63995-70-0Relevant articles and documents
Heterolytic splitting of allylic alcohols with palladium(O)-TPPTS in water. Stabilities of the allylphosphonium salt of TPPTS and of the ionic complex [Pd(η-allyl)(TPPTS)2]+
Basset, Jean-Marie,Bouchu, Denis,Godard, Gregory,Karame, Iyad,Kuntz, Emile,Lefebvre, Frederic,Legagneux, Nicolas,Lucas, Christine,Michelet, Daniel,Tommasino, Jean Bernard
, p. 4300 - 4309 (2008)
The Pd(TPPTS)3 complex (TPPTS is the sodium salt of tris(m-sulfophenyl)phosphine) easily ionizes allyl alcohol in water over a wide range of pH: OH- and TPPTS are released, and [Pd(η3- allyl)(TPPTS)2]+ is formed. The released TPPTS further reacts with the palladium cationic complex to reversibly produce both the allylphosphonium salt of TPPTS [(allyl)Ar3P]+ and Pd(TPPTS)3, the latter acting as the catalyst of the allylation of TPPTS by allyl alcohol. Primary allylic alcohols, such as butenol (trans-2-buten-1ol), prenol (3-methyl-2-buten-1-ol), geraniol, and cinnamyl alcohol, react with Pd(TPPTS)3 to produce hydroxide ion, the corresponding hydrosoluble cationic palladium complex, and allylic phosphonium salts. At room temperature, [Pd(η3-allyl)(TPPTS) 2]+ is stable up to pH 12, but beyond this value, palladium precipitates. The temperature has an adverse effect on the complex stability: palladium precipitates at 80 °C, even at pH 7, with the formation of a small amount of propylene. The addition of [(allyl)Ar3P] + increases the stability of [Pd(η3-allyl)(TPPTS) 2]+. Above pH 10, [(allyl)Ar3P]+ decomposes into OTPPTS and propylene by reaction with OH. At lower pH, [(allyl)Ar3P]+ is slowly isomerized into [(propenyl)Ar3P]+, which further reduces its stability toward pH and temperature. These consecutive reactions of the TPPTS ligand could explain most of the catalyst instability. This study outlines the basis for a better understanding of the instability phenomenon of the catalytic system Pd(0)-TPPTS in reactions with allylic intermediates, e.g. the Tsuji-Trost reaction, and in the reaction of dienes in aqueous media in which palladium often precipitates.
Wasserloesliche Metallkomplexe und Katalysatoren II. Verfahren zur Reindarstellung von Tris(natrium-m-sulfonatophenyl)phosphan (TPPTS) und katalyserelevanter Rhodium-Komplexe
Herrmann, Wolfgang A.,Kulpe, Juergen A.,Konkol, Werner,Bahrmann, Helmut
, p. 85 - 101 (1990)
Gel-permeation chromatography is recognized as the most reliable method for the purification of aqueous solutions of the ligand tris(sodium-m-sulfonato-phenyl)phosphane (TPPTS) and its industrially important rhodium complex derivatives (hydroformylation;
Interconversion between platinum (II) and platinum (0) with change of pH: Aqueous reactions of Pt(H)(TPPTS)3+ (TPPTS = P(m-C6H4SO3Na)3)
Helfer, Derrik S.,Atwood, Jim D.
, p. 250 - 252 (2002)
The interconversion between platinum(II) and platinum(0) with change of pH was investigated. It was shown that the oxidation state for platinum complexes can be controlled through variation of the pH of an aqueous solution. As the pH was decreased in wate
Preparation method of trisulfonated triphenylphosphine TPPTS
-
Paragraph 0009; 0024-0044; 0050, (2021/05/01)
The invention relates to a preparation method of trisulfonated triphenylphosphine TPPTS, which comprises the following steps: dissolving triphenylphosphine TPP in concentrated sulfuric acid, and dropwisely adding chlorosulfonic acid; after the reaction is completed, adding ice water to stop the reaction, and adding an organic solvent for extraction; neutralizing the extracted organic solvent with alkali, and adjusting the pH value to 7-8; separating the liquid, concentrating a water layer under reduced pressure until a solid is separated out, and then adding methanol to separate out a large amount of Na2SO4 solid; filtering the liquid, and concentrating filtrate under reduced pressure until the filtrate is dry, so as to obtain a trisulfonated triphenylphosphine TPPTS crude product; dissolving the obtained trisulfonated triphenylphosphine TPPTS crude product in water, dropwise adding a solvent, and crystallizing the solution to obtain the product trisulfonated triphenylphosphine TPPTS. The method has the advantages of short route synthesis steps, simple process operation, low cost of used raw materials, high product yield, high product purity and easiness in industrial production. The hydrochloric acid generated by chlorosulfonic acid reaction can be absorbed and neutralized by being introduced into alkali liquor, so that the reaction is not influenced, and no pollution is caused to the environment.
METHOD FOR PRODUCING 2,7-OCTADIEN-1-OL
-
Paragraph 0213-0215, (2016/03/13)
Provided is a simple and industrially advantageous method for producing 2,7-octadien-1-ol, in which an expensive palladium catalyst is recovered in high efficiency and the reaction rate per atom of palladium is enhanced. Specifically, provided is a method for producing 2,7-octadien-1-ol by subjecting butadiene and water to a telomerization in the presence of a palladium catalyst containing a water-soluble triarylphosphine having two or more sulfonate groups in the molecule and a palladium compound, a tertiary amine, and carbon dioxide, including a step of mixing the telomerization solution obtained by the telomerization with an organic solvent having a dielectric constant at 25° C. of 2 to 18, followed by carrying out phase separation in the presence of carbon dioxide, thereby obtaining 2,7-octadien-1-ol from an organic phase while recovering an aqueous phase including the palladium catalyst. By this production method, the selectivity for 2,7-octadien-1-ol is enhanced.
Optimisation of palladium-based supported liquid-phase catalysts in the heck reaction
Mirza, Amin R.,Anson, Michael S.,Hellgardt, Klaus,Leese, Matthew P.,Thompson, David F.,Tonks, Louise,Williams, Jonathan M.J.
, p. 325 - 331 (2013/09/08)
Heck reactions using sulphonated triphenylphosphine palladium complexes have been carried out using a supported liquid-phase catalysis system in a batch reactor. The catalyst complex is held in solution in a polar, hydrophilic film supported upon porous glass beads whilst reactants and products are restricted to a nonmiscible solvent phase. Several factors in the preparation of the supported catalyst were investigated with the aim of ensuring good assembly, distribution, and immobilisation of the catalyst complex across the surface of the beads. The thickness of the hydrophilic film upon the porous glass beads was varied. The hydrophilic nature of the ligand complex was studied using mono- and trisulphonated sodium and lithium salts of triphenylphosphine. The effects of level of catalyst loading and ligand/catalyst ratio upon leaching and activity were also examined. These factors have been examined to develop a better understanding of the catalysis occurring in supported liquid-phase systems.
Transition Metal Complexes of Diazenes XXXVI [1a]: Formation of Indoles from Azobenzene and Diphenylacetylene through Supported Aqueous Phase Catalysis by Rhodium(I) Complexes
Westernacher,Kisch
, p. 469 - 473 (2007/10/03)
A SiO2 supported Rh(I) catalyst of trisulfonated triphenylphosphine catalyzes the addition of diphenylacetylene to azobenzene in refluxing butanol in the presence of triphenylphosphine to afford N-anilino-2,3-diphenylindole and 2,3-diphenylindole with turnover numbers of 80 and 20, respectively. As compared to the known homogeneous or heterogeneous (SiO2) catalysis by RhCl(PPh3)3, the supported aqueous phase system retains a constant turnover frequency throughout the reaction and can be partially recycled.
Neues Verfahren zur Sulfonierung von Katalysator-Phosphanliganden
Herrmann, Wolfgang A.,Albanese, Guido P.,Manetsberger, Rainer B.,Lappe, Peter,Bahrmann, Helmut
, p. 893 - 895 (2007/10/02)
Stichworte: Katalyse * Phosphanliganden * Sulfonierung
TOWARDS WATER SLOLUBLE PHOSPHINES
Grzybek, Ryszard,Kupka, Teobald,Herbowski, Antoni
, p. 210 (2007/10/02)
Chlorosulfonated and sulfonamide substituted aromatic phosphines as precursors of water soluble phosphines have been synthesized.
