Xn:Harmful;
111-29-5Relevant articles and documents
Selective Hydrogenolysis of α-C-O Bond in Biomass-Derived 2-Furancarboxylic Acid to 5-Hydroxyvaleric Acid on Supported Pt Catalysts at Near-Ambient Temperature
Sun, Qianhui,Wang, Shuai,Liu, Haichao
, p. 11413 - 11425 (2019)
Hydrogenolysis of the α-C-O bond in abundantly available biomass-based furfural and its derivatives provides a viable route for sustainable synthesis of valuable C5 compounds, particularly with two terminal oxygen-containing functional groups. However, efficient cleavage of this bond under mild conditions still remains a crucial challenge, primarily because of the competing cleavage of the α-C-O bond and hydrogenation of furan ring. Here, we report that supported Pt catalysts were extremely active for the selective α-C-O cleavage in 2-furancarboxylic acid (FCA) hydrogenolysis to synthesize 5-hydroxyvaleric acid (5-HVA), affording a high yield (～78%) on Pt/SiO2 with a Pt particle size of 4.2 nm at an unprecedentedly low temperature of 313 K. In this reaction, the turnover rate and 5-HVA selectivity sensitively depend on the size of the Pt nanoparticles and the underlying support, as a consequence of their effects on the exposed Pt surfaces. Combined reaction kinetic, infrared spectroscopic, and theoretical assessments reveal that while the exposed high-index Pt surfaces (containing higher fraction of step sites) facilitate the kinetically relevant addition of the first H atom to the unsaturated C atom in furan ring and thus the hydrogenolysis activity, the low-index surfaces (containing higher fraction of terrace sites), together with the electron-withdrawing effect of the carboxylic substituent in FCA, favorably stabilize the dangling C2 atom in the transition states of α-C-O cleavage and lower their activation barriers, leading to the observed high 5-HVA selectivity. Such pivotal roles of the intrinsic properties of metal surfaces and substituents in tuning the reaction pathways will provide a viable strategy for highly selective upgrading of furan derivatives and other biomass-based oxygenates.
One-pot selective conversion of furfural into 1,5-pentanediol over a Pd-added Ir-ReOx/SiO2 bifunctional catalyst
Liu, Sibao,Amada, Yasushi,Tamura, Masazumi,Nakagawa, Yoshinao,Tomishige, Keiichi
, p. 617 - 626 (2014)
One-pot selective conversion of furfural into 1,5-pentanediol (1,5-PeD) was carried out over Pd-added Ir-ReOx/SiO2 catalysts through two-step reaction temperatures. The Pd(0.66 wt%)-Ir-ReOx/SiO 2 catalyst showed the best performance in the production of 1,5-PeD from furfural. The maximum yield of 1,5-PeD was 71.4%. The furfural conversion and yield of 1,5-PeD was almost maintained during four repeated tests when the catalyst was calcined again. The characterization results from TPR, XRD, XANES, EXAFS and FT-IR of adsorbed CO indicated that Pd-Ir-ReOx/SiO 2 catalysts consisted of ReOx-modified Pd metal particles and ReOx-modified Ir metal particles. The lower-temperature reaction step was very crucial for the total hydrogenation of furfural into a tetrahydrofurfuryl alcohol intermediate, which was converted into 1,5-PeD by hydrogenolysis during the high temperature step over the ReOx- modified Ir metal particles.
One-pot biosynthesis of 1,6-hexanediol from cyclohexane by: De novo designed cascade biocatalysis
Kang, Lixin,Li, Aitao,Li, Qian,Li, Renjie,Wang, Fei,Yu, Xiaojuan,Zhang, Zhongwei,Zhao, Jing
, p. 7476 - 7483 (2020)
1,6-Hexanediol (HDO) is an important precursor in the polymer industry. The current industrial route to produce HDO involves energy intensive and hazardous multistage (four-pot-four-step) chemical reactions using cyclohexane (CH) as the starting material, which leads to serious environmental problems. Here, we report the development of a biocatalytic cascade process for the biotransformation of CH to HDO under mild conditions in a one-pot-one-step manner. This cascade biocatalysis operates by using a microbial consortium composed of three E. coli cell modules, each containing the necessary enzymes. The cell modules with assigned functions were engineered in parallel, followed by combination to construct E. coli consortia for use in biotransformations. The engineered E. coli consortia, which contained the corresponding cell modules, efficiently converted not only CH or cyclohexanol to HDO, but also other cycloalkanes or cycloalkanols to related dihydric alcohols. In conclusion, the newly developed biocatalytic process provides a promising alternative to the current industrial process for manufacturing HDO and related dihydric alcohols. This journal is
RING CLEAVAGE REARRANGEMENT OF CYCLOBUTYLMETHYLBORANES
Hill. E. Alexander,Nylen, Patricia A.,Fellinger, John H.
, p. 279 - 292 (1982)
Boranes derived from hydroboration of methylenecyclobutane with borane/THF, 9-borabicyclononane, and borane-methyl sulfide rearranged on heating in situ at 100-160 deg C to open chain structures.Products after oxidation were the unrearranged cyclobutylmethanol, and 4-penten-1-ol, 1,4-pentane-diol and 1,5-pentanediol.The unsaturated alcohol was the major product in reactions with a stoichiometric ratio of alkene to BH bonds, and the diols were formed with excess borane.With borane-methyl sulfide as hydroborating reagent, the rate of rearrangement at 100 deg C in triglyme was not significantly dependent upon the initial alkene/borane ratio (3/1 or 1.15/1) or the presence of excess methyl sulfide.However, an equivalent amount of pyridine prevented rearrangement.Rearrangement in THF using borane/THF also occurred at comparable rates in the presence and absence of excess borane.Little or no isomerization of the boron function into the cyclobutane ring was observed.Results are interpreted on the basis of a concerted four-center mechanism which requires a vacant boron orbital.
One-pot selective conversion of C5-furan into 1,4-pentanediol over bulk Ni-Sn alloy catalysts in an ethanol/H2O solvent mixture
Rodiansono,Dewi Astuti, Maria,Hara, Takayoshi,Ichikuni, Nobuyuki,Shimazu, Shogo
, p. 2307 - 2315 (2019)
Inexpensive bulk Ni-Sn alloy-based catalysts demonstrated a unique catalytic property in the selective conversion of C5-furan compounds (e.g., furfuraldehyde (FFald), furfuryl alcohol (FFalc), and 2-methylfuran (2-MTF)) in an ethanol/H2O solvent mixture and selectively produced 1,4-pentanediol (1,4-PeD) in a one-pot reaction. The synergistic actions between the bulk Ni-Sn alloy catalyst, hydrogen gas, and the hydroxylated H2O or ethanol/H2O solvents are believed to play a prominent role in the catalytic reactions. Bulk Ni-Sn alloy catalysts that consisted of Ni3Sn or Ni3Sn2 alloy phases allowed an outstanding yield of 1,4-PeD up to 92% (from FFald), 67% (from FFalc), and 48% (from 2-MTF) in ethanol/H2O (1.5:2.0 volume ratio) at 433 K, 3.0 MPa H2 and 12 h. As the reaction temperature increased to 453 K, the yield of 1,4-PeD slightly decreased to 87% (from FFald), whereas it slightly increased to 71% (from FFalc). The bulk Ni-Sn alloy catalysts were reusable without any significant loss of selectivity.
Highly Efficient and Convenient Deprotection of Methoxymethyl Ethers and Esters Using Bismuth Triflate in an Aqueous Medium
Venkat Reddy,Jagadeeshwar Rao,Sampath Kumar,Madhusudana Rao
, p. 1038 - 1039 (2003)
A simple and efficient method has been developed for the hydrolysis of methoxymethyl (MOM) ethers and esters to the corresponding alcohols and acids employing a catalytic amount of bismuth triflate in an aqueous medium. The conversions occur at ambient temperature and the yields of the deprotected alcohols are very good. The reaction was highly selective in the presence of other protecting groups such as TBDMS, TBDPS, benzyl, and allyl ethers.
Pd/Lewis Acid Synergy in Macroporous Pd@Na-ZSM-5 for Enhancing Selective Conversion of Biomass
Liu, Jia-Wen,Wu, Si-Ming,Wang, Li-Ying,Tian, Ge,Qin, Yuan,Wu, Jing-Xian,Zhao, Xiao-Fang,Zhang, Yan-Xiang,Chang, Gang-Gang,Wu, Lu,Zhang, Yue-Xing,Li, Zhao-Fei,Guo, Cheng-Yu,Janiak, Christoph,Lenaerts, Silvia,Yang, Xiao-Yu
, p. 5364 - 5368 (2020)
Pd nanometal particles encapsulated in macroporous Na-ZSM-5 with only Lewis acid sites have been successfully synthesized by a steam-thermal approach. The synergistic effect of Pd and Lewis acid sites have been investigated for significant enhancement of the catalytic selectivity towards furfural alcohol in furfural hydroconversion.
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Zweifel,Plamondon
, p. 898 (1970)
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Direct catalytic conversion of furfural to 1,5-pentanediol by hydrogenolysis of the furan ring under mild conditions over Pt/Co 2AlO4 catalyst
Xu, Wenjie,Wang, Haifeng,Liu, Xiaohui,Ren, Jiawen,Wang, Yanqin,Lu, Guanzhong
, p. 3924 - 3926 (2011)
A new strategy was developed for the direct conversion of furfural to 1,5-pentanediol by the hydrogenolysis of the furan ring under mild conditions based on Pt/Co2AlO4 catalyst. This is the first report of the direct catalytic conversion of furfural to 1,5-pentanediol with high yield. The Royal Society of Chemistry.
Defining Pt-compressed CO2 synergy for selectivity control of furfural hydrogenation
Chatterjee, Maya,Chatterjee, Abhijit,Ishizaka, Takayuki,Kawanami, Hajime
, p. 20190 - 20201 (2018)
The development of a sustainable methodology for catalytic transformation of biomass-derived compounds to value-added chemicals is highly challenging. Most of the transitions are dominated by the use of additives, complicated reaction steps and large volumes of organic solvents. Compared to traditional organic solvents, alternative reaction media, which could be an ideal candidate for a viable extension of biomass-related reactions are rarely explored. Here, we elucidate a selective and efficient transformation of a biomass-derived aldehyde (furfural) to the corresponding alcohol, promoted in compressed CO2 using a Pt/Al2O3 catalyst. Furfural contains a furan ring with CC and an aldehyde group, and is extremely reactive in a hydrogen atmosphere, resulting in several by-products and a threat to alcohol selectivity as well as catalyst life. The process described has a very high reaction rate (6000 h-1) with an excellent selectivity/yield (99%) of alcohol, without any organic solvents or metal additives. This strategy has several key features over existing methodologies, such as reduced waste, and facile product separation and purification (reduced energy consumption). Combining the throughput of experimental observation and molecular dynamics simulation, indeed the high diffusivity of compressed CO2 controls the mobility of the compound, and eventually maintains the activity of the catalyst. Results are also compared for different solvents and solvent-less conditions. In particular, combination of an effective Pt catalyst with compressed CO2 provides an encouraging alternative solution for upgradation of biomass related platform molecules.
Synthesis of 1,5-Pentanediol by Hydrogenolysis of Furfuryl Alcohol over Ni–Y2O3 Composite Catalyst
Wijaya, Husni Wahyu,Kojima, Takashi,Hara, Takayoshi,Ichikuni, Nobuyuki,Shimazu, Shogo
, p. 2869 - 2874 (2017)
The addition of Y2O3 into Ni formed a composite catalyst that selectively produced 1,5-pentanediol rather than 1,2-pentanediol in the hydrogenolysis of furfuryl alcohol at 2.0 MPa H2 and 423 K. Clearly, 1,5-pentanediol was produced over the Ni0–Y2O3 boundary. This report highlights the properties of Ni–Y2O3, catalytic performance, and reaction route in the synthesis of 1,5-pentanediol from furfuryl alcohol.
Hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol over a nickel-yttrium oxide catalyst containing ruthenium
Wijaya, Husni Wahyu,Hara, Takayoshi,Ichikuni, Nobuyuki,Shimazu, Shogo
, p. 103 - 106 (2018)
A Ni-Y2O3 catalyst containing ruthenium (Ru/Ni-Y2O3) was synthesized and applied to the hydrogenolysis of tetrahydrofurfuryl alcohol (THFA) to produce 1,5-pentanediol (1,5-PeD), which showed superior catalytic performance over that of the Ni-Y2O3 catalyst itself. The optimized ruthenium-containing catalyst, which was prepared by impregnation of 1.0 wt% ruthenium in Ni-Y2O3, showed high catalytic activity for producing 1,5-PeD, giving an 86.5% yield at 93.4% conversion of THFA under 2.0 MPa of H2 at 423K after 40 h. The formation of Ru-Ni0-Y2O3 boundaries was proposed to accelerate the C-O bond scission of the tetrahydrofuran ring to give 1,5-PeD.
Insights on the One-Pot Formation of 1,5-Pentanediol from Furfural with Co?Al Spinel-based Nanoparticles as an Alternative to Noble Metal Catalysts
Gavilà,L?hde,Jokiniemi,Constanti,Medina,del Río,Tichit,álvarez
, p. 4944 - 4953 (2019)
CoAl-spinel nanoparticles prepared by liquid-feed flame spray pyrolysis (L?F FSP) and activated by reduction at different temperatures were used to investigate the hydrogenation process of furfural (FA) under mild conditions. Reduction of the spinel at 500 °C resulted in high FA conversion and selectivity to furfuryl alcohol (FFA, 81 % yield, in 1 hour). Reduction at higher temperatures (i. e., 700 and 850 °C) led to the direct formation of diols (i. e., 1,5-PeD and 1,2-PeD) from FA. The differences in activity are attributed to the formation of surface metallic cobalt nanoparticles upon reduction at high temperature. A maximum of 30 % 1,5-PeD was yielded after 8 hours of reaction under the optimized conditions of150 °C, 30 bar of H2 and with 40 mg of catalyst reduced at 700 °C. This is the first report on the direct catalytic conversion of furfural to1,5-pentanediol with a non-noble metal solid catalyst.
C?O Hydrogenolysis of Tetrahydrofurfuryl Alcohol to 1,5-Pentanediol Over Bi-functional Nickel-Tungsten Catalysts
Soghrati, Elmira,Kok Poh, Chee,Du, Yonghua,Gao, Feng,Kawi, Sibudjing,Borgna, Armando
, p. 4652 - 4664 (2018)
In this study, we report a series of bimetallic Ni?WOx catalyst for the ring-opening of THFA into 15PDO. The structure-performance relationship of the catalysts was discussed based on extensive characterization using techniques such as BET, H2-TPR, NH3-TPD, Pyr-IR, IPA-TPD-MS, XRD, XPS and EXAFS/XANES. The acidity measurements show that higher W density leads to the higher amount of acid density, which could be assigned to the creation of Lewis acid sites mainly on the surface of the calcined catalysts. H2-TPR profiles of Ni?WOx catalysts show that there is a strong interaction between Ni and W species, enhancing the reducibility of WOx. XRD measurements of calcined Ni?WOx catalysts reveal that the dispersion of Ni particles is enhanced after addition of WOx species. After reduction, different peaks corresponding to metallic Ni and WO3?x are identified for 10Ni?WOx catalysts, as well as new peak assigned to Ni?W intermetallic phase on 10Ni?30WOx catalyst. The formation of Ni?W intermetallic phase was further proved using XPS and EXAFS studies. THFA hydrogenolysis was also conducted under aqueous-phase conditions over Ni?WOx catalysts, yielding up to 47 % selectivity to 15PDO, along with a highest combined C5 polyols (i. e., 15PDO and 125PTO) selectivity of approximately 64 %. However, the Ni?WOx catalytic system suffers from deactivation process due to the hydrothermal dissolution of the active phase. Further investigation reveals the better stability of metallic tungsten and Ni?W intermetallic phase (Ni4W) against leaching since their corresponding peaks in the XRD patterns of spent catalysts remains nearly unchanged. Finally, 1,4-dioxane as an organic solvent was employed in THFA hydrogenolysis reaction, resulting in different product distribution, with a THP yield of around 54 %. The catalyst crystalline structure is preserved because of very low Ni and W leaching when 1,4-dioxane is used as solvent.
Method for preparing 1, 5-pentanediol or 1, 6-hexanediol from bio-based furan compound
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Paragraph 0006; 0017; 0019, (2021/06/26)
The invention discloses a method for preparing 1, 5-pentanediol or 1, 6-hexanediol by utilizing a bio-based furan compound, which comprises the following steps of: reacting the bio-based furan compound serving as a raw material for 1-48 hours in a proper solvent under the conditions of pressure of 0.5-10 MPa and temperature of 20-200 DEG C in a reducing gas atmosphere under the action of a catalyst, separating the catalyst, and distilling out the solvent to obtain the target product 1,5-pentanediol or 1, 6-hexanediol. According to the method disclosed by the invention, efficient conversion of the bio-based furan compound is realized under relatively mild and environment-friendly conditions by utilizing chemically synthesized renewable resource bio-based furan, and the produced 1, 5-pentanediol or 1, 6-hexanediol is a polymer monomer, so that the application range of the bio-based furan compound is expanded, the comprehensive utilization of the straws is further promoted, and carbon neutralization is promoted.
Hydrodeoxygenation of C4-C6 sugar alcohols to diols or mono-alcohols with the retention of the carbon chain over a silica-supported tungsten oxide-modified platinum catalyst
Betchaku, Mii,Cao, Ji,Liu, Lujie,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi,Yabushita, Mizuho
supporting information, p. 5665 - 5679 (2021/08/16)
The hydrodeoxygenation of erythritol, xylitol, and sorbitol was investigated over a Pt-WOx/SiO2 (4 wt% Pt, W/Pt = 0.25, molar ratio) catalyst. 1,4-Butanediol can be selectively produced with 51% yield (carbon based) by erythritol hydrodeoxygenation at 413 K, based on the selectivity over this catalyst toward the regioselective removal of the C-O bond in the -O-C-CH2OH structure. Because the catalyst is also active in the hydrodeoxygenation of other polyols to some extent but much less active in that of mono-alcohols, at higher temperature (453 K), mono-alcohols can be produced from sugar alcohols. A good total yield (59%) of pentanols can be obtained from xylitol, which is mainly converted to C2 + C3 products in the literature hydrogenolysis systems. It can be applied to the hydrodeoxygenation of other sugar alcohols to mono-alcohols with high yields as well, such as erythritol to butanols (74%) and sorbitol to hexanols (59%) with very small amounts of C-C bond cleavage products. The active site is suggested to be the Pt-WOx interfacial site, which is supported by the reaction and characterization results (TEM and XAFS). WOx/SiO2 selectively catalyzed the dehydration of xylitol to 1,4-anhydroxylitol, whereas Pt-WOx/SiO2 promoted the transformation of xylitol to pentanols with 1,3,5-pentanetriol as the main intermediate. Pre-calcination of the reused catalyst at 573 K is important to prevent coke formation and to improve the reusability.
Hydroformylation reaction ligand, hydroformylation catalyst and diol preparation method
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Paragraph 0069; 0075-0076, (2021/06/22)
The invention discloses a hydroformylation reaction ligand, a hydroformylation catalyst and a diol preparation method According to the invention, the structural formula of the hydroformylation reaction ligand is shown in the specification, wherein R1 and R2 are mutually independent one of H, aryl or substituted aryl, thienyl, pyrrolyl, thiazolyl, imidazolyl and pyridyl; the ligand disclosed by the invention is high in catalytic activity and good in metal active center stability, by-products of aldehyde in a conventional hydroformylation reaction can be reduced, and linear diol with a high normal/isomer ratio can be obtained by a one-step method; and the method has the advantages of simple and convenient process, low cost and energy consumption, good production safety, high product quality and the like, and is particularly suitable for large-scale industrial production.
