Triphenyl phosphine monosulfonated TPPMS

Hydrophilic Catalytic Systems The most commonly used procedure to increase the solubility of tertiary phosphines in water is to attach highly polar groups to the organic moiety of the phosphine. Monosulfonated triphenyl phosphine (TPPMS) palladium complexes can mediate the coupling of aryl iodides or bromides in a solvent mixture containing MeCN and water at ambient temperature, but require Cul as additive (Scheme 6.7) [38]. 

As a polar solvent for the catalyst ethylene carbonate (EC), propylene carbonate (PC) and acetonitrile were used. Tricyclohexylphosphine, triphenyl-phosphine and the monosulfonated triphenylphosphine (TPPMS) were investigated as ligands with Pd(acac)2 as the precursor. Cyclohexane, dodecane, p-xylene and alcohols (1-octanol, 2-octanol and 1-dodecanol) were tested as non-polar solvents for the product. To determine the distribution of the product and of the catalyst, the palladium precursor and the hgand were dissolved in the polar solvent and twice as much of the non-polar solvent was added. After the addition of 5-lactone, the amounts of the product in both phases was determined by gas chromatography. The product is not soluble in cyclohexane and dodecane, more than 99% of it can be found in the polar catalyst phase. With the alcohols 1-octanol, 2-octanol and dodecanol about 50 to 60% of the 5-lactone are located in the non-polar phase. With p-xylene biphasic systems can only be achieved when EC is used as the polar solvent and even in this solvent system one homogeneous phase is formed at a temperature higher than 70 °C. In a 1 1 mixture of EC and p-xylene about 50 to 60% of the product is contained in the polar phase. 

The sulfonation of triphenyl phosphine with fuming sulfuric acid can give three possible products monosulfonated triphenylphosphine (TPPMS), disulfonated triphenylphosphine (TPPDS), and TPPTS 1, depending on the reaction conditions (Figure 9). Using this method many sulfonated aryl phophines have been prepared (2b,... 

For propylene hydroformylation with Rh catalyst, PPh used to be the ligand of choice. Today in Rh-based technology, water-soluble 5.19 is used as the ligand. This ligand, triphenyl phosphine trisulfonated, is abbreviated as TPPTS. Ligand 5.22 is the monosulfonated analogue of 5.19 and is called TPPMS (triphenyl phosphine monosulfonated). The solubility properties of 5.19 and 5.22 in biphasic systems are somewhat different. 

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