- One-step solvent-free aerobic oxidation of aliphatic alcohols to esters using a tandem Sc-Ru?MOF catalyst
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Esters are an important class of chemicals in industry. Traditionally, ester production is a multi-step process involving the use of corrosive acids or acid derivatives (e.g. acid chloride, anhydride, etc.). Therefore, the development of a green synthetic protocol is highly desirable. This work reports the development of a metal-organic framework (MOF) supported tandem catalyst that can achieve direct alcohol to ester conversion (DAEC) using oxygen as the sole oxidizing agent under strictly solvent-free conditions. By incorporating Ru nanoparticles (NPs) along with a homogeneous Lewis acid catalyst, scandium triflate, into the nanocavities of a Zr MOF, MOF-808, the compound catalyst, Sc-Ru?MOF-808, can achieve aliphatic alcohol conversion up to 92% with ester selectivity up to 91%. A mechanistic study reveals a unique “via acetal” pathway in which the alcohol is first oxidized on Ru NPs and rapidly converted to an acetal on Sc(iii) sites. Then, the acetal slowly decomposes to release an aldehyde in a controlled manner for subsequent oxidation and esterification to the ester product. To the best of our knowledge, this is the first example of DAEC of aliphatic alcohols under solvent-free conditions with high conversion and ester selectivity.
- Feng, Tingkai,Li, Conger,Li, Tao,Zhang, Songwei
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p. 1474 - 1480
(2022/03/08)
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- Visible-Light-Driven Dehydrogenative Coupling of Primary Alcohols with Phenols Forming Aryl Carboxylates
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A preparative method for obtaining aryl esters from aliphatic primary alcohols and phenols was developed. The reaction proceeds under the irradiation of visible light at ambient temperature, dispensing with any oxidant or hydrogen acceptor. Primary alcohols having a variety of functional groups are successfully esterified with phenols. The produced esters can be utilized as the precursor of various carbonyl compounds.
- Ishida, Naoki,Kawasaki, Tairin,Murakami, Masahiro,Tosaki, Tomohiro
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supporting information
p. 7683 - 7687
(2021/10/12)
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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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- Photocatalytic Conversion of a FeCl3–CCl4–ROH System
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The photocatalytic transformations of carbon tetrachloride and aliphatic primary alcohols in the presence of iron trichloride and a molar ratio of components FeCl3: CCl4: ROH = 1: 300: 2550 were studied. CCl4 is transformed into chloroform and hexachloroethane after exposure to a mercury lamp (250 W) to the FeCl3–CCl4–ROH system at 20°C, whereas the primary ROH alcohols are selectively oxidized into acetals (1,1-dialkoxyalkanes). The maximum conversion of CCl4 reaches 80%. The kinetics and mechanism of the photocatalytic conversion of the FeCl3–CCl4–ROH system are considered.
- Makhmutov
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p. 695 - 700
(2018/03/08)
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- Acetals from primary alcohols with the use of tridentate proton responsive phosphinepyridonate iridium catalysts
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The association of the new phosphinepyridonate ligands along with an iridium metallic precursor resulted in the selective acetalization of various primary alcohols via a formal dehydrogenative coupling reaction.
- Sahoo,Jiang,Bruneau,Sharma,Suresh,Achard
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p. 100554 - 100558
(2016/11/09)
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- The levels of fatty alcohol dehydrogenation coupling method for preparing aldehyde-acetal
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The invention discloses a method for preparing acetal by dehydrogenation coupling of first-stage fatty alcohol. The method comprises the following steps: adding alcohol reaction liquid to commercial titanium dioxide P25, and simultaneously adding a precious metals source solution; vacuumizing or introducing argon under magnetic agitation; stopping vacuumizing or introducing argon after oxygen in the system is removed; turning on an ultraviolet light source; reducing a precious metal source into precious metal particles by in-situ photocatalysis, and loading to the titanium dioxide surface; carrying out dehydrogenation coupling on catalyzed alcohol to form the acetal; controlling the reaction temperature at 10-70 DEG C and the reaction time at 10-72 hours; separating a catalyst through centrifugal participation, vacuum filtration or static precipitation after the reaction is ended, and then carrying out reduced pressure distillation to remove alcohol, so as to obtain the acetal product. The method has the advantages of high selectivity, high yield, low cost and the like, and is environmental friendly, and the purity can be up to over 97%.
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Paragraph 0029; 0030
(2016/10/08)
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- TiO2-photocatalytic acceptorless dehydrogenation coupling of primary alkyl alcohols into acetals
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Primary alkyl alcohols can be directly converted into acetals and H 2via TiO2-photocatalytic dehydrogenation coupling at room temperature, with no need for any hydrogen acceptors. The reaction follows a tandem process integrating photocatalytic alcohol dehydrogenation and H +-catalytic acetalation, in which the H+ ion catalysts are provided by the alcohol dehydrogenation in real time. This approach exhibits a very high reaction rate and product selectivity, and represents a novel green process for the conversion of primary alkyl alcohols, especially for bio-renewable ethanol and 1-butanol. the Partner Organisations 2014.
- Zhang, Hongxia,Zhu, Zhenping,Wu, Yupeng,Zhao, Tianjian,Li, Li
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p. 4076 - 4080
(2014/10/15)
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- Expanding the scope of biomass-derived chemicals through tandem reactions based on oxorhenium-catalyzed deoxydehydration
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New modes of DODH: Oxorhenium compounds act as deoxydehydration(DODH)/acid dual-purpose catalysts to transform biomass-derived diol substrates into a variety of commodity chemical precursors. The power of this approach is highlighted by a tandem [1,3]-OH shift/DODH of 2-ene-1,4-diols and 2,4-diene-1,6-diols, and by a DODH/esterification sequence of sugar acids to unsaturated esters for the production of polymers and plasticizers. Copyright
- Shiramizu, Mika,Toste, F. Dean
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supporting information
p. 12905 - 12909
(2014/01/06)
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- Copper-catalyzed dehydrogenative coupling of arenes with alcohols
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What a couple! Arenes functionalized with donating groups undergo oxidative dehydrogenative coupling with alcohols in the presence of a copper/silver catalyst system. This intermolecular C-H alkoxylation provides a convenient synthetic route to the important class of aryl ethers. The catalyst system also allows the alkoxylation of benzylic C-H groups with formation of benzyl alkyl ethers. Copyright
- Bhadra, Sukalyan,Matheis, Christian,Katayev, Dmitry,Goo?en, Lukas J.
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supporting information
p. 9279 - 9283
(2013/09/12)
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- Selective acceptorless conversion of primary alcohols to acetals and dihydrogen catalyzed by the ruthenium(II) complex Ru(PPh3) 2(NCCH3)2(SO4)
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The complex bis(acetonitrile)bis(triphenylphosphine)ruthenium(II) sulfate [Ru(PPh3)2(NCCH3)2(SO4)], fully characterized spectroscopically and by a single crystal X-ray study, catalyzes at 110 °C the direct transformation of primary alcohols to the corresponding acetals with liberation of molecular hydrogen. The formation of acetals proceeds via direct substitution of the hydroxy group of the hemiacetal intermediate by an alcohol molecule. The closely related bis(triphenylphosphine) ruthenium(II) acetate [Ru(PPh3)2(OAc)2] catalyzes the conversion of primary alcohols to the corresponding esters rather than acetals. Copyright
- Kossoy, Elizaveta,Diskin-Posner, Yael,Leitus, Gregory,Milstein, David
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experimental part
p. 497 - 504
(2012/04/23)
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- Method for producing enol ethers
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Enol ethers of the formula I where R1is an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical which may carry further substituents which do not react with acetylenes or allenes, and the radicals R, independently of one another, are hydrogen or aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radicals, which may be bonded to one another to form a ring, and m is 0 or 1, are prepared by reacting an acetal or ketal of the formula II with an acetylene or allene of the formula III or IV where R and R1have the abovementioned meanings, in the gas phase at elevated temperatures in the presence of a zinc- or cadmium- and silicon- and oxygen-containing heterogeneous catalyst.
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- Processes for the preparation of n-butyraldehyde, n-butanol and mixtures thereof
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PCT No. PCT/EP98/01324 Sec. 371 Date Sep. 15, 1999 Sec. 102(e) Date Sep. 15, 1999 PCT Filed Mar. 6, 1998 PCT Pub. No. WO98/41494 PCT Pub. Date Sep. 24, 1998Process for the preparation of n-butyraldehyde and/or n-butanol, wherein a) 1,3-Butadiene or a butadiene-containing hydrocarbon mixture is reacted with an alcohol of the formula IROHI, where R is C2-C20-alkyl or alkenyl which is unsubstituted or substituted by 1 or 2 C1-C10-alkoxy or hydroxyl groups, or is C6-C10-aryl, C7-C11-aralkyl or methyl, at elevated temperatures and superatmospheric pressure in the presence of a Br+E,uml o+EE nsted acid or in the presence of a complex of an element of Group Ia, VIIA or VIIIA of the Periodic Table of Elements with phosphorus- or nitrogen-containing ligands to give a mixture of the adducts of the formulae II and III b) the adduct III is isomerized to the adduct II, c) the adduct II is converted into the acetal of the formula IV d) n-butyraldehyde and/or n-butanol are then produced from this acetal IV by reacting it, in the liquid phase, with hydrogen and water or water in the presence of a homogeneous or heterogeneous transition metal catalyst which differs from dicobaltoctacarbonyl or hydridocobalttetracarbonyl.
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- Hydrocarbons and chloroaromatics from anilines and n-butyl nitrite
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A single reagent, i.e. n-butyl nitrite, can be used to oxidize an aromatic amine, or the corresponding N-methylene derivative, to a diazo compound followed by its subsequent reduction to hydrocarbon in a single batch.Alternatively, a chloro derivative can be obtained if carbon tetrachloride is used as the solvent.The reactions appear to be general and complete product identification was accomplished.
- Giumanini, Angelo G.,Verardo, Giancarlo,Gorassini, Fausto,Strazzolini, Paolo
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p. 311 - 316
(2007/10/02)
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- Studies on the Reaction of Iron Sulphide with Butan-1-ol in the Vapour Phase
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A new reaction of iron sulphide with butan-1-ol in the vapour phase a 359-500 deg producing mainly 1,1'-thiobis(butane) and 1,1-dibutoxybutane is reported.Iron sulphide (FeS) catalyses the formation of 1,1-dibutoxybutane and decomposition of 1-butane thiol.
- D'Souza, Ita M.,Banerjee, Anil C.
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p. 739 - 742
(2007/10/03)
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- The Synthesis of Glycols by Mercury-Photosensitized Alcohol Dehydrodimerization
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A variety of alcohols can be dehydrodimerized to give 1,2-diols on a multigram scale at 1 atm pressure and reflux temperature on photolysis (254 nm) in the presence of a trace of Hg vapor.Initial C-H bond breaking is followed by recombination of the resulting α-centered radicals, which normally leads to C-C bond formation α to oxygen.The reaction rate and selectivity can be increased by operating at lower temperatures under H2, in which case H atoms replace Hg* as the principal abstracting reagent and H atom abstraction from the α-CH bond leads directly to the α-C-centered radical.Under H atom conditions, unsaturated alcohols also react, in which case diols other than the 1,2-isomer can be formed selectively.The product can be rationalized on the basis of H atom addition to the C=C double bond to give the most stable radical which then dimerizes.For the special case of t-BuOH, H atom abstraction from the t-BuOH β-CH group under H atom conditions leads to the β-centered radical, which dimerizes to the 1,4-diol.Radical disproportionation accounts for some of the byproducts observed.The following previously unknown C-H bond strengths (kcal/mol) were determined from the results, assuming the literature BDE for the α-C-H of 2-propanol (91.0 +/-1.0); n-butanol, 92.8 +/- 1.0( α), 95.2 +/- 1.0 (β), and 94.3 +/- 1.0 (γ); n-propanol, 93.1 +/- 1.0 (α), and 95.0 +/- 1.0 (β), respectively.
- Lee, Jesse C.,Boojamra, Constantine G.,Crabtree, Robert H.
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p. 3895 - 3900
(2007/10/02)
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- CATALYSED LIQUID PHASE OXIDATION OF ACETALS BY MOLECULAR OXYGEN
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Nine different acetals have been oxidized in the presence of Co(OOCCH3)2*4H2O under isobaric conditions (0.1 - 0.2 MPa O2) while following the uptake of molecular oxygen.The reactivity of acetals was expressed by the rate constants of the autocatalytic model of oxidation.The main product of the oxidation are alcohols, esters and acids.The distribution of products and the total reactivity of acetals are controlled by the structure of both parts of acetal molecule.The dominant effects of the course of the reaction exerts the type of carbon atoms on which radicals are formed.The oxidation is accompanied by consecutive and co-oxidation reactions, by deactivation of the catalysts and by decarbonylation of intermediate products.The effect of oxygen pressure is reported and the more detailed radical mechanism of the oxidation is proposed.
- Vcelak, Jaroslav,Klimova, Miroslava,Chvalovsky, Vaclav
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p. 847 - 866
(2007/10/02)
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- Catalytic oxidation of alcohols with molecular oxygen to form carbonyl compounds
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Carbonyl compounds are manufactured by oxidizing alcohols or polyalcohols with molecular oxygen in the presence of a catalyst which comprises ruthenium salts or complexes associated with copper or iron salts or complexes.
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