1120-21-4Relevant articles and documents
Development and mechanistic study of a new aldehyde decarbonylation catalyst
Abu-Hasanayn, Faraj,Goldman, Martin E.,Goldman, Alan S.
, p. 2520 - 2524 (1992)
Rh2(PMe3)2(CO)2Cl2 (2) has been found to catalyze the decarbonylation of aldehydes to give the corresponding alkanes. Reaction rates are comparable to those of the most active nonradical systems previously reported. A mechanistic study indicates that the turnover-limiting reaction step includes addition of the aldehydic C-H bond to an intact molecule of 2; ligand dissociation or cleavage of the chloride bridge does not occur prior to the C-H addition step. This conclusion is based on kinetic studies (d[R′H]/dt = kobs[2[R′CHO]; R′ = n-C11H23; kobs = 2.2 × 10-4 M-1 s-1; ΔS? = -26 eu) and the observation of a significant kinetic isotope effect (kRCHO/RCDO > 1.8).
ETUDE DES REACTIONS DE SUBSTITUTION HOMOLITIQUE SUR LE NOYAU PYRIDINIQUE; INFLUENCE DE L'ACIDITE DU MILIEU
Sebedio, J. L.,Sorba, J.,Fossey, J.,Lefort, D.
, p. 2829 - 2842 (1981)
Homolytic substitution by the 1-n-undecyl radical at positions 2 and 4 of the pyridine nucleus results from thermal decomposition of dodecanoyl peroxide in acetic acid.Rate dependence on pH shows that pyridine protonation increases the rate of addition of the alkyl radical to the pyridine ring but decreases the rate of the reaction of the intermediate radical with the peroxide.Results are interpreted in terms of orbital interaction theory.
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Sheppard,Burton
, p. 1636 (1946)
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Potassium on Alumina as a Reagent for Reductive Decyanation of Alkylnitriles.
Savoia, Diego,Tagliavini, Emilio,Trombini, Claudio,Umani-Ronchi, Achille
, p. 3227 - 3229 (1980)
Highly dispersed potassium over neutral alumina (K/Al2O3), easily prepared by melting potassium over alumina in an inert atmosphere, is capable of effecting reductive cleavage of the cyano group in alkylnitriles in hexane at room temperature in 70-91percent yield.This decyanation method is applied in the key step of a novel synthesis of (Z)-9-dodecen-1-yl acetate, the sex pheromone of Paralobesia viteana.
Synthesis of renewable diesel range alkanes by hydrodeoxygenation of furans over Ni/Hβ under mild conditions
Li, Guangyi,Li, Ning,Yang, Jinfan,Li, Lin,Wang, Aiqin,Wang, Xiaodong,Cong, Yu,Zhang, Tao
, p. 594 - 599 (2014)
Diesel range branched alkanes were synthesized by the solvent-free hydrodeoxygenation of 5,5′-(butane-1,1-diyl)bis(2-methylfuran), the hydroxyalkylation/alkylation product of 2-methylfuran and butanal. Over the non-noble metal catalyst Ni/Hβ-(394), ～90% carbon yield of diesel range alkanes was achieved at a much lower temperature (503 K) than the temperature (623 K) used in the literature over noble metal catalysts.
Magnetic-field effect on the thermal decomposition of dilauroyl peroxide
Tanimoto,Nishino,Itoh
, p. 3365 - 3366 (1985)
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Hydrothermal decarboxylation and hydrogenation of fatty acids over Pt/C
Fu, Jie,Lu, Xiuyang,Savage, Phillip E.
, p. 481 - 486 (2011)
We report herein on the conversion of saturated and unsaturated fatty acids to alkanes over Pt/C in high-temperature water. The reactions were done with no added H2. The saturated fatty acids (stearic, palmitic, and lauric acid) gave the corresponding decarboxylation products (n-alkanes) with greater than 90% selectivity, and the formation rates were independent of the fatty acid carbon number. The unsaturated fatty acids (oleic and linoleic acid) exhibited low selectivities to the decarboxylation product. Rather, the main pathway was hydrogenation to from stearic acid, the corresponding saturated fatty acid. This compound then underwent decarboxylation to form heptadecane. On the basis of these results, it appears that this reaction system promotes in situ H 2 formation. This hydrothermal decarboxylation route represents a new path for using renewable resources to make molecules with value as liquid transportation fuels.
Ni- or Cu-catalyzed cross-coupling reaction of alkyl fluorides with grignard reagents
Terao, Jun,Ikumi, Aki,Kuniyasu, Hitoshi,Kambe, Nobuaki
, p. 5646 - 5647 (2003)
n-Octyl fluoride underwent a cross-coupling reaction with n-propylmagnesium bromide in the presence of 1,3-butadiene using NiCl2 as a catalyst at room temperature to give undecane in moderate yields. This alkyl-alkyl cross-coupling proceeded more efficiently when CuCl2 was employed instead of NiCl2. Addition of 1,3-butadiene dramatically improved the yields of the coupling products from primary alkyl Grignard reagents in both Ni- and Cu-catalyzed reactions. Alkyl fluorides efficiently reacted with tertiary alkyl and phenyl Grignard reagents using CuCl2 in the absence of 1,3-butadiene to afford the coupling products in high yields. The competitive reaction of a mixture of alkyl halides (R-X; X = F, Cl, Br) with nC5H11MgBr showed that the reactivities of the halides increase in the order R-Cl R-F R-Br. In contrast, in the Cu-catalyzed reaction with PhMgBr, the reactivities increase in the order R-Cl R-Br R-F. Copyright
Kinetic studies of the ni-catalyzed cross-coupling of alkyl halides and a tosylate with butyl grignard reagent in the presence of 1,3-butadiene
Iwasaki, Takanori,Tsumura, Asako,Omori, Takehiro,Kuniyasu, Hitoshi,Terao, Jun,Kambe, Nobuaki
, p. 1024 - 1026 (2011)
Kinetic studies of the nickel-catalyzed cross-coupling reaction of alkyl bromides, iodides, and tosylates with butyl Grignard reagents in the presence of butadiene were performed. The reaction rate was first order with respect to the halides and the nickel catalyst. The butyl Grignard reagent, at concentrations of ca. 0.4M or higher, had little effect on the reaction rate. The relative reactivities and activation parameters were determined for these alkyl halides and a tosylate.
Light-Driven Enzymatic Decarboxylation of Fatty Acids
Huijbers, Mieke M. E.,Zhang, Wuyuan,Tonin, Fabio,Hollmann, Frank
, p. 13648 - 13651 (2018)
The photoenzymatic decarboxylation of fatty acids to alkanes is proposed as an alternative approach for the synthesis of biodiesel. By using a recently discovered photodecarboxylase from Chlorella variabilis NC64A (CvFAP) we demonstrate the irreversible preparation of alkanes from fatty acids and triglycerides. Several fatty acids and their triglycerides are converted by CvFAP in near-quantitative yield and exclusive selectivity upon illumination with blue light. Very promising turnover numbers of up to 8000 were achieved in this proof-of-concept study.
A novel photoinduced reduction system of low-valent samarium species: Reduction of organic halides and chalcogenides, and its application to carbonylation with carbon monoxide
Sumino, Yukihito,Harato, Nami,Tomisaka, Yuri,Ogawa, Akiya
, p. 10499 - 10508 (2003)
Visible light irradiation is found to enhance the reducing ability of samarium diiodide (SmI2) dramatically. Organic halides (RCl, RBr, RI) and chalcogenides (RSPh, RSePh, RTePh) are smoothly reduced to the corresponding hydrocarbons by using this SmI2-hv system. The photoactivation can be also applied to ytterbium diiodide (YbI2) successfully. When the reduction of alkyl chlorides (RCl) by using the SmI 2-hv system is conducted under the pressure of carbon monoxide, unsymmetric ketones (RC(O)CH2R) are obtained as carbonylating products. A mechanistic pathway may involve the formation of acylsamarium species (RC(O)SmI2), which undergo dimerization, followed by reduction with SmI2, leading to the unsymmetric ketones.
Novel enhancement of the reducing ability of ytterbium diiodide by irradiation with near-UV light
Ogawa, Akiya,Ohya, Syoji,Sumino, Yukihito,Sonoda, Noboru,Hirao, Toshikazu
, p. 9017 - 9018 (1997)
Irradiation with near-UV light dramatically enhances the reducing ability of ytterbium diiodide (Ybl2). Organic bromides, iodides, tosylates, and tellurides are reduced efficiently by a YbI2-hv system, while these can not be reduced with YbI2 in the dark.
Synthesis of Diesel and Jet Fuel Range Alkanes with Furfural and Angelica Lactone
Xu, Jilei,Li, Ning,Yang, Xiaofeng,Li, Guangyi,Wang, Aiqin,Cong, Yu,Wang, Xiaodong,Zhang, Tao
, p. 5880 - 5886 (2017)
A route was developed for the synthesis of diesel and jet fuel range C9 and C10 alkanes with furfural and angelica lactone, which can be obtained from hemicellulose and cellulose. It was found that angelica lactone is more reactive than levulinic acid or its other derivates in the aldol condensation with furfural. Among the investigated catalysts, Mn2O3 was found to be the most active and was very stable for the aldol condensation of furfural and angelica lactone. Over Mn2O3, a high carbon yield of C10 oxygenates (about 96%) can be achieved by the aldol condensation of furfural and angelica lactone under mild conditions (353 K, 4 h). By the hydrogenation and hydrodeoxygenation of the aldol condensation product over the Pd/C and Pd-FeOx/SiO2 catalysts, high carbon yields (～96%) of C9 and C10 alkanes were obtained.
Desulphurization of benzothiophene derivatives with nickel boride
Back, Thomas G.,Yang, Kexin
, p. 819 - 820 (1990)
Nickel boride, conveniently generated in situ from nickel chloride hexahydrate and sodium borohydride, has been used to desulphurize a variety of benzothiophene derivatives to the corresponding hydrocarbons under exceptionally mild conditions.
CONTINUOUS PROCESS FOR THE PRODUCTION OF ALKANES
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Page/Page column 12-13, (2021/11/13)
Continuous reductive dehydroxymethylation process for the preparation of alkanes from primary aliphatic alcohols, having 3 to 25 carbon atoms, in the presence of hydrogen and a catalyst in a reactor at a pressure of ≥ 2 bar, characterized in that the dehydroxymethylation takes place in the vapor phase.
Highly stable and selective catalytic deoxygenation of renewable bio-lipids over Ni/CeO2-Al2O3 for N-alkanes
Ba, Wenxia,Cui, Huamin,Fu, Lin,Li, Yongfei,Liu, Yuejin
, (2021/07/31)
Ni-based catalysts are easy deactivated in bio-lipids deoxygenation due to metal aggregation and Ni leaching. They also suffer from the hydrocracking of C–C bonds due to strong acidity at high reaction temperature (≥ 300 ℃). Herein, a series of Ni/CeO2-Al2O3 catalysts with different Ce/Al ratio were prepared by one-pot sol-gel method. The characteristic results showed that an appropriate addition of Ce both increase the catalytic activity and stability in bio-lipids deoxygenation. The oxygen vacancies formed by Ce introduction weaken the strong interaction of Ni-Al, thus improving Ni sites dispersion. Additional, Ce-addition in NiCeAl system increases weak and medium acidity and decreases strong acidity, preventing the C–C bond cleavage of hydrocarbon. As the result, the Ni/CeAl-3.0 catalyst afforded a 97.1 % n-C17 yield at 99.9 % MO conversion under 2.5 MPa H2 at 300 ℃ for 6 h. Minor C15-16 alkanes (17 yield). After simple regeneration, n-C17 yield was recovered to 95 %. Furthermore, non-edible bio-lipids (JO and WCO) can be converted to C13-18 alkanes with 95.2 % and 93.8 % yields, respectively.
Acidic metal-organic framework empowered precise hydrodeoxygenation of bio-based furan compounds and cyclic ethers for sustainable fuels
Gao, Xiang-Yu,He, Hai-Long,Li, Zhi,Liu, Dong-Huang,Wang, Jun-Jie,Xiao, Yao,Yi, Xianfeng,Zeng, Tengwu,Zhang, Yue-Biao,Zheng, Anmin,Zhou, Si-Yu
supporting information, p. 9974 - 9981 (2021/12/27)
Target synthesis of hydrocarbons from abundant biomass is highly desired for sustainable aviation fuels (SAFs) to meet the need for both net zero carbon emission and air pollution control. However, precise hydrodeoxygenation (PHDO) of bio-based furan compounds and cyclic ethers to isomerically pure alkanes remains a challenge in heterogenous catalysis, which usually requires delicate control of the distribution of acid and metal catalytic sites in nanoconfined space. Here we show that a nanoporous acidic metal-organic framework (MOF), namely MIL-101-SO3H, enables one-pot PHDO reactions from furan-derivative oxygenates to solely single-component alkanes by just mechanical mixing with commercial Pd/C towards highly efficient and highly selective hydrocarbon production. The superior performance of such tandem catalysts can be attributed to the preferential adsorption of oxygenate precursors and expulsion of deoxygenated intermediates benefiting from Lewis acid sites embedded in the MOF. The strong Br?nsted acidity of MIL-101-SO3H is contributed by both the -SO3H groups and the adsorbed H2O, which makes it a water-tolerant solid acid for durable PHDO processes. The simplicity of mechanical mixing of different heterogenous catalysts allows the modulation of the tandem catalysis system for optimization of the ultimate catalytic performance. This journal is
