Mono-sulfonated triphenylphosphine TPPMS

A. (MFT -SULFONATOPHENYL)DIPHENYLPHOSPHINE, SODIUM SALT (MONO-SULFONATED TRIPHENYLPHOSPHINE, TPPMS)... 

Sulfonation of triarylphosphines is a good procedure for preparing aqueous soluble phosphines. The mono-sulfonated triphenylphosphine (115) (frequently abbreviated as TPPMS) (<5(P) —4 ppm (D20)) is readily prepared from PPh3 and fuming sulfuric acid, followed by neutralization with NaOH solution (Equation (29)).238 The sodium salt has an approximate solubility of 12 gL-1 in water at room temperature and is virtually insoluble in most common organic solvents. 

With this last point in mind, the synthesis of mono-, bis- and tra-sulfonated triphenylphosphine will be described, but the same methodology can be applied to the preparation of other sulfonated arylphosphines. In general, these phosphines are made by direct sulfonation using fuming sulfuric acid (oleum) [21], The extent of sulfonation is determined by the SO3 strength, as well as factors such as the temperature and time of the reaction. The monosulfonated phosphine (tppms) is prepared using oleum of 20% SO3 strength, with typically 30% SO3 used... 

The other large group of water-soluble phosphines contains ionic substituents in the aryl or alkyl groups attached to phosphorus. Mono-, di-, and trisulfonated triphenylphosphine (TPPMS, TPPDS, and TPPTS, respectively), as well as several sulfonated diphosphines can be prepared by direct sulfona-tion with fuming sulfuric acid (52,59,60). Care should be taken to avoid oxidation of the phosphorus, this can be best achieved by using an anhydrous ortho-boric acid-sulfuric acid mixture (60). Sodium or potassium salts of TPPMS can... 

Water-soluble phosphine ligands TPPMS, TPPDS, and TPPTS (mono-, di-, and tri-sulfonated triphenylphosphine, respectively) were tested as ligands for the hydration of aUcynes in aqueous media [116]. Complexes 19 and 20 (Fig. 1) gave the highest turnover frequencies ever reported (1,000 and 1,060 h , respectively) for the hydration of phenylacetylene under optimum conditions (0.1 mol% catalyst loading, 10 mol% H2SO4, reflux, and MeOH/H20). 

The fact that water-soluble sulfonated phosphines may combine the properties of a ligand and a surfactant in the same molecule was first mentioned in 1978 by Wilkinson etal. [11] in their study of the hydroformylation of 1-hexene using rhodium and ruthenium catalysts modified with TPPMS (triphenylphosphine mono-... 

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