Xn:Harmful;
110-63-4Relevant articles and documents
Effect of boron content on 1,4-butanediol production by hydrogenation of succinic acid over Re-Ru/BMC (boron-modified mesoporous carbon) catalysts
Kang, Ki Hyuk,Han, Seung Ju,Lee, Jong Won,Kim, Tae Hyeop,Song, In Kyu
, p. 206 - 213 (2016)
A series of Re-Ru bimetallic catalysts supported on mesoporous boron-modified carbon (denoted as Re-Ru/xBMC, x?=?B/C molar ratio) were prepared by a single-step surfactant-templating method and a subsequent incipient wetness impregnation method, and they were used for liquid-phase hydrogenation of succinic acid to 1,4-butandiol (BDO). The effect of boron addition on the catalytic activities and physicochemical properties of Re-Ru/xBMC catalysts was investigated. It was found that the addition of boron into carbon support affected surface area, metal dispersion, and reducibility of rhenium and ruthenium species in the Re-Ru/xBMC catalysts. It was also observed that boron species in carbon framework existed in several different phases such as substituted boron, partial oxidized boron, and boron oxide. In particular, the amount of substituted boron species was closely related to the hydrogen adsorption behavior of Re-Ru/xBMC catalysts. The amount of weak hydrogen-binding sites increased with increasing the amount of substituted boron species of the catalysts. Yield for BDO in the hydrogenation of succinic acid showed a volcano-shaped trend with respect to B/C molar ratio. This result was in good agreement with the amount of weak hydrogen-binding sites of the catalysts. It was revealed that TOFBDO increased with increasing the amount of weak hydrogen-binding sites of Re-Ru/xBMC catalysts. Among the catalysts, Re-Ru/0.04BMC with the largest amount of weak hydrogen-binding sites served as an efficient catalyst in the selective formation of BDO by hydrogenation of succinic acid.
Hydrogenation of γ-Butyrolactone to 1,4-Butanediol over CuCo/TiO2 Bimetallic Catalysts
Huang, Zhiwei,Barnett, Kevin J.,Chada, Joseph P.,Brentzel, Zachary J.,Xu, Zhuoran,Dumesic, James A.,Huber, George W.
, p. 8429 - 8440 (2017)
Titania-supported monometallic and bimetallic Cu-Co catalysts were prepared using (co)impregnation and studied for the hydrogenation of γ-butyrolactone (GBL) to 1,4-butanediol (BDO) at temperatures from 100 to 180 °C and a hydrogen pressure of 3.4 MPa. The highest catalytic activity occurred at a Cu:Co atomic ratio of 1:9 (Cu0.1Co0.9/TiO2), and a 95% yield of BDO was obtained. Characterization results showed mainly small nanoparticles (average size 2.6 nm) for pure Cu/TiO2, large particles (～19.8 nm) for pure Co/TiO2, and a bimodal particle size distribution of both small (～2.3 nm) and large (～16.5 nm) particles for the bimetallic catalyst with a Cu:Co ratio of 1:1. The addition of ～10 mol % Cu to Co/TiO2 increased the reducibility of the Co and resulted in the formation of core-shell CuCo bimetallic nanoparticles with a Co-rich core and Cu-rich shell. GBL hydrogenation in liquid ethanol and water produced an ester (ethyl 4-hydroxybutanoate) and a carboxylic acid (4-hydroxybutanoic acid) as the major products, respectively. GBL hydrogenation in 1,4-dioxane likely went through a 2-hydroxytetrahydrofuran (2-HTHF) intermediate. The 2-HTHF underwent facile ring-opening tautomerization to 4-hydroxybutanal (4-HB), followed by rapid hydrogenation to BDO at a reaction rate up to 700 times faster than GBL hydrogenation. The Cu0.1Co0.9/TiO2 catalyst maintained the BDO selectivity and about 80% of initial activity for GBL hydrogenation after 150 h time on stream in a continuous flow reactor.
Extremely facile and selective nickel-catalyzed allyl ether cleavage
Taniguchi, Takahiko,Ogasawara, Kunio
, p. 1136 - 1137 (1998)
Child's play! Allyl ethers as protecting groups for hydroxyl functions can be removed readily with a combination of DIBAL and catalytic amounts of [NiCl2(dppp)]. Propene is expelled in this remarkably selective reaction, and a nickel-catalyzed hydroalumination-elimination pathway is proposed. dppp = propane-1,3-diylbis(diphenylphosphane).
Thermodynamic equilibria between polyalcohols and cyclic ethers in high-temperature liquid water
Yamaguchi, Aritomo,Hiyoshi, Norihito,Sato, Osamu,Bando, Kyoko K.,Masuda, Yoshio,Shirai, Masayuki
, p. 2666 - 2668 (2009)
Thermodynamic equilibrium constants between polyalcohols and cyclic ethers in water at 573 K were determined by measuring their concentrations after the long-term reaction in a batch reactor. Intramolecular dehydration reactions of polyalcohols were important for conversion of biomass-derived carbohydrates; however, the yields of products were limited by thermodynamic equilibria between polyalcohols and products. All the thermodynamic equilibrium constants were estimated by the long-term dehydration reaction of 1 mol ·dm-3 polyalcohol aqueous solutions at 573 K. The thermodynamic equilibrium constants between butanepolyols or pentanepolyols and five-membered or six-membered cyclic ethers were within a range from (39 to 337) mol ·dm-3.
A temperature-controlled reversible ionic liquid - Water two phase - Single phase protocol for hydrogenation catalysis
Dyson,Ellis,Welton
, p. 705 - 708 (2001)
An ionic liquid - water system that undergoes a reversible two phase - single phase transformation dependent upon temperature has been used as a novel medium for the transition-metal-catalyzed hydrogenation of a water soluble substrate. At room temperature, the ionic liquid 1-octyl-3-methylimidizolium tetrafluoroborate, containing [Rh(η4-C7H8)(PPh3) 2][BF4] catalyst, forms a separate layer to water containing 2-butyne-1,4-diol. In a stirred autoclave the mixture was pressurized with hydrogen to 60 atm (1 atm = 101.325 kPa) and heated to 80°C giving a homogeneous single phase solution. On cooling to room temperature, two phases reform, with the ionic liquid phase containing the catalyst and the aqueous phase containing a mixture of 2-butene-1,4-diol and butane-1,4-diol products that can be simply removed without catalyst contamination.
Comparison of Carbon-13 Nuclear Magnetic Resonance Methods for the Analysis of Multiple Partially Deuteriated Products from Catalytic Reactions: Heptan-1-ol and 2-Methylpropanol
MacDougall, Joanna K.,Simpson, Michael C.,Cole-Hamilton, David J.
, p. 3061 - 3066 (1994)
Products from the hydrocarbonylation of hex-1-ene or prop-2-en-1-ol using H2-CO or D2-CO in EtOH or EtOD have been analysed using 13C NMR techniques.Where there are up to four isotopomers in the products, analysis of β-shifted resonances in the 13C- NMR spectrum can give enough information for quantification of all isotopomers.Using prop-2-en-1-ol, D2-CO and EtOH, the 2-methylpropanol produced is a mixture of 16 different isotopomers.These can be individually quantified by analysis of the 13C- NMR spectrum.In particular, the resonance from the methyl C atom shows β and γ shifts, the latter being different for different types of γ-D atom.These analytical methods are shown to be superior to other possibilities including 1H NMR and mass spectrometry.
High chemo and regioselective formation of alcohols from the hydrocarbonylation of alkenes using cooperative ligand effects
Boogaerts, Ine T.I. F.,White, Daniel F. S.,Cole-Hamilton, David J.
, p. 2194 - 2196 (2010)
The hydrocarbonylation of alkenes, including allyl alcohol, catalysed by rhodium complexes and wide angle bidentate ligands together with PEt 3, gives alcohols as the primary products with high chemo and regio-selectivity.
Continuous hydrogenation of 2-butyne-1,4-diol to 2-butene- and butane-1,4-diols
Rode,Tayade,Nadgeri,Jaganathan,Chaudhari
, p. 278 - 284 (2006)
Continuous catalytic hydrogenation of 2-butyne-1,4-diol (B3D) was carried out in a fixed-bed reactor over 1% Pt/CaCO3 catalyst to give 2-butene-1,4-diol (B2D) and butane-1,4-diol (B1D) without formation of any other side products. In case of continuous hydrogenation, higher selectivity (66%) to B2D could be obtained and the selectivity pattern was completely different from that found in case of batch slurry operation in which B1D selectivity was very much higher (83%) than the B2D selectivity (17%). Another interesting feature was that by varying the contact time, the selectivity to both B2D as well as B1D could be varied over a wide range which is an attractive option to obtain the desired products mix of B1D and B2D, depending on the fluctuation in the market demand. Further, a mathematical model for reactor performance was also developed on the basis of the kinetic data obtained previously in a batch slurry reactor. The predicted values of conversion, selectivity, and rate of hydrogenation were found to agree with the experimental data over a wide range of conditions.
A new carboxylesterase from Brevibacterium linens IFO 12171 responsible for the conversion of 1,4-butanediol diacrylate to 4-hydroxybutyl acrylate: Purification, characterization, gene cloning, and gene expression in Escherichia coli
Sakai, Yasuyoshi,Ishikawa, Junko,Fukasaka, Shunji,Yurimoto, Hiroya,Mitsui, Ryoji,Yanase, Hideshi,Kato, Nobuo
, p. 688 - 697 (1999)
A carboxylesterase that is responsible for conversion of 1,4-butanediol diacrylate (BDA) to 4-hydroxybutyl acrylate (4HBA) was found in Brevibacterium lines IFO 12171, and purified to homogeneity. The purified enzyme was active toward a variety of diesters of ethylene glycol, 1,4-butanediol, and 1,6-hexanediol. The Km and kcat of the enzyme for BDA were 3.04 mM and 203,000 s-1, respectively. The reaction with the purified enzyme gave 98 mM 4HBA from 100 mM BDA for 60 min. The enzyme gene was cloned from the chromosomal DNA of the bacterium. The open reading frame encoding the enzyme was 1176 bp long, corresponding to a protein of 393 amino acid residues (molecular mass=42,569Da). The deduced amino acid sequence contained the tetra peptide motif sequence, STTK, and the serine residue was confirmed to be the catalytic center of BDA esterase by site-directed mutagenesis for several amino acid residues. The gene was expressed in Escherichia coli under the control of the lac promoter, and the gene product (a fusion protein with 6 amino acid residues from β-galactosidase) showed the same catalytic properties as the enzyme from the parent strain.
Effect of Ethers on Reactions of Butylcoppers with α,β-Unsaturated Ketones in Toluene
Kingsbury, Celia L.,Smith, Robin A. J.
, p. 7637 - 7643 (1997)
Mixtures of butyllithium and copper iodide prepared in toluene react with α,β-unsaturated ketones predominantly in a 1,2-fashion. Addition of various ethers to the system results in some preference for the 1,4-product. The structural characteristics of ethers which influence 1,4-addition have been revealed. Reactions with chiral ethers did not alter the stereochemistry of the product. The results are correlated with the current views on the mechanism of organocuprate reactions.
