Synthesis of Phosphino Alkane Sulfonates and their corresponding sulfonic acids by reaction of alkalimetal‐phosphides with sultones

Abstract

Alkalimetal salts of dialkyl‐ and diphenylphosphino alkane sulfonic acids (1–4, 6, 7) were prepared by reaction of alkalimetalphosphides with sultones at ambient temperature. The sulfonates can be converted into the free sulfonic acids by ion exchange. This method opens an access to water soluble phosphines (8, 9) which can be important as ligands in transition metal complexes for catalytic processes. The use of water soluble tertiary phosphines as ligands in catalytic active transition metal complexes seems to be an achievement of the last ten or twelve years [1]. An important aspect of application is the realization of two phase systems with the catalyst in the water phase acting in the interface. After the catalytic process the catalyst can be separated easily from the product and the recovery of the expensive transition metal is possible. Hydrophilicity of phosphines usually is achieved introducing highly polar hydroxy‐, amino‐, carboxylato‐, ammonium‐, sulfonato‐, and polyether‐groups, respectively, but only tetraalkylammonium‐, polyether‐ and sulfonato‐groups are suitable for a large pH‐range. Sulfonato groups can be introduced into phenylphosphines by sulfonation with sulfur trioxide in sulfuric acid leading to meta sulfonated products. Especially mono‐ and polysulfonation of triphenylphosphine was investigated by AHRLAND, CHATT et al. [2]. Monosulfonation occurs under mild conditions, but the selectivity of a multiple sulfonation is low, and there are some problems with the separation of reaction products [3]. Nevertheless, phenylphosphines with chiral substituents were sulfonated by this method and used as ligands in rhodium complexes for asymmetric syntheses [4]. A way to a triphenylphosphine sulfonated in the para position was given by SCHINDLBAUER [5], but his method seems to be less satisfactory with respect to yield and selectivity.

Water-soluble palladium(II)phosphine complexes as catalysts in the Hydrodehalogenation of Allyl and Benzyl Halogenides under biphasic and phase transfer conditions

“…In our experience potassium formate is a better agent than sodium or ammonium formate. Except for the meta-sulfonated triphenylphosphine [ 121 the ligands were prepared in our laboratory by reaction of a alkalimetal diphenylphosphide with a sultone [7]. The dehalogenation was carried out at 80 -90 "C under stirring in a simple apparatus.…”

“…Before use all chemicals were purified by distillation or recrystallization, respectively. The preparation of water soluble phosphines and their corresponding palladium complexes is described in [7]. (E)-Phenylallyl chloride was synthesized starting from cinnamic alcohol and thionylchloride in chloroform/pyridine [14].…”

“…The authors could give some arguments for a reverse phase transfer catalysis [5], what means that the reaction takes place in the water phase [6]. We synthesized water-soluble palladium complexes on the basis of a new type of sulfonated phosphines prepared in our laboratory [7]. The use of sulfonated phosphines as ligands in transi-tion metal complexes is very common [S] and was successful especially for instances in hydroformylation reaction [9].…”

Palladium-Catalyzed Cross-Coupling in Aqueous Media: Recent Progress and Current Applications

“…3) [117] has been applied to the Suzuki coupling of aryl iodides and bromides at 78 ˚C in a toluene/ethanol/water mixed solvent system in the presence of surfactants [118]. Incorporation of functionalized alkyl substituents provides a larger range of possible hydrophilic substituents that can be appended to the phosphine.…”

Darstellung und Stabilität von Triorganostannylalkylsulfonsäuren

“…Fur die y-substituierten Vertreter empfiehlt sich eine vorteilhaftere Synthesevariante, die in Analogie zur Darstellung von Alkali-3-diorganophosphinopropylsulfonaten [9] in der Umsetzung von Alkali-triorganostanniden mit Propansulton besteht (Gl. (2)).…”