- Acid catalysts based on Cu/Ru alumina: Conversion of butyraldehyde to dibutyl ether
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A system made by combining two nonalloying metals, ruthenium and copper, using alumina as the oxide support was studied. This bimetallic supported catalyst has been used mainly in hydrogenolysis, dehydrogenation, and oxidation reactions of hydrocarbons. The preparation of such materials has been proposed to effect the selectivity and activity of a highly active metal by inclusion of a second less active metal. The samples were characterized by electron paramagnetic resonance spectrometry (EPR), X-ray diffraction (XRD), surface area, and surface acidities. The techniques EPR and XRD are ideal for studying the electronic and structural changes of the samples at different temperatures and concentrations. The primary reaction involved in this study was the hydrogenation of an aldehyde to the corresponding alcohol. A secondary reaction occurred as well. The acid catalyzed, substitution or bimolecular dehydration of the alcohol to the dibutyl ether was observed under certain catalytic conditions. These catalysts appeared to act as acid/base. Therefore this reaction to produce the ether is of special importance. A correlation between the electronic, structural and catalytic properties has been made to understand molecular processes' role in catalytic phenomena.
- Jansen, Susan,Palmieri, Michael,Gomez, Maria,Lawrence, Steve
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- Etherification of n-butanol to di-n-butyl ether over Keggin-, wells-Dawson-, and preyssler-type heteropolyacid catalysts
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Etherification of n-butanol to di-n-butyl ether was carried out over various structural classes of heteropolyacid (HPA) catalysts, including Keggin- (H3PW12O40), Wells-Dawson- (H6P2W18O62), and Preyssler-type (H14[NaP5W30O110]) HPA catalysts. Successful formation of HPA catalysts was well confirmed by FT-IR, 31P NMR, and ICP-AES analyses. Acid properties of HPA catalysts were determined by NH3-TPD (temperature-programmed desorption) measurements. Acid strength of the catalysts increased in the order of H14 [NaP5W30O110] 6P2W18O62 3PW12O40. The catalytic performance of HPA catalysts was closely related to the acid strength of the catalysts. In the etherification of n-butanol to di-n-butyl ether over various structural classes of HPA catalysts, Conversion of n-butanol and yield for di-n-butyl ether increased with increasing acid strength of HPA catalysts. Among the catalysts tested, Keggin-type (H3PW12O40) HPA catalyst with the strongest acid strength showed the best catalytic performance. Acid strength of HPAs served as an important factor determining the catalytic performance in the etherification of n-butanol to di-n-butyl ether. Copyright
- Kim, Jeong Kwon,Choi, Jung Ho,Park, Dong Ryul,Song, In Kyu
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- Influence of butanol isomers on the reactivity of cellulose towards the synthesis of butyl levulinates catalyzed by liquid and solid acid catalysts
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Butyl esters of levulinic acid form an interesting class of bio-based compounds that can be used, for example, as fuel additives. Their preparation mainly proceeds through the esterification of levulinic acid while the few reported studies on their direct synthesis from cellulose give limited information. In the present work, we studied for the first time in detail the influence of butanol isomers on the non-catalyzed cellulose liquefaction and the acid catalyzed formation of butyl levulinates from cellulose. In the absence of catalysts there was no influence of the alcohol class on liquefaction which reached 70-85% after 2 hours at 300 °C. In the presence of catalysts, we showed that the class of the alcohol had a significant influence on the butyl levulinate yield. With primary alcohols yields of 50% were obtained in the presence of H2SO4 (200 °C, 30 min). This level of yield can be considered as very interesting for these kinds of one-pot transformations involving cellulose. With secondary alcohols, yields less than 20% were obtained while no butyl levulinate was formed with tertiary alcohols. We also report for the first time this transformation in the presence of solid acids. Insoluble Cs2HPW12O40 or sulfated zirconia catalyzed the reaction heterogeneously despite deactivation leading to limited yields of 13% (200 °C, 1 hour). We finally show that water in butanol had an ambivalent role in enhancing the cellulose reactivity but limiting the esterification step and found that 5-7 wt%/butanol of water was the optimum amount.
- Démolis, Alexandre,Eternot, Marion,Essayem, Nadine,Rataboul, Franck
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- Etherification of n-butanol to di-n-butyl ether over HnXW 12O40 (XCo2+, B3+, Si4+, and P5+) Keggin heteropolyacid catalysts
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Etherification of n-butanol to di-n-butyl ether was carried out over heteroatom-substituted HnXW12O40 (XCo 2+, B3+, Si4+, and P5+) Keggin heteropolyacid (HPA) catalysts. Acid properties of HPA catalysts were determined by NH3-TPD measurements. Acid strength of HnXW 12O40 Keggin HPA catalysts increased in the order of H6CoW12O40 5BW 12O40 4SiW12O40 3PW12O40. Yield for di-n-butyl ether increased with increasing acid strength of the catalysts. Acid strength of HPAs served as an important factor determining the catalytic performance in the etherification of n-butanol to di-n-butyl ether.
- Kim, Jeong Kwon,Choi, Jung Ho,Song, Ji Hwan,Yi, Jongheop,Song, In Kyu
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- AQUIVION perfluorosulfonic acid resin for butyl levulinate production from furfuryl alcohol
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This study reports the sustainable production of butyl levulinate (BL) from furfuryl alcohol (FA), a highly abundant biomass derived platform obtained from C5 sugars in hemicellulose. FA upgrading is performed adopting a robust and easily recyclable commercial perfluorosulfonic acid resin, Aquivion P87S, used as cylinder shaped pellets. This approach avoids the use of corrosive and harmful mineral acids allowing a simple separation of the catalyst from the reaction mixture, reducing the cost of equipment materials and disposal or neutralization issues, also resulting in reduced solvent dehydration. Moreover, FA alcoholysis to BL involves butanol as a sustainable reaction medium, also readily obtained from biomass. The catalyst remains stable up to 6 recycles. Furthermore, the absence of heavy by-products and the stability of the catalyst allowed us to perform successive additions of the substrate to the reaction medium to increase the BL concentrations up to 0.66 M (13 wt%).
- Bernal, Hilda Gómez,Oldani, Claudio,Funaioli, Tiziana,Raspolli Galletti, Anna Maria
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- Ion exchange resins as catalysts for the liquid-phase dehydration of 1-butanol to di-n-butyl ether
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This work reports the production of di-n-butyl ether (DNBE) by means of 1-butanol dehydration in the liquid phase on acidic ion-exchange resins. Dehydration experiments were performed at 150 °C and 40 bar on 13 styrene-codivinylbenzene ion exchangers of different morphology. By comparing 1-butanol conversions to DNBE and initial reaction rates it is concluded that oversulfonated resins are the most active catalysts for 1-butanol dehydration reaction whereas gel-type resins that swell significantly in the reaction medium as well as the macroreticular thermostable resin Amberlyst 70 are the most selective to DNBE. The highest DNBE yield was achieved on Amberlyst 36. The influence of typical 1-butanol impurities on the dehydration reaction were also investigated showing that the presence of 2-methyl-1-propanol (isobutanol) enhances the formation of branched ethers such as 1-(1-methylpropoxy) butane and 1-(2-methylpropoxy) butane, whereas the presence of ethanol and acetone yields ethyl butyl ether and, to a much lesser extent, diethyl ether.
- Pérez,Bringué,Iborra,Tejero,Cunill
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- Polymer-supported catalysts for clean preparation of n-butanol
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A new type of RANEY metal catalyst supported by polymer was developed for the clean preparation of n-butanol. Unlike traditional supported catalysts, the newly developed alkalescent polyamide 6 (PA6) supported RANEY nickel catalyst provided a 100.0% conversion of n-butyraldehyde without producing any detectable n-butyl ether, the main byproduct in industry. The significantly enhanced catalyst selectivity of the polymer-supported RANEY metal catalyst was attributed to the elimination of the acid-catalyzed side reaction associated with RANEY metals and traditional catalyst supports, such as Al2O3 and SiO2. By eliminating acid-catalyzed side reactions, therefore, green chemistry could be achieved through reducing resources and energy consumption in chemical reactions. Furthermore, the preparation and recycling of the polymer-supported catalysts are also much more eco-friendly than for traditional Al2O3-/SiO 2-supported catalysts. The methodology developed in this study to use alkalescent polymers as the catalyst support could be applied to the whole catalyst family, including a series of important RANEY metal catalysts (e.g., RANEY nickel, RANEY cobalt, RANEY copper) used routinely in the chemical industry.
- Jiang, Haibin,Lu, Shuliang,Zhang, Xiaohong,Peng, Hui,Dai, Wei,Qiao, Jinliang
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- A catalytic symmetrical etherification
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A novel, catalytic, thermal etherification produces minimal waste and can be carried out under almost neutral conditions.
- Bagnell, Laurence,Cablewski, Teresa,Strauss, Christopher R.
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- The Guanidine-Promoted Direct Synthesis of Open-Chained Carbonates
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In order to reduce CO2 accumulation in the atmosphere, chemical fixation methodologies were developed and proved to be promising. In general, CO2 was turned into cyclic carbonates by cycloaddition with epoxides. However, the cyclic carbonates need to be converted into open-chained carbonates by transesterification for industrial usage, which results in wasted energy and materials. Herein, we report a process catalyzed by tetramethylguanidine (TMG) to afford linear carbonates directly. This process is greener and shows potential for industrial applications.
- Shang, Yuhan,Zheng, Mai,Zhang, Haibo,Zhou, Xiaohai
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- Reactions of Ionized Dibutyl Ether
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The reactions of ionized di-n-butyl ether are reported and compared with those of ionized n-butyl sec-butyl and di-sec-butyl ether.The main fragmentation of metastable (CH3CH2CH2CH2)O+. is C2H5. loss (ca. 85percent), but minor amounts (2-4percent of CH3., C4H7., C4H9., C4H10 and C4H10O are also eliminated.In contrast, C2H5. elimination is of much lower abundance (20 and 4percent, respectively) from metastable CH3CH2CH2CH2OCH(CH3)CH2CH3+. and 2O+., which expel mainly C2H6 and CH3. (35percent-55percent).Studies on collisional activation spectra of the C6H13O+ oxonium ions reveal that C2H5. loss from (CH3CH2CH2CH2)2O+. gives the same product, (CH3CH2CH2CH2+O=CHCH3) as that formed by direct cleavage of CH3CH2CH2CH2OCH(CH3)CH2CH3+..Elimination of C2H5. from (CH3CH2CH2CH2O+. is interpreted by means of a mechanism in which a 1,4-H shift to the oxygen atom initiates a unidirectional skeletal rearrangement to CH3CH2CH2CH2OCH(CH3)CH2CH3+., which than undergoes cleavage to CH3CH2CH2CH2+O=CHCH3 and C2H5..Further support for this mechanism is obtained from considering the collisional activation and neutralization-reionization mass spectra of the (C4H9)2O+. species and the behaviour of the labelled analogues of the (CH3CH2CH2CH2)2O+..The rate of ethyl radical loss is suppressed relative to those of alternative dissociations by deuteriation at the γ-position of either or both butyl substituents.Moreover, C2H5. loss via skeletal rearrangement and fragmentation of the unlabelled butyl group in CH3CH2CH2CH2OCH2CH2CD2CH3+. occurs approximately five times more rapidly than C2H4D. expulsion via isomerization and fission of the labelled butyl substituent.These findings indicate that the initial 1,4-hydrogen shift is influenced by a significant isotope effect, as would be expected if this step is rate limiting in ethyl radical loss.
- Bowen, Richard D.,Suh, Dennis,Terlouw, Johan K.
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- Silver(I)-Catalyzed Reductive Cross-Coupling of Aldehydes to Structurally Diverse Cyclic and Acyclic Ethers
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A range of medium-sized cyclic ethers (5 to 11 membered) have been effectively synthesized through intramolecular reductive coupling of dialdehydes initiated by 50 ppm to 0.5% of AgNTf2 with hydrosilane at 25 °C. The catalytic system is also suitable for the coupling of two different monoaldehydes to provide unsymmetrical ethers. This protocol features broad functional group compatibility, high product diversity, high efficiency, and utility in the late-stage modification of complex biorelevant molecules.
- Dong, Guichao,Li, Chuang,Liang, Ting,Xu, Xin,Xu, Zhou
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supporting information
p. 1817 - 1821
(2022/03/16)
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- Selective dehydration of 1-butanol to butenes over silica supported heteropolyacid catalysts: Mechanistic aspect
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Butenes are considered as important olefinic building block to produce fuels/fuel additives and commodity chemicals. In the present investigation, selective dehydration of 1-butanol to butenes was studied in a continuous-flow fixed-bed reactor using various silica-supported heteropolyacid (HPA) catalysts such as phosphotungstic acid (PTA), silicotungstic acid (STA), phosphomolybdic acid (PMA), and silicomolybdic acid (SMA) as the solid acid catalysts. The physicochemical properties of these HPA were determined by BET, powder XRD, FTIR, NH3-TPD, and Py-FTIR. The acid strength and Br?nsted/Lewis (B/L) acid ratio were increased with higher loading of HPA on silica. The nature of HPA (addenda and hetero atom) and loading of HPA are important factors for the dehydration of 1-butanol and selectivity towards butenes. PTA and STA showed superior catalytic activity than PMA and SMA. The reaction temperature and WHSV also strongly affected the butanol conversion and selectivity of butenes. The selectivity of di-n?butyl ether decreases with the rising temperature from 523 K to 623 K. The isomerization of 1-butene leading to the formation of other butene isomers depends on the HPA loading, temperature, and WHSV. The presence of molybdenum addendum atom in PMA and SMA promotes dehydrogenation and hydrogenation, leading to the formation of various light hydrocarbons. The 20PTA/SiO2 catalyst afforded 99.8% selectivity towards butenes at quantitative conversion of 1-butanol, whereas the 20STA/SiO2 catalyst gave nearly 97.0% conversion of 1-butanol and 99.9% butenes selectivity at 673 K, 37.4 h?1 of WHSV.
- Dutta, Saikat,Kella, Tatinaidu,Mal, Sib Sankar,Shee, Debaprasad,Vennathan, Anjana Anandan
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- PROCESSES FOR PRODUCING ALCOHOLS FROM BIOMASS AND FURTHER PRODUCTS DERIVED THEREFROM
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Processes for producing alcohols from biomass are provided. The processes utilize supercritical methanol to depolymerize biomass with subsequent conversion to a mixture of alcohols. In particular the disclosure relates to continuous processes which produce high yields of alcohols through recycling gases and further employ dual reactor configurations which improve overall alcohol yields. Processes for producing higher ethers and olefins from the so-formed alcohols, through alcohol coupling and subsequent dehydration are also provided. The resulting distillate range ethers and olefins are useful as components in liquid fuels, such as diesel and jet fuel.
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Paragraph 0530-0534
(2021/11/26)
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- Transition Metal-Free Direct Hydrogenation of Esters via a Frustrated Lewis Pair
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"Frustrated Lewis pairs"(FLPs) continue to exhibit unique reactivity for the reduction of organic substrates, yet to date, the catalytic hydrogenation of an ester functionality has not been demonstrated. Here, we report that iPr3SnNTf2 (1-NTf2; Tf = SO2CF3) is a more potent Lewis acid than the previously studied iPr3SnOTf; in an FLP with 2,4,6-collidine/2,6-lutidine (col/lut), this translates to faster H2 activation and the catalytic hydrogenolysis of an ester bond by a main-group compound, furnishing alcohol and ether (minor) products. The reaction outcome is sensitive to the steric and electronic properties of the substrate; CF3CO2Et and simple formates (HCO2Me and HCO2Et) are catalytically reduced, whereas related esters CF3CO2nBu and CH3CO2Et show only stoichiometric reactivity. A computational case study on the hydrogenation of CF3CO2Et and CH3CO2Et reveals that both share a common mechanistic pathway; however, key differences in the energies of a Sn-acetal intermediate and transition states emerge, favoring CF3CO2Et reduction. The alcohol products reversibly inhibit 1-NTf2/lut via formation of resting-state species 1-OR/[1·(1-OR)]+[NTf2]- however, the extra energy required to regenerate 1-NTf2/lut exacerbates the unfavorable reduction energy profile for CH3CO2Et, ultimately preventing turnover. These findings will assist the design of future main-group catalysts for ester hydrogenation, with improved performance.
- Sapsford, Joshua S.,Csókás, Dániel,Turnell-Ritson, Roland C.,Parkin, Liam A.,Crawford, Andrew D.,Pápai, Imre,Ashley, Andrew E.
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p. 9143 - 9150
(2021/07/31)
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- SATURATED HOMOETHER MANUFACTURING METHOD FROM UNSATURATED CARBONYL COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for manufacturing saturated homoether from an unsaturated carboxyl compound at good efficiency. SOLUTION: There is provided a manufacturing method of saturated homoether using an unsaturated carboxyl compound and hydrogen as raw materials, and a catalyst in which a metal is carried on an acidic catalyst carrier. The metal of the catalyst is for example palladium, and the carrier of the catalyst is alumina, silica, silica-alumina, or the like. The unsaturated carbonyl compound as the raw material is 2-butenal, 2-ethyl-2-hexenal, 2-ethyl-2-butenal, 2-hexenal, and manufactured saturated homoether is dibuthylether, bis(2-ethylhexyl)ether, bis(2-ethylbuty)ether, dihexylether, or the like. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPO&INPIT
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Paragraph 0045-0046
(2020/05/14)
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- A Catalyst System Based on Copper(II) Bromide Supported on Zeolite HY with a Hierarchical Pore Structure in Benzyl Butyl Ether Synthesis
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Abstract: Novel catalyst systems based on CuBr2 supported on zeolite HY with a hierarchical pore structure have been proposed for benzyl butyl ether synthesis by the intermolecular dehydration of benzyl and butyl alcohols. It has been shown that catalyst systems with a CuBr2 content of ~10 wt percent provide a benzyl butyl ether yield of ~95percent at 150°C.
- Agliullin, M. R.,Bayguzina, A. R.,Gallyamova, L. I.,Khusnutdinov, R. I.
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p. 937 - 941
(2020/09/02)
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- Successive vapour phase Guerbet condensation of ethanol and 1-butanol over Mg-Al oxide catalysts in a flow reactor
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The successive vapour phase condensation of ethanol and 1-butanol (via Guerbet reaction) in a flow reactor under atmospheric pressure was studied over catalytic Mg-Al oxide compositions. Wherein the vapour phase condensation of 1-butanol to 2-ethyl-1-hexanol in flow has been investigated for the first time. The acid/base capacity ratio, which is determined by the Mg/Al ratio, is an important characteristic for the activity and selectivity of Mg-Al oxide catalysts in the abovementioned processes. The carbon chain length of the reacting alcohols, an arrangement of surface active sites and other steric factors also have an impact on Guerbet condensation in the vapour phase. High productivity of Mg-Al oxide system to the Guerbet alcohols: 1-butanol – 25 g/(Lcat·h), 2-ethyl-1-hexanol – 19 g/(Lcat·h), has been achieved. The results have shown a prospect of successive conversion realization: 1) ethanol → 1-butanol; 2) 1-butanol → 2-ethyl-1-hexanol for the production of 2-ethyl-1-hexanol from ethanol.
- Larina, Olga V.,Valihura, Karina V.,Kyriienko, Pavlo I.,Vlasenko, Nina V.,Balakin, Dmytro Yu.,Khalakhan, Ivan,?endak, Toma?,Soloviev, Sergiy O.,Orlyk, Svitlana M.
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- Synthesis of Benzyl Alkyl Ethers by Intermolecular Dehydration of Benzyl Alcohol with Aliphatic Alcohols under the Effect of Copper Containing Catalysts
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Synthesis of benzyl alkyl ethers was performed in high yields by intermolecular dehydration of benzyl and primary, secondary, tertiary alcohols under the effect of copper containing catalysts. The formation of benzyl alkyl ethers occurs with participation of benzyl cation.
- Bayguzina,Gimaletdinova,Khusnutdinov
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p. 1148 - 1155
(2018/10/24)
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- Iron-Catalyzed Ring-Closing C?O/C?O Metathesis of Aliphatic Ethers
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Among all metathesis reactions known to date in organic chemistry, the metathesis of multiple bonds such as alkenes and alkynes has evolved into one of the most powerful methods to construct molecular complexity. In contrast, metathesis reactions involving single bonds are scarce and far less developed, particularly in the context of synthetically valuable ring-closing reactions. Herein, we report an iron-catalyzed ring-closing metathesis of aliphatic ethers for the synthesis of substituted tetrahydropyrans and tetrahydrofurans, as well as morpholines and polycyclic ethers. This transformation is enabled by a simple iron catalyst and likely proceeds via cyclic oxonium intermediates.
- Biberger, Tobias,Makai, Szabolcs,Lian, Zhong,Morandi, Bill
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supporting information
p. 6940 - 6944
(2018/05/14)
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- Continuous-Flow Reductive Alkylation: Synthesis of Bio-based Symmetrical and Disymmetrical Ethers
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For the first time, a reductive alkylation process in continuous flow has been elaborated for the conversion of bio-based alcohols and aldehydes into symmetrical and dissymmetrical high-value-added ethers for industrial companies. The developed method is an etherification associating liquid, solid and gas phases under green conditions (continuous flow, catalysis, bio-based starting materials).
- Bruniaux, Sophie,Luart, Denis,Len, Christophe
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p. 1849 - 1856
(2018/02/06)
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- An ether compound of green high-efficient synthetic method (by machine translation)
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The invention discloses an ether compound of green high-efficient synthetic method, energy-saving environmental protection, comprising: mild reaction system, uses aldehyde, silane as the starting material, under the action of the silver salt in a price, for in solvent-free conditions, through reducing the - coupling - cheng mi reaction, realization of high efficiency alcohol of preparation. Synthesis method of the invention has the advantages of low dosage of catalyst, solvent-free, conversion and high yield, the reaction time is short, safe and stable, easy to operate, the product only distillation purification without any additional organic solvent, the whole range of green, environmental protection, high efficiency and the like, can overcome the defects of the prior art, it has very good industrial application value. (by machine translation)
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Paragraph 0052
(2018/07/07)
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- ABE Condensation over Monometallic Catalysts: Catalyst Characterization and Kinetics
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Herein, we present work on the catalyst development and the kinetics of acetone-butanol-ethanol (ABE) condensation. After examining multiple combinations of metal and basic catalysts reported in the literature, Cu supported on calcined hydrotalcites (HT) was found to be the optimal catalyst for the ABE condensation. This catalyst gave a six-fold increase in reaction rates over previously reported catalysts. Kinetic analysis of the reaction over CuHT and HT revealed that the rate-determining step is the C?H bond activation of alkoxides that are formed from alcohols on the Cu surface. This step is followed by the addition of the resulting aldehydes to an acetone enolate formed by deprotonation of the acetone over basic sites on the HT surface. The presence of alcohols reduces aldol condensation rates, as a result of the coverage of catalytic sites by alkoxides.
- Goulas, Konstantinos A.,Gunbas, Gorkem,Dietrich, Paul J.,Sreekumar, Sanil,Grippo, Adam,Chen, Justin P.,Gokhale, Amit A.,Toste, F. Dean
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p. 677 - 684
(2017/02/26)
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- Ether formation through reductive coupling of ketones or aldehydes catalyzed by a mesoionic carbene iridium complex
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An iridium(iii) Cp? complex containing a triazolylidene-pyridyl C,N-bidentate-coordinating ligand is a very powerful catalyst for the transformation of ketones and aldehydes into symmetrical ethers. This highly efficient reductive coupling proceeds immediately at room temperature and at a low catalyst loading (0.1 mol%) when Ph2SiH2 is used as an additive. Aromatic carbonyl substrates react faster than aliphatic ketones or aldehydes, and the substrate scope suggests some functional group tolerance. Likewise, the condensation of alcohols to symmetrical ethers is catalyzed by this triazolylidene iridium complex, though ether formation is an order of magnitude slower than when starting from the analogous ketone or aldehyde as a substrate, suggesting that alcohols are not potential intermediates in the reductive coupling process. Prolonged reactions or modification of the silane additive lead to ether cleavage and dehydration, thus affording the corresponding olefin. Mechanistic insights and in particular the different reactivities of alcohols and ketones have been exploited to develop a synthetic methodology for the iridium-catalyzed formation of unsymmetrical methyl ethers (R-OMe) in good yields.
- Petronilho,Vivancos,Albrecht
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p. 5766 - 5774
(2017/12/07)
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- Oxidative alkoxylation of phosphine in alcohol solutions of copper halides
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The phosphine oxidation reaction with oxygen in alcohol solutions of copper (I, II) halides is studied. Kinetic parameters, intermediates, and by-products are studied by means of NMR 31Р-, IR-, UV-, and ESR- spectroscopy; and by magnetic susceptibility, redox potentiometry, gas chromatography, and elemental analysis. A reaction mechanism is proposed, and the optimum conditions are found for the reaction of oxidative alkoxylation phosphine.
- Polimbetova,Borangazieva,Ibraimova, Zh. U.,Bugubaeva,Keynbay
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p. 1539 - 1544
(2016/08/26)
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- Heterogeneous catalytic conversion of glycerol with n-butyl alcohol
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The etherification of glycerol with n-butyl alcohol at 140°C in the presence of sulfonated cation-exchange resins and zeolite catalysts in an autoclave reactor has been studied. It has been shown that styrene - divinylbenzene ion-exchange resins are effective catalysts for the production of glycerol n-butyl ethers: the glycerol conversion is about 98% with an n-butyl ether selectivity of about 88 mol % (140°C, 5 h, 5 wt % Amberlyst 36 catalyst, and 10 wt % glycerol in n-butanol). Zeolites Y and β in the H+ form exhibit comparable specific activity (glycerol conversion of no more than 25% under similar conditions) in combination with high selectivity for glycerol di-n-butyl ethers (up to 28%).
- Samoilov,Ramazanov,Nekhaev,Maksimov
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p. 125 - 130
(2016/04/20)
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- Antimony(v) cations for the selective catalytic transformation of aldehydes into symmetric ethers, α,β-unsaturated aldehydes, and 1,3,5-trioxanes
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1-Diphenylphosphinonaphthyl-8-triphenylstibonium triflate ([2][OTf]) was prepared in excellent yield by treating 1-lithio-8-diphenylphosphinonaphthalene with dibromotriphenylstiborane followed by halide abstraction with AgOTf. This antimony(v) cation was found to be stable toward oxygen and water, and exhibited exceptional Lewis acidity. The Lewis acidity of [2][OTf] was exploited in the catalytic reductive coupling of a variety of aldehydes into symmetric ethers of type L in good to excellent yields under mild conditions using Et3SiH as the reductant. Additionally, [2][OTf] was found to selectively catalyze the Aldol condensation reaction to afford α-β unsaturated aldehydes (M) when aldehydes with 2 α-hydrogen atoms were used. Finally, [2][OTf] catalyzed the cyclotrimerization of aliphatic and aromatic aldehydes to afford the industrially-useful 1,3,5 trioxanes (N) in good yields, and with great selectivity. This phosphine-stibonium motif represents one of the first catalytic systems of its kind that is able to catalyze these reactions with aldehydes in a controlled, efficient manner. The mechanism of these processes has been explored both experimentally and theoretically. In all cases the Lewis acidic nature of the antimony(v) cation was found to promote these reactions.
- Arias Ugarte, Renzo,Devarajan, Deepa,Mushinski, Ryan M.,Hudnall, Todd W.
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supporting information
p. 11150 - 11161
(2016/07/20)
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- Indium(III) triflate promoted synthesis of alkyl levulinates from furyl alcohols and furyl aldehydes
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A facile protocol for the alcoholysis of furfuryl alcohol into levulinate esters has been developed employing low catalyst loadings of indium(III) triflate. This method provides a rapid and efficient route for the synthesis of these useful materials. The alcoholysis reactions of 5-hydroxymethylfurfural (HMF), furfural and furfural dimethylacetal were also investigated under these reaction conditions.
- Kean, Jacqueline R.,Graham, Andrew E.
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p. 175 - 179
(2015/02/19)
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- Non-Oxidative Dehydrogenation Pathways for the Conversion of C2-C4 Alcohols to Carbonyl Compounds
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Gold nanoparticles (NPs) supported on hydrotalcite (Au/HT) are highly active and selective catalysts for the continuous, gas-phase, non-oxidative dehydrogenation of bioderived C2-C4 alcohols. A sharp increase in turn over frequency (TOF) is noted when the size of Au NPs is less than 5 'nm relating to the strong synergy between metallic Au NPs and the acid-base groups on the support surface. It is shown that catalytic activity depends critically on Au NP size, support composition, and support pretreatments. A reaction pathway elucidated from kinetic isotope effects suggests that the abstraction of β-H by Au NPs (C-H activation) is the rate-determining step in the dehydrogenation of bioderived C2-C4 alcohols. All that′s good is gold: Gold nanoparticles supported on calcined hydrotalcite (Au/HT) are highly active and very selective catalysts for the continuous, gas-phase, non-oxidative dehydrogenation of bioderived C2-C4 alcohols.
- Shylesh, Sankaranarayanapillai,Kim, Daeyoup,Ho, Christopher R.,Johnson, Gregory R.,Wu, Jason,Bell, Alexis T.
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p. 3959 - 3962
(2015/12/17)
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- Biobased n-Butanol Prepared from Poly-3-hydroxybutyrate: Optimization of the Reduction of n-Butyl Crotonate to n-Butanol
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Using metabolic engineering approaches, the biopolymer poly-3-hydroxybutyrate (P3HB) can be overproduced in organisms such as bacteria and plants. Thermolysis of P3HB, either in isolated form or within biomass, yields crotonic acid, a potential bioderived platform chemical. Reduction of crotonic acid provides n-butanol, which has value as a fuel and as a commodity chemical. Herein, we report optimization work on the hydrogenation of the n-butyl ester of crotonic acid to n-butanol and the potential of this chemistry to be incorporated into the production of bio-n-butanol from P3HB containing biomass.
- Schweitzer, Dirk,Mullen, Charles A.,Boateng, Akwasi A.,Snell, Kristi D.
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supporting information
p. 710 - 714
(2015/07/27)
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- Rapid ether and alcohol C-O bond hydrogenolysis catalyzed by tandem high-valent metal triflate + supported Pd catalysts
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The thermodynamically leveraged conversion of ethers and alcohols to saturated hydrocarbons is achieved efficiently with low loadings of homogeneous M(OTf)n + heterogeneous Pd tandem catalysts (M = transition metal; OTf = triflate; n = 4). For example, Hf(OTf)4 mediates rapid endothermic ether a? alcohol and alcohol a? alkene equilibria, while Pd/C catalyzes the subsequent, exothermic alkene hydrogenation. The relative C-O cleavage rates scale as 3 > 2 > 1. The reaction scope extends to efficient conversion of biomass-derived ethers, such as THF derivatives, to the corresponding alkanes.
- Li, Zhi,Assary, Rajeev S.,Atesin, Abdurrahman C.,Curtiss, Larry A.,Marks, Tobin J.
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supporting information
p. 104 - 107
(2014/01/23)
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- Conversion of fructose into 5-hydroxymethylfurfural and alkyl levulinates catalyzed by sulfonic acid-functionalized carbon materials
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A series of sulfonic acid-functionalized carbon materials (C-SO 3H), including poly(p-styrenesulfonic acid)-grafted carbon nanotubes (CNT-PSSA), poly(p-styrenesulfonic acid)-grafted carbon nanofibers (CNF-PSSA), benzenesulfonic acid-grafted CMK-5 (CMK-5-BSA), and benzenesulfonic acid-grafted carbon nanotubes (CNT-BSA), have been studied for fructose dehydration to 5-hydroxymethylfurfural (HMF) and fructose alcoholysis to alkyl levulinate. A study for optimizing the reaction conditions such as the catalyst loading, the reaction time, and the temperature has been performed. Under the optimal conditions, high HMF and ethyl levulinate yields of up to 89% and 86%, respectively, are obtained. The catalytic activities of C-SO3H for the conversions of fructose into both HMF and ethyl levulinate follow the order of their acid strength. The relationship between the catalytic activity and acid density of C-SO3H shows a linear correspondence in the fructose dehydration to HMF. The facile separation, ease of recovery, and high thermal stability make the developed C-SO3H efficient and environment-friendly catalytic materials for transforming biomass carbohydrate into fine chemicals.
- Liu, Ruliang,Chen, Jinzhu,Huang, Xing,Chen, Limin,Ma, Longlong,Li, Xinjun
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supporting information
p. 2895 - 2903
(2013/10/08)
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- Catalytic etherification of glycerol with short chain alkyl alcohols in the presence of Lewis acids
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Here we report the homogeneously-catalyzed etherification of glycerol with short chain alkyl alcohols. Among the large variety of Bronsted and Lewis acids tested, we show here that metal triflates are not only the most active but are also capable of catalyzing this reaction with an unprecedented selectivity. In particular, in the presence of Bi(OTf)3, the targeted monoalkylglyceryl ethers were obtained with up to 70% yield. Although tested Bronsted acids were also capable of catalyzing the etherification of glycerol with alkyl alcohols, they were found however less active and less selective than Bi(OTf)3. By means of counter experiments, we highlighted that the high activity and selectivity of Bi(OTf)3 may rely on a synergistic effect between Bi(OTf)3 and triflic acid, a Bronsted acid that can be released by in situ glycerolysis of Bi(OTf)3. The scope of this methodology was also extended to other polyols and, in all cases, the monoalkylpolyol ethers were conveniently obtained with fair to good yields.
- Liu, Fei,De Oliveira Vigier, Karine,Pera-Titus, Marc,Pouilloux, Yannick,Clacens, Jean-Marc,Decampo, Floryan,Jerome, Francois
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p. 901 - 909
(2013/07/26)
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- Synthesis of ethers from esters via Fe-catalyzed hydrosilylation
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Triiron dodecacarbonyl allows for the selective reduction of esters into the corresponding ethers. This protocol has a wide substrate scope. In addition, cholesteryl pelarogonate has been reduced under the reaction conditions with an excellent yield.
- Das, Shoubhik,Li, Yuehui,Junge, Kathrin,Beller, Matthias
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supporting information
p. 10742 - 10744
(2013/01/15)
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- Investigation of the stability of quaternary ammonium methyl carbonates
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Quaternary ammonium compounds are used commercially for a variety of applications and some are of interest as ionic liquids. For many years dimethyl carbonate has been touted as a green reagent, including its use for methylation (quaternization) of tertiary amines. In addition, substitution of the methyl carbonate by other anions can be efficiently and cleanly accomplished by reaction with the corresponding acid. How stable are these methyl carbonate quaternary compounds? High field 13C NMR shows that in the presence of water, the methyl carbonate is converted to bicarbonate. Headspace GCMS indicates that the alkylammonium methyl carbonate salts are stable below 170-180 °C while the bicarbonate salts are stable to only about 140 °C. Thermal decomposition occurs by decarboxylation and by dealkylation. AOCS 2011.
- Weisshaar, Duane E.,Earl, Gary W.,Amolins, Michael W.,Mickalowski, Kyle L.,Norberg, Justin G.,Rekken, Brian D.,Burgess, Angela M.,Kaemingk, Bethany D.,Behrens, Katherine C.
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body text
p. 199 - 205
(2012/06/16)
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- An antimony(V) substituted Keggin heteropolyacid, H4PSbMo 11O40: Why is its catalytic activity in oxidation reactions so different from that of H4PVMo11O 40?
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An antimony(V) containing α-Keggin type acidic polyoxometalate, H4PSbMo11O40, was prepared by reacting NaMoO4, H3PO4 and Sb2O3 in the presence of aqua regia to appraise its reactivity compared to the well known vanadate analog, H4PVMo11O40. Characterization was by X-ray diffraction, MALDI-TOF MS, IR, UV-vis and 31P NMR spectroscopy. Catalytic redox reactions, such as oxidative dehydrogenation using O2 and N2O as terminal oxidants were studied and showed very different reactivity of H4PSbMo 11O40 versus H4PVMo11O40. It was found by DFT calculations that in contrast to analogous H 4PVMo11O40 where vanadium centered catalysis is observed, in H4PSbMo11O40 catalysis is molybdenum and not antimony centered.
- Goldberg, Hila,Kumar, Devesh,Sastry, G. Narahari,Leitus, Gregory,Neumann, Ronny
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experimental part
p. 152 - 157
(2012/04/17)
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- Intermolecular dehydration of alcohols by the action of copper compounds activated with carbon tetrabromide. synthesis of ethers
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Copper compounds of the general formula CuXn (X = Cl, Br, I, acac, OAc, C7H4O3, C7H 5O2; n = 1, 2) activated by carbon tetrabromide catalyzed intermolecular dehydration of primary and secondary alcohols with formation of the corresponding ethers.
- Khusnutdinov, R. I.,Bayguzina, A. R.,Gimaletdinova, L. I.,Dzhemilev, U. M.
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p. 1191 - 1196,6
(2020/10/15)
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- A crystalline catalyst based on a porous metal-organic framework and 12-tungstosilicic acid: Particle size control by hydrothermal synthesis for the formation of dimethyl ether
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The strategy for obtaining a crystalline catalyst based on a porous copper-based metal-organic framework and 12-tungstosilicic acid with different particle sizes is reported. Through the control of hydrothermal synthesis and some simple treatments, catalyst samples with average particle diameters of 23, 105, and 450-μm, respectively, were prepared. This crystal catalyst has both the Bronsted acidity of 12-tungstosilicic acid and the Lewis acidity of the copper-based metal-organic framework, and has high density of accessible acid sites. Its catalytic activity was fully assessed in the dehydration of methanol to dimethyl ether. The effect of particle size on the catalytic activity of catalyst was studied, in order to select the particle size appropriate for avoiding the diffusion limitation in heterogeneous gas-phase catalysis. In the selective dehydration of methanol to dimethyl ether, this catalyst exhibited higher catalytic activity than the copper-based metal-organic framework, γ-alumina, and γ-alumina-supported 12-tungstosilicic acid catalysts. It showed high catalytic performances, even at higher space velocity or in the presence of excess water. In addition, the catalyst was also preliminarily assessed in the formation of ethyl acetate from acetic acid and ethylene. It also exhibited a high activity which was comparable with that of silica-supported 12-tungstosilicic acid catalyst. Copyright
- Liang, Da-Dong,Liu, Shu-Xia,Ma, Feng-Ji,Wei, Feng,Chen, Ya-Guang
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supporting information; scheme or table
p. 733 - 742
(2011/05/06)
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- METHOD OF PRODUCING A CARBOXYLIC ALKYL ESTER
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The present invention relates to a novel process for preparing alkyl polycarboxylates from an aqueous solution of an ammonium salt of the polycarboxylic acid by reactive distillation, and to a process for hydrogenating the alkyl carboxylates prepared in this way.
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Page/Page column 7
(2009/06/27)
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- Effect of sulfation of zirconia on catalytic performance in the dehydration of aliphatic alcohols
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Catalytic dehydration of 2-propanol and that of 1-butanol were performed at atmospheric pressure and 150-300 °C over ZrO2 and sulfated ZrO2 (S/ZrO2) in a fixed-bed, tubular reactor. The catalysts were characterized with XRD, elemental analysis, FT-IR, N2 physisorption, TG/DTA, TPD, and TPR. Themain structures of ZrO2 and S/ZrO2 were monoclinic and tetragonal, respectively. As ZrO 2 was modified with sulfuric acid, its surface area and acid amount were greatly increased, whereas the pore volume, the pore diameter, and the particle size were reduced. Both samples owned weak basicity. For both reactions, only dehydration products of alkene and ether were obtained. The alcohol conversion enhanced remarkably with the catalyst acid amount and the surface area as well as the reaction temperature. In addition, the ether selectivity on S/ZrO2 decreased with raising the reaction temperature. The activation energy was 81.0 kJ/mol in the propene formation from 2-propanol over S/ZrO2. The corresponding value was 94.4 kJ/mol for the dehydration of 1-butanol.
- Hsu, Ya-Sun,Wang, Yin-Lan,Ko, An-Nan
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scheme or table
p. 314 - 322
(2009/12/03)
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- PROCESS FOR MAKING A COMPOSITION COMPRISING AT LEAST TWO DIFFERENT DIALKYL ETHERS
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The present invention relates to a process for making a composition comprising at least two different ethers using ethanol, or a combination of ethanol and methanol, as a starting material.
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Page/Page column 16-17
(2009/06/27)
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- CONTROLLED CATALYSIS
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The present invention provides methods of using a novel sulfonated resin catalyst, showing improved performance. The catalyst has reduced or partial functionalization, throughout the sulfonated region of the polymer, leading to reduced by-product formation and other desirable features. This catalyst has particular usefulness in reactions or processes sensitive to high acidity, e.g., esterification-transesterification.
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Page/Page column 9
(2009/05/28)
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- Process for making dibutyl ethers from dry 1-butanol
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The present invention relates to a process for making dibutyl ethers using dry 1-butanol derived from fermentation broth. The dibutyl ethers so produced are useful in transportation fuels.
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Page/Page column 8
(2009/02/11)
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- PROCESSES FOR MAKING DIALKYL ETHERS FROM ALCOHOLS
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Processes for the preparation of dialkyl ethers from C4 to C8 straight-chain alcohols using an ionic liquid.
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Page/Page column 56-58
(2009/04/25)
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- [IrCl2Cp*(NHC)] complexes as highly versatile efficient catalysts for the cross-coupling of alcohols and amines
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A comparative study on the catalytic activity of a series of [IrCl 2Cp*(NHC)] complexes in several C-O and C-N coupling processes implying hydrogen-borrowing mechanisms has been performed. The compound [IrCl2Cp*(InBu)] (Cp* = pentamethyl cyclopentadiene; InBu = 1,3-di-n-butylimidazolylidene) showed to be highly effective in the cross-coupling reactions of amines and alcohols, providing high yields in the production of unsymmetrical ethers and N-alkylated amines. A remarkable feature is that the processes were carried out in the absence of base, phosphine, or any other external additive. A comparative study with other known catalysts, such as Shvo's catalyst, is also reported.
- Prades, Amparo,Corberan, Rosa,Poyatos, Macarena,Peris, Eduardo
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scheme or table
p. 11474 - 11479
(2009/12/03)
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- PROCESS FOR MAKING DIBUTYL ETHERS FROM AQUEOUS ETHANOL
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The present invention relates to a process for making dibutyl ethers using aqueous ethanol optionally obtained from a fermentation broth. The dibutyl ethers made by this process find use as additives for fuels, including transportation fuels such as gasoline and diesel fuels.
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Page/Page column 11-12
(2008/12/06)
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- PROCESS FOR MAKING DIBUTYL ETHERS FROM DRY ETHANOL
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The present invention relates to a process for making dibutyl ethers using dry ethanol optionally obtained from a fermentation broth. The dibutyl ethers thus made are useful as additives for fuels.
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Page/Page column 11-12
(2008/12/06)
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- PROCESS FOR MAKING DIBUTYL ETHERS FROM AQUEOUS ETHANOL
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The present invention relates to processes for making dibutyl ethers using aqueous ethanol optionally obtained from a fermentation broth. The dibutyl ethers so formed find use as additives for fuels, including transportation fuels.
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Page/Page column 11-12
(2008/12/06)
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- PROCESS FOR MAKING DIBUTYL ETHERS FROM DRY ETHANOL
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The present invention relates to a process for making dibutyl ethers using dry ethanol optionally obtained from a fermentation broth. The dibutyl ethers made by this process find use as additives for fuels, including transportation fuels such as gasoline and diesel fuels.
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Page/Page column 10-11
(2008/12/06)
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- DEHYDRATION PROCESS
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A process for producing an olefin and/or an ether is described, which comprises heating an alcohol in the presence of an acidic ionic compound which exists in a liquid state at a temperature of below 150°C.
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Page/Page column 13
(2008/06/13)
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- PROCESS FOR THE MANUFACTURE OF C1 -C4 ALKYL (METH)ACRYLATES
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The invention relates to an improved process for the manufacture of C1-C4 alkyl (meth)acrylates by a direct esterification of (meth)acrylic acid by the corresponding alcohol in the presence of sulphuric acid, phenothiazine being used as polymerization inhibitor. The said process comprises a stage of recovering in value the heavy byproducts generated during this manufacture which consists of a distillation at a relatively low temperature and under an inert atmosphere, followed by a catalytic cracking under an inert atmosphere.
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Page/Page column 4
(2008/06/13)
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- Process for reactive esterification distillation
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A process for producing organic acid di- or tri-esters, particularly citric acid tri-esters, with the available acid groups esterified using countercurrent reactive distillation using acid catalysts in a structured packing is described. In the reactive distillation an organic acid di- or triester is formed by chemical reaction and purified to its final state within the single column. Organic acid di- or tri-esters are produced at relatively low cost, with less waste production in by-products of the reaction, and in a less complicated manner than prior processes. Organic acid di- and tri-esters have uses as solvents, as plasticizers and in conversion products.
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Page/Page column 21-22
(2008/06/13)
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- Process and catalyst for synthesis of mercaptans and sulfides from alcohols
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A process and catalyst blend for selectively producing mercaptans and sulfides from alcohols. The alcohol is reacted with hydrogen sulfide, in the presence of a catalyst blend containing a hydrotreating catalyst and a dehydration catalyst to convert the alcohol to mercaptan or sulfide in one-pass. The alcohols can include primary and secondary alcohols. The mercaptan or sulfide having less than about 30% unreacted alcohol contained therein.
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Page/Page column 8-9
(2008/06/13)
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- Oxidation of monohydric and dihydric alcohols with CCl4 catalyzed by molybdenum compounds
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Mo(CO)6 catalyzed oxidation of alcohols and diols with tetrachloromethane. Primary oxidation products in reaction of alcohols with CCl4 are alkyl hypochlorites, and final products depending on the structure of initial alcohol are aldehydes (as acetals), ketones, chloroketones, and esters.
- Khusnutdinov,Shchadneva,Burangulova,Muslimov,Dzhemilev
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p. 1615 - 1621
(2007/10/03)
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