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.
Rate Constants for the Reaction of Acyl Radicals with Bu3SnH and (TMS)3SiH
Chatgilialoglu, Chryssostomos,Lucarini, Marco
, p. 1299 - 1302 (1995)
The rate constants for the hydrogen abstraction from Bu3SnH and (TMS)3SiH by acyl radicals have been measured by using competing decarbonylation reactions as timing devices.
Hydrogenation of quinolines, alkenes, and biodiesel by palladium nanoparticles supported on magnesium oxide
Rahi, Reena,Fang, Minfeng,Ahmed, Atif,Sánchez-Delgado, Roberto A.
, p. 14490 - 14497 (2012)
A new catalyst composed of Pd nanoparticles supported on MgO has been prepared by the room temperature NaBH4 reduction of Na 2PdCl4 in methanol in the presence of the support. TEM measurements reveal well-dispersed Pd particles of mean diameter 1.7 nm attached to the MgO surface. Further characterization was achieved by ICP-AES, XPS, XRD, H2 pulse chemisorption and H2-TPR. The new catalyst is efficient for the regioselective hydrogenation of the heterocyclic ring of quinolines, as well as for the mild reduction of a variety of alkenes representative of fuel components, and the partial saturation of biodiesel. The new material is considerably more reactive than commercial Pd/SiO2 and Pd/Al2O3 catalysts under analogous reaction conditions.
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.
Fatty methyl ester hydrogenation to fatty alcohol part I: Correlation between catalyst properties and activity/selectivity
Rieke, Ross D.,Thakur, Deepak S.,Roberts, Brian D.,White, Geoffrey T.
, p. 333 - 339 (1997)
Fatty alcohols, derived from natural sources, are commercially produced by hydrogenation of fatty acids or methyl esters in slurry-phase or fixed-bed reactors. One slurry-phase hydrogenation of methyl ester process flows methyl esters and powdered copper chromite catalyst into tubular reactors under high hydrogen pressure and elevated temperature. In the present investigation, slurry-phase hydrogenations of C12 methyl ester were carried out in semi-batch reactions at non-optimal conditions (i.e., low hydrogen pressure and elevated temperature). These conditions were used to accentuate the host of side reactions that occur during the hydrogenation. Some 14 side reaction routes are outlined. As an extension of this study, copper chromite catalyst was produced under a number of varying calcination temperatures. Differences in catalytic activity and selectivity were determined by closely following side reaction products. Both activity and selectivity correlate well with the crystallinity of the copper chromite surface; they increase with decreasing crystallinity. The ability to follow the wide variety of side reactions may well provide an additional tool for the optimized design of hydrogenation catalysts.
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.
Cross-coupling of alkyl halides with Grignard reagents using nickel and palladium complexes bearing η3-allyl ligand as catalysts
Terao, Jun,Naitoh, Yoshitaka,Kuniyasu, Hitoshi,Kambe, Nobuaki
, p. 825 - 827 (2007)
The cross-coupling of Grignard reagents with alkyl bromides and tosylates has been achieved by the use of η3-allylnickel and η3-allylpalladium complexes as catalysts. The Royal Society of Chemistry.
Catalyst-free synthesis of biodiesel precursors from biomass-based furfuryl alcohols in the presence of H2O and air
Qin, Shengxiang,Li, Teng,Zhang, Man,Liu, Hongyu,Yang, Xin,Rong, Nianxin,Jiang, Jun,Wang, Yalin,Zhang, Hua,Yang, Weiran
, p. 6326 - 6334 (2019)
Production of biodiesel from biomass resources usually requires elongation of carbon numbers from typical C5 and C6 platform molecules through C-C coupling reactions, which were catalyzed by acid, base or metal catalysts traditionally. Herein, a catalyst-free method was developed to produce bis(furan-2-yl)methane derivatives (BFMs) from furfuryl alcohol derivatives (FAs) in the presence of H2O and air without any other additional catalysts. An 81% yield of bis(5-methylfuran-2-yl)methane (BMFM) can be obtained from 5-methylfurfuryl alcohol (5-MFA) and a 59% total yield of C11 biodiesel was obtained from 5-methylfurfural (5-MF). In addition, a H2O and air mediated free radical decarboxylation mechanism was proposed based on the detailed mechanistic studies. This strategy offers a green, low-cost and environmentally friendly approach to synthesize biodiesel precursors from biomass based platform molecules.
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.
