123-15-9Relevant articles and documents
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Jardine,Wilkinson
, p. 270 (1967)
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Modification of rhodium catalyst with stibines for hydroformylation of 1-pentene
Sharma, Pankaj,Arias, Jose Luis,Vasquez, Jaime,Gomez, Valente,Guiterrez, Rene
, p. 681 - 684 (2007)
Homogeneous hydroformylation of 1-pentene under synthesis gas experimental conditions was studied using RhClCO(PPh3)2 complex with different triarylstibines. Three different stibine ligands SbR3 [where R = 2,4,6-mesityl (TMS), 2-furyl (TFS), 2-N,N-dimethylbenzylamine (TDMBAS)], have been tested. It is interesting to note that 2:1 addition of these stibine ligands to the RhClCO(PPh3)2 complex catalyst increases the aldehydes yields with an appreciable n:iso ratio. The catalytic activity of the system shows a TDMBAS > TMS > TFS pattern which indicates that not only basicity of the ligand alone is playing a role in the activity but the steric effect is also very important, and it is combination of these two factors that contributes to the resulting catalytical activity. The maximum yield of aldehydes obtained were 98.7% with n/iso = 1.4 when RhClCO(PPh3)2 + TFS system was used and 93.7% with n/iso = 2.43 when TDMBAS ligand was studied.
1-Pentene Hydroformylation Catalyzed by Polymer-Bound Ruthenium Complexes
Pittman, Charles U.,Wilemon, Gary M.
, p. 1901 - 1905 (1981)
Polymer-bound ruthenium hydroformylation catalysts were prepared by reacting diphenylphosphinated styrene-1percent divinylbenzene resins with Ru(CO)3(PPh3)2 under a carbon monoxide atmosphere.Resins with 29percent and 5percent ring-substitution loading levels of phosphine were prepared, and resins with P/Ru ratios of 3.1, 6.7, and 11.3 were made with the 29percent phosphine loading.These resins functioned as 1-pentene hydroformylation catalysts and were compared to the homogeneous use of Ru(CO)3(PPh3)2 as the catalyst.No olefin isomerization occured.The resin catalysts with P/Ru ratios of 3.1 and 6.7 at 29percent loading gave higher n/b aldehyde selectivities (3.5-3.8) than the homogeneous catalyst when employed at P/Ru ratios of 20 but not as high as was achieved by using Ru(CO)3(PPh3)2 in molten PPh3 (5.1).The n/b selectivity was discussed in terms of the equilibrium between (polymer-PPh2)2RuH2(alkene)(CO) and polymer-PPh2RuH2(alkene)(CO)2 within the resin matrix where phosphine loading, P/Ru, ligand mobility, and swelling play contributing roles.The novel 1,1'-bis(diphenylphosphino)ferrocene ligand induced higher n/b selectivities than PPh3 in homogeneous Ru-catalyzed reactions.
Recycling of two molecular catalysts in the hydroformylation/aldol condensation tandem reaction using one multiphase system
Leitner, Walter,Strohmann, Marc,Vorholt, Andreas J.,Vossen, Jeroen T.
, p. 8444 - 8451 (2020)
Tandem reactions are of great importance to efficiently execute multiple conversions in one synthesis step. Herein we present a multiphase system for the hydroformylation/aldol condensation, which is able to recycle both optimized catalysts multiple times. The system consists of an organometallic rhodium/sulfoXantphos hydroformylation catalyst and basic NaOH as aldol condensation initiator, which are both immobilized in a polyethylene glycol phase. Under reaction conditions, NaOH is converted to sodium formate, which is still able to catalyse the aldol condensation. The reaction and recycling are demonstrated by the conversion of 1-pentene to the corresponding aldol product in a recycling experiment. During nine consecutive runs, no significant loss of activity is found with an overall TON of 8700 in regard to the rhodium catalyst and an average rhodium leaching of only of 0.07% per run is observed.
Synthesis of novel rhodium phosphite catalysts for efficient and selective isomerization-hydroformylation reactions
Piras, Irene,Jennerjahn, Reiko,Jackstell, Ralf,Baumann, Wolfgang,Spannenberg, Anke,Franke, Robert,Wiese, Klaus-Diether,Beller, Matthias
, p. 479 - 486 (2010)
New modular H8-BINOL-based phosphite ligands have been synthesized. High activity and regioselectivity has been achieved in the rhodium-catalyzed isomerization-hydroformylation of internal olefins. The active catalysts have been characterized by in situ NMR studies.
n-pentane carbonylation with CO on sulfated zirconia: An in situ solid-state 13C NMR study
Luzgin,Stepanov,Shmachkova,Kotsarenko
, p. 23 - 25 (2001)
Using 13C CP/MAS NMR, the first evidence has been obtained for n-pentane carbonylation with carbon monoxide into C6 aldehydes, ketones and carboxylic acids on a sulfated zirconia catalyst.
Zeolite-Encaged Isolated Platinum Ions Enable Heterolytic Dihydrogen Activation and Selective Hydrogenations
Dai, Weili,Deng, Xin,Guan, Naijia,Li, Landong,Liu, Runze,Ma, Ding,Qin, Bin,Qin, Xuetao,Wu, Guangjun
supporting information, p. 20898 - 20906 (2021/12/14)
Understanding the unique behaviors of atomically dispersed catalysts and the origin thereof is a challenging topic. Herein, we demonstrate a facile strategy to encapsulate Ptδ+ species within Y zeolite and reveal the nature of selective hydrogenation over a Pt@Y model catalyst. The unique configuration of Pt@Y, namely atomically dispersed Ptδ+ stabilized by the surrounding oxygen atoms of six-membered rings shared by sodalite cages and supercages, enables the exclusive heterolytic activation of dihydrogen over Ptδ+···O2- units, resembling the well-known classical Lewis pairs. The charged hydrogen species, i.e., H+ and Hδ-, are active reagents for selective hydrogenations, and therefore, the Pt@Y catalyst exhibits remarkable performance in the selective hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols and of nitroarenes to arylamines.
Method for synthesizing fluorescent dye intermediate aldehyde by hydroformylation of 1,3-diene compound
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Paragraph 0053-0054; 0056-0057, (2021/08/07)
The invention discloses a method for synthesizing a fluorescent dye intermediate aldehyde by hydroformylation of 1,3-diene compound. The method comprises the following steps: S1, sequentially adding 0.01 mmol (1 mol%) of [Rh(cod)Cl]2, 0.1 mmol of a phosphine ligand(P/Rh=10/1) and 1 mmol of diene into a reaction flask, adding 1 ml of a solvent DMF, putting the reaction flask into a high-pressure reaction kettle, after the reaction is finished, transferring a mixed solution into a 25 mL glass bottle with 200 microliters of n-tridecane as an internal standard by using a rubber head dropper, and detecting; and S2, determining the product yield and the structure through a gas chromatograph and a nuclear magnetic resonance spectrum, wherein the obtained olefin conversion rate is larger than 99%, the aldehyde yield ranges from 61% to 99%, and the regioselectivity of the product aldehyde ranges from 70/30 to 100/0. According to the method disclosed by the invention, the separation and purification steps of aldehyde products are simplified, and the substrate of the dialkene hydroformylation reaction is excellent in universality.