- Fluorescence excitation spectrum of the 2-butoxyl radical and kinetics of its reactions with NO and NO2
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The (A ← X) fluorescence excitation spectrum of the 2-C4H9O(X) (2-butoxyl) radical in the wavelength range 345-390 nm was obtained using a combined laser photolysis/laser-induced fluorescence (LIF) technique following the generation of the radicals by excimer laser photolysis of 2-butylnitrite at λ = 351 nm. The fluorescence excitation spectrum shows 5 vibronic bands, where the dominant progression corresponds to the CO-stretching vibration in the first electronically excited state with v′CO = (560 ± 10) cm-1. The transition origin was assigned at v00 = (26768 ± 10) cm-1 (λ00 = (373.58 ± 0.15) nm). The kinetics of the reactions of the 2-butoxyl radical with NO and NO2 at temperatures between T = 223-305 K and pressures between p = 6.5-104 mbar have been determined. The rate coefficients for both reactions were found to be independent of total pressure with kNO = (3.9 ± 0.3) × 10-11 cm3 s-1 and kNO2 = (3.6 ± 0.3) times; 10-11 cm3 s-1 at T = 295 K. The Arrhenius expressions have been determined to be kNO = (9.1 ± 2.7) × 10-12 exp((3.4 ± 0.6) kJ mol-1/RT) cm3 s-1 and kNO2 = (8.6 ± 3.3) × 10-12 exp((3.3 ± 0.8) kJ mol-1/RT) cm3 s-1. In addition, the radiative lifetime of the 2-C4H9O(A) radical after excitation at λ = 365.938 nm in the (0,1) band has been determined to be τrad(2-C4H9O(A)) = (440 ± 80) ns. Quenching rate constants of the 2-C4H9O(A) radical were measured to be kq = (4.7 ± 0.3) × 10-10 cm3 s-1 and kq = (5.0 ± 0.4) × 10-12 cm3 s-1 for 2-butylnitrite and nitrogen, respectively.
- Lotz,Zellner
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- Homogeneous Hydrogenation of α,β-Unsaturated Ketones and Aldehydes Catalyzed by Co2(CO)8-Di(tertiary phosphine) Complexes
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The cobalt complexes modified by some di(tertiary phosphine)s as ligands were found to be much more active catalysts than Co2(CO)8 for the hydrogenation of α,β-unsaturated ketones and aldehydes under hydroformylation conditions.
- Murata, Kazuhisa,Matsuda, Akio
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- Isoxazoles. 8. Preformulation studies of an isoxazolylnaphthoquinone derivative
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The degradation kinetics of 2-hydroxy-N-(3,4-dimethyl-5-isoxazolyl)-1,4- naphthoquinone 4-imine (1) in a 25% solution of ethyl alcohol in water has been studied. The rate constants were observed to follow pseudo-first-order kinetics in all cases. The pH-rate profile indicated a negligible decomposition at pH values higher than its pK(a2) value [5.40 ± 0.14 (*n = 6)]. Un-ionized 1 was subject to specific acid catalysis. The ionic strength did not affect the stability of the drug. These data can be used to develop a stable oral liquid dosage form of the drug.
- Longhi,De Bertorello,Granero
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- Mutation of serine-39 to threonine in thermostable secondary alcohol dehydrogenase from Thermoanaerobacter ethanolicus changes enantiospecificity
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The substrate specificity of wild-type and Ser39 → Thr (S39T) secondary alcohol dehydrogenase (SADH) from Thermoanaerobacter ethanolicus was examined. The S39T mutation increases activity for 2-propanol without any significant effect on NADP+ binding. There is no significant effect of the mutation on the primary and secondary alcohol specificity of SADH. However, an effect on the enantiospecificity of SADH by the S39T mutation is demonstrated. Throughout the temperature range from 15 to 55 °C, wild-type SADH exhibits a preference for (S)-2-pentanol. In contrast, a temperature- dependent reversal of enantiospecificity is observed for 2-butanol, with a racemic temperature of 297 K. Throughout the same range of temperatures, S39T SADH exhibits higher enantiospecificity for the (R)-enantiomers of both 2- butanol and 2-pentanol. Examination of individual k(cat)/K(m) values for each enantiomer of the chiral alcohols reveals that the effect of the mutation is to decrease (S)-2-butanol specificity, and to preferentially enhance (R)-2- pentanol specificity relative to (S)-2-pentanol. These results are the first step toward expanding the synthetic utility of SADH to allow efficient preparation of a range of (R)-alcohols.
- Tripp, Allie E.,Burdette, Douglas S.,Zeikus, J. Gregory,Phillips, Robert S.
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- Phosphomolybdic Acid as a Reoxidant in the Palladium(II)-catalysed Oxidation of But-1-ene to Butan-2-one
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Phosphomolybdic and a variety of phosphomolybdovanadic acids were examined as reoxidants for the palladium sulphate-catalysed oxidation of but-1-ene to butan-2-one both in the absence and the presence of oxygen.All of these co-oxidants were approximately equally effective in reoxidising Pd0 to PdII but they varied substantially in their ability to be reoxidised themselves by air under the optimum reaction conditions in aqueous acid.Phosphomolybdovanadate systems were the most effective at a pH>0, but VIV itself could not be reoxidised by air under these conditions and therefore the molybdenum must play a vital role.Phosphomolybdic acid, H3, itself was quite a good co-oxidant under more acid conditions (1 mol dm-3 sulphuric), but 31P n.m.r. spectroscopy showed that in dilute solution it was largely dissociated into phosphoric acid; evidence for the presence under some conditions of other phosphomolybdic acids, which may be related to the active species, is presented.
- Davison, Suzanne F.,Mann, Brian E.,Maitlis, Peter M.
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- Isoxazoles VI: Aspects of the chemical stability of a new naphthoquinone-amine in acidic aqueous solution
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Some aspects of the chemical degradation of N-(3,4-dimethyl-5-isoxazolyl)-4-amino-1,2-naphthoquinone were investigated as a function of pH and temperature. In acid and neutral pH, four main degradation products were identified: 2-hydroxy-1,4-naphthoquinone, 2-butanone, ammonia, and hydroxylamine. No significant buffer effects were observed for the buffer species used in this study. The pH-rate profile exhibited a specific acid catalysis which is important at pH values 3.5, and an inflection point at pH 1.10 corresponding to a pK(a) value. From Arrhenius plots, the activation energy was found to be 17.8 ± 0.3 kcal/mol.
- Longhi,De Bertorello
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- Syntheses of ketonated disulfide-bridged diruthenium complexes via C-H bond activation and C-S bond formation
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The α-C-H bonds of 3-methyl-2-butanone, 3-pentanone, and 2-methyl-3-pentanone were activated on the sulfur center of the disulfide-bridged ruthenium dinuclear complex [{RuCl(P(OCH3)3)2}2(μ-S2)(μ-Cl)2] (1) in the presence of AgX (X = PF6, SbF6) with concomitant formation of C-S bonds to give the corresponding ketonated complexes [{Ru(CH3CN)2(P(OCH3)3)2}(μ-SSCHR1COR2){Ru(CH3CN)3( P(OCH3)3)2}]X3 ([5](PF6)3, R1 = H, R2 = CH(CH3)2, X = PF6; [6](PF6)3, R1 = CH3, R2 = CH2CH3, X = PF6; [7](SbF6)3, R1 = CH3, R2 = CH(CH3)2, X = SbF6). For unsymmetric ketones, the primary or the secondary carbon of the α-C-H bond, rather than the tertiary carbon, is preferentially bound to one of the two bridging sulfur atoms. The α-C-H bond of the cyclic ketone cyclohexanone was cleaved to give the complex [{Ru(CH3CN)2(P(OCH3)3)2}(μ-SS-1-cyclohexanon-2-yl){Ru(CH3CN)3(P(OC H3)3)2}](SbF6)3 ([8](SBF6)3). And the reactions of acetophenone and p-methoxyacetophenone, respectively, with the chloride-free complex [{Ru(CH3CN)3(P(OCH3)3)2}2(μ-S2)]4+ (3) gave [{Ru(CH3CN)2(P(OCH3)3)2}(μ-SSCH2COAr){Ru(CH3CN)3(P(OCH3)3)2}] (CF3SO3)3 ([9](CF3SO3)3, Ar = Ph; [10](CF3SO3)3, Ar = p-CH3OC6H4). The relative reactivities of a primary and a secondary C-H bond were clearly observed in the reaction of butanone with complex 3, which gave a mixture of two complexes, i.e., [{Ru(CH3CN)2(P(OCH3)3)2}(μ-SSCH2COCH2-CH3){Ru(CH3CN)3 (P(OCH3)3)2}](CF3SO3)3 ([11](CF3SO3)3) and [{Ru(CH3CN)2(P(OCH3)3)2} (μ-SSCHCH3COCH3){Ru(CH3CN)3(P(OCH3)3)2}](CF3SO3)3 ([12](CF3SO3)3), in a molar ratio of 1:1.8. Complex 12 was converted to 11 at room temperature if the reaction time was prolonged. The relative reactivities of the α-C-H bonds of the ketones were deduced to be in the order 2°> 1°> 3°, on the basis of the consideration of contributions from both electronic and steric effects. Additionally, the C-S bonds in the ketonated complexes were found to be cleaved easily by protonation at room temperature. The mechanism for the formation of the ketonated disulfide-bridged ruthenium dinuclear complexes is as follows: Initial coordination of the oxygen atom of the carbonyl group to the ruthenium center, followed by addition of an α-C-H bond to the disulfide bridging ligand, having S=S double-bond character, to form a C-S-S-H moiety, and finally completion of the reaction by deprotonation of the S-H bond.
- Sugiyama, Hiroyasu,Hossain, Md. Munkir,Lin, Yong-Shou,Matsumoto, Kazuko
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- Palladium Salts of Heteropolyacids as Catalysts in the Wacker Oxidation of 1-Butene
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Palladium salts of heteropolyacids (PdHPAs) of the Keggin series H3+nPVnMo12-nO40 supported on silica, have been used successfully as catalysts in the gas-phase Wacker oxidation of 1-butene.In such catalysts the palladium reaction centre and the redox component are combined in one complex.At 343 K and atmospheric pressure a high initial butanone yield of more than 0.2 g g-1cat h-1, in combination with a very high butanone selectivity of more than 98percent, can be obtained.In the steady state, the activity of the catalyst is more than a factor of 10 lower than the initial activity, due to slow reoxidation of reduced palladium-heteropolyanion complexes.The rate of reoxidation depends on the composition of the HPA, the palladium loading, and the reaction conditions.The reaction order of 0.5 in the O2 partial pressure indicates the dissociation of dioxygen to be rate determining.The degree of hydration of the HPA appears to be important for the acitivity and stability of the catalysts.Spent catalysts can be regenerated by an oxidation treatment in air at temperatures around 525 K.Regeneration becomes more difficult with high palladium loading of the catalyst.
- Stobbe-Kreemers, A. W.,Lans, G. van der,Makkee, M.,Scholten, J. J. F.
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- High-turnover supramolecular catalysis by a protected ruthenium(II) complex in aqueous solution
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The design of a supramolecular catalyst capable of high-turnover catalysis is reported. A ruthenium(II) catalyst is incorporated into a water-soluble supramolecular assembly, imparting the ability to catalyze allyl alcohol isomerization. The catalyst is protected from decomposition by sequestration inside the host but retains its catalytic activity with scope governed by confinement within the host. This host-guest complex is a uniquely active supramolecular catalyst, capable of >1000 turnovers.
- Brown, Casey J.,Miller, Gregory M.,Johnson, Miles W.,Bergman, Robert G.,Raymond, Kenneth N.
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- Greatly improved activity in ruthenium catalysed butanone synthesis
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In situ mixing of ruthenium trichloride with one equivalent of 1,10-phenanthroline yields a highly active catalyst for synthesis of butanone from buta-1,3-diene.
- Van der Drift,Mul,Bouwman,Drent
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- Synthesis of Chiral Amines via a Bi-Enzymatic Cascade Using an Ene-Reductase and Amine Dehydrogenase
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Access to chiral amines with more than one stereocentre remains challenging, although an increasing number of methods are emerging. Here we developed a proof-of-concept bi-enzymatic cascade, consisting of an ene reductase and amine dehydrogenase (AmDH), to afford chiral diastereomerically enriched amines in one pot. The asymmetric reduction of unsaturated ketones and aldehydes by ene reductases from the Old Yellow Enzyme family (OYE) was adapted to reaction conditions for the reductive amination by amine dehydrogenases. By studying the substrate profiles of both reported biocatalysts, thirteen unsaturated carbonyl substrates were assayed against the best duo OYE/AmDH. Low (5 %) to high (97 %) conversion rates were obtained with enantiomeric and diastereomeric excess of up to 99 %. We expect our established bi-enzymatic cascade to allow access to chiral amines with both high enantiomeric and diastereomeric excess from varying alkene substrates depending on the combination of enzymes.
- Fossey-Jouenne, Aurélie,Jongkind, Ewald P. J.,Mayol, Ombeline,Paul, Caroline E.,Vergne-Vaxelaire, Carine,Zaparucha, Anne
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- Homogeneous Redox Catalysts Based on Heteropoly Acid Solutions: IV. Tests of Methyl Ethyl Ketone Synthesis Catalysts in the Presence of Equipment Corrosion Products (Metal Cations)
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Abstract: The effect of equipment corrosion products (transition metal cations) on the physicochemical and catalytic properties of a homogeneous Pd(II)+HPA-x (Mo–V–P heteropoly acid containing x vanadium atoms) catalyst developed for the two-stage oxidation of n-butene to methyl ethyl ketone (MEK) with oxygen has been studied. The thermal stability of a solution of a catalyst based on HPA-x in the presence of transition metal cations has been determined. The composition of the two-component catalyst recommended for pilot testing of the MEK process has been optimized.
- Gogin, L. L.,Zhizhina, E. G.
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p. 580 - 591
(2021/09/28)
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- Vapor-phase dehydration of 1,4-butanediol to 1,3-butadiene over Y2Zr2O7 catalyst
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Vapor-phase catalytic dehydration of 1,4-butanediol (1,4-BDO) was investigated over Y2O3-ZrO2 catalysts. In the dehydration, 1,3-butadiene (BD) together with 3-buten-1-ol (3B1OL), tetrahydrofuran, and propylene was produced depending on the reaction conditions. In the dehydration over Y2O3-ZrO2 catalysts with different Y contents at 325°C, Y2Zr2O7 with an equimolar ratio of Y/Zr showed high selectivity to 3B1OL, an intermediate to BD. In the dehydration at 360°C, a BD yield higher than 90% was achieved over the Y2Zr2O7 calcined at 700°C throughout 10 h. In the dehydration of 3B1OL over Y2Zr2O7, however, the catalytic activity affected by the calcination temperature is roughly proportional to the specific surface area of the sample. The highest activity of Y2Zr2O7 calcined at 700 °C for the BD formation from 1,4-BDO is explained by the trade-off relation in the activities for the first-step dehydration of 1,4-BDO to 3B1OL and for the second-step dehydration of 3B1OL to BD. The higher reactivity of 3B1OL than saturated alcohols such as 1-butanol and 2-butanol suggests that the C=C double bond of 3B1OL induces an attractive interaction to anchor the catalyst surface and promotes the dehydration. A probable mechanism for the one-step dehydration of 1,4-BDO to BD was discussed.
- Matsuda, Asami,Matsumura, Yoshitaka,Sato, Satoshi,Yamada, Yasuhiro
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- Green oxidation of amines by a novel cold-adapted monoamine oxidase mao p3 from psychrophilic fungi pseudogymnoascus sp. p3
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The use of monoamine oxidases (MAOs) in amine oxidation is a great example of how biocatalysis can be applied in the agricultural or pharmaceutical industry and manufacturing of fine chemicals to make a shift from traditional chemical synthesis towards more sustainable green chemistry. This article reports the screening of fourteen Antarctic fungi strains for MAO activity and the discovery of a novel psychrozyme MAOP3 isolated from the Pseudogymnoascus sp. P3. The activity of the native enzyme was 1350 ± 10.5 U/L towards a primary (n-butylamine) amine, and 1470 ± 10.6 U/L towards a secondary (6,6-dimethyl-3-azabicyclohexane) amine. MAO P3 has the potential for applications in biotransformations due to its wide substrate specificity (aliphatic and cyclic amines, pyrrolidine derivatives). The psychrozyme operates at an optimal temperature of 30? C, retains 75% of activity at 20? C, and is rather thermolabile, which is beneficial for a reduction in the overall costs of a bioprocess and offers a convenient way of heat inactivation. The reported biocatalyst is the first psychrophilic MAO; its unique biochemical properties, substrate specificity, and effectiveness predispose MAO P3 for use in environmentally friendly, low-emission biotransformations.
- Bia?kowska, Aneta M.,Jod?owska, Iga,Szymczak, Kamil,Twarda-Clapa, Aleksandra
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supporting information
(2021/10/25)
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- Selective Functionalization of Hydrocarbons Using a ppm Bioinspired Molecular Tweezer via Proton-Coupled Electron Transfer
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An expanded porphyrin-biscopper hexaphyrin was introduced as a bioinspired molecular tweezer to co-catalyze functionalization of C(sp3)-H bonds. Theoretical and experimental investigations suggested that the biscopper hexaphyrin served as a molecular tweezer to mimic the enzymatic orientation/proximity effect, efficiently activating the N-hydroxyphthalimide (NHPI) via light-free proton-coupled electron transfer (PCET), at an exceptionally low catalyst loading of 10 mol ppm. The resulting N-oxyl radical (PINO) was versatile for chemoselective C-H oxidation and amination of hydrocarbons.
- Chen, Hongyu,Wang, Lingling,Xu, Sheng,Liu, Xiaohui,He, Qian,Song, Lijuan,Ji, Hongbing
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p. 6810 - 6815
(2021/06/28)
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- Selective production of 1,3-butadiene from 1,3-butanediol over Y2Zr2O7 catalyst
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The vapor-phase dehydration of 1,3-butanediol (1,3-BDO) to produce 1,3-butadiene (BD) was evaluated over yttrium zirconate, which was prepared through a hydrothermal aging process. 1,3-BDO was initially dehydrated to three unsaturated alcohols, namely 3-buten-2-ol, 3-buten-1-ol, and 2-buten-1-ol, followed by the further dehydration to BD. The catalytic activity of yttrium zirconate was greatly dependent on the calcination temperature. Also, the reaction temperature was one of the important factors to produce BD efficiently. The selectivity to BD was increased with increasing reaction temperature up to 375°C, while coke formation resulted in catalyst deactivation together with by-product formation at higher temperatures. Yttrium zirconate catalyst calcined at 900°C showed a high BD yield of 95% at 375°C and 10 hr on stream.
- Matsuda, Asami,Matsumura, Yoshitaka,Sato, Satoshi,Yamada, Yasuhiro
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p. 1651 - 1658
(2021/07/21)
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- Simultaneous Preparation of (S)-2-Aminobutane and d -Alanine or d -Homoalanine via Biocatalytic Transamination at High Substrate Concentration
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(S)-2-Aminobutane, d-alanine, and d-homoalanine are important intermediates for the production of various active pharmaceutical ingredients and food additives. The preparation of these small chiral amine or amino acids with high water solubility still demands searching for efficient methods. In this work, we identified an ω-transaminase (ω-TA) from Sinirhodobacter hungdaonensis (ShdTA) that catalyzed the kinetic resolution of racemic 2-aminobutane at a concentration of 800 mM using pyruvate as the amino acceptor, leading to the simultaneous isolation of enantiopure (S)-2-aminobutane and d-alanine in 46% and 90% yield, respectively. In addition, (S)-2-aminobutane (98% ee) and d-homoalanine (99% ee) were isolated in 45% and 93% yield, respectively, in the kinetic resolution of racemic 2-aminobutane at a concentration of 400 mM coupled with deamination of l-threonine by threonine deaminase. We thus developed a biocatalytic process for the practical synthesis of these valuable small chiral amine and d-amino acids.
- Li, Jianjiong,Wang, Yingang,Wu, Qiaqing,Yao, Peiyuan,Yu, Shanshan,Zhu, Dunming
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supporting information
(2022/03/01)
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- Catalytic α-Hydroarylation of Acrylates and Acrylamides via an Interrupted Hydrodehalogenation Reaction
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The palladium-catalyzed, α-selective hydroarylation of acrylates and acrylamides is reported. Under optimized conditions, this method is highly tolerant of a wide range of substrates including those with base sensitive functional groups and/or multiple enolizable carbonyl groups. A detailed mechanistic study was undertaken, and the high selectivity of this transformation was shown to be enabled by the formation of a [PdII(Ar)(H)] intermediate, which performs selective hydride insertion into the β-position of α,β-unsaturated carbonyl compounds.
- Cherney, Emily C.,Engle, Keary M.,Gurak, John A.,Joe, Candice L.,Vasquez, Alena M.
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supporting information
p. 10477 - 10484
(2020/08/07)
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- The influence of H/D kinetic isotope effect on radiation-induced transformations of hydroxyl-containing compounds in aqueous solutions
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Vicinal diols and its derivatives can be exploited as model compounds for the investigation of radiation-induced free-radical transformations of hydroxyl-containing biomolecules such as carbohydrates, phospholipids, ribonucleotides, amino acids, and peptides. In this paper, for the first time, the prospects of isotope reinforcement approach in inhibiting free-radical transformations of hydroxyl-containing compounds in aqueous solutions are investigated on the example of radiolysis of 1,2-propanediol and 1,2-propanediol-2-d1 aqueous solutions. At an absorbed dose rate of 0.110 ± 0.003 Gy·s?1 a profound kinetic isotope effect (KIE) is observed for the non-branched chain formation of acetone, which is a final dehydration product of predominant carbon-centred radicals CH3·C(OH)CH2OH. In 0.1 and 1 M deaerated solutions at pH 7.00 ± 0.01, the values of KIE are 8.9 ± 1.7 and 15.3 ± 3.1, respectively. A rationale for the fact that a strong KIE takes place only in the case of chain processes, which may occur during free-radical transformations of vicinal diols, is also provided herein based on the results of 2-propanol and 2-propanol-2-d1 indirect radiolysis. Lastly, the lack of KIE is shown in the case of 2-butanone formation from 2,3-butanediol or 2,3-butanediol-2,3-d2. This indicates that the type (primary, secondary) of the β-carbonyl radicals formed as a result of CH3·C(OH)CH(OH)R (R = H, CH3) dehydration determines the manifestation of the effect.
- Bekish, Andrei V.,Nepachalovich, Palina S.,Shadyro, Oleg I.,Shmanai, Vadim V.
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p. 732 - 744
(2020/12/28)
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- Preparation method of methyl ethyl ketone
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The invention provides a preparation method of methyl ethyl ketone, which comprises the following steps: by using n-butane as a raw material, dispersing n-butane, a radical initiator and a catalyst ina solvent, and reacting at 50-90 DEG C under the reaction pressure of 0.5-1.5 MPa for 6-10 hours by using air as an oxidant to catalyze and oxidize n-butane to obtain methyl ethyl ketone; wherein thecatalyst is a bi-nuclear copper porphyrin compound with a structure shown as a general formula (I), M is Cu, and R is selected from halogen; wherein the dosage of the catalyst is 0.0001-0.005% of themolar weight of the n-butane, and the dosage of the radical initiator is 1-2% of the molar weight of the n-butane. The preparation method disclosed by the invention can be used for preparing methyl ethyl ketone by directly oxidizing n-butane by taking air as an oxidizing agent through a one-step method, is mild in reaction condition and small in catalyst dosage, effectively avoids the explosion limit problem of n-butane, ensures the single-pass conversion rate and selectivity of butane, and meets the requirements of industrial production and application.
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Paragraph 0030-0036
(2020/12/29)
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- Catalytic conversion of propan-2-ol and butan-2-ol on carbon nanotubes with different carbon structures Evgeniya
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Cylindrical and conical carbon nanotubes were used as catalysts for the conversion of C3–C4 secondary aliphatic alcohols. The effect of the oxidative and reductive treatment of carbon nanotubes on the catalytic activity, selectivity and the conversion of propan-2-ol and butan-2-ol related to the structure of carbon matrix was revealed.
- Arkhipova, Ekaterina A.,Chernyak, Sergey A.,Ivanov, Anton S.,Lunin, Valery V.,Savilov, Sergey V.,Tveritinova, A.,Zhitnev, Yurii N.
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p. 355 - 358
(2020/06/19)
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- Enzymatic Oxidation of Butane to 2-Butanol in a Bubble Column
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Unspecific peroxygenases have recently gained significant interest due to their ability to catalyse the hydroxylation of non-activated C?H bonds using only hydrogen peroxide as a co-substrate. However, the development of preparative processes has so far mostly concentrated on benzylic hydroxylations using liquid substrates. Herein, we demonstrate the application of a peroxygenase for the hydroxylation of the inert, gaseous substrate butane to 2-butanol in a bubble column reactor. The influence of hydrogen peroxide feed rate and enzyme loading on product formation, overoxidation to butanone and catalytic efficiency is investigated at 200 mL scale. The process is scaled up to 2 L and coupled with continuous extraction. This setup allowed the production of 115 mmol 2-butanol and 70 mmol butanone with an overall total turnover number (TTN) of over 15.000, thereby demonstrating the applicability of peroxygenases for preparative hydroxylation of such inert, gaseous substrates at mild reaction conditions.
- Perz, Frederic,Bormann, Sebastian,Ulber, Roland,Alcalde, Miguel,Bubenheim, Paul,Hollmann, Frank,Holtmann, Dirk,Liese, Andreas
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p. 3666 - 3669
(2020/06/17)
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- H2-free Synthesis of Aromatic, Cyclic and Linear Oxygenates from CO2
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The synthesis of oxygenate products, including cyclic ketones and phenol, from carbon dioxide and water in the absence of gas-phase hydrogen has been demonstrated. The reaction takes place in subcritical conditions at 300 °C and pressure at room temperature of 25 barg. This is the first observation of the production of cyclic ketones by this route and represents a step towards the synthesis of valuable intermediates and products, including methanol, without relying on fossil sources or hydrogen, which carries a high carbon footprint in its production by conventional methods. Inspiration for these studies was taken directly from natural processes occurring in hydrothermal environments around ocean vents. Bulk iron and iron oxides were investigated to provide a benchmark for further studies, whereas reactions over alumina and zeolite-based catalysts were employed to demonstrate, for the first time, the ability to use catalyst properties such as acidity and pore size to direct the reaction towards specific products. Bulk iron and iron oxides produced methanol as the major product in concentrations of approximately 2–3 mmol L?1. By limiting the hydrogen availability through increasing the initial CO2/H2O ratio the reaction could be directed to yield phenol. Alumina and zeolites were both observed to enhance the production of longer-chained species (up to C8), likely owing to the role of acid sites in catalysing rapid oligomerisation reactions. Notably, zeolite-based catalysts promoted the formation of cyclic ketones. These proof-of-concept studies show the potential of this process to contribute to sustainable development through either targeting methanol production as part of a “methanol economy” or longer-chained species including phenol and cyclic ketones.
- Gomez, Laura Quintana,Shehab, Amal K.,Al-Shathr, Ali,Ingram, William,Konstantinova, Mariia,Cumming, Denis,McGregor, James
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p. 647 - 658
(2020/01/24)
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- Preparation method of methoxylamine hydrochloride
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The invention provides a preparation method of methoxylamine hydrochloride. The method comprises the following steps of adding diacetylmonoxime (C4H9NO), dimethyl sulfoxide (DMSO, C2H6OS), triethylamine (C6H15N) and a methylation reagent into a reaction vessel, and reacting at 15-75 DEG C to generate O-methyl-2-diacetylmonoxime ether. Compared with the prior art. The method has the advantages thatthe operation is simple, wastes are few, furthermore, reaction raw materials can be completely converted, a generated intermediate by-product can be decomposed into diacetylmonoxime (C4H9NO) and triethylamine (C6H15N), equivalently, no side reaction exists, the yield of synthesized methoxylamine hydrochloride is improved, the use of toxic substances such as sulfur dioxide and sodium nitrite is avoided, the emission of toxic gases such as nitric oxide is reduced, and the sustainable development of enterprises is facilitated.
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Paragraph 0017-0022
(2020/04/06)
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- One-pot synthesis of 1,3-butanediol by 1,4-anhydroerythritol hydrogenolysis over a tungsten-modified platinum on silica catalyst
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Chemical production of 1,3-butanediol from biomass-derived compounds was first reported by 1,4-anhydroerythritol hydrogenolysis over a Pt-WOx/SiO2 catalyst. The reaction proceeded by ring opening hydrogenolysis of 1,4-anhydroerythritol followed by selective removal of secondary OH groups in 1,2,3-butanetriol, and an overall 1,3-butanediol yield up to 54% was then obtained. The performance of the Pt-WOx/SiO2 catalyst for 1,4-anhydroerythritol hydrogenolysis was closely correlated with that for glycerol hydrogenolysis to 1,3-propanediol. The optimized Pt-WOx/SiO2 (Pt: 4 wt% and W: 0.94 wt%) catalyst showed 57% yield of 1,3-propanediol.
- Asano, Takehiro,Liu, Lujie,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi
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supporting information
p. 2375 - 2380
(2020/05/14)
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- Single-reactor conversion of ethanol to 1-/2-butenes
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A simplified processes for producing desired chemicals such as butenes from feedstock mixtures containing ethanol. In one set of embodiments this is performed in a single step, wherein a feed containing ethanol in a gas phase is passed over an acidic metal oxide catalyst having a transition metal dispersion of at least 5% on a metal oxide support. The ethanol content of the feedstock mixture may vary from 10 to 100 percent of the feed and in those non-eat applications the ethanol feed may contain water.
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Page/Page column 9
(2020/06/03)
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- Propargyl alcohols as alkyne sources: Synthesis of heterocyclic compounds under microwave irradiation
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Fused heterocyclic compounds with alkyne substituent, have been achieved using a domino microwave-assisted [Pd]-catalysis. Interestingly, tert-propargyl alcohols underwent a selective degradative β-carbon cleavage and served as masked alkynyl equivalents, in water as the sole reaction medium. Dihydrobenzofurans, indolines, and oxindoles have been accomplished using this dual C–C bond-forming strategy.
- Ramesh, Karu,Satyanarayana, Gedu
-
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- Enhanced stability and activity for solvent-free selective oxidation of cyclohexane over Cu2O/CuO fabricated by facile alkali etching method
-
The easy deactivation of cuprous oxide (Cu2O) have significantly limited their practical applications in catalysis. Formation of composites with other semiconductors including CuO is an crucial strategy for stability improvement of Cu2O. However, this strategy developed so far has often focused on only Cu2O thin film systems. Herein, Cu2O/CuO composites were fabricated via a simple alkali etching method, for the first time, to stabilize the powdered Cu2O in liquid-phase selective oxidation of cyclohexane under solvent-free conditions. The etching method presented remarkable high dispersion of copper species and an appropriate Cu+/Cu2+ ratio on catalyst surface, which leads to superior catalytic activity and stability. Hot filtration experiment confirmed that Cu2O/CuO composite was a heterogeneous catalyst which could be reused at least five times without considerable loss of catalytic activity, whereas the pure Cu2O suffered from severe deactivation caused by oxidative decomposition of Cu2O and copper leaching. Moreover, the amount of Cu+ and Cu2+ sites on catalyst surface are dramatically affected by the amount of alkali during etching process and the catalytic performance can be further tuned by regulating the Cu+/Cu2+ ratio. The Cu2O/CuO with a molar ratio of NaOH/Cu2O = 1:1 exhibited the highest catalytic activity with a cyclohexane conversion of 84.3 percent and cyclohexanone selectivity of 77.0 percent. The present work provides a promising strategy to stabilize Cu2O catalysts in catalytic oxidation systems.
- Chen, Yongjuan,He, Jiao,Jiang, Liang,Wang, Jiaqiang,Wang, Wei,Xie, Congjia,Yang, Yepeng
-
-
- Describing the Reaction of the Hydrocarboxylation of 1-Hexene, Catalyzed by Co2(CO)8, in Marcelin–de Donde Kinetics
-
Abstract: An equation is derived for calculating the rate coefficient of the 1-hexene hydrocarboxylation reaction in Marcelin–de Donde kinetics. The equation correctly describes experimental data in the range of concentrations of an unsaturated substrate,
- Vigranenko, Yu. T.,de Vekki,Krylova,Koluzhnikova
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p. 2209 - 2211
(2020/11/04)
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- METHOD FOR THE HYDRODEOXYGENATION OF OXYGENATED COMPOUNDS TO UNSATURATED PRODUCTS
-
The invention relates to methods of hydrodeoxygenation of oxygenated compounds into compounds with unsaturated carbon-carbon bonds, comprising the steps of: a) providing a reaction mixture comprising, an oxygenated compound containing one or more of a hydroxyl, keto or aldehyde group, an ionic liquid, a homogeneous metal catalyst, and carbon monoxide or a carbon monoxide releasing compound, b) reacting said reaction mixture under a H2 atmosphere at acidic conditions at a temperature between 180 and 250 °C and a pressure between 10 and 200 bar.
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Page/Page column 12-13
(2021/01/23)
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- Direct Observation of Primary C?H Bond Oxidation by an Oxido-Iron(IV) Porphyrin π-Radical Cation Complex in a Fluorinated Carbon Solvent
-
Oxido-iron(IV) porphyrin π-radical cation species are involved in a variety of heme-containing enzymes and have characteristic oxidation states consisting of a high-valent iron center and a π-conjugated macrocyclic ligand. However, the short lifetime of the complex has hampered detailed reactivity studies. Reported herein is a remarkable increase in the lifetime (80 s at 10 °C) of FeIV(TMP+.)(O)(Cl) (2; TMP=5,10,15,20-tetramesitylporphyrin dianion), produced by the oxidation of FeIII(TMP)(Cl) (1) by ozone in α,α,α-trifluorotoluene (TFT). The lifetime is 720 times longer compared to that of the currently most stable species reported to date. The increase in the lifetime improves the reaction efficiency of 2 toward inert alkane substrates, and allowed observation of the reaction of 2 with a primary C?H bond (BDEC-H=ca. 100 kcal mol?1) directly. Activation parameters for cyclohexane hydroxylation were also obtained.
- Morimoto, Yuma,Shimaoka, Yuki,Ishimizu, Yuri,Fujii, Hiroshi,Itoh, Shinobu
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supporting information
p. 10863 - 10866
(2019/07/17)
-
- Selective Visible Light Aerobic Photocatalytic Oxygenation of Alkanes to the Corresponding Carbonyl Compounds
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The aerobic, selective oxygenation of alkanes via C-H bond activation is an important research challenge. Photocatalysis offers the potential for the introduction of additional concepts for such reactions. Visible light photoactive semiconductors such as bismuth oxyhalides (BiOX, X = Cl and Br) used in this research typically oxidize organic compounds through photocatalyzed formation of strongly oxidizing holes. The reactive oxygen species formed react with organic compounds in one-electron processes, leading to radical intermediates and nonselective oxidation. Such oxidation reactions generally lead to total oxidation. Here, impregnation of BiOX with a polyoxometalate, H5PV2Mo10O40, as a strong electron acceptor changed the reactivity of BiOX, leading to Mars-van Krevelen-type reactivity, that is, photoactivated oxygen donation from BiOX to the organic substrate followed by reoxidation by O2 and catalysis. This conclusion was supported by mechanistic studies involving isotope labeling studies. In this way, ethane was selectively oxidized to acetaldehyde in a flow reactor with a turnover number (24 h) of 415.
- Somekh, Miriam,Khenkin, Alexander M.,Herman, Adi,Neumann, Ronny
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p. 8819 - 8824
(2019/09/30)
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- New Insights in the Catalytic Activity of Cobalt Orthophosphate Co3(PO4)2 from Charge Density Analysis
-
An extensive characterization of Co3(PO4)2 was performed by topological analysis according to Bader‘s Quantum Theory of Atoms in Molecules from the experimentally and theoretically determined electron density. This study sheds light on the reactivity of cobalt orthophosphate as a solid-state heterogeneous oxidative-dehydration and -dehydrogenation catalyst. Various faces of the bulk catalyst were identified as possible reactive sites given their topological properties. The charge accumulations and depletions around the two independent five- and sixfold-coordinated cobalt atoms, found in the topological analysis, are correlated to the orientation and population of the d-orbitals. It is shown that the (011) face has the best structural features for catalysis. Fivefold-coordinated ions in close proximity to advantageously oriented vacant coordination sites and electron depletions suit the oxygen lone pairs of the reactant, mainly for chemisorption. This is confirmed both from the multipole refinement as well as from density functional theory calculations. Nearby basic phosphate ions are readily available for C?H activation.
- Keil, Helena,Hellstr?m, Matti,Stückl, Claudia,Herbst-Irmer, Regine,Behler, J?rg,Stalke, Dietmar
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p. 15786 - 15794
(2019/11/16)
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- Nucleophilic Isomerization of Epoxides by Pincer-Rhodium Catalysts: Activity Increase and Mechanistic Insights
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Herein, we present the efficient isomerization of epoxides into methyl ketones with a novel pincer-rhodium complex under very mild conditions. The catalyst system has an excellent functional group tolerance and a wide array of epoxides was tested. The corresponding methyl ketones were obtained in very high yields with excellent chemo- and regioselectivity. In addition, we investigated mechanistic details like the isomerization of the catalyst, and we obtained evidence that the catalytic cycle follows a β-hydride elimination-reductive elimination pathway after the nucleophilic ring opening of the epoxide.
- Tian, Yingying,Jürgens, Eva,Mill, Katharina,Jordan, Ronja,Maulbetsch, Theo,Kunz, Doris
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p. 4028 - 4035
(2019/06/25)
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- Deracemization of Racemic Amines to Enantiopure (R)- and (S)-amines by Biocatalytic Cascade Employing ω-Transaminase and Amine Dehydrogenase
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A one-pot deracemization strategy for α-chiral amines is reported involving an enantioselective deamination to the corresponding ketone followed by a stereoselective amination by enantiocomplementary biocatalysts. Notably, this cascade employing a ω-transaminase and amine dehydrogenase enabled the access to both (R)-and (S)-amine products, just by controlling the directions of the reactions catalyzed by them. A wide range of (R)-and (S)-amines was obtained with excellent conversions (>80 %) and enantiomeric excess (>99 % ee). Finally, preparative scale syntheses led to obtain enantiopure (R)- and (S)-13 with the isolated yields of 53 and 75 %, respectively.
- Yoon, Sanghan,Patil, Mahesh D.,Sarak, Sharad,Jeon, Hyunwoo,Kim, Geon-Hee,Khobragade, Taresh P.,Sung, Sihyong,Yun, Hyungdon
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p. 1898 - 1902
(2019/02/27)
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- Vapor-phase catalytic dehydration of butanediols to unsaturated alcohols over yttria-stabilized zirconia catalysts
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Vapor-phase catalytic dehydration of butanediols (BDOs) such as 1,3-, 1,4-, and 2,3-butanediol was investigated over yttria-stabilized tetragonal zirconia (YSZ) catalysts as well as monoclinic zirconia (MZ). BDOs were converted to unsaturated alcohols with some by-products over YSZ and MZ. YSZ is superior to MZ for these reactions in a view point of selective formation of unsaturated alcohols. Calcination temperature of YSZ significantly affected the products selectivity as well as the conversion of BDOs: high selectivity to unsaturated alcohols was obtained over the YSZ calcined at high temperatures over 800 °C. In the conversion of 1,4-butanediol at 325 °C, the highest 3-buten-1-ol selectivity of 75.3% was obtained over the YSZ calcined at 1050 °C, whereas 2,3-butanediol was less reactive than the other BDOs. In the dehydration of 1,3-butanediol at 325 °C, in particular, it was found that a YSZ catalyst with a Y2O3 content of 3.2 wt.% exhibited an excellent stable catalytic activity: the highest selectivity to unsaturated alcohols such as 2-buten-1-ol and 3-buten-2-ol over 98% was obtained at a conversion of 66%. Structures of active sites for the dehydration of 1,3-butanediol were discussed using a crystal model of tetragonal ZrO2 and a probable model structure of active site was proposed. The well-crystalized YSZ inevitably has oxygen defect sites on the most stable surface of tetragonal ZrO2 (101). The defect site, which exposes three cations such as Zr4+ and Y3+, is surrounded by six O2? anions. The selective dehydration of 1,3-butanediol to produce 3-buten-2-ol over the YSZ could be explained by tridentate interactions followed by sequential dehydration: the position-2 hydrogen is firstly abstracted by a basic O2? anion and then the position-1 hydroxyl group is subsequently or simultaneously abstracted by an acidic Y3+ cation. Another OH group at position 3 plays an important role of anchoring 1,3-butanediol to the catalyst surface. Thus, the selective dehydration of 1,3-butanediol could proceed via the speculative base-acid-concerted mechanism.
- Ohtsuka, Shota,Nemoto, Takuma,Yotsumoto, Rikako,Yamada, Yasuhiro,Sato, Fumiya,Takahashi, Ryoji,Sato, Satoshi
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- CATALYSTS FOR CONVERSION OF 2,3-BUTANEDIOL-CONTAINING FERMENTATION MIXTURE TO HYDROCARBONS
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A method for producing one or more hydrocarbon compounds from at least one of 2,3-butanediol, acetoin, and ethanol, the method comprising contacting said at least one of 2,3-butanediol, acetoin, and ethanol with a catalyst at a temperature of at least 100° C. and up to 500° C. to result in said 2,3-butanediol, acetoin, and/or ethanol being converted to said one or more hydrocarbon compounds, wherein said catalyst is either: (i) a catalyst comprising nanoparticles composed of (a) a first metal oxide selected from the group consisting of zirconium oxide, cerium oxide, titanium oxide, and lanthanum oxide, and (b) a main group metal oxide; or (ii) a catalyst comprising a zeolite loaded with at least one metal selected from the group consisting of copper, silver, nickel, palladium, platinum, rhodium, and ruthenium in an amount of 1-30 wt % by weight of the zeolite.
- -
-
Paragraph 0035-0041
(2019/02/25)
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- Production of 1,3-butadiene in one step catalytic dehydration of 2,3-butanediol
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Catalysts able to selectively dehydrate 2,3-butanediol into butadiene have been designed. These catalysts, based on rare-earth orthophosphates showed that 58% selectivity to butadiene could be obtained at total conversion at only 300 °C, and were relatively stable. While the deactivation could be delayed by addition of water to the gas feeds, it could not be avoided and a regeneration was necessary. This regeneration was achieved by a simple heat treatment under air for a few hours at 450 °C. All results showed that Lewis acid sites corresponding to the rare earth cations are involved in the dehydration of 2,3-butanediol into butadiene. This dehydration occurs with the intermediate formation of 3-buten-2ol, probably over acid-base concerted sites and the subsequent dehydration of 3BDOL to butadiene over weak Br?nsted acid sites. All types of sites appear present on the catalysts surface and distributed in a relatively optimal way.
- Nguyen,Matei-Rutkovska,Huchede,Jaillardon,Qingyi,Michel,Millet
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- Cobalt-Catalyzed Alkoxycarbonylation of Epoxides to β-Hydroxyesters
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Herein, we developed a new and practical catalytic system for the carbonylative synthesis of β-hydroxyesters. By using simple, cheap, and air-stable cobalt(II) bromide as the catalyst, combined with pyrazole and catalytic amount of manganese, active cobalt complex can be generated in situ and can catalyze various epoxides to give the corresponding β-hydroxyesters in moderate to excellent yields. Mechanism studies indicate that pyrazole plays a crucial role in this reaction. Moreover, with the addition of the catalytic amount of manganese, the active cobalt catalyst can be regenerated, which provides a possibility for reusing the cobalt catalyst.
- Xu, Jian-Xing,Wu, Xiao-Feng
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p. 9907 - 9912
(2019/08/26)
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- Reactions in the Photocatalytic Conversion of Tertiary Alcohols on Rutile TiO2(110)
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According to textbooks, tertiary alcohols are inert towards oxidation. The photocatalysis of tertiary alcohols under highly defined vacuum conditions on a titania single crystal reveals unexpected and new reactions, which can be described as disproportionation into an alkane and the respective ketone. In contrast to primary and secondary alcohols, in tertiary alcohols the absence of an α-H leads to a C?C-bond cleavage instead of the common abstraction of hydrogen. Surprisingly, bonds to methyl groups are not cleaved when the alcohol exhibits longer alkyl chains in the α-position to the hydroxyl group. The presence of platinum loadings not only increases the reaction rate but also opens up a new reaction channel: the formation of molecular hydrogen and a long-chain alkane resulting from recombination of two alkyl moieties. This work demonstrates that new synthetic routes may become possible by introducing photocatalytic reaction steps in which the co-catalysts may also play a decisive role.
- Courtois, Carla,Eder, Moritz,Schnabl, Kordula,Walenta, Constantin A.,Tschurl, Martin,Heiz, Ulrich
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supporting information
p. 14255 - 14259
(2019/09/06)
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- Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: Kinetics, product yields and mechanism at 298 K and atmospheric pressure
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Relative rate coefficients and product distribution of the reaction of 2-butanethiol (2butSH) with OH radicals and Cl atoms were obtained at atmospheric pressure and 298 K. The experiments were performed in a 480 L borosilicate glass photoreactor in synthetic air coupled to a long path "in situ" FTIR spectrometer. The rate coefficients obtained by averaging the values from different experiments were: kOH = (2.58 ± 0.21) × 10-11 cm3 per molecule per s and kCl = (2.49 ± 0.19) × 10-10 cm3 per molecule per s. The kinetic values were compared with related alkyl thiols and homologous alkyl alcohols, where it was found that thiols react faster with both oxidants, OH radicals and Cl atoms. SO2 and 2-butanone were the major products identified for the reactions of 2-butanethiol with OH radicals and Cl atoms. The product yield of the reaction of 2-butanethiol and OH radicals were (81 ± 2)percent, and (42 ± 1)percent for SO2 and 2-butanone, respectively. For the reactions of 2-butanethiol with Cl atom, yields of SO2 and 2-butanone were (59 ± 2)percent and (39 ± 2)percent, respectively. A degradation mechanism was proposed for the pathways that leads to formation of identified products. The product distribution observed indicated that the H-atom of the S-H group abstraction channel is the main pathway for the reaction of OH radicals and Cl atoms with 2-butanethiol.
- Blanco, María B.,Cardona, Alejandro L.,Gibilisco, Rodrigo G.,Teruel, Mariano,Wiesen, Peter
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p. 22618 - 22626
(2019/07/31)
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- Photolysis of Tp′Rh(CNneopentyl)(PhNCNneopentyl) in the presence of ketones and esters: Kinetic and thermodynamic selectivity for activation of different aliphatic C-H bonds
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The active fragment [Tp′Rh(CNneopentyl)], generated from the precursor Tp′Rh(CNneopentyl)(PhNCNneopentyl), underwent oxidative addition of substituted ketones and esters resulting in Tp′Rh(CNneopentyl)(R)(H) complexes (Tp′ = tris-(3,5-dimethylpyrazolyl)borate). These C-H activated complexes underwent reductive elimination at varying temperatures (24-70 °C) in C6D6 or C6D12. Using previously established kinetic techniques, the relative Rh-C bond strengths were calculated. Analysis of the relative Rh-C bond strengths vs. C-H bond strengths shows a linear correlation with slope RM-C/C-H = 1.22 (12). In general, α-substituents increase the relative Rh-C bond strengths compared to the C-H bond that is broken.
- Jones, William D.,Parsons, Astrid M.
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supporting information
p. 10945 - 10952
(2019/08/01)
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- 2,3-Butanediol dehydration catalyzed by silica-supported alkali phosphates
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Characterization of acid-base centers and catalytic dehydration of 2,3-butanediol (BDO) was performed over a wide range of silica-supported alkali phosphates (M_P/SiO2; M = Na, K, Cs; M:P = 0.5–3 mol:mol). Selectivity to 1,3-butadiene (BD) and 3-butene-2-ol (3B2OL) formed by elimination correlates with the densities of conjugated acid-base pairs and increases in the order Na ??M+ moieties. Isolated Br?nsted acid centers are probably silica grafted phosphoric acid molecules at low M/P and –PO(OH)2 end groups of oligophosphates at M/P > 1.5. Deactivation rate increases with the increase of M/P ratio in order Na K Cs. Deactivation patterns imply that sites responsible for elimination are active in dehydrative epoxidation. Dehydration of 3B2OL smoothly proceeds to BD, but the catalysts deactivate faster compared to BDO dehydration.
- Kim, Wooyoung,Shin, Wookyun,Lee, Kyoung Jun,Cho, YongSeok,Kim, Hyung Soon,Filimonov, Igor N.
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p. 148 - 163
(2018/11/26)
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- Electrosynthesis of 2,3-butanediol and methyl ethyl ketone from acetoin in flow cells
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Acetoin could shortly become a platform molecule due to current progress in fermentation technology, the megatrend for shifting from an oil-based economy to the one based on biomass, the quest for green manufacturing processes and its two highly reactive carbonyl and hydroxyl moieties. In this paper, the successful electro-conversion of acetoin into two valuable chemicals, 2,3-butanediol (2,3-BD) and methyl ethyl ketone (MEK), at a constant electrical current in an aqueous phase at room temperature using both divided and undivided 20 cm2 filter-press flow cells under experimental conditions suitable for industrial production is reported. Cathode material is the key parameter to drive the electroreduction towards one or another chemical. 2,3-BD is the major chemical produced by electrohydrogenation when low hydrogen overvoltage cathodes, such as Pt and Ni, of high surface areas obtained by PVD coating on a carbon gas diffusion layer are used, while MEK is the principal product produced by electrohydrogenolysis when high hydrogen overvoltage cathodes, such as graphite, Pb and Cd foils, are employed. 2,3-BD and MEK can be obtained, respectively, in 92.8% and 85.7% selectivities, 71.7% and 80.4% current efficiencies, with 1.21 and 1.08 kg h-1 m-2 productivities and power consumptions of 2.94 and 4.1 kWh kg-1 using undivided cells and aqueous K2HPO4 electrolysis media at pH values of 3.6 and 5.5. The reported electroconversion of acetoin is highly flexible because 2,3-BD and MEK can be produced by changing just the cathode but using the same cell, with the same electrolyte at the same current density.
- Ochoa-Gómez, José R.,Fernández-Carretero, Francisco,Río-Pérez, Francisca,García-Luis, Alberto,Roncal, Tomás,García-Suárez, Eduardo J.
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p. 164 - 177
(2019/01/14)
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- Hydrogenation of Ketones and Esters Catalyzed by Pd/C?SiO2
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Hydrogenation of unsaturated ketones and esters with molecular hydrogen on the 5%Pd/C?SiO2 heterogeneous catalyst has been studied. The reaction direction and yield are determined by the starting compounds structure. Hydrogenation of unsaturated ketones containing phenyl group at the double carbon–carbon atom is accompanied by the reduction of the ketone group into the alcohol one. Hydrogenation of unsaturated esters is accompanied by transesterification.
- Akchurin,Baibulatov,Dokichev
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p. 195 - 198
(2018/03/26)
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- Two efficient pathways for the synthesis of aryl ketones catalyzed by phosphorus-free palladium catalysts
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Allylic alcohols, 1-buten-3-ol, 1-penten-3-ol and 1-octen-3-ol, reacted with aryl iodides (iodotoluene, 4-iodotoluene, 4-iodophenol and 4-iodanisole) under Heck reaction conditions to form corresponding saturated aryl ketones in one step. The same products were obtained in a two-step tandem reaction consisted of the Heck coupling of allylic alcohols with aryl iodides, followed by hydrogenation. Reactions were catalyzed by phosphorus-free palladium precursors modified with the menthol-substituted imidazolium chlorides. Formation of crystalline palladium nanoparticles, of the diameter up to 65 nm, in the reaction mixture was evidenced by TEM.
- Wirwis,Feder-Kubis,Trzeciak
-
-
- BORYL ETHERS, CARBONATES, AND CYCLIC ACETALS AS OXIDATIVELY-TRIGGERED DRUG DELIVERY VEHICLES
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A compound, or a pharmaceutically acceptable salt thereof, having a structure of Formula (I), wherein L is a cleavable linker group; X is a cargo moiety-containing group; and R1 and R2 are each independently hydrogen, alkyl, or substituted alkyl; or R1 and R2 together form a boronic ester ring or a substituted boronic ester group.
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Page/Page column 26; 27
(2018/03/28)
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- Green synthesis of low-carbon chain nitroalkanes via a novel tandem reaction of ketones catalyzed by TS-1
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A green and efficient one-pot method has been developed for the synthesis of low-carbon chain nitroalkanes via a novel TS-1 catalyzed tandem oxidation of ketones with H2O2 and NH3. The tandem reaction including ammoxidation, oximation and oxidation of oximes, afforded up to 88% yield and 98% chemo-selectivity requiring only 90 min, at 70 °C and atmospheric pressure. Moreover, this method was even amenable to 100-fold scale-up without loss of chemical efficiency with 87% yield, represents a significant advance towards industrial production of nitroalkanes. Furthermore, the plausible mechanism of TS-1 catalyzed tandem oxidation of ketones to prepare nitroalkanes was proposed.
- Chu, Qingyan,He, Guangke,Xi, Yang,Wang, Ping,Yu, Haoxuan,Liu, Rui,Zhu, Hongjun
-
-
- Gas phase hydrogenation of furaldehydes via coupling with alcohol dehydrogenation over ceria supported Au-Cu
-
We have investigated the synthesis and application of Au-Cu/CeO2 (Cu: Au = 2) in the continuous gas phase (P = 1 atm; T = 498 K) coupled hydrogenation of 5-hydroxymethyl-2-furaldehyde (HMF) with 2-butanol dehydrogenation. STEM-EDX analysis revealed a close surface proximity of both metals in Au-Cu/CeO2 post-TPR. XPS measurements suggest (support → metal) charge transfer to form Auδ? and strong metal-support interactions to generate Cu0 and Cu+. Au-Cu/CeO2 promoted the sole formation of 2,5-dihydroxymethylfuran (DHMF) and 2-butanone in the HMF/2-butanol coupling with full hydrogen utilisation. Under the same reaction conditions, Au/CeO2 was fully selective to DHMF in standard HMF hydrogenation (using an external hydrogen supply), but delivered a lower production rate and utilised less than 0.2% of the hydrogen supplied. Exclusive -C=O hydrogenation and -OH dehydrogenation is also demonstrated for the coupling of a series of m-substituted (-CH3, -CH2CH3, -CH2OH, -CF3, -N(CH3)2, -H) furaldehydes with alcohol (1-propanol, 1-butanol, 2-propanol, 2-butanol, cyclohexanol) dehydrogenation over Au-Cu/CeO2, consistent with a nucleophilic mechanism. In each case, we observed a greater hydrogenation rate and hydrogen utilisation efficiency with a 3–15 times lower E-factor in the coupling process relative to standard hydrogenation. Our results demonstrate the feasibility of using hydrogen generated in situ through alcohol dehydrogenation for the selective hydrogenation of m-furaldehydes with important industrial applications.
- Pischetola, Chiara,Collado, Laura,Keane, Mark A.,Cárdenas-Lizana, Fernando
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-
- Preparation method of 3-methyl-5-(2,2,3-trimethyl-3-cyclopentene-1-yl)-4-pentene-2-alcohol
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The invention provides a preparation method of 3-methyl-5-(2,2,3-trimethyl-3-cyclopentene-1-yl)-4-pentene-2-alcohol. The preparation method comprises the following steps: 1, conducting isomerization reaction on sandatone under the catalytic action of zinc bromide; and 2, enabling the reactant in the step 1 and sec-butyl alcohol to generate the 3-methyl-5-(2,2,3-trimethyl-3-cyclopentene-1-yl)-4-pentene-2-alcohol under the catalytic action of aluminum tri-sec-butoxide. The preparation method of the 3-methyl-5-(2,2,3-trimethyl-3-cyclopentene-1-yl)-4-pentene-2-alcohol has the advantages of environment protection and high yield.
- -
-
Paragraph 0017; 0018; 0019; 0021
(2018/11/22)
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- Selective Alkene Insertion into Inert Hydrogen-Metal Bonds Catalyzed by Mono(phosphorus ligand)palladium(0) Complexes
-
Isolated mono(phosphorus ligand)palladium(0) complexes catalyzed alkene insertions into hydrogen-tungsten bonds. These insertions using WHCp(CO)3 with ethyl acrylate and dimethyl fumarate smoothly gave the corresponding alkyltungsten complexes. Kinetic studies involving the stoichiometric reactions and DFT calculations suggest the following steps: (i) formation of a mono(phosphorus ligand)mono(alkene)palladium(0) species, (ii) subsequent reaction of a metal hydride with the palladium(0), (iii) insertion of the coordinated alkene into the resulting palladium hydride, and (iv) reductive elimination between the alkyl and metal on the palladium center to release the alkylmetal species with regeneration of a palladium(0) by a reaction with alkene.
- Komine, Nobuyuki,Ito, Ryo,Suda, Hiromi,Hirano, Masafumi,Komiya, Sanshiro
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p. 4160 - 4168
(2017/11/21)
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- Citric acid catalyzed deprotection of carbonyl compounds from phenylhydrazones, semicarbazones and oximes under microwave irradiations
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Deprotection of phenylhydrazones, semicarbazones and oximes to their corresponding carbonyl compounds have been carried out in good to excellent yields (83-96 %) by using citric acid as organic catalyst in water as a medium of reaction under microwave irradiation.
- Abd El Rahman, Naglaa M.,Nasreen, Aayesha
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p. 2030 - 2035
(2017/10/19)
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- Mixed-valence μ3-oxo-centered triruthenium cluster [Ru3(II,III,III)(μ3-O)(μ-CH3CO2)6(H2O)3]·2H2O: Synthesis, structural characterization, valence-state delocalization and catalytic behavior
-
The oxo-centered, trinuclear, mixed valence [Ru3(II,III,III)O(CH3CO2)6(H2O)3]·2H2O (2) acetate complex has been prepared with high yield through reduction of [Ru3(III,III,III)O(CH3CO2)6(CH3OH)3]·CH3CO2precursor compound in presence of muccic acid under hydrothermal conditions. The crystalline trinuclear oxo-cluster has been obtained as crystalline powder and characterized by single-crystal and powder X-ray diffraction, elemental analysis, SEM, TGA, IR spectroscopy. Complex 2 composes of μ3-oxocentered trinuclear ruthenium array and exhibits the oxidation state delocalization between three Ru atoms at 293 K. Accurate single-crystal analysis along with valence bond calculations reveal trapped-valence state delocalization at room temperature, whereas three-site relaxation occurs at 100 K leading to Ru(II) and Ru2(III) formal states. Moreover, the mixed valence of RuIIRu2IIIunit in compound 2 has been confirmed by XANES spectroscopy. The catalytic behavior of oxo-centered triruthenium complex 2 has been examined in hydration of nitriles and isomerization of allylic alcohols reactions both realized in aqueous media.
- Dikhtiarenko, Alla,Khainakov, Sergei,García, José R.,Gimeno, José
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p. 107 - 116
(2016/11/19)
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- Facile synthesis of [Ru(η2-O2CO)(pta)(η6-p-cymene)], an outstandingly active Ru(II) half-sandwich complex for redox isomerization of allylic alcohols
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The water-soluble [RuCl2(pta)(η6-p-cymene)] (pta = 1,3,5-triaza-7-phosphaadamantane) was applied as catalyst in the transposition of allylic alcohols, such as oct-1-en-3-ol in aqueous media. The isomerisation of oct-1-en-3-ol to octan-3-one took place only at pH > 10 buffer solutions or in the presence of alkali metal carbonates. The aqueous solution of “in situ” catalyst ([RuCl2(pta)(η6-p-cymene)] + 2 eq Na2CO3) could be reused in the biphasic isomerization of oct-1-en-3-ol for at least five times without a significant loss of the catalytic activity. It was demonstrated that carbonate is not only a base in this reaction but leads to formation of a highly active catalyst, [Ru(η2-O2CO)(pta)(η6-p-cymene)]. This compound was isolated as crystalline solid and characterized in detail (including X-ray diffraction).
- Bolyog-Nagy, Evelin,Udvardy, Antal,Barczáné-Bertók, ágnes,Joó, Ferenc,Kathó, ágnes
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p. 514 - 520
(2016/12/02)
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- Water and catalytic isomerization of linear allylic alcohols by [RuCp(H2O-κO)(PTA)2]+ (PTA = 1,3,5-triaza-7-phosphaadamantane)
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A new water soluble complex [RuCp(H2O-κO)(PTA)2]+ (1) (PTA = 1,3,5-triaza-7-phosphaadamantane) has been synthesized and fully characterized by NMR and IR. The crystal structure of 1(CF3SO3)·3.5H2O was characterized by single crystal X-ray determination. The catalytic activity of this complex was evaluated for the isomerisation of linear allylic alcohols from 3-buten-2-ol to 1-octen-3-ol into the correspondent ketones under both an inert atmosphere and in air, using as solvents: water, the substrate, mixtures of water/substrate, MeOH and mixtures of MeOH/water. An isomerization experiment on a mixture of all the studied allylic alcohols was also carried out.
- Scalambra, Franco,Serrano-Ruiz, Manuel,Romerosa, Antonio
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supporting information
p. 5864 - 5871
(2017/07/10)
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- Tetrabutylphosphonium Bromide Catalyzed Dehydration of Diols to Dienes and Its Application in the Biobased Production of Butadiene
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We report the use of the ionic liquid tetrabutylphosphonium bromide as a solvent and catalyst for dehydration of diols to conjugated dienes. This system combines stability, high reaction rates, and easy product separation. A reaction mechanism for the model compound 1,2-hexanediol is proposed and experimentally corroborated. This particular mechanism allows for the selective formation of conjugated dienes, in contrast with purely acidic catalysis. Next, the reaction is also performed on various other diols. As a first application, we assessed the biobased production of 1,3-butadiene. With 1,4-butanediol as the starting material, a 94% yield of butadiene was reached at 100% conversion.
- Stalpaert, Maxime,Cirujano, Francisco G.,De Vos, Dirk E.
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p. 5802 - 5809
(2017/09/15)
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- Vapor-phase catalytic dehydration of 2,3-butanediol to 3-buten-2-ol over ZrO2 modified with alkaline earth metal oxides
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Vapor-phase catalytic dehydration of 2,3-butanediol (2,3-BDO) to produce 3-buten-2-ol (3B2OL) was investigated over several monoclinic ZrO2 (m-ZrO2) catalysts modified with alkaline earth metal oxides (MOs), such as SrO, BaO, and MgO, to compare with the previously reported CaO/m-ZrO2. It was found that these modifiers enhanced the 3B2OL formation to the same level as CaO did by loading an appropriate MO content. Among all the tested catalysts, the BaO/m-ZrO2 calcined at 800?°C with a low BaO content (molar ratio of BaO/ZrO2?=?0.0452) shows the highest 2,3-BDO conversion (72.4%) and 3B2OL selectivity (74.4%) in the initial stage of 5?h at 350?°C. In order to characterize those catalysts, their catalytic activities, crystal structures, and basic properties were studied in detail. In X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) experiment, it was elucidated that highly dispersed M-O-Zr (M?=?Ca, Sr, and Ba) hetero-linkages were formed on the surface by loading these MOs onto m-ZrO2 with an appropriate content and then calcining at 800?°C. It can be concluded that the M-O-Zr hetero-linkages generate the proper base-acid balance for the efficient formation of 3B2OL from 2,3-BDO.
- Duan, Hailing,Yamada, Yasuhiro,Kubo, Shingo,Sato, Satoshi
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- Hydrogen-Free Gas-Phase Deoxydehydration of 2,3-Butanediol to Butene on Silica-Supported Vanadium Catalysts
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The gas-phase deoxydehydration of 2,3-butanediol to butene was investigated in a plug flow reactor over SiO2-supported vanadium oxide, γ-alumina, P/ZSM-5, and MgO catalysts with acid/base sites of varying strengths. 5 wt % vanadium on SiO2 (i.e., 5V/SiO2) showed the best performance with 100 % conversion and up to 45.2 % butene selectivity. The combination of weak acid sites and polymeric VOx surface species provided the 5V/SiO2 catalyst with bifunctional capabilities to achieve both dehydration and transfer hydrogenation, which allowed it to catalyze the deoxydehydration of 2,3-butanediol to butene even in the absence of H2. As 2,3-butanediol is a common yet underutilized biomass product, this reaction may provide a viable route for a biomass-to-chemicals application for 2,3-butanediol.
- Kwok, Kelvin Mingyao,Choong, Catherine Kai Shin,Ong, Daniel Sze Wei,Ng, Joy Chun Qi,Gwie, Chuandayani Gunawan,Chen, Luwei,Borgna, Armando
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p. 2443 - 2447
(2017/07/12)
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- METHOD OF PREPARING 1,3-BUTADIENE AND METHYL ETHYL KETONE FROM 2,3-BUTANEDIOL USING ADIABATIC REACTOR
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Disclosed is a method of preparing 1,3-butadiene and methyl ethyl ketone from 2,3-butanediol, including: a) providing a plurality of adiabatic reactors, which include a catalyst bed for dehydrating 2,3-butanediol, without a heat transfer medium, and are connected in series; b) introducing a stream including 2,3-butanediol at a temperature ranging from 200° C. to 400° C. into a first adiabatic reactor among the plurality of adiabatic reactors; c) dehydrating the 2,3-butanediol so as to be converted into 1,3-butadiene and methyl ethyl ketone and discharging a product stream including 1,3-butadiene and methyl ethyl ketone; d) heating the discharged product stream to 200° C. to 400° C.; and e) introducing the heated product stream into a second adiabatic reactor so that 2,3-butanediol is further dehydrated and converted into 1,3-butadiene and methyl ethyl ketone and then discharging the product stream including 1,3-butadiene and methyl ethyl ketone.
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Paragraph 0079; 0083
(2018/01/04)
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