as a catalyst and takes formaldehyde and ethanol as reactants to react for 0.5h to 6h in a nitrogen atmosphere under conditions that the reaction temperature is 80 DEG C to 160 DEG C and the reaction pressure is 0.5Mpa to 5.0MPa; a positive ion part of the ionic liquid is selected from imidazole positive ions, pyridine positive ions, quaternary ammonium positive ions, quaternary phosphonate positive ions and heterocyclic positive ions. According to the method disclosed by the invention, raw materials are obtained from coal chemical industry and biomass and are cheap and easy to obtain; the catalyst has high activity, can be repeatedly used, has low corrosion and has no special requirements on equipment; reaction conditions are moderate, and reaction and separation processes are simple.
- -
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Paragraph 0018; 0022
(2017/07/20)
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- Br?nsted-acidic ionic liquids as efficient catalysts for the synthesis of polyoxymethylene dialkyl ethers
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Acetalation of formaldehyde (HCHO) with dialkyl formal or aliphatic alcohol to prepare polyoxymethylene dialkyl ethers (RO(CH2O)nR, n ≥ 1) catalyzed by Br?nsted-acidic ionic liquids has been developed. The correlation between the structure and acidity activity of various ionic liquids was studied. Among the ionic liquids investigated, 1-(4-sulfonic acid)butyl-3-methylimidazolium hydrogen sulfate ([MIMBs]HSO4) exhibited the best catalytic performance in the reaction of diethoxymethane (DEM1) with trioxane. The influences of ionic liquid loading, molar ratio of DEM1 to HCHO, reaction temperature, pressure, time, and reactant source on the catalytic reaction were explored using [MIMBs]HSO4 as the catalyst. Under the optimal conditions of n([MIMBs]HSO4):n(DEM1):n(HCHO) = 1:80:80, 140 °C, and 4 h, the conversion of HCHO and selectivity for DEM2–8 were 92.6% and 95.1%, respectively. The [MIMBs]HSO4 catalyst could be easily separated and reused. A feasible mechanism for the catalytic performance of [MIMBs]HSO4 was proposed.
- Song, Heyuan,Kang, Meirong,Jin, Fuxiang,Wang, Guoqin,Li, Zhen,Chen, Jing
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p. 853 - 861
(2017/05/24)
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- Tailor-made Molecular Cobalt Catalyst System for the Selective Transformation of Carbon Dioxide to Dialkoxymethane Ethers
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Herein a non-precious transition-metal catalyst system for the selective synthesis of dialkoxymethane ethers from carbon dioxide and molecular hydrogen is presented. The development of a tailored catalyst system based on cobalt salts in combination with selected Triphos ligands and acidic co-catalysts enabled a synthetic pathway, avoiding the oxidation of methanol to attain the formaldehyde level of the central CH2 unit. This unprecedented productivity based on the molecular cobalt catalyst is the first example of a non-precious transition-metal system for this transformation utilizing renewable carbon dioxide sources.
- Schieweck, Benjamin G.,Klankermayer, Jürgen
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supporting information
p. 10854 - 10857
(2017/08/30)
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- Method for preparing diethoxymethane by supported heteropolyacid catalyst
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The invention relates to a method for preparing diethoxymethane, in particular to a method for for preparing diethoxymethane by a supported heteropolyacid catalyst. According to the method, dimethoxymethane and ethanol are taken as raw materials, liquid acid and supported liquid acid are taken as catalysts, the preparation method of the supported heteropolyacid catalyst, for example 33% of H3PW12O40/SiO2, comprises the following steps that a phosphotungstic acid aqueous solution with the concentration of 33% by mass is used, SiO2 is taken as a carrier, the impregnation liquid volume is the approximate to the pore volume, a catalyst sample is obtained after the phosphotungstic acid aqueous solution and the SiO2 are mixed uniformly and stood at the normal temperature by 10h, the sample is dried at the temperature of 120 DEG C, and calcination is performed at the temperature of 350 DEG C to obtain the 33% of H3PW12O40/SiO2 catalyst by the mass is prepared. According to the method, the product is relatively simple, the selectivity is high, and the method has an excellent application prospect. The raw materials required by the method are easy to obtain, the whole process operation is simple, at the same time, the method doesn't produce any chemical substances polluting the environment, and the method belongs to the environment-friendly technology route.
- -
-
Paragraph 0031; 0032
(2017/03/17)
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- Ruthenium-Catalyzed Synthesis of Dialkoxymethane Ethers Utilizing Carbon Dioxide and Molecular Hydrogen
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The synthesis of dimethoxymethane (DMM) by a multistep reaction of methanol with carbon dioxide and molecular hydrogen is reported. Using the molecular catalyst [Ru(triphos)(tmm)] in combination with the Lewis acid Al(OTf)3resulted in a versatile catalytic system for the synthesis of various dialkoxymethane ethers. This new catalytic reaction provides the first synthetic example for the selective conversion of carbon dioxide and hydrogen into a formaldehyde oxidation level, thus opening access to new molecular structures using this important C1source.
- Thenert, Katharina,Beydoun, Kassem,Wiesenthal, Jan,Leitner, Walter,Klankermayer, Jürgen
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supporting information
p. 12266 - 12269
(2016/10/13)
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- Preparation method of ethoxymethoxy methane
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The invention relates to a method for preparing methane, particularly a method for preparing ethoxymethoxy methane. According to the method, dimethoxymethane and ethanol are used as raw materials to prepare the ethoxymethoxy methane under the conditions of certain temperature and pressure by using a resin as a catalyst. The resin catalyst is one or more of KAD302, KC107, NKC-9, DA-330, D009B, Amberlyst-15 and D072H. The resin catalyst is mainly composed of a sulfo-containing resin catalyst. The reaction temperature is 0-160 DEG C, and the reaction pressure is 0.1-10.0 MPa. The filling gas is inert gas which is argon, helium, carbon dioxide or nitrogen or a gas mixture thereof. The reactor is a fixed-bed or tank reactor. The mole ratio of the raw material dimethoxymethane to the ethanol is 1:2-5:1. The synthesis process has the advantages of simple product, fewer side reactions and high selectivity for the required product ethoxymethoxy methane. The method provided by the invention basically does not pollute the environment.
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Paragraph 0020
(2017/01/02)
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- Method for preparing ethoxy methoxy methane using molecular sieves with different topological structures
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The invention discloses a method for preparing ethoxy methoxy methane using molecular sieves with different topological structures and relates to a method for preparing ethoxy methoxy methane. The ethoxy methoxy methane is prepared by taking dimethoxymethane and ethanol as raw materials and molecular sieves with different topological structures as catalysts at certain temperature and pressure; the silicon-aluminum atom ratio Si/Al in the molecular sieve catalysts with different topological structures is 3-100; the molecular sieves with different topological structures refer to one or more of hydrogen type MCM-22 molecular sieve, hydrogen type ZSM-35 molecular sieve, hydrogen type ZSM-5 molecular sieve, hydrogen type mordenite, hydrogen type Y zeolite and hydrogen type Beta molecular sieve; and the structure types of the molecular sieve catalysts with different topological structures are at least one of MWW, FER, MFI, MOR, FAU and BEA. The method disclosed by the invention has the advantages of relatively single product, high selectivity, cheap and easily available raw materials, easiness in operation of whole process and no production of chemical substances polluting environment and is an environment-friendly technological path.
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Paragraph 0018; 0019; 0020; 0021; 0022; 0023; 0024-0036
(2017/02/28)
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- PROCESS FOR REMOVING FORMALDEHYDE FROM A COMPOSITION COMPRISING GLYCOLALDHEDYDE
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A process for reducing the percentage by weight of formaldehyde present in a composition comprising glycolaldehyde, wherein formaldehyde is transformed into one or more formaldehyde acetal(s) and removed from the reactive distillation reaction solution by reactive distillation in the presence of at least one alcohol and a catalyst.
- -
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Page/Page column 15; 16
(2014/09/16)
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- PIFA-mediated esterification reaction of alkynes with alcohols via oxidative cleavage of carbon triple bonds
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A metal-free esterification of alkynes via C≡C triple bond cleavage has been developed. In the presence of phenyliodine bis(trifluoroacetate), a diverse range of alkyne and alcohol substrates undergoes triple bond cleavage to produce carboxylic ester motifs in moderate to good yields. The transformation is proposed to proceed via hydroxyethanones and ethanediones as intermediates on the basis of mechanistic studies and exhibits a broad substrate scope and good functional group tolerance.
- Jiang, Qing,Zhao, An,Xu, Bin,Jia, Jing,Liu, Xin,Guo, Cancheng
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supporting information
p. 2709 - 2715
(2014/04/17)
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- Catalytic hydrosilylation of carbonyls via Re(CO)5Cl photolysis
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The hydrosilylation reaction between silanes and various carbonyl substrates such as aldehyde, ketone, ester, and carbonate has been catalyzed by Re(CO)5Cl UV photolysis. Kinetic studies have shown that the reaction is favored for the least sterically hindered silanes with aldehydes followed by aliphatic ketones. The IR spectrum of the rhenium carbonyl dimer HRe 2(CO)9(SiR3) has been recorded in the reaction mixture. This complex is believed to be the resting state of the active catalyst Re(CO)4SiR3, which could be released upon photactivation. A catalytic mechanism involving this species has been proposed and shown to be thermodynamically feasible using computational studies. In addition, the relative hydrosilylation rates among the various carbonyl substrates can be explained using the same mechanism.
- Toh, Chun Keong,Sum, Yin Ngai,Fong, Wai Kit,Ang, Siau Gek,Fan, Wai Yip
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experimental part
p. 3880 - 3887
(2012/07/02)
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- Synthesis of [3-13C]-, [4-13C]- and [11- 13C]-porphobilinogen
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[4-13C]-porphobilinogen 1a, [3-13C]-porphobilinogen 1b and [11-13C]-porphobilinogen 1c are prepared from [1- 13C]-3-(tetrahydropyran-20-yloxy)-propionaldehyde 2a, methyl [4- 13C]-4-nitrobutyrate 3b and [1-13C]-isocyanoacetonitrile 5c, respectively. The building blocks 2, 3 and 5 can be prepared efficiently in any isotopomeric form. Via base-catalyzed condensation of these building blocks porphobilinogen can be enriched with 13C and 15N stable isotopes at any position and combination of positions. Copyright
- Dawadi, Prativa B. S.,Schulten, Els A. M.,Lugtenburg, Johan
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scheme or table
p. 341 - 349
(2011/07/08)
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- An efficient and convenient method for the synthesis of dialkoxymethanes using kaolinite as a catalyst
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A one pot synthesis of dialkoxymethanes (2a-h) is described from the reaction of alcohols (1a-h) with paraformaldehyde under reflux in the presence of catalytic amount of kaolinite.
- Pathak, Devendra D.,Gerald, J. Joe
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p. 1557 - 1561
(2007/10/03)
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- Rhodium-catalyzed double carbonylation of diiodomethane in the presence of triethylorthoformate
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Catalytic double carbonylation of diiodomethane in triethylorthoformate in the presence of a homogeneous rhodium complex gives diethylmalonate in a fairly good yield.
- Cheong, Minserk,Kim, Mi-Na,Shim, Ji Yeon
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p. 253 - 255
(2007/10/03)
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- Montmorillonite, an efficient catalyst for the preparation of dialkoxymethanes
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The reaction of various alcohols with paraformaldehyde in presence of montmorillonite to give dialkoxymethanes (2a-g) in very good yield is described.
- Deshmukh,Gumaste,Bhawal
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p. 3939 - 3944
(2007/10/03)
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- The Double Carbonylation of Diiodomethane Catalysed by Rhodium Complexes
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In alcohols, ROH, in the presence of and optionally also in the presence of a tertiary phosphorus ligand PR'3, CH2I2 reacts with CO to give CH2(CO2R)2, CH2(OR)2 and RI.
- Weston, William S.,Gash, Rosslyn C.,Cole-Hamilton, David J.
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p. 745 - 746
(2007/10/02)
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- Oxidative-addition reactions of alkyl chlorides with chlorobis(cyclooctene)rhodium(I) and the bis(oxazolinyl)pyridine ligand: Formation of stable (chloromethyl)rhodium(III) complexes and their reactions
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Dichloromethane and chloroform readily react with chlorobis(cyclooctene)rhodium(I) (1) and 2,6-bis-(4,4-dimethyloxazolin-2-yl)pyridine, dm-pybox, at room temperature to give the stable (chloromethyl)rhodium(III) complex 2 and (dichloromethyl)rhodium(III)
- Nishiyama, Hisao,Horihata, Mihoko,Hirai, Tsuyoshi,Wakamatsu, Shigeru,Itoh, Kenji
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p. 2706 - 2708
(2008/10/08)
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- Hydrocarbonylation of ethyl orthoformate in the presence of rhodium catalysts
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The reaction of ethyl orthoformate with a mixture of CO and H2 (P 8 MPa) in the presence of various rhodium carbonyl catalysts with and without iodide promoters at temperatures of 150-170 deg C has been studied.The -/CH3I systems mainly catalyze the hydrogenation of ethyl orthoformate to diethoxymethane without any subsequent hydrogenation to methyl derivatives and methane.Carbonylation and hydrocarbonylation products of the ethyl moiety, i.e. ethyl propionate and 1,1-diethoxypropane together with diethyl carbonate coming from carbonylation of the ethoxy group, are produced, with a maximum selectivity of 12percent.Chlorocarbonylrhodium systems without iodide promoters are active in the hydrogenation and hydrocarbonylation of the substrate, whereas carbonylrhodium derivatives without halide ligands and promoters only catalyze the hydrogenation to diethoxymethane.IR spectroscopic studies show that the rhodium species produced under the reaction conditions are in all cases anionic halocarbonyl or carbonyl complexes, and the course of the reaction seems to depend on the hydrido character of the parent derivative.
- Raspolli Galletti, A.M.,Braca, G.,Sbrana, G.
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p. 221 - 232
(2007/10/02)
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- HOMOLOGATION WITH CO+H2 OF ETHYL ORTHOFORMATE IN THE PRESENCE OF RUTHENIUM CATALYSTS: A STEPWISE HYDROGENATION AND CARBONYLATION REACTION
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The reaction of ethyl orthoformate with CO+H2 (P 10-15 MPa) in the presence of ruthenium carbonyl iodide catalysts at temperatures of 130-200 deg C has been studied.Products of hydrogenation, carbonylation and homologation of the CH, Et and EtO moieties of the ester are formed, indicating that the catalyst can activate the substrate in three ways.Diethoxymethane was the main product at lower temperatures, whereas methyl ethyl ether, methanol, and ethyl propionate predominate at higher temperatures.The formation of significant amounts of diethyl carbonate and diethoxyethane indicates the intermediate formation of EtO-Ru derivatives.Results of experiments with CO+D2 suggest a step-wise process of hydrogenation and carbonylation of the substrate, and shed new light on the mechanism of activation of esters by ruthenium carbonyl iodide catalysts.
- Braca, G.,Galletti, A. M. Raspolli,Sbrana, G.,Lazzaroni, R.
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p. 107 - 116
(2007/10/02)
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- Kinetics of Reaction of Methylene Iodide with Alkoxide Ion in Binary Solvent Mixtures
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Methylene iodide-alkoxide reactions in the respective alcohol-DMSO/DMF mixtures are bimolecular two-step consecutive processes, the first step being slower than the second step.The reactivity increases with increase in dipolar aprotic component of the solvent mixture.The results have been rationalised in the light of solvent polarity parameters.
- Panigrahi, G. P.,Sinha, T. K.
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p. 136 - 140
(2007/10/02)
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- SYNTHESIS OF UNSYMMETRICAL 1,1-DIALKOXYALKANES AND THEIR SULFUR-CONTAINING ANALOGS
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Acyclic acetals and 1,1-di(alkylthio)alkanes enter into exchange reactions in the presence of aprotic acids and of the KU-2 cation-exchange resin with the formation of the unsymmetric acetals and 1-alkoxy-1-alkylthioalkanes.In reaction with ethylal di(ethylthio)methane forms 3,5,7-trioxanonane in addition to ethylthioethoxymethane. 2-Methyl-4-thia-2-hexene was found in the products from the reaction of 1,1-di(ethylthio)-2-methylpropane with methylal.
- Gazizova, L. B.,Imashev, U. B.,Musavirov, R. S.,Kantor, E. A.,Zlotskii, S. S.,et al.
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p. 226 - 231
(2007/10/02)
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