Triphenyl phosphine trisulfonated TPPTS

Following the recommendations of Manassen [18] the history of biphasic hydroformylation began with work on various water-soluble ligands (Table 1). After this preparatory work on various aspects [30], Kuntz [22, 199] expressed the basic idea of a new generation of water-soluble oxo catalysts with triphenyl-phosphine trisulfonate (TPPT S, as the Na salt, as compared with TPPMS and TPPDS, the mono- and disulfonate) as ligands for a Rh-based oxo process, mainly for the hydroformylation of lower olefins such as propene (eq. (5)). 

Roughly at the same time (in contradiction to a misleading publication by Papado-gianakis [2]) and parallel to work done by Joo [3] and others [4], one of us (EK, then at Rhone-Poulenc) devoted time and effort to starting practical work on biphasic catalysis with organometallic catalysts (especially hydroformylation), developing the biphasic principle and the current well-known standard ligand triphenyl-phosphine trisulfonate (TPPTS, cf. Section 3.2.1). 

A very important process with the solvent water is the hydroformylation of propene to butyraldehydes, known as the Ruhrchemie/Rhone-Poulenc process. The reaction is catalyzed by a rhodium complex containing the water-soluble ligand triphenyl-phosphine trisulfonate (TPPTS) (see Section Lower Alkenes [6-11]). 

An early example of Suzuki-Miyaura coupling smdied at an industrial laboratory is shown by reaction 7.4.2.3. The product 2-cyano-4 -methylbiphenyl is a building block for a class of antihypertensive pharmaceuticals. The use of triphenyl phosphine trisulfonated (TPPTS) as the ligand allows the formation of a biphasic system and easy catalyst recycle. 

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. 

TPPTS Triphenyl phosphine-3,3, 3 -trisulfonic acid trisodium salt... 

An example of a large scale application of this concept is the Ruhrchemie/ Rhone Poulenc process for the hydroformylation of propylene to n-butanal, which employs a water-soluble rhodium(I) complex of trisulfonated triphenyl-phosphine (tppts) as the catalyst [103]. The same complex also functions as the catalyst in the Rhone Poulenc process for the manufacture of the vitamin A intermediate, geranylacetone, via reaction of myrcene with methyl acetoacetate in an aqueous biphasic system (Fig. 1.35) [104]. 

Metal-carbonyl complexes of the sodium salt of trisulfonated triphenyl-phosphine TPPTS (Section III-A) have also been synthesized. The prepar-... 

C6H4-4-OCH2C7F15)3).325 High-pressure 31P H NMR spectra were also reported for RhH(CO)(TPPTS)3 in the presence of methylated cyclodextrins (TPPTS = trisulfonated triphenyl-phosphine.326... 

---