- Gas-phase etherification of cyclopentanol with methanol to cyclopentyl methyl ether catalyzed by zeolites
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Symmetric ethers can be synthesized through the acid-catalyzed self-etherification of biomass-derived alcohols. However, synthesis of asymmetric ethers via catalytic cross-etherification of alcohols is limited by poor selectivity. Herein, we developed an efficient zeolite-catalyzed one-step synthesis of valuable asymmetric cyclopentyl methyl ether (CPME) using gas-phase reaction of bio-based cyclopentanol and methanol. Among different medium- (FER, MCM-22, ZSM-5) and large-pore (BEA, MOR, USY) aluminosilicate zeolites, commercial ZSM-5 catalysts with 2D system of intersecting channels are markedly more selective to CPME. The targeted CPME was produced with a selectivity of 83 % and a yield higher than 80 % over the ZSM-5 catalysts with Si/Al ratios ranging from 15 to 40. Decrease in Si/Al ratio in ZSM-5 enhanced the conversion value, while not affecting the selectivity. FTIR study of the step-by-step adsorption of both reactants in ZSM-5 evidenced the Rideal-Eley mechanism with cyclopentanol adsorbed on acid sites. Therefore, heterogeneously catalyzed gas-phase cross-etherification of renewable cyclopentanol and methanol is a promising process for large-scale applications thanks to its mild operating conditions, high yields and selectivity when using commercial ZSM-5 zeolites as catalysts.
- Soták, Tomá?,Magyarová, Zuzana,Shamzhy, Mariya,Kub?, Martin,Go??bek, Kinga,?ejka, Ji?í,Hronec, Milan
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- HYDROSILANE/LEWIS ACID ADDUCT, PARTICULARLY ALUMINUM, IRON, AND ZINC, METHOD FOR PREPARING SAME, AND USE OF SAID SAME IN REACTIONS FOR REDUCING CARBONYL DERIVATIVES
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Disclosed is an adduct between a Lewis acid, preferably aluminum trichloride, iron trichloride, or zinc dichloride, and a hydrosilane;—a method for preparing same; and a method for for reducing, particularly, an aldehyde, a ketone, an α,β-unsaturated ketone, an imine, or an α,β-unsaturated imine.
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Paragraph 0205; 0206
(2018/02/28)
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- METHOD FOR PRODUCING CYCLOPENTYL ALKYL ETHER COMPOUND
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The present invention is a method for producing a cyclopentyl alkyl ether compound comprising reacting substituted or unsubstituted cyclopentene with an alcohol compound represented by a formula (2): R1OH in the presence of an acidic zeolite, the cyclopentyl alkyl ether compound being represented by a formula (1): R1—O—R2, wherein R1 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, and R2 represents a substituted or unsubstituted cyclopentyl group. The present invention provides a method that can produce a cyclopentyl alkyl ether with high reaction efficiency through a liquid-phase reaction even when the raw material feed rate (amount) is increased.
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Paragraph 0061; 0062; 0064; 0066; 0067
(2017/12/27)
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- METHOD FOR PRODUCING CYCLOALKYL ALKYL ETHER COMPOUND
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The present invention is a method for producing a cycloalkyl alkyl ether compound comprising reacting substituted or unsubstituted cyclopentene or substituted or unsubstituted cyclohexene with an alcohol compound represented by a formula (2): R1OH (wherein R1 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms) in a gaseous state in presence of an acidic ion-exchange resin to produce a cycloalkyl alkyl ether compound represented by a formula (1): R1—O—R2 (wherein R1 is the same as defined above, and R2 is a substituted or unsubstituted cyclopentyl group or a substituted or unsubstituted cyclohexyl group), the acidic ion-exchange resin having a specific surface area of 20 to 50 m2/g, an average pore size of 20 to 70 nm, and a total exchange capacity of 4.8 to 6.0 eq/L-R wet resin.
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Paragraph 0075-0076
(2016/05/02)
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- Cyclopentyl methyl ether production method
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The invention discloses a method for producing cyclopentyl methyl ether. According to the method, cyclopentene and methanol used as the raw materials are subjected to etherification reaction to produce cyclopentyl methyl ether, and the method comprises the following steps: (1) etherification, i.e. cyclopentene and methanol are mixed and heated for gasification to perform etherification reaction through a strong acid cation exchange resin fixed bed, the volume liquid hourly space velocity of the materials is controlled at 0.5-4.0 hr-1, the system pressure is controlled at 0.01-0.10 MPa, the feeding temperature is 75-90 DEG C, the mol ratio of cyclopentene to methanol is 1:(0.5-0.8); (2) regeneration, i.e. in the process of etherification, when the conversion rate of cyclopentene is reduced to 10.0 percent below, feeding is stopped and catalyst is regenerated under the conditions that the materials for etherification reaction are used as a regeneration solvent, the volume liquid hourly space velocity of the materials is controlled at 0.1-1.0 hr-1, the system pressure is controlled at 0.3-1.0 MPa, the feeding temperature is 20-90 DEG C, and the regeneration time is 10-30 hours. According to the method for producing cyclopentyl methyl ether, the activity stability of the catalyst is achieved by using the catalytic etherification-regeneration-catalytic etherification circulation process of the resin catalyst, so that the service life and the use period of the catalyst are prolonged, and the regeneration is simple, and the method is easy to achieve industrial operation.
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Paragraph 0026; 0027; 0034
(2016/10/27)
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- Continuous cyclopentylmethyl ether production process and production system
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The present invention discloses a continuous cyclopentylmethyl ether production process and production system, the production process comprises vaporization of cyclopentene, filteration through an adsorption column, mixing with methanol and vaporization in a raw material vaporizer, catalytic addition reaction of the cyclopentene by entering a fixed bed reactor, distillation of the reaction solution by a light component removal tower, recovery and reuse of CPE and the methanol from light components, and rectification of a light component removal tower kettle liquid by a CPME rectification device to obtain cyclopentylmethyl ether, wherein the temperature of the catalytic addition reaction is 100-105 DEG C, the liquid hourly space velocity is 0.35-0.55hr, the gas hourly space velocity is 110-125hr, the pressure is 0.1-0.12Mpa. The conversion rate of the methanol is greater than 95%, the gas chromatography (GC) purity of a product in the reaction solution is greater than 90%, the purity of the cyclopentylmethyl ether prepared by refining is greater than 99.5% (the purity is detected by GC area normalization method), and the total yield of the cyclopentylmethyl ether is more than 80%.
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Paragraph 0039; 0074; 0075
(2016/11/28)
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- METHOD FOR PRODUCING CYCLOALKYL ALKYL ETHER
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PROBLEM TO BE SOLVED: To provide a method for producing a cycloalkyl alkyl ether through efficiently retrieving it in high purity and high yield as the objective product from a reaction mixture resulted from the addition reaction between an alicyclic olefin and an alcohol. SOLUTION: The method for producing the cycloalkyl alkyl ether comprises the following process: The reaction mixture resulted from the addition reaction between the alicyclic olefin and the alcohol is incorporated with another batch of the alicyclic olefin followed by carrying out a distillation, wherein it is especially preferable that the alicyclic olefin has a cyclopentene skeleton or cyclohexene skeleton and the alcohol is methanol.
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Page/Page column 6
(2008/06/13)
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- SOLVENTS CONTAINING CYCLOALKYL ALKYL ETHERS AND PROCESS FOR PRODUCTION OF THE ETHERS
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The present inventions are (A) a solvent comprising at least one cycloalkyl alkyl ether (1) represented by the general formula: R1-O-R2 (wherein R1 is cyclopentyl or the like; and R2 is C1-10 alkyl or the like); (B) a method of preparations the ethers (1) characterized by reacting an alicyclic olefin with an alcohol in the presence of an acid ion-exchange resin having a water content of 5 wt% or less. The solvent is useful as cleaning solvent for electronic components, precision machinery components or the like, reaction solvent using various chemical reactions, extraction solvent for extracting objective organic substances, solvent or remover for electronic and electrical materials, and so on. The process enables industrially advantageous production of the objective cycloalkyl alkyl ethers (1).
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- Direct methylation of primary and secondary alcohols by trimethyl phosphate to prepare pure alkyl methyl ethers
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Primary and secondary alcohols and diols react autocatalytically with trimelhyl phosphate plus small amounts of polyphosphoric acid at 185°C to give the corresponding methyl ethers. High purity and good yields are achieved when the ether is distilled from the reaction mixture as it is formed. By controlled addition even low-boiling alcohols can be methylated successfully. The reaction mechanism is undetermined. Peroxide formation in ethers is inhibited by storage over 10 molal KOH. Pure isotropic optical crystals are used for refractometer calibration. Improved physical property and NMR data (1H and 13C) are reported for thirteen methyl ethers. Simple two-point linear extrapolation of NMR shifts (especially 13C) to infinite dilution produces highly reproducible δ°-values (to 0.01 ppm or better) which uniquely characterize a molecule even when unidentified and/or not isolated from a mixture. This capability appears not to have been recognized in the literature. Acta Chemica Scandinavica 1998.
- Van Dyke Tiers, George
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p. 1223 - 1233
(2007/10/03)
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- Reactions of alkali metal anions. XV. Reaction of ketones with alkali metal anions
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The potassium anions were found to react with ketones to39 yield both alcoholates and enolates. On the basis of the ESR and K NMR measurements the mechanism of this reaction is proposed. According to the proposed mechanism in the first step a ketyl radical is formed which after disproportionation yields an enolate and an alcoholate but only in the case of ketones having hydrogen atom in α-position in respect to carbonyl group.
- Jedlinski,Misioiek,Giowkowski,Janeczek,Wolinska
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p. 3547 - 3558
(2007/10/02)
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- Solvomercuration-Demercuration. 12. The Solvomercuration-Demercuration of Olefins in Alcohol Solvents with Mercuric Trifluoroacetate--An Ether Synthesis of Wide Generality
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Studies on the solvomercuration-demercuration (SM-DM) of olefins in methyl, ethyl, isopropyl, and tert-butyl alcohols with mercuric trifluoroacetate have been extended. 1-Dodecene undergoes the SM-DM sequence with typical results for a monosubstituted olefin.Cyclopentene similarly exhibited behavior characteristic of a 1,2-disubstituted olefin in methanol, ethanol, and 2-propanol, giving high yields, >90percent of the corresponding ethers.However, in tert-butyl alcohol, the yields of ether were lower than normal and decreased somewhat with time. 2-Methyl-1-butene gives >90percent yields of the Markovnikov methyl ether.On the other hand, the yields of ethyl, isopropyl, and tert-butyl ethers are lower and decrease with time.Major improvements in yields, however, are possible by lowering the reaction temperature from room temperature to 0 deg C.Cyclooctene, surprisingly, behaves more like a tri-, tetra-, or isosubstituted olefin than a 1,2-disubstituted olefin.The yields of cyclooctyl methyl ether are >90percent and do not decrease with time.However, yields of the ethyl, isopropyl, and tert-butyl ethers are lower and drop with time.Again, lowering the reaction temperature from room temperature to 0 deg C markedly improves the yields of the cyclooctyl ethers.These results, coupled with those of a previous study, clearly reveal the exceptional superiority of mercuric trifluoroacetate for the SM-DM of olefins in alcohol solvents.
- Brown, Herbert C.,Kurek, Joseph T.,Rei, Min-Hon,Thompson, Kerry L.
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p. 1171 - 1174
(2007/10/02)
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- PHASE TRANSFER CATALYSIS AND HOMOGENEOUS REACTIONS WITH β-OXYALKYL RADICALS FROM ORGANOMERCURIALS
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β-Alkoxy- and β-hydroxyalkyl radicals generated by sodium borohydride reduction of oxymercurials react with electron deficient olefins to give addition compounds in a homogeneous process.Heterogeneous reactions are also successful in the presence of catalytic amounts of surfactants and provide a superior method for the "one pot" reductive alkylation of oxymercurials.
- Barluenga, Jose,Lopez-Prado, Joaquin,Campos, Pedro J.,Asensio, Gregorio
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p. 2863 - 2868
(2007/10/02)
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- MASSENSPEKTREN ALICYCLISCHER VERBINDUNGEN, VIII; trans-1-BROM-2-HYDROXYCYCLOALKANE UND trans-1-BROM-2-METHOXYCYCLOALKANE
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Die massenspektrometrische Fragmentierung der trans-1-Brom-2-hydroxycycloalkane und der trans-1-Brom-2-methoxycycloalkane der Ringgroessen C5 bis C8 und C12 wird diskutiert und mit der Fragmentierung der Bromcycloalkane, der Hydroxycycloalkane bzw. der Methoxycycloalkane gleicher Ringgroesse verglichen.Die dominierenden Zerfallsreaktionen sind einmal die Abspaltung der funktionellen Gruppen unter Bildung der Fragmente M-H2O, M-HOCH3 bzw.M-Br.Zum anderen der Abbau des Rings unter Bildung der Fragmente C3H4X (X=Br, OH, OCH3).Die Intensitaeten der wichstigten Fragmente zeigen eine deutliche Abhaengigkeit von der Ringgroesse.Die Unterschiede in den Intensitaeten von cis- und von trans-1-Brom-2-hydroxycyclododecan sowie von cis- und von trans-1-Brom-2-methoxycyclododecan erlauben die prinzipielle Unterscheidung der Isomeren an Hand ihrer Massenspektren.Aus dem Vergleich der Fragmentierung der bifunktionellen 1-Brom-2-hydroxycycloalkane bzw. der 1-Brom-2-methoxycycloalkane mit der Fragmentierung der monofunktionellen Verbidungen kann der Schluss gezogen werden, dass sich die funktionellen Gruppen beim massenspektrometrischen Abbau beeinflussen.
- Remane, H.,Haufe, G.
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p. 145 - 154
(2007/10/02)
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