- Pitfalls in the toxicological analysis of an isobutyl nitrite-adulterated coffee drink
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A forensic investigation was carried out on one poisoning case, where cyanide was first detected in an evidence sample of a canned coffee drink. A more complete study revealed that it had been adulterated with isobutyl nitrite (IBN) and not cyanide. We examined the detectivity of IBN and related compounds by headspace gas chromatography and capillary electrophoresis. IBN decomposes to isobutyl alcohol (iBuOH) and nitrite in aqueous solution, and under higher temperature and more acidic conditions, the rate of this reaction becomes more rapid. IBN was also produced by the esterification of iBuOH with nitrite below pH 5. Cyanide was produced in a coffee solution by the addition of nitrite below pH 6. An IBN-spiked canned coffee drink solution was stored at 4 °C and periodically analyzed for IBN, iBuOH, nitrite, nitrate, and cyanide. Since the IBN level decreased rapidly, 1BuOH was produced in an almost 90% molar yield. Nitrite production reached a maximum of 40% molar recovery on the first day and then gradually disappeared. The nitrate level reached a plateau of ~60% molar recovery. Cyanide was also detected, and its level at the 14th day was ~0.26% molar recovery. These findings suggest that, in a coffee drink solution, IBN undergoes hydrolysis to produce iBuOH and nitric acid, which is oxidized to nitrate and also produces cyanide through the nonspecific oxidation of organic compounds under acidic conditions.
- Seto, Yasuo,Kataoka, Mieko,Tsuge, Kouichiro,Takaesu, Hajime
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Read Online
- Manganese-Catalyzed Selective Upgrading of Ethanol with Methanol into Isobutanol
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Isobutanol serves as an ideal gasoline additive owing to its good compatibility with current engine technology, high energy density, and high octane number. Herein, an efficient and selective Mn-catalyzed upgrading of ethanol with methanol into isobutanol is reported. This is the first example of deoxygenative coupling of lower alcohols to isobutanol by using a homogeneous non-noble-metal catalyst. This transformation proceeded at very low catalyst loading with a high turnover number (9233) and up to 96 % isobutanol selectivity.
- Liu, Yaqian,Shao, Zhihui,Wang, Yujie,Xu, Lijin,Yu, Zhiyong,Liu, Qiang
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Read Online
- METHOD FOR PRODUCING BIO ALCOHOL FROM INTERMEDIATE PRODUCTS OF ANAEROBIC DIGESTION TANK
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The present invention relates to a method for producing a bio-alcohol by reacting a mixture of volatile fatty acid with methanol in 2 through 11 in a reactor in the presence of a 280 °C-membered alkaline earth metal catalyst or 400 °C transition metal catalyst formed based on a support.
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Paragraph 0057-0060; 0063; 0065-0066; 0068-0069; 0071
(2021/05/25)
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- (Hexamethylbenzene)Ru catalysts for the Aldehyde-Water Shift reaction
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The Aldehyde-Water Shift (AWS) reaction uses H2O as a benign oxidant to convert aldehydes to carboxylic acids, producing H2, a valuable reagent and fuel, as its sole byproduct. (Hexamethylbenzene)RuIIcomplexes are demonstrated to have higher activity and selectivity (up to 95%) for AWS over disproportionation than previously reported catalysts.
- Phearman, Alexander S.,Moore, Jewelianna M.,Bhagwandin, Dayanni D.,Goldberg, Jonathan M.,Heinekey, D. Michael,Goldberg, Karen I.
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supporting information
p. 1609 - 1615
(2021/03/09)
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- Efficient and chemoselective hydrogenation of aldehydes catalyzed by well-defined PN3-pincer manganese(ii) catalyst precursors: An application in furfural conversion
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Well-defined and air-stable PN3-pincer manganese(ii) complexes were synthesized and used for the hydrogenation of aldehydes into alcohols under mild conditions using MeOH as a solvent. This protocol is applicable for a wide range of aldehydes containing various functional groups. Importantly, α,β-unsaturated aldehydes, including ynals, are hydrogenated with the CC double bond/CC triple bond intact. Our methodology was demonstrated for the conversion of biomass derived feedstocks such as furfural and 5-formylfurfural to furfuryl alcohol and 5-(hydroxymethyl)furfuryl alcohol respectively.
- Gholap, Sandeep Suryabhan,Dakhil, Abdullah Al,Chakraborty, Priyanka,Li, Huaifeng,Dutta, Indranil,Das, Pradip K.,Huang, Kuo-Wei
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supporting information
p. 11815 - 11818
(2021/11/30)
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- Disproportionation of aliphatic and aromatic aldehydes through Cannizzaro, Tishchenko, and Meerwein–Ponndorf–Verley reactions
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Disproportionation of aldehydes through Cannizzaro, Tishchenko, and Meerwein–Ponndorf–Verley reactions often requires the application of high temperatures, equimolar or excess quantities of strong bases, and is mostly limited to the aldehydes with no CH2 or CH3 adjacent to the carbonyl group. Herein, we developed an efficient, mild, and multifunctional catalytic system consisting AlCl3/Et3N in CH2Cl2, that can selectively convert a wide range of not only aliphatic, but also aromatic aldehydes to the corresponding alcohols, acids, and dimerized esters at room temperature, and in high yields, without formation of the side products that are generally observed. We have also shown that higher AlCl3 content favors the reaction towards Cannizzaro reaction, yet lower content favors Tishchenko reaction. Moreover, the presence of hydride donor alcohols in the reaction mixture completely directs the reaction towards the Meerwein–Ponndorf–Verley reaction. Graphic abstract: [Figure not available: see fulltext.].
- Sharifi, Sina,Sharifi, Hannah,Koza, Darrell,Aminkhani, Ali
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p. 803 - 808
(2021/07/20)
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- Highly efficient NHC-iridium-catalyzed β-methylation of alcohols with methanol at low catalyst loadings
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The methylation of alcohols is of great importance since a broad number of bioactive and pharmaceutical alcohols contain methyl groups. Here, a highly efficient β-methylation of primary and secondary alcohols with methanol has been achieved by using bis-N-heterocyclic carbene iridium (bis-NHC-Ir) complexes. Broad substrate scope and up to quantitative yields were achieved at low catalyst loadings with only hydrogen and water as by-products. The protocol was readily extended to the β-alkylation of alcohols with several primary alcohols. Control experiments, along with DFT calculations and crystallographic studies, revealed that the ligand effect is critical to their excellent catalytic performance, shedding light on more challenging Guerbet reactions with simple alcohols. [Figure not available: see fulltext.].
- Lu, Zeye,Zheng, Qingshu,Zeng, Guangkuo,Kuang, Yunyan,Clark, James H.,Tu, Tao
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p. 1361 - 1366
(2021/06/30)
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- PROCESS FOR ISOBUTANOL PRODUCTION FROM ETHANOL AND SYNGAS
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Processes for converting ethanol and syngas (CO and H2) to isobutanol are disclosed. Syngas and ethanol are reacted in the first reaction zone in the presence of a first heterogeneous catalyst to produce a first reactor effluent comprising a first mixture of alcohols. The first reactor effluent is reacted a second reaction zone in the presence of a second heterogeneous catalyst to produce a second reactor effluent comprising a second mixture of alcohols. The second reactor effluent is separated into an overhead gas stream and a liquid bottom stream. The liquid bottom stream is separated into at least a C1-2 stream, a C3 stream, and a C4+ stream. The isobutanol is recovered from the C4+ stream.
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Page/Page column 10-11
(2021/04/01)
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- Role of Ga3+promoter in the direct synthesis of iso-butanolviasyngas over a K-ZnO/ZnCr2O4catalyst
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The direct synthesis of iso-butanol is an important reaction in syngas (composed of CO and H2) conversion. K-ZnO/ZnCr2O4(K-ZnCr) is a commonly used catalyst. Here, Ga3+is used as an effective promoter to boost the efficiency of the catalyst and retard the production of CO2. X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet-visible diffuse reflection spectroscopy and electron microscopy were used to characterize the structural variations with different amounts of Ga3+, the results showed that the particle size of the catalyst decreases with the addition of Ga3+. The temperature-programmed desorption of NH3and CO2, and diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTs) analysis of the CO adsorption revealed that the acidity and basicity were altered owing to the different forms of Ga3+adoption. X-ray photoelectron spectroscopy and density functional theory (DFT) calculations revealed that the formation of Ga clusters that are coordinated on the exposed surfaces of ZnCr2O4, and undergo a tetra-coordinated Ga3+exchange with one of the Zn in ZnCr2O4(ZG) and ZnGa2O4, probably depends on the amount of Ga added. The structural evolution of the Ga3+promoted K-ZnO/ZnCr2O4catalysts can be described as follows: (i) the main forms are ZG and Ga coordinated ZnCr2O4, in which the amount of Ga3+is below 1.10 wt%; and (ii) the Ga3+containing compound is gradually changed from ZG to ZnGa2O4and the amount of gallium clusters increased when the amount of Ga3+was higher than 1.10 wt%. The catalytic performance evaluation results show that K-Ga1.10ZnCr exhibits the highest space time yield and selectivity of alcohols, in which the three compounds play different roles in syngas conversion: ZG is the main active site that boosts the efficiency of the catalysts, owing to the intensified CO adsorption and decreased activation energy of CHO formation through CO hydrogenation; ZnGa2O4only modifies the surface basicity and acidity on the catalyst, thereby impacting the carbon chain growth after the CO is adsorbed. The effects of Ga coordinated with ZnCr2O4shows little impact on the CO adsorption owing to the weak electron donating effects of Ga.
- Zhang, Tao,Zeng, Chunyang,Wu, Yingquan,Gong, Nana,Yang, Jiaqian,Yang, Guohui,Tsubaki, Noritatsu,Tan, Yisheng
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p. 1077 - 1088
(2021/02/26)
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- Primary Alcohols via Nickel Pentacarboxycyclopentadienyl Diamide Catalyzed Hydrosilylation of Terminal Epoxides
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The efficient and regioselective hydrosilylation of epoxides co-catalyzed by a pentacarboxycyclopentadienyl (PCCP) diamide nickel complex and Lewis acid is reported. This method allows for the reductive opening of terminal, monosubstituted epoxides to form unbranched, primary alcohols. A range of substrates including both terminal and nonterminal epoxides are shown to work, and a mechanistic rationale is provided. This work represents the first use of a PCCP derivative as a ligand for transition-metal catalysis.
- Lambert, Tristan H.,Steiniger, Keri A.
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supporting information
p. 8013 - 8017
(2021/10/25)
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- SYSTEMS AND METHODS FOR REGIOSELECTIVE CARBONYLATION OF 2,2-DISUBSTITUTED EPOXIDES FOR THE PRODUCTION OF ALPHA,ALPHA-DISUBSTITUTED BETA-LACTONES
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Provided are methods of producing carbonyl compounds (e.g., carbonyl containing compounds) and catalysts for producing carbonyl compounds. Also provided are methods of making polymers from carbonyl compounds and polymers formed from carbonyl compounds. A method may produce carbonyl compounds, such as, for example α,α-disubstituted carbonyl compounds (e.g., α,α-disubstituted β-lactones). The polymers may be produced from α,α-disubstituted β-lactones, which may be produced by a method described herein.
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Paragraph 0082
(2021/01/29)
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- Carbon monoxide and hydrogen (syngas) as a C1-building block for selective catalytic methylation
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A catalytic reaction using syngas (CO/H2) as feedstock for the selective β-methylation of alcohols was developed whereby carbon monoxide acts as a C1 source and hydrogen gas as a reducing agent. The overall transformation occurs through an intricate network of metal-catalyzed and base-mediated reactions. The molecular complex [Mn(CO)2Br[HN(C2H4PiPr2)2]]1comprising earth-abundant manganese acts as the metal component in the catalytic system enabling the generation of formaldehyde from syngas in a synthetically useful reaction. This new syngas conversion opens pathways to install methyl branches at sp3carbon centers utilizing renewable feedstocks and energy for the synthesis of biologically active compounds, fine chemicals, and advanced biofuels.
- Kaithal, Akash,H?lscher, Markus,Leitner, Walter
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p. 976 - 982
(2021/02/06)
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- Chromium-Catalyzed Production of Diols From Olefins
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Processes for converting an olefin reactant into a diol compound are disclosed, and these processes include the steps of contacting the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and hydrolyzing the reduced chromium catalyst to form a reaction product comprising the diol compound. While being contacted, the olefin reactant and the supported chromium catalyst can be irradiated with a light beam at a wavelength in the UV-visible spectrum. Optionally, these processes can further comprise a step of calcining at least a portion of the reduced chromium catalyst to regenerate the supported chromium catalyst.
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Paragraph 0111
(2021/03/19)
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- METHOD FOR PREPARING ISOBUTENOL
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The present invention provides a method for preparing isobutanol, which comprises a step of selectively hydrogenating methacrolein in the presence of a catalyst and additives. The preparation method according to the present invention can increase the selectivity of the isobutanol.
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Paragraph 0070-0071; 0078-0079; 0083
(2021/06/15)
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- METHOD FOR PREPARING ISOBUTENOL
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The present invention provides a method for preparing isobutanol, which comprises a step of selectively hydrogenating methacrolein in the presence of a pincer ligand catalyst. The preparation method according to the present invention can increase the selectivity of the isobutanol.
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Paragraph 0052-0053; 0068-0069
(2021/06/15)
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- METHOD FOR PREPARING ISOBUTENOL
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The present invention provides a method for manufacturing isobutenol comprising a step of selectively hydrogenating methacrolein in the presence of an additive. A manufacturing method according to the present invention can increase the selectivity of isobutenol. In the manufacturing method according to an exemplary embodiment of the present invention, the additive represented by the chemical formula 1 is added to provide isobutenol with high selectivity, and the selective hydrogenation reaction is predominant, so that the amount of a catalyst can be reduced.
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Paragraph 0077; 0092-0096
(2021/06/15)
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- Ultrastable Cu Catalyst for CO2 Electroreduction to Multicarbon Liquid Fuels by Tuning C–C Coupling with CuTi Subsurface
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Production of multicarbon (C2+) liquid fuels is a challenging task for electrocatalytic CO2 reduction, mainly limited by the stabilization of reaction intermediates and their subsequent C?C couplings. In this work, we report a unique catalyst, the coordinatively unsaturated Cu sites on amorphous CuTi alloy (a-CuTi@Cu) toward electrocatalytic CO2 reduction to multicarbon (C2-4) liquid fuels. Remarkably, the electrocatalyst yields ethanol, acetone, and n-butanol as major products with a total C2-4 faradaic efficiency of about 49 % at ?0.8 V vs. reversible hydrogen electrode (RHE), which can be maintained for at least 3 months. Theoretical simulations and in situ characterization reveals that subsurface Ti atoms can increase the electron density of surface Cu sites and enhance the adsorption of *CO intermediate, which in turn reduces the energy barriers required for *CO dimerization and trimerization.
- Duan, Chongxiong,Duan, Delong,Hu, Fei,Jiang, Jun,Jiang, Yawen,Kong, Tingting,Liu, Qi,Long, Ran,Lv, Xuefeng,Wang, Xiaonong,Xiong, Yujie,Yang, Li,Zeng, Longjiao
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supporting information
p. 26122 - 26127
(2021/11/12)
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- Manganese Diphosphine and Phosphinoamine Complexes Are Effective Catalysts for the Production of Biofuel Alcohols via the Guerbet Reaction
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We report a variety of manganese-based catalysts containing both chelating diphosphine (bis(diphenylphosphino)methane (dppm: 1, 2, and 7) or 1,2-bis(diphenylphosphino)ethane (dppe: 3)), and mixed-donor phosphinoamine (2-(diphenylphosphino)ethylamine (dppea: 4-6)) ligands for the upgrading of ethanol and methanol to the advanced biofuel isobutanol. These catalysts show moderate selectivity up to 74% along with turnover numbers greater than 100 over 90 h, with catalyst 2 supported by dppm demonstrating superior performance. The positive effect of substituting the ligand backbone was also displayed with a catalyst supported by C-phenyl-substituted dppm (8) having markedly improved performance compared to the parent dppm catalysts. Catalysts supported by the phosphinoamine ligand dppea are also active for the upgrading of ethanol to n-butanol. These results show that so-called PNP-pincer ligands are not a prerequisite for the use of manganese catalysts in Guerbet chemistry and that simple chelates can be used effectively.
- King, Ashley M.,Sparkes, Hazel A.,Wingad, Richard L.,Wass, Duncan F.
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supporting information
p. 3873 - 3878
(2020/11/13)
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- Manganese(I)-Catalyzed β-Methylation of Alcohols Using Methanol as C1 Source
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Highly selective β-methylation of alcohols was achieved using an earth-abundant first row transition metal in the air stable molecular manganese complex [Mn(CO)2Br[HN(C2H4PiPr2)2]] 1 ([HN(C2H4PiPr2)2]=MACHO-iPr). The reaction requires only low loadings of 1 (0.5 mol %), methanolate as base and MeOH as methylation reagent as well as solvent. Various alcohols were β-methylated with very good selectivity (>99 %) and excellent yield (up to 94 %). Biomass derived aliphatic alcohols and diols were also selectively methylated on the β-position, opening a pathway to “biohybrid” molecules constructed entirely from non-fossil carbon. Mechanistic studies indicate that the reaction proceeds through a borrowing hydrogen pathway involving metal–ligand cooperation at the Mn-pincer complex. This transformation provides a convenient, economical, and environmentally benign pathway for the selective C?C bond formation with potential applications for the preparation of advanced biofuels, fine chemicals, and biologically active molecules.
- Kaithal, Akash,van Bonn, Pit,H?lscher, Markus,Leitner, Walter
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supporting information
p. 215 - 220
(2019/12/03)
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- Effect of Promoter Nature on Synthesis Gas Conversion to Alcohols over (K)MeMoS2/Al2O3 Catalysts
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The influence of the promoter nature and of a modifier in (K)(Me)MoS2/Al2O3 (Me=Fe, Co, Ni) catalysts on the conversion and selectivity of products of synthesis gas conversion to alcohols and jnl oxygenates was investigated. Relationships between promoter nature, hydrocarbon chain length and selectivity in the formed alcohols were established. Electronic structure of a promoter atom in an active site (AS) was found to strongly affect selectivity of alcohol formation. Promotion of the S-edge by Fe, Co or Ni suppressed hydrogen activation, which resulted in a lower synthesis gas conversion. Promotion of the M-edge by Fe, Co, or Ni entailed the formation of double vacancies which are active sites of synthesis gas conversion. Potassium affected the oxophilicity of Mo atoms and reduced Co/Ni-promoted MoS AS. It decreased the probability of C?O bond breaking in the adsorbed intermediate and shifted selectivity from the formation of alkyl towards alkoxide fragments over these catalysts.
- Maximov, Vladimir V.,Permyakov, Eugenii A.,Dorokhov, Viktor S.,Wang, Anjie,Kooyman, Patricia J.,Kogan, Victor M.
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p. 1443 - 1452
(2020/02/11)
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- Metal complex catalysts and method for catalytically reducing carboxylic acids
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The invention relates to a metal complex catalyst, which contains at least one of metal complexes with a chemical formula comprising a structural unit represented by a formula I. According to the invention, the center metal of the metal complex catalyst is iridium, and the metal complex catalyst is composed of pentamethylcyclopentadienyl, a bitetrahydropyrimidine ligand and proper coordination anions; the metal complex catalyst has activity on a carboxylic acid reduction reaction, and a carboxylic acid compound is reduced into an alcohol compound in the presence of hydrogen; and the method ismild in reaction condition, can be carried out at room temperature, and is good in catalytic performance and high in reduction product yield.
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Paragraph 0085-0144; 0149; 0150; 0167-0168; 0178-0179
(2020/06/20)
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- Tailoring Interfacial Lewis Acid-Basic Pair on ZnO/4Mg1ZrOx Allows Dehydrogenative α-Methylenation of Alcohols with Methanol to Allylic Alcohols
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Allylic alcohols are the essential building blocks widely used in diverse streams of organic inventions for pharmaceuticals, fragrances, agrochemicals and polymers. Currently, allylic alcohols are industrially produced from petroleum-based feedstocks via atom uneconomic processes. More sustainable synthesis route for allylic alcohols is limited. Herein, a methodology for the direct and highly selective production of allylic alcohols has been accomplished by controlled dehydrogenative α-methylenation of alcohols with methanol. This transformation is enabled by interfacial Lewis acid-basic pair on tailor-made ZnO/4Mg1ZrOx mixed oxide. High selectivity (83~92%) of allylic alcohols is the consequence of alcohols acceptorless dehydrogenation to liberation of H2 and Meerwein-Ponndorf-Verley type hydrogen transfer onto C = O bonds of unsaturated aldehydes. Furthermore, the prepared ZnO/4Mg1ZrOx mixed oxide shows good stability after 200 h time on stream test. These observations could additionally allow us to design multifunctional solid acid-basic catalysts for the transformations of renewable oxygenates into value-added chemicals.
- Fu, Aixiao,Jiang, Shifeng,Liu, Qiang,Liu, Xiaoran,Liu, Xiuyun,Mu, Xindong,Sun, Mengqing,Wang, Xicheng,Xu, Guoqiang,Zhao, Lingling
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- Catalyst-controlled regioselective carbonylation of isobutylene oxide to pivalolactone
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Poly(pivalolactone) (PPVL) is a crystalline polyester with attractive physical and mechanical properties; however, prohibitively expensive syntheses of pivalolactone have thwarted efforts to produce PPVL on an industrial scale. Therefore, we developed a class of highly regioselective sandwich-type catalysts for the carbonylation of isobutylene oxide. These sterically encumbered complexes install carbon monoxide at the substituted epoxide carbon, generating a high level of contrasteric selectivity (up to >99:1). Further catalyst development improved catalyst solubility and reproducibility while maintaining high regioselectivity. In addition, a dibasic ester solvent extended catalyst lifetimes and suppressed side product formation. This contrasteric carbonylation of isobutylene oxide offers a route to sought-after pivalolactone and, therefore, PPVL.
- Hubbell, Aran K.,Lamb, Jessica R.,Klimovica, Kristine,Mulzer, Michael,Shaffer, Timothy D.,MacMillan, Samantha N.,Coates, Geoffrey W.
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p. 12537 - 12543
(2020/11/10)
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- Ruthenium(II)-Catalyzed β-Methylation of Alcohols using Methanol as C1 Source
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Selective introduction of methyl branches into the carbon chains of alcohols can be achieved with low loadings of ruthenium precatalyst [RuH(CO)(BH4)(HN(C2H4PPh2)2)] (Ru-MACHO-BH) using methanol both as methylating reagent and as reaction medium. A wide range of structurally divers alcohols was β-methylated with excellent selectivity (>99 %) in fair to high yields (up to 94 %) under standard conditions, and turnover numbers up to 18,000 could be established. The overall reaction rate of the complex catalytic network appears to be governed by interconnection of the individual subcycles through availability of the reactive intermediates. The synthetic procedure opens pathways to important structural motifs following the Green Chemistry principles.
- Kaithal, Akash,Schmitz, Marc,H?lscher, Markus,Leitner, Walter
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p. 5287 - 5291
(2019/05/28)
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- PROCESS FOR MAKING FORMIC ACID UTILIZING LOWER-BOILING FORMATE ESTERS
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Disclosed is a process for recovering formic acid from a formate ester of a C3 to C4 alcohol. Disclosed is also a process for producing formic acid by carbonylating a C3 to C4 alcohol, hydrolyzing the formate ester of the alcohol, and recovering a formic acid product. The alcohol may be dried and returned to the reactor. The process enables a more energy efficient production of formic acid than the carbonylation of methanol to produce methyl formate.
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Paragraph 00177; 00178
(2019/02/15)
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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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- 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 27; 28
(2018/03/28)
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- Selective Hydrogenation of Carboxylic Acids to Alcohols or Alkanes Employing a Heterogeneous Catalyst
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The chemoselective hydrogenation of carboxylic acids to either alcohols or alkanes is reported, employing a heterogeneous bimetallic catalyst consisting of rhenium and palladium supported on graphite. α-Chiral carboxylic acids were hydrogenated without loss of optical purity. The catalyst displays a reverse order of reactivity upon hydrogenation of different carboxylic functions with esters being less reactive than amides and carboxylic acids. This allows for chemoselective hydrogenation of an acid in the presence of an ester or an amide function.
- Ullrich, Johannes,Breit, Bernhard
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p. 785 - 789
(2018/02/14)
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- Two isomers of a bis(diphenylphosphino)phosphinine, and the synthesis and reactivity of Ru arene/Cp* phosphinophosphinine complexes
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The reaction of 4,6-di(tert-butyl)-1,3,2-diazaphosphinine (3) with two equivalents of MeCCPPh2 gave two isomeric products, 2,6-bis(diphenylphosphino)-3,5-dimethylphosphinine (5) and 2,5-bis(diphenylphosphino)-3,6-dimethylphosphinine (6), which were successfully separated and their molecular structures determined by X-ray crystallography. Although the 2,6-bis(iminophosphorano)phosphinine 7 was readily synthesised from 5 using mesityl azide, its coordination to late transition metals was not achieved. The reaction of 2-diphenylphosphino-3-methyl-6-trimethylsilylphosphinine (1) with [{Ru(Cl)(μ-Cl)(p-cymene)}2] generated two products: cis-[Ru(Cl)2(1)2] (2) and the dinuclear species [Ru(μ-Cl)3(p-cymene)Ru(Cl)(1)] (8), which was characterised by single crystal X-ray diffraction. The reaction of 1 with [{Ru(Cl)(μ-Cl)(C6Me6)}2]/NH4PF6 led to cleavage of the SiMe3 group and addition of H2O across a P═C bond to generate [Ru(C6Me6)(1-OH-2-PPh2-3-MePC5H4)][PF6] (9). The reaction of 1 with [{Ru(Cp*)(μ3-Cl)}4] yielded [Ru(Cp*)(Cl)(1)] (10) which readily reacted with H2O across a P═C bond to form [Ru(Cp*)(Cl)(1-OH-2-PPh2-3-Me-6-SiMe3PC5H3)] (11). Neither 9, 10, 11 or cis-[Ru(Cl)2(dppm)2] were effective precatalysts for the transfer hydrogenation (TH) of acetophenone, unlike 2 which in addition was also found to catalyse the TH of benzophenone at 82 °C (0.1 mol% 2 with 0.5 mol% KOtBu in iPrOH), with much lower activity for 2-fluorobenzaldehyde and 4-methylcyclohexanone. 11 was a competent precatalyst for the hydrogen-borrowing upgrading of EtOH/MeOH to isobutanol, albeit in lower yields compared to 2.
- Newland, Robert J.,Delve, Matthew P.,Wingad, Richard L.,Mansell, Stephen M.
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supporting information
p. 19625 - 19636
(2018/12/13)
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- Ionic Liquids Derived from Proline: Application as Surfactants
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Ionic liquids derived from prolinium esters, previously described as fully green and stable, were found to decompose in the presence of water by ester hydrolysis. To avoid this problem, a new family of these biodegradable salts incorporating an alcohol instead of the ester group is proposed. From this family, two novel ionic liquids that incorporate the prolinolium cation [HOPro] and the [DS] or [DBS] anion were selected (DS=dodecylsulfate; DBS=dodecylbenzenesulfonate). Both salts are liquid at room temperature, a property not usually found in ionic surfactants, and are also chemically and thermally stable. Moreover, they are more effective in reducing the surface tension of water than the corresponding traditional surfactants in the form of sodium salts, being useful for applications related to their aggregation capacity. They were tested for surfactant enhanced oil recovery and an optimal formulation for reservoirs at high salinity and temperature, able to produce ultra-low interfacial tension, was found with [HOPro][DBS].
- Fernández-Stefanuto, Verónica,Corchero, Raquel,Rodríguez-Escontrela, Iria,Soto, Ana,Tojo, Emilia
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p. 2885 - 2893
(2018/09/10)
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- Nickel boride mediated chemoselective deprotection of 1,1-diacetates to aldehydes and deprotection with concomitant reduction to alcohols at ambient temperature
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A variety of 1,1-diacetates have been chemoselectively and efficiently deprotected to the corresponding aldehydes as well as deprotected and concomitantly reduced to the corresponding alcohols in high yields at ambient temperature with nickel boride generated in situ using different molar ratios of sodium borohydride and nickel (II) chloride in methanol at room temperature. Deprotection and reduction of a variety of aromatic, aliphatic and heterocyclic acylals have been achieved efficiently. Mild reaction conditions, easy work-up, high yields and chemoselectivity demonstrate the efficiency of this new method.
- Bartwal, Gaurav,Saroha, Mohit,Khurana, Jitender.M.
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- Direct Reductive Amination of Carbonyl Compounds Catalyzed by a Moisture Tolerant Tin(IV) Lewis Acid
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Despite the ever-broadening applications of main-group ‘frustrated Lewis pair’ (FLP) chemistry to both new and established reactions, their typical intolerance of water, especially at elevated temperatures (>100 °C), represents a key barrier to their mainstream adoption. Herein we report that FLPs based on the Lewis acid iPr3SnOTf are moisture tolerant in the presence of moderately strong nitrogenous bases, even under high temperature regimes, allowing them to operate as simple and effective catalysts for the reductive amination of organic carbonyls, including for challenging bulky amine and carbonyl substrate partners. (Figure presented.).
- Sapsford, Joshua S.,Scott, Daniel J.,Allcock, Nathan J.,Fuchter, Matthew J.,Tighe, Christopher J.,Ashley, Andrew E.
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supporting information
p. 1066 - 1071
(2018/01/27)
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- Binary ZnO/Zn-Cr nanospinel catalysts prepared by a hydrothermal method for isobutanol synthesis from syngas
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A series of binary ZnO/Zn-Cr nanospinel catalysts were prepared by a hydrothermal method and applied in direct synthesis of isobutanol from syngas, during which the effect of the hydrothermal time/temperature on the catalytic performance in the isobutanol synthesis has been investigated at 400 °C and 10 MPa. The catalysts were characterized by XRD, N2 adsorption-desorption, TPR, TPD, FT-IR spectroscopy, XPS, XRF, SEM and TEM. The XRD and TEM results show that the binary ZnO/Zn-Cr nanospinel structure forms well by the hydrothermal method. Compared with other ZnCr catalysts, the catalyst prepared under the hydrothermal conditions of 16 h and 160 °C has the largest BET area with the largest amount of active sites, leading to a high total alcohol production rate (TAPR). Meanwhile, the surface Zn/Cr molar ratio (1.27) and K content (1.64%) on the ZnCr-16-160 catalyst are higher. The enrichment phenomenon of Zn on the catalyst surface could improve the interaction between ZnO and a non-stoichiometric Zn-Cr spinel, forming a ZnO layer mixed with the Zn-Cr spinel. Since K is known as a C-chain increasing promoter, the high K content is helpful in improving the total alcohol and isobutanol selectivity. Thus, the appropriate hydrothermal time and temperature for the binary ZnO/Zn-Cr catalyst preparation are 16 h and 160 °C, respectively, and the best catalytic performance is obtained on the ZnCr-16-160 catalyst with a total alcohol selectivity of 60.2% and an isobutanol distribution of 27.0 wt%.
- Gao, Xiaofeng,Wu, Yingquan,Zhang, Tao,Wang, Liyan,Li, Xiaoli,Xie, Hongjuan,Tan, Yisheng
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p. 2975 - 2986
(2018/06/18)
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- Selective hydrogenation of amides to alcohols in water solvent over a heterogeneous CeO2-supported Ru catalyst
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CeO2-supported Ru (Ru/CeO2) worked as an effective and reusable heterogeneous catalyst for the selective dissociation of the C-N bond in amides, particularly primary amides, with H2 in water solvent at low reaction temperature of 333 K, and high yields of the corresponding alcohols were obtained from primary amides.
- Tamura, Masazumi,Ishikawa, Susumu,Betchaku, Mii,Nakagawa, Yoshinao,Tomishige, Keiichi
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p. 7503 - 7506
(2018/07/13)
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- Correlating the Surface Basicity of Metal Oxides with Photocatalytic Hydroxylation of Boronic Acids to Alcohols
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Photoredox catalysis provides opportunities in harnessing clean and green resources such as sunlight and O2, while the acid and base surface sites of metal oxides are critical for industrial catalysis such as oil cracking. The contribution of metal oxide surfaces towards photocatalytic aerobic reactions was elucidated, as demonstrated through the hydroxylation of boronic acids to alcohols. The strength and proximity of the surface base sites appeared to be two key factors in driving the reaction; basic and amphoteric oxides such as MgO, TiO2, ZnO, and Al2O3 enabled high alcohol yields, while acidic oxides such as SiO2 and B2O3 gave only low yields. The reaction is tunable to different irradiation sources by merely selecting photosensitizers of compatible excitation wavelengths. Such surface complexation mechanisms between reactants and earth abundant materials can be effectively utilized to achieve a wider range of photoredox reactions.
- Leow, Wan Ru,Yu, Jiancan,Li, Bin,Hu, Benhui,Li, Wei,Chen, Xiaodong
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supporting information
p. 9780 - 9784
(2018/07/31)
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- Investigation of the Reaction Pathways of Biomass-Derived Oxygenate Conversion into Monoalcohols in Supercritical Methanol with CuMgAl-Mixed-Metal Oxide
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Reaction pathways for the conversion of cellulose into C2–C6 monoalcohols by supercritical methanol depolymerization and hydrodeoxygenation (SCM-DHDO) over a CuMgAl oxide catalyst have been elucidated using a range of model compounds. SCM-DHDO of intermediate oxygenates including glycerol, methyl lactate, and 1,2-ethanediol produces similar products as those produced from the SCM-DHDO of cellulose. The pathway to C2–C6 monoalcohols occurs through rapid C?C coupling reactions between methanol and diols followed by C?C scission between vicinal alcohol groups to produce two monoalcohols. Methyl-branched monoalcohols are produced through a methyl shift in a secondary diol followed by dehydration. Esters are produced by dehydrogenative coupling between an adsorbed methoxy and a primary alcohol. Both dehydrogenation to a ketone and esterification to a methyl ester are in equilibrium with the corresponding alcohol and were reversible. Dehydration of diols is the slowest observed reaction and not a main pathway to monoalcohols. SCM-DHDO of glucose, dihydroxyacetone, and cellulose all produced similar high molecular weight species indicating that condensation of intermediates can produce undesired side products.
- Galebach, Peter H.,Thompson, Sean,Wittrig, Ashley M.,Buchanan, J. Scott,Huber, George W.
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p. 4007 - 4017
(2018/11/23)
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- Cooperative interplay between a flexible PNN-Ru(II) complex and a NaBH4 additive in the efficient catalytic hydrogenation of esters
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A catalyst loading of between 0.001-0.05 mol% of the PNN-bearing ruthenium(II) complex [fac-PNN]RuH(PPh3)(CO) (PNN = 8-(2-diphenylphosphinoethyl)amidotrihydroquinoline), in combination with 5 mol% NaBH4, efficiently catalyzes the hydrogenation of esters to their corresponding alcohols under mild pressures of hydrogen. Both aromatic and aliphatic esters can be converted with high values of TON or TOF achievable. Mechanistic investigations using both DFT calculations and labeling experiments highlight the cooperative role of NaBH4 in the catalysis while the catalytically active species has been established as trans-dihydride [mer-PNHN]RuH2(CO) (PNHN = 8-(2-diphenylphosphinoethyl)aminotrihydroquinoline). The stereo-structure of the PNHN-ruthenium species greatly affects the activity of the catalyst, and indeed the cis-dihydride isomer [fac-PNHN]RuH2(CO) is unable to catalyze the hydrogenation of esters until ligand reorganization occurs to give the trans isomer.
- Wang, Zheng,Chen, Xiangyang,Liu, Bo,Liu, Qing-Bin,Solan, Gregory A.,Yang, Xinzheng,Sun, Wen-Hua
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p. 1297 - 1304
(2017/05/05)
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- Towards the upgrading of fermentation broths to advanced biofuels: A water tolerant catalyst for the conversion of ethanol to isobutanol
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Isobutanol is an ideal gasoline replacement due to its high energy density, suitable octane number and compatibility with current engine technology. It can be formed by the Guerbet reaction in which (bio)ethanol and methanol mixtures are converted to this higher alcohol in the presence of a suitable catalyst under basic conditions. A possible limitation of this process is the catalyst's water tolerance; a twofold problem given that water is produced as a by-product of the Guerbet reaction but also due to the need to use anhydrous alcoholic feedstocks, which contributes significantly to the cost of advanced biofuel production. Isobutanol formation with pre-catalyst trans-[RuCl2(dppm)2] (1) has been shown to be tolerant to the addition of water to the system, achieving an isobutanol yield of 36% at 78% selectivity with water concentrations typical of that of a crude fermentation broth. Key to this success is both the catalyst's tolerance to water itself and the use of a hydroxide rather than an alkoxide base; other catalysts explored are less effective with hydroxides. Alcoholic drinks have also been used as surrogates for the fermentation broth: the use of lager as the ethanol source yielded 29% isobutanol at 85% selectivity in the liquid phase.
- Pellow, Katy J.,Wingad, Richard L.,Wass, Duncan F.
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p. 5128 - 5134
(2017/11/07)
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- A ruthenium(II) bis(phosphinophosphinine) complex as a precatalyst for transfer-hydrogenation and hydrogen-borrowing reactions
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The 2-phosphinophosphinine 2-PPh2-3-Me-6-SiMe3-PC5H2 (2) has been prepared and was shown to act as a κ2-chelating ligand in cis-[RuCl2(2)2] (4). Complex 4 was a competent precatalyst for the room temperature transfer hydrogenation of acetophenone (0.1 mol% 4 and 0.5 mol% KOtBu) and the conversion of methanol/ethanol mixtures to the advanced biofuel isobutanol in 50% yield and 96% selectivity.
- Newland,Wyatt,Wingad,Mansell
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supporting information
p. 6172 - 6176
(2017/07/11)
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- Iridium Clusters Encapsulated in Carbon Nanospheres as Nanocatalysts for Methylation of (Bio)Alcohols
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C?H methylation is an attractive chemical transformation for C?C bonds construction in organic chemistry, yet efficient methylation of readily available (bio)alcohols in water using methanol as sustainable C1 feedstock is limited. Herein, iridium nanocatalysts encapsulated in yolk–shell-structured mesoporous carbon nanospheres (Ir@YSMCNs) were synthesized for this transformation. Monodispersed Ir clusters (ca. 1.0 nm) were encapsulated in situ and spatially isolated within YSMCNs by a silica-assisted sol–gel emulsion strategy. A selection of (bio)alcohols (19 examples) was selectively methylated in aqueous phase with good-to-high yields over the developed Ir@YSMCNs. The improved catalytic efficiencies in terms of activity and selectivity together with the good stability and recyclability were contributable to the ultrasmall Ir clusters with oxidation chemical state as a consequence of the confinement effect of YSMCNs with interconnected nanostructures.
- Liu, Qiang,Xu, Guoqiang,Wang, Zhendong,Liu, Xiaoran,Wang, Xicheng,Dong, Linlin,Mu, Xindong,Liu, Huizhou
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p. 4748 - 4755
(2017/12/15)
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- The role of non-stoichiometric spinel for iso-butanol formation from biomass syngas over Zn-Cr based catalysts
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A series of Zn-Cr based catalysts modified by K promoter has been prepared by different methods and their performances for iso-butanol formation from biomass syngas were investigated in a fixed bed reactor. The ZnCr-c catalyst which was prepared by co-precipitation method showed the best catalytic performance for iso-butanol formation, over which ca. 30% of CO conversion and ca. 20% of iso-butanol selectivity were achieved. Multi-characterization studies were then conducted to reveal the internal causes for different performances for iso-butanol formation over different catalysts including high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), temperature programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS). The results reveal that ZnCr-c catalyst contains the maximum amount of non-stoichiometric spinel among all the catalysts. This fact implies that the non-stoichiometric spinel is the active phase for iso-butanol synthesis from syngas. The reducibility, texture parameters and basic property of catalysts are further important factors for the formation of iso-butanol over Zn-Cr based catalysts from biomass syngas.
- Tian, Shaopeng,Ding, Siyi,Yang, Qianqian,Ren, Huaping,Ma, Qiang,Zhao, Yunzhen,Miao, Zongcheng
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p. 20135 - 20145
(2017/04/19)
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- Insight into the role of hydroxyl groups on the ZnCr catalyst for isobutanol synthesis from syngas
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A series of ZnO, ZnCr catalysts were prepared by a sol-gel method and ammonia solution was used to adjust the pH of the sol solution. The catalysts were characterized by XRD, in-situ FR-IR, NH3-TPD, in-situ XPS, HRTEM. The results show that lower calcination temperature is helpful to reduce the crystal size and crystallinity of ZnCr nanocrystal, as well as forming a certain amount of structure defects and hydroxyl groups. The hydroxyl groups could be consumed by CO under the interaction between ZnO and ZnCr spinel, resulting in more exposed oxygen vacancies. We find the proper calcination temperature and Zn/Cr molar ratio for the ZnCr catalysts preparation are 400 °C and 1.0, respectively. The Zn1Cr1–400 ~ 2.0 catalyst prepared with the pH value of 2 shows more hydroxyl groups and small particle size, exhibiting the best catalytic performance both on the CO conversion (20.9%) and isobutanol selectivity (24.2 wt%).
- Gao, Xiaofeng,Wu, Yingquan,Yang, Guohui,Zhang, Tao,Li, Xiaoli,Xie, Hongjuan,Pan, Junxuan,Tan, Yisheng
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- Direct synthesis of isobutyraldehyde from methanol and ethanol on Cu-Mg/Ti-SBA-15 catalysts: The role of Ti
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Herein, Cu-Mg/Ti-SBA-15 catalysts were prepared through the modification of Cu and Mg to mesoporous Ti-SBA-15 zeolites with different Ti/Si ratios and used for the synthesis of isobutyraldehyde (IBA) from methanol and ethanol. The catalysts were characterized via various techniques including XRF, XRD, TEM, N2 sorption, CO2-TPD, FT-IR, and XPS. With an increase in Ti content, CuO was well dispersed accordingly, and the amounts and strength of the basic sites were reduced. However, an excess introduction of Ti led to the accumulation of single TiO2 crystals, inducing a decrease in the surface area and a deviation from the regular pattern such that the binding energies of Cu 2p, Mg 2p, and Si 2p shifted to lower values. This precisely affected the catalytic behaviors of the prepared catalysts synergistically. The catalyst stability was improved with the increasing Ti content accordingly, and over the catalyst with a Ti/Si ratio = 4/15, the IBA selectivity, after 24 h reaction, could still reach 25%, which was the best durability ever reported for IBA synthesis from methanol and ethanol. The catalytic performance test conducted using a regenerated catalyst and IR measurement of the spent catalyst indicated that carbon deposition on the catalyst surface could be depressed to some extent with the increasing Ti content.
- Zhang, Junfeng,Zhang, Meng,Wang, Xiaoxing,Zhang, Qingde,Song, Faen,Tan, Yisheng,Han, Yizhuo
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p. 9639 - 9648
(2017/09/18)
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- Rearrangement in Stereoretentive Syntheses of Menthyl Chloride from Menthol: Insight into Competing Reaction Pathways through Component Quantification Analysis
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The enantiopure reagent menthyl chloride (2) is generally prepared from (–)-(1R)-menthol (1) with Lucas' reagent (ZnCl2 in conc. aqueous HCl) in a stereoretentive reaction that appeared to be free from accompanying rearrangements. The same was assumed for a recent synthesis of 2 through TiCl4-catalyzed extrusion of SO2 from menthyl chlorosulfite (3). The products of both syntheses have now been analyzed by quantitative 1H and 13C NMR methods, and all reaction components have been identified down to the ≤ 0.5 mol-% level. Either reaction is accompanied by cationic rearrangement to the considerable extent of 18–25 mol-%. Besides the expected 2, neomenthylchloride (4) and five rearrangement products have been identified, among them three regioisomeric tertiary chloromenthanes (9, 10, 11), and both a secondary (12) and tertiary chloride (16) derived from ψ-menthane (1-isobutyl-3-methylcyclopentane). A scheme of rearrangement pathways starting from a common menthyl carbenium ion pair is derived. The effect of purification protocols on crude 2 has been studied quantitatively. Either selective solvolysis of tertiary sideproducts (98 mol-% purity) or low-temperature crystallization (≥ 97 mol-% purity) was successful. An improved, scalable synthesis of 2 through the catalytic rearrangement of chlorosulfite 3 is reported.
- Hintermann, Lukas,Wong, Kit Ming
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supporting information
p. 5527 - 5536
(2017/10/06)
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- Method for preparing alcohol through catalytic hydrogenation reduction of carboxylate
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The invention discloses a method for preparing alcohol through catalytic hydrogenation reduction of a carboxylate compound with 2-(diphenylphosphinoethyl)-(5,6,7,8-tetrahydroquinolyl)amine as a ruthenium complex catalyst of ligand. The catalyst has high-efficiency catalysis activity on alkyl benzoate, aromatic esters and fatty esters. The preparation method is simple and has good stability, the catalysis activity of the catalyst is high, and the dosage of the catalyst is 0.025-0.005% of the mole of a substrate. The method can be used for producing alcohols, and has the advantages of simplicity, small pollution to environment, high yield and low cost. Most of carboxylate can be hydrogenated and reduced to form alcohols by using a complex represented by formula (1) with sodium borohydride as an additive, and the conversion number TOC can reach 50000; and a cocaalyst sodium borohydride is used to substitute most of alcoholic alkalis used as a catalyst in especially used in aromatic esters with electron-withdrawing substituent, so the cost is reduced, operation is simple, and industrial production is easy.
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Paragraph 0044; 0049; 0053
(2016/12/07)
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- Photocatalytic Regeneration of Nicotinamide Cofactors by Quantum Dot-Enzyme Biohybrid Complexes
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We report the characterization of biohybrid complexes of CdSe quantum dots and ferredoxin NADP+-reductase for photocatalytic regeneration of NADPH. Illumination with visible light led to reduction of NADP+ to NADPH, with an apparent kcat of 1400 h-1. Regeneration of NADPH was coupled to reduction of aldehydes to alcohols catalyzed by a NADPH-dependent alcohol dehydrogenase, with each NADPH molecule recycled an average of 7.5 times. The quantum yield both of NADPH and alcohol production were 5-6% for both products. Light-driven NADPH regeneration was also demonstrated in a multienzyme system, showing the capacity of QD-FNR complexes to drive continuous NADPH-dependent transformations.
- Brown, Katherine A.,Wilker, Molly B.,Boehm, Marko,Hamby, Hayden,Dukovic, Gordana,King, Paul W.
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p. 2201 - 2204
(2016/04/26)
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- ENZYMATIC METHODS FOR ISOBUTANOL PRODUCTION
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The present invention relates to a process of producing isobutanol, including: mixing water, lactate, an enzyme mixture including at least one enzyme, at least one cofactor, and at least one coenzyme, to prepare a reaction mixture; allowing catalytic conversions of lactate in the reaction mixture for a sufficient amount of time to produce isobutanol; and separating the isobutanol from a reactant obtained by the catalytic conversions, in which the conversion of lactate into isobutanol is in association with a NAD+/NADH and/or NADP+/NADPH regenerating system.
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Paragraph 00158-00167
(2016/07/05)
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- Acid-base bifunctional zirconium N-alkyltriphosphate nanohybrid for hydrogen transfer of biomass-derived carboxides
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Catalytic transfer hydrogenation (CTH) reactions are efficient transformation routes to upgrade biobased chemicals. Herein, we report a facile and template-free route to synthesize a series of heterogeneous nitrogen-containing alkyltriphosphonatemetal hybrids with enhancive Lewis acid and base sites, and their catalytic activity in converting biomass-derived carbonyl compounds to corresponding alcohols in 2-propanol. Particularly, a quantitative yield of furfuryl alcohol (FFA) was obtained from furfural (FUR) over organotriphosphate-zirconium hybrid (ZrPN) under mild conditions. The presence of Lewis basic sites adjacent to acid sites with an appropriate base/acid site ratio (1:0.7) in ZrPN significantly improved the yield of FFA. Mechanistic studies for the transformation of FUR to FFA with ZrPN in 2-propanol-d8 evidently indicate CTH reaction proceeding via a direct intermolecular hydrogen transfer route. It was also found that ZrPN could catalyze isomerization of C3-C6 aldoses to ketoses involving intramolecular hydrogen transfer in water.
- Li, Hu,He, Jian,Riisager, Anders,Saravanamurugan, Shunmugavel,Song, Baoan,Yang, Song
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p. 7722 - 7727
(2018/05/22)
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- Catalytic conversion of methanol/ethanol to isobutanol - A highly selective route to an advanced biofuel
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Catalysts based on ruthenium diphosphine complexes convert methanol/ethanol mixtures to the advanced biofuel isobutanol, with extremely high selectivity (>99%) at good (>75%) conversion via a Guerbet-type mechanism.
- Wingad, Richard L.,Bergstr?m, Emilie J. E.,Everett, Matthew,Pellow, Katy J.,Wass, Duncan F.
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supporting information
p. 5202 - 5204
(2016/04/26)
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- PRODUCING METHOD OF ISOBUTANOL
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PROBLEM TO BE SOLVED: To provide a producing method of isobutanol which can prevent side reaction and superior in selectivity. SOLUTION: A producing method of isobutanol includes a reaction step of producing isobutanol by reacting at least one kind selected from a group consisting of ethanol and propanol with methanol under a presence of hydroxyapatite, and in the reaction step, a ratio shown with (mole number of methanol)/(mole number of the at least one kind selected from the group consisting of ethanol and propanol) is 2.0-15. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPO&INPIT
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Paragraph 0039-0041; 0052; 0053; 0069
(2017/03/24)
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- Method of manufacturing hydroxyisobutyramide aminoaldehyde (by machine translation)
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PROBLEM TO BE SOLVED: starting material while suppressing the decomposition of the methanol and aldehydes halogenoimides efficiently. SOLUTION: the present invention relating to the production of aldehydes halogenoimides, presence of hydroxylapatite hydroxyacid, ethanol, and propanol, and at least one kind selected from the group consisting of, and methanol, isopropyl by reaction and generating a first process, the first process of a second process isopropyl and Dehydrogenative αolefin, includes, in the first step, (the number of moles of methanol) / (ethanol and propanol, selected from the group consisting of at least one of the number of moles) is expressed by a ratio, 2.0-15. Selected drawing: no (by machine translation)
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Paragraph 0046-0050
(2017/03/28)
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