2765-11-9Relevant articles and documents
Triphasic liquid systems for improved separations. Trioctylmethylammonium chloride-immobilised rhodium trichloride: A phosphine-free hydroformylation catalytic system
Paganelli, Stefano,Perosa, Alvise,Selva, Maurizio
, p. 1858 - 1862 (2007)
A liquid triphasic system made of isooctane, water, and trioctylmethylammonium chloride allows one to carry out the hydroformylation of model olefins using neat RhCl3 as catalyst precursor. By using the triphasic system, the catalyst is kept separate from the reagents and products. This allows one to simply remove the product and to recycle the catalyst numerous times. No leaching of rhodium into the organic phase is observed.
Mn(VII) Oxidation using Cetyltrimethylammonium Permanganate: Self-Oxidation of CTAP and Oxidation of Benzyl Alcohol
Dash, Sukalyan,Mishra, Bijay K.
, p. 627 - 636 (1995)
Cetyltrimethylammonium permanganate (CTAP) has been prepared and characterized from IR and NMR data.At room temperature the compound is stable when kept in dark but at 115 deg C it undergoes a violent thermal decomposition.In different organic solvents self-oxidation takes place giving rise to pentadecanal.The rate of self-oxidation in different solvents are in the order: benzonitrile > benzene > chloroform > carbon tetrachloride.A mechanism involving proton transfer from the β-methylene group to the permanganate ion, thereby forming an olefinic intermediate, has been suggested.The oxidation kinetics of benzyl alcohol have been st udied in chloroform medium.The thermodynamic parameters for the oxidation reactions have been evaluated.
Hydroformylation with Water- and Methanol-soluble Rhodium Carbonyl/phenyl-sulfonatoalkylphosphine Catalyst Systems - A New Concept for the Hydroformylation of Higher Molecular Olefins
Kanagasabapathy, S.,Xia, Zhigao,Papadogianakis, Georgios,Fell, Bernhard
, p. 446 - 450 (1995)
The heterogenization of the homogenous hydroformylating catalyst system enables the recorvery of the catalyst from the reaction products by a simple phase separation but it is unfavourable that many advantages of the homogeneous catalysis are given up by this procedure.To avoid this drawback we used rhodium carbonyl/tert. phosphine catalyst systems soluble as good in methanol as in water for the homogeneously catalyzed hydroformylation of the olefin in methanolic solution.Only after reaction the product mixture is heterogenized by adding water forming an aqueous phase containing the catalyst system.It was shown by the hydroformylation of n-tetradecene-1 with rhodium carbonyl/phenylsulfonatoalkyl-phosphine catalyst systems that this new conception is very useful for the oxo reaction of high-molecular olefins.
Enantioselective syntheses of xylo-C18-phytosphingosines using double stereodifferentiation
Fernandes, Rodney A.,Kumar, Pradeep
, p. 129 - 135 (2003)
The concept of double stereodifferentiation in Sharpless asymmetric dihydroxylation has been studied and the results obtained are applied to the diastereoselective syntheses of xylo-isomers of C18-phytosphingosine. The diastereomeric mixture obtained could be separated by column chromatography. Thus, the L-xylo-(2R,3S,4S)-C18- and D-xylo-(2S,3R,4R)-C18-phytosphingosines as their tetraacetate derivatives were synthesized in diastereomerically pure form.
Free-of-loss catalyst recycling in the hydroformylation of higher molecular olefins by a novel process technology
Xia, Zhigao,Fell, Bernhard
, p. 140 - 144 (1997)
In this paper a novel homogenous-heterogeneous procedure for the hydroformylation reaction of higher molecular olefins is presented, at which the reaction itself is homogeneously catalyzed and only after the reaction the catalyst complex is heterogenized only for separation. This procedure is achieved by using the lithium salt of triphenylphosphine monosulfonic acid (Li-TPPMS) as complex ligand for the hydroformylation catalyst and methanol as solubilizer. Li-TPPMS and its complexes with metal carbonyls are highly soluble in water and methanol, but completely insoluble in almost all other organic solvents. After the reaction the methanol is distilled off. The catalyst system becomes insoluble and can be separated from the reaction product by filtration or by extraction with water. The aqueous catalyst solution is evaporated to dryness and the catalyst system dissolved in methanol for a new reaction. Johann Ambrosius Barth 1997.
Integration of phosphine ligands and ionic liquids both in structure and properties-a new strategy for separation, recovery, and recycling of homogeneous catalyst
Jin, Xin,Feng, Jianying,Song, Hongbing,Yao, Jiajun,Ma, Qingqing,Zhang, Mei,Yu, Cong,Li, Shumei,Yu, Shitao
, p. 3583 - 3596 (2019/07/10)
The major limitation of classic biphasic ionic liquid (IL) catalysis is the heavy use of solvent ILs, which not only violates green chemistry principles but also even worsens catalytic efficiency. So it has always been a challenge finding ways to use ILs more efficiently, economically, and greenly to construct highly effective and long term stable IL catalytic systems. In this work, we synthesized a class of room temperature phosphine-functionalized polyether guanidinium ionic liquids (RTP-PolyGILs) by a convenient ion exchange reaction of polyether guanidinium ionic liquids (PolyGILs) with phosphine-sulfonate ligands based on the concept of the integration of both the phosphine ligand and IL. The resulting RTP-PolyGILs existed as liquids at room temperature and possessed dual functions of both the phosphine ligand and solvent IL; therefore they could both form catalysts by complexing with transition metals and act as catalyst carriers, thus achieving the integration of phosphine ligands with ILs both in structure and properties. Based on the unique properties of these multi-functional integrated RTP-PolyGILs, we constructed a highly effective homogeneous catalysis-biphasic separation (HCBS) system for Rh-catalyzed hydroformylation of higher olefins using only a catalytic amount of RTP-PolyGILs (equivalent to 0.025-0.4 mol% of 1-alkenes). Our HCBS system could be flexibly regulated with regard to catalytic performance (activity and linear selectivity) by changing the structure or type of the sulfonated ligand anion on RTP-PolyGILs. Specifically, it presented a TOF value of 3000-26000 h-1 and a linear selectivity of 68%-98% (corresponding to the l/b ratio of 2.2-37.5) with a total turnover number (TTON) of 11000-45000 and an extremely low Rh leaching of only 0.02-0.4 ppm. Therefore, the HCBS system can effectively combine the advantages of both homogeneous (high activity and good selectivity) and biphasic catalysis (easy catalyst separation). We additionally extended the application of the HCBS system to the hydrogenation of olefins to demonstrate the universality of the RTP-PolyGILs in catalytic reactions.
A kind of [...] functionalized polyether pyridine salt ion liquid and its olefin hydroformylation reaction in the application of the
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Paragraph 0063; 0064; 0074; 0076, (2018/05/24)
The present invention relates to a phosphine-functionalized polyether pyridinium salt ionic liquid and a method for biphasic hydroformaylation of olefins based on the phosphine-functionalized polyether pyridinium salt ionic liquid. A biphasic catalytic system is used in the method, wherein the catalytic system consists of a phosphine-functionalized polyether pyridinium salt ionic liquid, a rhodium catalyst, a reaction substrate, olefins, and a reaction product, aldehydes; liquid/liquid biphasic hydroformylation of olefins is performed at a certain reaction temperature and syngas pressure; the phosphine-functionalized polyether pyridinium salt ionic liquid acts both as a phosphine ligand and as a rhodium catalyst carrier; there is no need to add any other ionic liquid to the system; and separation and recycling of the rhodium catalyst are realized by liquid/liquid biphasic separation after the reaction. The catalytic system provided by the present invention is high in catalytic activity. The rhodium catalyst is capable of being recycled for many times with no obvious decrease in catalytic activity or selectivity.
A kind of [...] functionalized polyether quaternary phosphonium ionic liquid and its olefin hydroformylation reaction in the application of the (by machine translation)
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Paragraph 0070-0072, (2017/11/16)
The invention relates to a functionalized polyether quaternary phosphonium salt [...] ionic liquid, and a functionalized polyether quaternary phosphonium salt based on [...] ionic liquid two-phase hydroformylation of olefins of the method, the method uses a two-phase catalytic system, the catalytic system is composed of [...] functionalized polyether quaternary phosphonium ion liquid, rhodium catalyst and reaction substrate olefin and reaction aldehyde composition, in a certain reaction temperature and the synthesis gas is conducted under a pressure liquid/liquid two-phase hydroformylation reaction, [...] functionalized polyether quaternary phosphonium ionic liquid is phosphine, at the same time also acts as the rhodium catalyst carrier, system do not need in in addition introducing other ionic liquid, after the reaction through a simple liquid/liquid two-phase separation [...] separation and recycle of the catalyst, the catalytic system has higher catalytic activity, rhodium catalyst can be circulated many times, catalytic activity and selectivity without significant decrease. (by machine translation)