- Synthesis and characterization of a well-defined carbon nanohorn- supported molybdenum dioxo catalyst by SMART-EM imaging. surface structure at the atomic level
-
The molybdenum dioxo catalyst CNH/MoO2 is prepared via direct grafting of (dme)MoO2Cl2 (dme = 1,2-dimethoxyethane) onto the graphitic surfaces of carbon nanohorn (CNH) substrates. The structure of this heterogeneous catalyst was characterized by SMART-EM, XPS, and ICP, and is found to have single isolated MoO2 species on the surface as well as a few multi-Mo species. The CNH/MoO2 complex exhibits excellent catalytic activity for polyethylene terephthalate (PET) hydrogenolysis, N-oxide reductions, and reductive carbonyl coupling, representing an informative model catalyst for structural and mechanistic investigations.
- Kratish, Yosi,Nakamuro, Takayuki,Liu, Yiqi,Li, Jiaqi,Tomotsuka, Issei,Harano, Koji,Nakamura, Eiichi,Marks, Tobin J.
-
supporting information
p. 427 - 432
(2021/03/15)
-
- Low-Temperature Hypergolic Ignition of 1-Octene with Low Ignition Delay Time
-
The attainment of the efficient ignition of traditional liquid hydrocarbons of scramjet combustors at low flight Mach numbers is a challenging task. In this study, a novel chemical strategy to improve the reliable ignition and efficient combustion of hydrocarbon fuels was proposed. A directional hydroboration reaction was used to convert hydrocarbon fuel into highly active alkylborane, thereby leading to changes in the combustion reaction pathway of hydrocarbon fuel. A directional reaction to achieve the hypergolic ignition of 1-octene was designed and developed by using Gaussian simulation. Borane dimethyl sulfide (BDMS), a high-energy additive, was allowed to react spontaneously with 1-octene to achieve the hypergolic ignition of liquid hydrocarbon fuel at -15 °C. Compared with the ignition delay time of pure 1-octene (565 °C), the ignition delay time of 1-octene/BDMS (9:1.2) decreased by 3850% at 50 °C. Fourier transform infrared spectroscopy and gas chromatography-mass spectrometry confirmed the directional reaction of the hypergolic ignition reaction pathway of 1-octene and BDMS. Moreover, optical measurements showed the development trend of hydroxyl radicals (OH·) in the lower temperature hypergolic ignition and combustion of 1-octene. Finally, this study indicates that the enhancement of the low-temperature ignition performance of 1-octene by hydroboration in the presence of BDMS is feasible and promising for jet propellant design with tremendous future applications.
- Sheng, Haoqiang,Huang, Xiaobin,Chen, Zhijia,Zhao, Zhengchuang,Liu, Hong
-
p. 423 - 434
(2021/02/05)
-
- ALCOHOL DEHYDRATION CATALYST, PREPARATION METHOD THE SAME AND METHOD FOR PREPARING ALPHA-OLEFINS USING THE SAME
-
The present invention relates to a catalyst for dehydration of a primary alcohol, a method of preparing the same, and a method of producing an alpha-olefin using the same. The catalyst for dehydration of a primary alcohol according to the present invention has an excellent catalyst stability while having an excellent activity with respect to dehydration, and a high turnover frequency, such that a linear alpha-olefin with high purity may be produced with a high selectivity even in a case where a relatively small amount of a cocatalyst is added as compared with a homogeneous catalyst system.
- -
-
Paragraph 0128; 0129
(2020/11/24)
-
- METAL-IODIDE CATALYTIC SYSTEM FOR DIRECT ETHERIFICATION FROM ALDEHYDES AND/OR KETONES
-
A process for etherification of aldehydes and/or ketones in the presence of a catalyst and an iodine source.
- -
-
Page/Page column 13
(2020/01/24)
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- METHOD FOR PRODUCING ALIPHATIC LINEAR PRIMARY ALCOHOLS
-
Provided are a method of preparing a linear primary alcohol, a catalyst for converting an α-olefin into an alcohol, and a method of converting an α-olefin into a linear primary alcohol, and the method of preparing a linear primary alcohol according to the present invention includes: charging a reactor with a heterogeneous catalyst including a cobalt oxide and a Cn olefin (S1); bringing the heterogeneous catalyst including a cobalt oxide into contact with the Cn olefin (S2); and supplying the reactor with a synthetic gas to obtain a Cn+1 alcohol (S3).
- -
-
Paragraph 0103; 0109
(2020/05/06)
-
- Highly Efficient and Selective N-Alkylation of Amines with Alcohols Catalyzed by in Situ Rehydrated Titanium Hydroxide
-
Catalytic N-alkylation of amines by alcohols to produce desired amines is an important catalytic reaction in industry. Various noble-metal-based homogeneous and heterogeneous catalysts have been reported for this process. The development of cheap non-noble-metal heterogeneous catalysts for the N-alkylation reaction would be highly desirable. Hereby, we propose the N-alkylation of amines by alcohols over a cheap and efficient heterogeneous catalyst-titanium hydroxide. This catalyst provides a selectivity higher than 90% to secondary amines for functionalized aromatic and aliphatic alcohols and amines with high catalytic activity and stability. Mild Br?nsted acidity formed by the continuous rehydration of Lewis acidity excludes the side reactions and deactivation by adsorbed species. The mechanism of the reaction involves dehydration of alcohols to ethers with subsequent C-O bond cleavage by amine with the formation of secondary amine and recovery of alcohol.
- Khodakov, Andrei Y.,Kusema, Bright T.,Niu, Feng,Ordomsky, Vitaly V.,Wang, Qiyan,Yan, Zhen
-
p. 3404 - 3414
(2020/03/23)
-
- Selective Oxidation of Alcohols to Carbonyl Compounds over Small Size Colloidal Ru Nanoparticles
-
The selective oxidation of alcohols to corresponding aldehydes is one of the most challenging problems in modern chemistry due to over-oxidation of these products further into corresponding acids and esters. Herein, we report an efficient and eco-friendly method for selective oxidation of aliphatic, unsaturated and aromatic alcohols to aldehydes (>90 %) using small size (2 nm) non-supported colloidal Ru nanoparticles. The selectivity rapidly decreases with increase of the size of nanoparticles (from 2 to 10 nm) or after their deposition over support. X-ray photoelectron spectroscopy suggests that this catalytic performance can be attributed to high content Ru?O species on the surface of small size Ru nanoparticles, which undergo reduction with formation of water and aldehyde and easy oxidation cycles during the reaction according to the Mars-van Krevelen mechanism. The presence of surface oxide layer over small size Ru nanoparticles suppresses over-oxidation of aldehydes to acids.
- Zhao, JingPeng,Hernández, Willinton Y.,Zhou, WenJuan,Yang, Yong,Vovk, Evgeny I.,Capron, Mickael,Ordomsky, Vitaly
-
p. 238 - 247
(2019/11/14)
-
- Nanocell type Ru?quinone core-shell catalyst for selective oxidation of alcohols to carbonyl compounds
-
Selective aerobic oxidation of alcohols to corresponding carbonyl compounds is one of the most important challenges in the modern chemical industry. The existing metal based heterogeneous catalysts provide low selectivity due to over-oxidation of aldehydes to acids and esters. We have found that coating of Ru nanoparticles by disodium anthraquinone-2,6-disulfonate (SQ) results in selective oxidation of aliphatic, unsaturated and aromatic alcohols to aldehydes. Analysis of core-shell Ru?SQ catalyst shows strong interaction between Ru and SQ leading to change of their electronic state and structure. In-situ study of alcohol oxidation using FTIR and electrochemistry indicates on hydrogen abstraction by shell quinone species with hydrogen transfer by quinone to Ru core for water generation. Thus, the catalyst behavior mimics nano-electrocell by separation of oxidation reaction over quinone and reduction of oxygen over Ru providing higher selectivity to aldehyde.
- Capron, M.,Hernández, W. Y.,Naghavi, N.,Ordomsky, V.,Vovk, E. I.,Wu, M.,Yang, Y.,Zhao, J. P.,Zhou, W. J.
-
-
- Application of Yttrium Iron Garnet as a Powerful and Recyclable Nanocatalyst for One-Pot Synthesis of Pyrano[2,3-c]pyrazole Derivatives under Solvent-Free Conditions
-
The application of yttrium iron garnet (YIG) superparamagnetic nanoparticles as a new recyclable and highly efficient heterogeneous magnetic catalyst for one-pot synthesis of pyrano[2,3-c]pyrazole derivatives under solvent-free conditions, as well as etherification and esterification reactions are described. The advantages of the proposed method include the lack of organic solvents, clean reaction, rapid removal of the catalyst, short reaction times, excellent yields, and recyclability of the catalyst.
- Sedighinia,Badri,Kiasat
-
p. 1755 - 1763
(2020/01/11)
-
- METHOD FOR PRODUCING FAT ALCOHOL ETHOXYLATES
-
The invention relates to a process for preparing fatty alcohol ethoxylates. According to the invention, the fatty alcohol ethoxylates are not obtained by means of the reaction of the fatty alcohols with ethylene oxide, as known from the prior art, but rat
- -
-
Page/Page column 5-8
(2020/01/11)
-
- Tailor-made biofuel 2-butyltetrahydrofuran from the continuous flow hydrogenation and deoxygenation of furfuralacetone
-
In this work, we present the first continuous flow process to produce the tailored biofuel 2-butyltetrahydrofuran from renewable resources. In a two-step approach lignocellulose-derived furfuralacetone is first hydrogenated and then deoxygenated over commercial catalysts to form the desired product. Both reactions were studied independently in batch conditions. The transition to a continuous flow system was done and various parameters were tested in the miniplant. Both reactions were performed in a two-reactor-concept approach to yield the desired 2-butyltetrahydrofuran in a high yield directly from furfuralacetone.
- Strohmann, Marc,Bordet, Alexis,Vorholt, Andreas J.,Leitner, Walter
-
p. 6299 - 6306
(2019/12/03)
-
- The novel transition metal complex (by machine translation)
-
[Problem] simple and safe, novel transition metal complexes can be used as an industrial catalyst suitable for the production of ether compound. (1) A transition metal complex represented by the formula [a] or the like. [Substituted/unsubstituted/substituted or unsubstituted cyclopentadienyl group of the aromatic compound Ar; M1 The, ruthenium, rhodium or iridium; L is a ligand sulfoxide, amide ligand, nitrogen-containing aromatic ring ligands, amine ligand, the ligand ether, nitrile ligands or [...] ligand; also shown in dashed lines, a single bond or a double bond; Y- The trifluoromethane sulfonic acid ion anion other than][Drawing] no (by machine translation)
- -
-
Paragraph 0173; 0174; 0175; 0176; 0177; 0178; 0179-0181
(2018/07/14)
-
- Transition metal triflate catalyzed conversion of alcohols, ethers and esters to olefins
-
Herein, we report an efficient transition metal triflate catalyzed approach to convert biomass-based compounds, such as monoterpene alcohols, sugar alcohols, octyl acetate and tea tree oil, to their corresponding olefins in high yields. The reaction proceeds through C-O bond cleavage under solvent-free conditions, where the catalytic activity is determined by the oxophilicity and the Lewis acidity of the metal catalyst. In addition, we demonstrate how the oxygen containing functionality affects the formation of the olefins. Furthermore, the robustness of the used metal triflate catalysts, Fe(OTf)3 and Hf(OTf)4, is highlighted by their ability to convert an over 2400-fold excess of 2-octanol to octenes in high isolated yields.
- Keskiv?li,Parviainen,Lagerblom,Repo
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p. 15111 - 15118
(2018/05/04)
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- Effect of Alcohol Structure on the Kinetics of Etherification and Dehydration over Tungstated Zirconia
-
Linear and branched ether molecules have attracted recent interest as diesel additives and lubricants that can be produced from biomass-derived alcohols. In this study, tungstated zirconia was identified as a selective and green solid acid catalyst for the direct etherification of primary alcohols in the liquid phase, achieving ether selectivities of >94 % for C6–C12 linear alcohol coupling at 393 K. The length of linear primary alcohols (C6–C12) was shown to have a negligible effect on apparent activation energies for etherification and dehydration, demonstrating the possibility to produce both symmetrical and asymmetrical linear ethers. Reactions over a series of C6 alcohols with varying methyl branch positions indicated that substituted alcohols (2°, 3°) and alcohols with branches on the β-carbon readily undergo dehydration, but alcohols with branches at least three carbons away from the -OH group are highly selective to ether. A novel model compound, 4-hexyl-1dodecanol, was synthesized and tested to further demonstrate this structure–activity relationship. Trends in the effects of alcohol structure on selectivity were consistent with previously proposed mechanisms for etherification and dehydration, and help to define possible pathways to selectively form ethers from biomass-derived alcohols.
- Rorrer, Julie,Pindi, Suresh,Toste, F. Dean,Bell, Alexis T.
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p. 3104 - 3111
(2018/09/06)
-
- Synthesis of Benzyl Alkyl Ethers by Intermolecular Dehydration of Benzyl Alcohol with Aliphatic Alcohols under the Effect of Copper Containing Catalysts
-
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
-
p. 1148 - 1155
(2018/10/24)
-
- Methylation of Polyols with Trimethylphosphate in the Presence of a Lewis or Br?nsted Acid Catalyst
-
The alkylation of alcohols and polyols has been investigated with alkylphosphates in the presence of a Lewis or Br?nsted acid catalyst. The permethylation of polyols was developed under solvent-free conditions at 100 °C with either iron triflate or Aquivion PW98, affording the isolated products in yields between 52 and 95 %. The methodology was also adjusted to carry out peralkylation with longer alkyl chains.
- Duclos, Marie-Christine,Herbinski, Aurélien,Mora, Anne-Sophie,Métay, Estelle,Lemaire, Marc
-
p. 547 - 551
(2018/01/16)
-
- Efficient carbon-supported heterogeneous molybdenum-dioxo catalyst for chemoselective reductive carbonyl coupling
-
Reductive coupling of various carbonyl compounds to the corresponding symmetric ethers with dimethylphenylsilane is reported using a carbon-supported dioxo-molybdenum catalyst. The catalyst is air- and moisture-stable and can be easily separated from the reaction mixture for recycling. In addition, the catalyst is chemoselective, thus enabling the synthesis of functionalized ethers without requiring sacrificial ligands or protecting groups.
- Liu, Shengsi,Li, Jiaqi,Jurca, Titel,Stair, Peter C.,Lohr, Tracy L.,Marks, Tobin J.
-
p. 2165 - 2169
(2017/07/22)
-
- Organohalide-catalyzed dehydrative O-alkylation between alcohols: A facile etherification method for aliphatic ether synthesis
-
Organohalides are found to be effective catalysts for dehydrative O-alkylation reactions between alcohols, providing selective, practical, green, and easily scalable homo- and cross-etherification methods for the preparation of useful symmetrical and unsymmetrical aliphatic ethers from the readily available alcohols. Mechanistic studies revealed that organohalides are regenerated as reactive intermediates and recycled to catalyze the reactions.
- Xu, Qing,Xie, Huamei,Chen, Pingliang,Yu, Lei,Chen, Jianhui,Hu, Xingen
-
supporting information
p. 2774 - 2779
(2015/05/27)
-
- Pd/Nb2O5/SiO2 catalyst for the direct hydrodeoxygenation of biomass-related compounds to liquid alkanes under mild conditions
-
A simple Pd-loaded Nb2O5/SiO2 catalyst was prepared for the hydrodeoxygenation of biomass-related compounds to alkanes under mild conditions. Niobium oxide dispersed in silica (Nb2O5/SiO2) as the support was prepared by the sol-gel method and characterized by various techniques, including N2 adsorption, XRD, NH3 temperature-programmed desorption (TPD), TEM, and energy-dispersive X-ray spectroscopy (EDAX) atomic mapping. The characterization results showed that the niobium oxide species were amorphous and well dispersed in silica. Compared to commercial Nb2O5, Nb2O5/SiO2 has significantly more active niobium oxide species exposed on the surface. Under mild conditions (170°C, 2.5 MPa), Pd/10 %Nb2O5/SiO2 was effective for the hydrodeoxygenation reactions of 4-(2-furyl)-3-buten-2-one (aldol adduct of furfural with acetone), palmitic acid, tristearin, and diphenyl ether (model compounds of microalgae oils, vegetable oils, and lignin), which gave high yields (>94 %) of alkanes with little C-C bond cleavage. More importantly, owing to the significant promotion effect of NbOx species on C-O bond cleavage and the mild reaction conditions, the C-C cleavage was considerably restrained, and the catalyst showed an excellent activity and stability for the hydrodeoxygenation of palmitic acid with almost no decrease in hexadecane yield (94-95 %) in a 150 h time-on-stream test.
- Shao, Yi,Xia, Qineng,Liu, Xiaohui,Lu, Guanzhong,Wang, Yanqin
-
p. 1761 - 1767
(2015/06/02)
-
- Dimethyl sulfite a potential agent for methylation
-
The synthesis of methylated ether compounds is an important challenge. A pathway for the synthesis of methyl ethers was investigated using dimethyl sulfite (DMSi). Methylation of 1-octanol was carried out in liquid phase upon different heterogeneous organic and inorganic catalysts at 130°C. Aluminium oxide gave the best result with high conversion and moderate selectivity for methyl 1-octyl ether. Reactions in gas phase at higher temperatures (200°C) were also performed. Methyl 1-octyl ether was obtained in a very high level of selectivity up to 98%. Primary and secondary ethers from unsymmetrical alkyl methyl sulfite were also performed by SO2 extrusion.
- Mouselmani, Rim,Da Silva, Eric,Lemaire, Marc
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p. 8905 - 8910
(2015/11/02)
-
- Thermodynamically leveraged tandem catalysis for ester RC(O)O-R′ bond hydrogenolysis. scope and mechanism
-
Rapid and selective formal hydrogenolysis of aliphatic ester RC(O)O-R′ linkages is achieved by a tandem homogeneous metal triflate + supported palladium catalytic system. The triflate catalyzes the mildly exothermic, turnover-limiting O-R′ cleavage process, whereas the exothermic hydrogenation of the intermediate alkene further drives the overall reaction to completion.
- Lohr, Tracy L.,Li, Zhi,Assary, Rajeev S.,Curtiss, Larry A.,Marks, Tobin J.
-
p. 3675 - 3679
(2015/06/16)
-
- Influence of the functionalization degree of acidic ion-exchange resins on ethyl octyl ether formation
-
Ethyl octyl ether (EOE) can be obtained by the ethylation of 1-octanol by means of ethanol or diethyl carbonate over acidic ion-exchange resins. However, EOE formation has to compete with the less steric demanding formation of diethyl ether, by-product obtained from ethanol dehydration or diethyl carbonate decomposition. In the present work, the influence of the resin functionalization degree on EOE formation has been evaluated. A series of partially sulfonated resins (0.87-4.31 mmol H+/g) were prepared by the sulfonation of a macroreticular styrene-divinylbenzene copolymer. The catalysts were characterized, and subsequently, tested in a batch reactor (T = 150 C, P = 25 bar). Amberlyst 15 and 46 were also tested for comparison purposes. Catalytic runs revealed that EOE formation occurred mainly in the firstly sulfonated domain of the polymer skeleton, the least crosslinked; while diethyl ether was formed in the whole polymer bead. Accordingly, the functionalization of the least accessible polymer domain, as a result of increasing the sulfonation temperature or by using a pre-swelling solvent, is not suitable to produce long chain ethers such as EOE; which are preferred as diesel fuels.
- Guilera, Jordi,Hanková, Libuse,Jerabek, Karel,Ramírez, Eliana,Tejero, Javier
-
-
- Kinetics of hydrodeoxygenation of octanol over supported nickel catalysts: A mechanistic study
-
The hydrodeoxygenation (HDO) of 1-octanol as a model aliphatic alcohol of bio-oil was investigated in a continuous down-flow fixed-bed reactor over γ-Al2O3, SiO2, and HZSM-5 supported nickel catalysts in the temperature range of 488-533 K. The supported nickel catalysts were prepared by incipient wetness impregnation method and characterized by BET, XRD, TPR, TPD, H2pulse chemisorption, and UV-vis spectroscopy. Characterization of supported nickel (or nickel oxide) catalysts revealed existence of dispersed as well as bulk nickel (or nickel oxide) depending on the extent of nickel loading and the nature of the support. The acidity of γ-Al2O3supported nickel catalysts decreased with increasing the nickel loading on γ-Al2O3. n-Heptane, n-octane, di-n-octyl ether, 1-octanal, isomers of heptene and octene, tetradecane, and hexadecane were identified as products of HDO of 1-octanol. The C7hydrocarbons were observed as primary products for catalysts with active metal sites such as γ-Al2O3and SiO2supported nickel catalysts. However, C8hydrocarbons were primarily formed over acidic catalysts such as pure HZSM-5 and HZSM-5 supported nickel catalyst. The 1-octanol conversion increased with increasing nickel loading on γ-Al2O3, and temperature and decreasing pressure and WHSV. The selectivity to products was strongly influenced by temperature, nickel loading on γ-Al2O3, pressure, and types of carrier gases (nitrogen and hydrogen). The selectivity to C7hydrocarbons was favoured over catalysts with increased nickel loading on γ-Al2O3at elevated temperature and lower pressure. A comprehensive reaction mechanism of HDO of 1-octanol was delineated based on product distribution under various process conditions over different catalysts. This journal is
- Chandra Sekhar Palla, Venkata,Shee, Debaprasad,Maity, Sunil K.
-
p. 41612 - 41621
(2015/01/08)
-
- Bifunctional nanoparticle-SILP catalysts (NPs@SILP) for the selective deoxygenation of biomass substrates
-
Ruthenium nanoparticles were immobilized onto an acidic supported ionic liquid phase (RuNPs@SILP) in the development of bifunctional catalysts for the selective deoxygenation of biomass substrates. RuNPs@SILPs possessed high catalytic activities, selectivities and recyclabilities in the hydrogenolytic deoxygenation and ring opening of C8- and C9-substrates derived from furfural or 5-hydroxymethylfurfural and acetone. Tailoring the acidity of the SILP through the ionic liquid loading provided a molecular parameter by which the catalytic activity and selectivity of the RuNPs@SILPs were controlled to provide a flexible catalyst system toward the formation of different classes of value-added products: cyclic ethers, primary alcohols or aliphatic ethers. This journal is
- Luska, Kylie L.,Julis, Jennifer,Stavitski, Eli,Zakharov, Dmitri N.,Adams, Alina,Leitner, Walter
-
supporting information
p. 4895 - 4905
(2015/02/19)
-
- Pd/NbOPO4 multifunctional catalyst for the direct production of liquid alkanes from aldol adducts of furans
-
Great efforts have been made to convert renewable biomass into transportation fuels. Herein, we report the novel properties of NbO x-based catalysts in the hydrodeoxygenation of furan-derived adducts to liquid alkanes. Excellent activity and st
- Xia, Qi-Neng,Cuan, Qian,Liu, Xiao-Hui,Gong, Xue-Qing,Lu, Guan-Zhong,Wang, Yan-Qin
-
p. 9755 - 9760,6
(2015/01/16)
-
- Kinetics of hydrodeoxygenation of octanol over supported nickel catalysts: A mechanistic study
-
The hydrodeoxygenation (HDO) of 1-octanol as a model aliphatic alcohol of bio-oil was investigated in a continuous down-flow fixed-bed reactor over γ-Al2O3, SiO2, and HZSM-5 supported nickel catalysts in the temperature range of 488-533 K. The supported nickel catalysts were prepared by incipient wetness impregnation method and characterized by BET, XRD, TPR, TPD, H2 pulse chemisorption, and UV-vis spectroscopy. Characterization of supported nickel (or nickel oxide) catalysts revealed existence of dispersed as well as bulk nickel (or nickel oxide) depending on the extent of nickel loading and the nature of the support. The acidity of γ-Al2O3 supported nickel catalysts decreased with increasing the nickel loading on γ-Al2O3. n-Heptane, n-octane, di-n-octyl ether, 1-octanal, isomers of heptene and octene, tetradecane, and hexadecane were identified as products of HDO of 1-octanol. The C7 hydrocarbons were observed as primary products for catalysts with active metal sites such as γ-Al2O3 and SiO2 supported nickel catalysts. However, C8 hydrocarbons were primarily formed over acidic catalysts such as pure HZSM-5 and HZSM-5 supported nickel catalyst. The 1-octanol conversion increased with increasing nickel loading on γ-Al2O3, and temperature and decreasing pressure and WHSV. The selectivity to products was strongly influenced by temperature, nickel loading on γ-Al2O3, pressure, and types of carrier gases (nitrogen and hydrogen). The selectivity to C7 hydrocarbons was favoured over catalysts with increased nickel loading on γ-Al2O3 at elevated temperature and lower pressure. A comprehensive reaction mechanism of HDO of 1-octanol was delineated based on product distribution under various process conditions over different catalysts. This journal is
- Chandra Sekhar Palla, Venkata,Shee, Debaprasad,Maity, Sunil K.
-
p. 41612 - 41621
(2015/05/20)
-
- Rapid ether and alcohol C-O bond hydrogenolysis catalyzed by tandem high-valent metal triflate + supported Pd catalysts
-
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.
-
p. 104 - 107
(2014/01/23)
-
- Chemical equilibrium of the liquid-phase dehydration of 1-octanol to 1-(octyloxy)octane
-
The equilibrium constants for the liquid-phase dehydration of 1-octanol to 1-(octyloxy)octane (DNOE) and water have been determined in the temperature range (413 to 453) K over Amberlyst 70. The equilibrium constants for the main side reactions, intramolecular dehydration of 1-octanol to 1-octene and 1-octene isomerization to 2-octene, have been determined as well. Etherification of 1-octanol was shown to be exothermic, with reaction enthalpy change of (-13.6 ± 1.7) kJ·mol-1 at 298.15 K. The standard formation enthalpy of 1-(octyloxy)octane was computed to be (-581 ± 2) kJ·mol-1, in good agreement with the estimated value by a modified Benson method. A standard molar entropy of (658 ± 4) J·mol-1·K-1 in the liquid phase has been found for 1-(octyloxy)octane from the entropy change of reaction at 298.15 K. Intramolecular dehydration of 1-octanol has been found to be endothermic and isomerization of 1-octene to 2-octene exothermic.
- Casas, Carlos,Fite, Carles,Iborra, Monsterrat,Tejero, Javier,Cunill, Fidel
-
p. 741 - 748
(2013/05/08)
-
- Method for the production of aliphatic alcohols and/or their ethers
-
A method for the production of aliphatic alcohols and/or their ethers, comprising the step of reacting a substrate of the general formula (I): in which m is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9 and n is 1 or 2; R1 is hydrogen, a linear, branched or cyclic alkyl rest, a primary alkanol rest, an aryl rest or one of the following radicals: and R2 is hydrogen or -CH2OH; with hydrogen in the presence of a hydrogenation catalyst system, wherein the hydrogenation catalyst system comprises: - a hydrogenation catalyst comprising Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and/or Pt; and - an acidic additive selected from the group of organoperfluorocarboxylic acids, hydrochloric acid, formic acid, acetic acid, phosphoric acid, sulfuric acid, sulfonic acid and/or organic compounds comprising sulfonic acid groups, phosphoric acid groups and/or phosphonic acid groups; with the proviso that the acidic additive is a liquid and/or at least partially dissolved in the substrate (I) during the reaction of (I) with hydrogen in the case that R2 is CH2OH.
- -
-
Paragraph 0065-0066
(2013/10/21)
-
- METHOD FOR THE PRODUCTION OF ALIPHATIC ALCOHOLS AND/OR THEIR ETHERS, IN PARTICULAR 1-OCTANOL
-
Method for the production of aliphatic alcohols and/or their ethers, in particular 1-octanol A method for the production of aliphatic alcohols and/or their ethers, comprising the step of reacting a substrate of the general formula (I): in which m is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9 and n is 1 or 2; R1 is hydrogen, a linear, branched or cyclic alkyl rest, a primary alkanol rest, an aryl rest or one of the following radicals: and R2 is hydrogen or -CH2OH; with hydrogen in the presence of a hydrogenation catalyst system, wherein the hydrogenation catalyst system comprises: - a hydrogenation catalyst comprising Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and/or Pt; and - an acidic additive selected from the group of organoperfluorocarboxylic acids, hydrochloric acid, formic acid, acetic acid, phosphoric acid, sulfuric acid, sulfonic acid and/or organic compounds comprising sulfonic acid groups, phosphoric acid groups and/or phosphonic acid groups; with the proviso that the acidic additive is a liquid and/or at least partially dissolved in the substrate (I) during the reaction of (I) with hydrogen in the case that R2 is CH2OH.
- -
-
Page/Page column 15; 16; 17
(2013/10/21)
-
- Thermal stability and water effect on ion-exchange resins in ethyl octyl ether production at high temperature
-
Abstract Thermal stability and water inhibition effects were studied at 150 and 190 C on the chlorinated acidic polystyrene-divinylbenzene resins Amberlyst 70, Amberlyst XE804 and Purolite CT482, and the non-chlorinated one Dowex 50Wx2. Catalytic activity in the reaction between ethanol and 1-octanol to form ethyl octyl ether (EOE) was monitored for 70 h in a continuous fixed-bed reactor. Leaching of sulfonic groups at 190 C was found to be negligible for Purolite CT482 and Amberlyst 70, but it was significant for Amberlyst XE804 and Dowex 50Wx2. The activity decay to a steady EOE reaction rate on Purolite CT482 and Amberlyst 70 has been ascribed to the reaction rate inhibition by the formed water. However, water adsorption on the catalyst also modified the resin morphology during the course of the reaction. Adsorbed water swelled the gel-phase and more acid sites became accessible for 1-octanol molecules. As a result, the activity decay of EOE and the longer byproduct di-n-octyl ether syntheses was smaller than that of the shorter one diethyl ether.
- Guilera, Jordi,Ramírez, Eliana,Fité, Carles,Iborra, Montserrat,Tejero, Javier
-
p. 301 - 309
(2013/09/02)
-
- 1,2,4-triazol-3-ylidenes with an N-2,4-dinitrophenyl substituent as strongly π-accepting N-heterocyclic carbenes
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The synthesis and characterisation of a series of new Rh and Au complexes bearing 1,2,4-triazol-3-ylidenes with a N-2,4-dinitrophenyl (N-DNP) substituent are described. IR, NMR, single-crystal X-ray diffraction and computational analyses of the Rh complexes revealed that the N-heterocyclic carbenes (NHCs) behaved as strong π acceptors and weak σ donors. In particular, a natural bond orbital (NBO) analysis revealed that the contributions of the Rh→Ccarbene π backbonding interaction energies (ΔE bb) to the bond dissociation energies (BDE) of the Rh-C carbene bond for [RhCl(NHC)(cod)] (cod=1,5-cyclooctadiene) reached up to 63 %. The Au complex exhibited superior catalytic activity in the intermolecular hydroalkoxylation of cyclohexene with 2-methoxyethanol. The NBO analysis suggested that the high catalytic activity of the AuI complex resulted from the enhanced π acidity of the Au atom. π-Acidic carbene complexes: A series of Rh and Au complexes bearing 1,2,4-triazol-3- ylidenes with a N-2,4-dinitrophenyl (DNP) substituent were synthesised. Experimental and theoretical analyses revealed that these N-heterocyclic carbenes (NHCs) behave as strong π acceptors and weak σ donors, and the metal centers exibit enhanced π acidity compared to complexes with traditional σ-donating NHCs (see figure, EWG=electron withdrawing group). Copyright
- Sato, Tetsuo,Hirose, Yoichi,Yoshioka, Daisuke,Shimojo, Tsubasa,Oi, Shuichi
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p. 15710 - 15718
(2013/11/19)
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- Graphite oxide activated zeolite NaY: Applications in alcohol dehydration
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A mixture of graphite oxide (GO) and the zeolite NaY (Si/Al = 5.1) was used to dehydrate various alcohols to their respective olefinic products. Using conditions optimized for 4-heptanol (15 wt% GO-NaY (1 : 1 wt/wt), 150°C, 30 min), a series of secondary and tertiary aliphatic alcohols were cleanly dehydrated in moderate to excellent conversions (27.5-97.2%). Several primary alcohols were also dehydrated, although higher catalyst loadings (200 wt% GO-NaY (1 : 1) and longer reaction times (3 h) were required. The enhanced dehydration activity was attributed to the ability of GO to convert NaY to an acidic form and without the need for ammonium cation exchange and/or high temperature calcination. The Royal Society of Chemistry 2013.
- Todd, Alexander D.,Bielawski, Christopher W.
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p. 135 - 139
(2013/03/29)
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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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- 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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- Indium, as an efficient co-catalyst of Cu/Al2O3 in the selective hydrogenation of biomass derived fatty acids to alcohols
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Octanoic acid (OA) as model reactant of medium chain length, and its reduced products, octanal and octanol were hydroconverted over different components of a CuIn/Al2O3 composite catalyst. A fixed-bed flow through reactor was used at 21 bar total pressure in the temperature range of 240-360 °C. Fatty acid hydroconversion activity of alumina supported Cu catalyst and mainly the yield of selectively produced octanol can be greatly increased by In2O3 doping, suppressing the dehydration side reactions. Appearance of metallic indium on alumina supported reduced copper catalyst can arrest the consecutive catalytic reaction at the alcohol formation step prior to further dehydration to ether or alkenes. An industrial, conventionally used Adkins catalyst (72 wt.% CuCr2O4 and 28 wt.% CuO) and the novel bimetallic composite (CuIn/Al2O 3) were compared: both produce octanol with high selectivity, but the new chromium-free fatty acid hydrogenation catalyst is more active, nearly as active as earlier investigated NiIn/Al2O3.
- Onyestyák, Gy?rgy,Harnos, Szabolcs,Kalló, Dénes
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experimental part
p. 19 - 24
(2012/10/07)
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- Synthesis of 3-substituted tetrahydrofuran and 4-substituted tetrahydropyran derivatives by cyclization of dicarboxylic acids with InBr 3/TMDS
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An efficient reduction followed by cyclization of diacid compounds with the InBr3/TMDS system is reported. This system allows the formation of five- and six-membered ring ethers substituted in the 3- or 4-position. Copyright
- Pehlivan, Leyla,Metay, Estelle,Delbrayelle, Dominique,Mignani, Gerard,Lemaire, Marc
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scheme or table
p. 4689 - 4693
(2012/09/22)
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- Synthesis of 1-octanol and 1,1-dioctyl ether from biomass-derived platform chemicals
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The happy medium: A new catalytic pathway for the synthesis of the linear primary C8?alcohol products 1-octanol and dioctyl ether from furfural and acetone has been developed using retrosynthetic analysis. This opens a general strategy for the synthesis of medium-chain-length alcohols from carbohydrate feedstock.
- Julis, Jennifer,Leitner, Walter
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supporting information; experimental part
p. 8615 - 8619
(2012/09/21)
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- ALPHA-CYANOACRYLATE ESTER SYNTHESIS
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The high temperatures required for cracking the cyanoacrylate oligomers, produced by the Knovenagel condensation of formaldehyde and a cyanoacetate, limit the synthetic diversity and the number of different side chains that can be incorporated into a cyanoacrylate prepared using this method. Accordingly, the diversity of cyanoacrylate monomers prepared industrially is quite limited. Disclosed herein is a method for the preparation of alpha-Cyanoacrylate ester monomers from a variety of phosphonium and ammonium alpha-cyanoacrylate salts. The phosphonium and ammonium alpha-cyanoacrylate salts are of the general formula: (I).
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Page/Page column 10-12
(2012/04/17)
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- Synthesis of ethyl octyl ether from diethyl carbonate and 1-octanol over solid catalysts. A screening study
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The synthesis of ethyl octyl ether (EOE) from a mixture of diethyl carbonate (DEC) and 1-octanol (1:2 molar ratio) over several solid catalysts was studied in batch mode at 150 °C and 25 bar. Catalyst screening revealed that EOE could be successfully obtained over some acid catalysts. In particular the highest yield was achieved over acid ion-exchange resins (33% after 8 h). A reaction scheme of the process is proposed. Selectivity to EOE was mainly affected by the production of diethyl ether (DEE) and di-n-octyl ether (DNOE). However, EOE was the main ether obtained (60 mol%), followed by DEE (20 mol%) and DNOE (20 mol%). By comparing the behavior of several acid resins, it was seen that the synthesis of EOE was highly related to the structural resin properties. It was found that the accessibility of DEC and 1-octanol to acid centers was improved over highly swollen and low polymer density resins. Thus, gel-type resins with low divinylbenzene content are the most suitable to produce EOE (e.g., Amberlyst 121, Dowex 50Wx2-100 and CT224).
- Guilera,Bringué,Ramírez,Iborra,Tejero
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body text
p. 21 - 29
(2012/03/27)
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- Silica chloride and boron sulfonic acid as solid acid catalysts in preparation of ethers and esters under solvent-free condition
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Boron sulfonic acid was easily prepared from the reaction of boric acid and chlorosulfonic acid under solvent free condition. The prepared solid acid was supported on silica gel by simple grinding and used as efficient solid acid catalyst in the preparation of ethers from the aliphatic and aromatic alcohols. The ethers were prepared in high isolated yields and in lesser times. Silica chloride was prepared by refluxing of silica gel in thionyl chloride. The obtained solid acid was efficiently used for the conditions of alcohols to the corresponding ethers and acetyl esters in less reaction time and in high isolated yields.
- Elham, Sedighinia,Mozhgan, Zahed Sargoli
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supporting information; experimental part
p. 1456 - 1458
(2012/01/06)
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- Improving the catalytic behavior of Ni/Al2O3 by indium in reduction of carboxylic acid to alcohol
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Octanoic acid (OA) was used as reactant with medium chain length to model the aliphatic carboxylic acids which can be produced by catalytic, thermochemical or biological degradation of biomass. A flow through reactor was applied at 21 bar total pressure (in general 20 bar hydrogen and 1 bar octanoic acid partial pressures) and 240-360°C. Fatty acid conversion activity of alumina supported Ni catalysts and the yield of selectively produced alcohol can be increased drastically by In2O3 doping. Appearance of metallic indium can effectively direct the step by step catalytic reduction to alcohol formation over partly reduced Ni catalysts instead of chain shortening hydrodecarbonylation. On comparing a commercial, conventionally used Adkins catalyst (consisting of 72 wt.% CuCr2O4 and 28 wt.% CuO) and novel bimetallic alumina supported composite (InNi/Al2O 3) producing alcohol with high selectivity, the chromium-free, environmental benign hydrogenation catalyst seems to be much more active.
- Onyestyák, Gy?rgy,Harnos, Szabolcs,Kalló, Dénes
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scheme or table
p. 184 - 188
(2012/03/10)
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- Liquid-phase dehydration of 1-octanol, 1-hexanol and 1-pentanol to linear symmetrical ethers over ion exchange resins
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Dehydration of 1-octanol, 1-hexanol and 1-pentanol to di-n-octyl ether (DNOE), di-n-hexyl ether (DNHE) and di-n-pentyl ether (DNPE), respectively, has been studied in the liquid phase at 423K in a batch reactor on ion exchange resins as catalysts. Tested catalysts were the macroporous resins Amberlyst 15, Amberlyst 35, CT175, CT275 and CT276 (high crosslinking degree); Amberlyst 16, Amberlyst 36 and CT252 (medium crosslinking degree); Amberlyst 39 and Amberlyst 70 (low crosslinking degree), and the gel type ones CT224, Amberlyst 31, Amberlyst 121 and Dowex 50Wx4-50. Amberlyst 46, an ion-exchange resin sulfonated only at the polymer surface and Nafion NR50 were also tested for comparison purposes. Data show that the yield of linear symmetrical ethers (DNOE, DNHE and DNPE) highly depends on the resin structure so that best results are obtained on Amberlyst 121, Amberlyst 31 and Dowex 50Wx4-50 (the most swollen resins in reaction medium). The high ether yields are due both to the high alcohol conversions and especially to the very high selectivity to ethers (≥94%) shown by that resins. Finally, by comparing initial reaction rates of ether formation with those obtained on Amberlyst 46 an estimation of the fraction of sulfonic groups that take part in the reaction is given.
- Casas,Bringué,Ramírez,Iborra,Tejero
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experimental part
p. 129 - 139
(2012/01/13)
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- Decarboxylation of dialkyl carbonates to dialkyl ethers over alkali metal-exchanged faujasites
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Non-toxic DAlCs, especially lighter dimethyl- and diethyl-carbonate, are regarded as very green alkylating reagents, particularly when coupled with metal-exchanged Y- and X-faujasites as catalysts. These reactions are selective, free from wastes or byproducts, and often require no additional solvent other than the carbonate. Nonetheless, this paper demonstrates that the operating temperature and the nature of the faujasite must be carefully chosen in order to avoid DAlC decomposition. In fact, at temperatures ranging from 150 to 240°C, faujasites can promote decarboxylation of light DAlCs to the corresponding ethers CH3OCH3 and CH3CH 2OCH2CH3 plus CO2. Heavier DAlCs (dipropyl- and dioctyl-carbonate) undergo a similar decomposition pathway, followed by further reactions to the corresponding alcohols (n-propanol and n-octanol) and alkenes [propylene and octene(s)]. These transformations not only consume DAlCs, but also give rise to dangerously flammable ethers, as well as undesirable alcohols, alkenes and CO2. The present work reports an original investigation of the decarboxylation of DAlCs on faujasites with the aim of providing operative boundaries to the experimental conditions to minimise unwanted decomposition. The reaction is strongly affected by the nature of the catalyst: the more basic zeolites, NaX and CsY, are by far more active systems than NaY and LiY. However, solid K2CO3 proves to be rather inefficient. The temperature also plays a crucial role: for example, the onset of the decarboxylation of DMC requires a temperature of ~30°C lower than that for DEC and DPrC. Overall, awareness that certain zeolites cause decomposition of DAlCs under conditions similar to the ones used for DAlC-promoted alkylations allows determination of the correct experimental boundaries for a safer and more productive use of DAlCs as alkylating agents. The Royal Society of Chemistry.
- Selva, Maurizio,Fabris, Massimo,Perosa, Alvise
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experimental part
p. 863 - 872
(2011/06/20)
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- The continuous acid-catalysed etherification of aliphatic alcohols using stoichiometric quantities of dialkyl carbonates
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A range of methyl and ethyl ethers of aliphatic alcohols have been synthesized cleanly in high yield by reacting the corresponding alcohol with dimethyl carbonate or diethyl carbonate over the solid acid catalyst, I-alumina. The reaction could be conducted at ambient pressure without the need for the large excess of dialkyl carbonate as previously reported in the literature. If the reaction was conducted at high pressure, the conversion of the starting alcohol was greatly reduced. However, high pressure CO2 can be used as the solvent without significant reduction in yield. This has implications for tandem reactions.
- Parrott, Andrew J.,Bourne, Richard A.,Gooden, Peter N.,Poliakoff, Martyn,Irvine, Derek J.,Bevinakatti, Han. S.
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experimental part
p. 1420 - 1426
(2011/09/20)
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- Continuous acid-catalyzed methylations in supercritical carbon dioxide: Comparison of methanol dimethyl ether and dimethyl carbonate as methylating agents
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The development of high-yielding, "greener" chemistry-based routes for the continuous synthesis of methyl ethers are reported in this study. Ethers have been efficiently produced using a methodology which eliminates the use of toxic alkylating agents and reduces the waste generation that is characteristic of traditional etherification processes. For the first time it is shown that the use of acidic heterogeneous catalysts can successfully achieve etherification when using scCO2 as a reaction medium. Furthermore, the relative efficiencies of three alternative methylating agents, dimethyl carbonate, dimethyl ether and MeOH, have been compared and contrasted for the methylation of 1-octanol. Dimethyl carbonate has proven to be the superior methylating agent, demonstrating higher conversion and selectivity. Successful methylation of secondary alcohols, diols, carboxylic acids and amines using dimethyl carbonate in supercritical carbon dioxide has also been shown. Substrate structure was found to influence the temperature required to maximize the yield of the desired product, substrates with multiple hydroxyl groups requiring the highest temperatures.
- Gooden, Peter N.,Bourne, Richard A.,Parrott, Andrew J.,Bevinakatti, Han S.,Irvine, Derek J.,Poliakoff, Martyn
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experimental part
p. 411 - 416
(2011/04/22)
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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 17
(2009/06/27)
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- Catalytic cracking of ethers to 1-olefins
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The current invention provides a process in which ethers are converted into α-olefins by passage over a modified alumina catalyst. The alumina catalyst is made by treating gamma-alumina with a rare earth metal oxide such as lanthanum oxide, La2O3. The modified aluminum catalysts convert 1-methoxyoctane into 1-octene with high selectivity at high conversion rates.
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Page/Page column 2-3
(2008/12/07)
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- High-efficiency conversion of trimethylsilyl ethers to their corresponding ethers using carbon-based solid acid as a new catalyst in heterogeneous mixtures
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Carbon-based solid acid was used as a new catalyst for conversion of trimethylsilyl ethers to their corresponding ethers in heterogeneous mixtures. The experiments were done moderately at room temperature, and high yields in suitable times were obtained under these conditions. Copyright Taylor & Francis Group, LLC.
- Shokrollahi, Arash,Zali, Abbas,Pouretedal, Hamid Reza
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p. 371 - 375
(2008/04/01)
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- CaS2O8: An efficient reagent for etherification of alcohols under microwave irradiation in solvent-free conditions
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A new facile and efficient one-pot method for the synthesis of ethers by the reaction of alcohols with calcium peroxodisulfate under microwave irradiation is described. Copyright Taylor & Francis Group, LLC.
- Badri, Rashid,Kiasat, Ali Reza,Nazari, Simin
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p. 589 - 593
(2007/10/03)
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