111-84-2Relevant articles and documents
Specifics of the stearic acid deoxygenation reaction on a copper catalyst
Berenblyum,Danyushevsky,Katsman,Shamsiev,Flid
, p. 362 - 366 (2013)
Decarbonylation of stearic acid, which is industrially manufactured from oils and fats, to higher olefins on a Cu/γ-Al2O 3catalyst has been first studied. It has been shown that the selectivity for heptadecenes is 67% and that for CO is close to 100% at 350°C. The activity of this catalyst in the further hydrogenation of resulting heptadecenes to heptadecane is well below that of a palladium catalyst. The conversion is slightly varied when hydrogen pressure increases from 4 to 14 bar; however, the selectivity for olefins increases and the selectivity for paraffins remains low. According to quantum-chemical simulation data, hydrides form on the surface of copper clusters in the presence of hydrogen. It is presumably these compounds that inhibit the side oligomerization reaction of olefins. The hydrogen-to-water concentration ratio does not affect the selectivity for CO and CO2; the only effect of the presence of water is a decrease in the stearic acid conversion rate. Pleiades Publishing, Ltd., 2013.
Guyer et al.
, p. 976,978 (1955)
Catalytic Upgrading of 5-Hydroxymethylfurfural to Drop-in Biofuels by Solid Base and Bifunctional Metal-Acid Catalysts
Bohre, Ashish,Saha, Basudeb,Abu-Omar, Mahdi M.
, p. 4022 - 4029 (2015)
Design and synthesis of effective heterogeneous catalysts for the conversion of biomass intermediates into long chain hydrocarbon precursors and their subsequent deoxygenation to hydrocarbons is a viable strategy for upgrading lignocellulose into distillate range drop-in biofuels. Herein, we report a two-step process for upgrading 5-hydroxymethylfurfural (HMF) to C9 and C11 fuels with high yield and selectivity. The first step involves aldol condensation of HMF and acetone with a water tolerant solid base catalyst, zirconium carbonate (Zr(CO3)x), which gave 92 % C9-aldol product with high selectivity at nearly 100 % HMF conversion. The as-synthesised Zr(CO3)x was analysed by several analytical methods for elucidating its structural properties. Recyclability studies of Zr(CO3)x revealed a negligible loss of its activity after five consecutive cycles over 120 h of operation. Isolated aldol product from the first step was hydrodeoxygenated with a bifunctional Pd/Zeolite-β catalyst in ethanol, which showed quantitative conversion of the aldol product to n-nonane and 1-ethoxynonane with 40 and 56 % selectivity, respectively. 1-Ethoxynonane, a low oxygenate diesel range fuel, which we report for the first time in this paper, is believed to form through etherification of the hydroxymethyl group of the aldol product with ethanol followed by opening of the furan ring and hydrodeoxygenation of the ether intermediate. Two-stepping to Biofuels! A recyclable and water tolerant heterogeneous base catalyst produced 92 % C9-aldol product from 5-hydroxymethylfurfural and acetone in water. Subsequent hydrogenation of the isolated aldol product with a metal-acid Pd/zeolite-β catalyst produced gasoline and diesel range n-nonane and 1-ethoxynonane with an overall 96 % yield.
Production of high-quality diesel from biomass waste products
Corma, Avelino,De La Torre, Olalla,Renz, Michael,Villandier, Nicolas
, p. 2375 - 2378 (2011)
(Chemical Equation Presented) High-quality liquid fuels are obtained from non-edible carbohydrates by energy-efficient processes. 2-Methylfuran, produced by hydrogenation of furfural, is converted into 6-alkyl undecanes in a catalytic solvent-free process (see scheme with 6-butylundecane). A diesel fuel is produced with an excellent motor cetane number (71) and pour point (-90°C) and with global process conversions and selectivities close to 90%.
α-Deuterium and Carbon-13 Kinetic Isotope Effects Associated with the SN2 Displacement of Iodide and Tosylate by Lithium Organocuprates
Guo, Cong-yuan,Brownawell, Marilyn L.,Filippo, Joseph San, Jr.
, p. 6028 - 6030 (1985)
The secondary α-deuterium and 13C isotope effects associated with the competitive methylation of two cuprates, (n-C8H17)2CuLi(PBu3) and (n-C8H17)4CuLi3(PBu3), by CH3X-CD3X and 12,13CH3X (X=I or OTs) together with their related temperature dependences are reported.
Alkanes from Bioderived Furans by using Metal Triflates and Palladium-Catalyzed Hydrodeoxygenation of Cyclic Ethers
Song, Hai-Jie,Deng, Jin,Cui, Min-Shu,Li, Xing-Long,Liu, Xin-Xin,Zhu, Rui,Wu, Wei-Peng,Fu, Yao
, p. 4250 - 4255 (2015)
Using a metal triflate and Pd/C as catalysts, alkanes were prepared from bioderived furans in a one-pot hydrodeoxygenation (HDO) process. During the reaction, the metal triflate plays a crucial role in the ring-opening HDO of furan compounds. The entire reaction process has goes through two major phases: at low temperatures, saturation of the exocyclic double bond and furan ring are catalyzed by Pd/C; at high temperatures, the HDO of saturated furan compounds is catalyzed by the metal triflate. The reaction mechanism was verified by analyzing the changes of the intermediates during the reaction. In addition, different metal triflates, solvents, and catalyst recycling were also investigated. Fu, Fu, Fu (tri-f): Metal triflates (tri-f) act as an axe (, Fu), cleaving the C-O bond of cyclic ethers and luckily (, Fu) transforming bioderived furans into alkanes in a one-pot (, Fu) process. The mechanism of the reaction is verified by analyzing the changes of the intermediates during the reaction. Different metal triflates, solvents, and catalyst recycling are investigated, also.
Reductive defluorination of fluoroalkanes
Guijarro, David,Martínez, Pedro,Yus, Miguel
, p. 1237 - 1244 (2003)
The reaction of an excess of lithium powder and a catalytic amount of DTBB with primary, secondary and tertiary fluoroalkanes in the presence of a substoichiometric amount of 1,2-bis(trimethylsilyl)benzene 1 afforded the corresponding alkanes resulting from a fluorine-hydrogen exchange. The method could be extended to non-geminal difluorides. The effect of the disilylated compound in the naphthalene-catalysed lithiation of fluorobenzene and benzyl fluoride was also studied.
H2-Free Selective Dehydroxymethylation of Primary Alcohols over Palladium Nanoparticle Catalysts
Yamaguchi, Sho,Kondo, Hiroki,Uesugi, Kohei,Sakoda, Katsumasa,Jitsukawa, Koichiro,Mitsudome, Takato,Mizugaki, Tomoo
, p. 1135 - 1139 (2020/12/29)
The dehydroxymethylation of primary alcohols is a promising strategy to transform biomass-derived oxygenates into hydrocarbon fuels. In this study, a novel, highly efficient, and reusable heterogeneous catalyst system was established for the H2-free dehydroxymethylation of primary alcohol using cerium oxide-supported palladium nanoparticles (Pd/CeO2). A wide range of aliphatic and aromatic alcohols including biomass-derived alcohols were converted into the corresponding one-carbon shorter hydrocarbons in high yields in the absence of any additives, accompanied by the production of H2 and CO. Pd/CeO2 was easily recovered from the reaction mixture and reused, retaining its high activity, thus, providing a simple and sustainable methodology to produce hydrocarbon fuels from biomass-derived oxygenates.
Hydrogenation of Alkenes Catalyzed by a Non-pincer Mn Complex
Rahaman, S. M. Wahidur,Pandey, Dilip K.,Rivada-Wheelaghan, Orestes,Dubey, Abhishek,Fayzullin, Robert R.,Khusnutdinova, Julia R.
, p. 5912 - 5918 (2020/10/30)
Hydrogenation of substituted styrenes and unactivated aliphatic alkenes by molecular hydrogen has been achieved using a Mn catalyst with a non-pincer, picolylphosphine ligand. This is the second reported example of alkene hydrogenation catalyzed by a Mn complex. Mechanistic studies showed that a Mn hydride formed by H2 activation in the presence of a base is the catalytically active species. Based on experimental and DFT studies, H2 splitting is proposed to occur via a metal-ligand cooperative pathway involving deprotonation of the CH2 arm of the ligand, leading to pyridine dearomatization.