TPPTS preparation

Amatore et al. developed an aqueous cross-coupling reaction of terminal alkynes with 1-iodoalkynes using a water-soluble Pd(0) catalyst prepared in situ from Pd(OAc)2 and sulfonated triphenylphosphine P(C6H4 — m-SCENa (TPPTS) without Cu(I) promoter, giving diynes with moderate yields (43-65%)(Eq. 4.22) 42... 

The compound of the distinct three oxo processes, all rhodium-based, enables a highly efficient recovery system to be achieved. Figure 5.17 describes the TPPTS manufacture and its use for the preparation of the rhodium catalyst, using either freshly introduced Rh acetate or recycled Rh 2-ethylhexanoate. The recycle technique of the RCH/RP process and its performance is depicted earlier. Spent Rh-TPPTS solutions are worked-up (see Figures 5.18 and 5.19), the resulting TPPTS returns to the RCH/RP process. The rhodium portion passes also a work-up stage and is reformulated as Rh 2-ethylhexanoate. This Rh salt may serve all various oxo processes of the oxo loop and will compensate for possible Rh losses as mentioned earlier. 

The "real" oxo precatalyst [HRh(CO)(TPPTS)3] is easily made in the oxo reactor by reacting suitable Rh salts (e.g., rhodium acetate or rhodium 2-ethylhexanoate) with TPPTS - both components freshly prepared or recovered and recycled - without any additional preformation step. The reaction starts after formation of the active species and adjustment of the whole system with water to the desired P/Rh ratio (ensuring the stability of the catalyst and the desired n/iso ratio). 

Water-soluble complexes constitute an important class of rhodium catalysts as they permit hydrogenation using either molecular hydrogen or transfer hydrogenation with formic acid or propan-2-ol. The advantages of these catalysts are that they combine high reactivity and selectivity with an ability to perform the reactions in a biphasic system. This allows the product to be kept separate from the catalyst and allows for an ease of work-up and cost-effective catalyst recycling. The water-soluble Rh-TPPTS catalysts can easily be prepared in situ from the reaction of [RhCl(COD)]2 with the sulfonated phosphine (Fig. 15.4) in water [17]. 

The use of water-soluble ligands was referred to previously for both ruthenium and rhodium complexes. As in the case of ruthenium complexes, the use of an aqueous biphasic system leads to a clear enhancement of selectivity towards the unsaturated alcohol [34]. Among the series of systems tested, the most convenient catalysts were obtained from mixtures of OsCl3 3H20 with TPPMS (or better still TPPTS) as they are easily prepared and provide reasonable activities and modest selectivities. As with their ruthenium and rhodium analogues, the main advantage is the ease of catalyst recycling with no loss of activity or selectivity. However, the ruthenium-based catalysts are far superior. 

To prepare more hydrophobic starches for specific applications, the partial substitution of starch with acetate, hydroxypropyl, alkylsiliconate or fatty-acid ester groups has been described in the literature. A new route, however, consists of grafting octadienyl chains by butadiene telomerization (Scheme 3.9) [79, 82, 83], The reaction was catalyzed by hydrosoluble palladium-catalytic systems prepared from palladium diacetate and trisodium tris(m-sulfonatophenyl)phosphine (TPPTS). 

The etherified starch was further transformed by hydrogenation of the double bonds to yield the corresponding linear octyl groups using [RhCl(TPPTS)3] catalyst soluble in EtOH-H20 mixtures. Complete hydrogenation was obtained at 40 °C under 30 bar of H2 after 12 h using 0.8-wt.% Rh-catalyst [84]. Other catalytic transformations such as double bond oxidation and olefin metathesis could possibly be used to prepare other modified starches for various applications. 

For monosulfonation of PPh3 the reaction mixture can be heated for a limited time [1-3] while multiple sulfonation is achieved hy letting the solution stand at room temperature for a few days [4-10], In this simplest way of the preparation several problems may arise. Under the harsh conditions of sulfonation there is always some oxidation of the phosphine into phosphine oxide and phosphine sulfides are formed, too. Furthermore, selective preparation of TPPMS (1) or TPPDS (2) requires optimum reaction temperature and time and is best achieved by constantly monitoring the reaction by NMR [10] or HPLC [7]. Even then, the product can be contaminated with unreacted starting material. However, 1 can be freed of both the non-sulfonated and the multiply sulfonated contaminants by simple methods, and in the preparation of TPPTS (3) contamination with PPh3, 1 or 2 is usually not the case. Direct sulfonation with fuming sulfuric add was also used for the preparation of the chelating diphosphines 34-38, 51, 52. 

In a different approach [11] to access pure products, the use of strong oleum (65% SO3) for sulfonation of PPh3 resulted in quantitative formation of TPPTS oxide. This was converted to the ethyl suhbester through the reaction of an intermediate silver sulfonate salt (isolated) with iodoethane. Reduction with SiHCls in toluene/THF afforded tris(3-ethylsulfonatophenyl)phosphine which was finally converted to pure 3 with NaBr in wet acetone. In four steps the overall yield was 40% (for PPhs) which compares fairly with other procedures to obtain pure TPPTS. Since phosphine oxides are readily available from easily formed quaternary phosphonium salts this method potentially allows preparation of a variety of sulfonated phosphines (e.g. (CH3)P(C6H4-3-S03Na)2). 

Even in an excess of ligands capable of stabilizing low oxidation state transition metal ions in aqueous systems, one may often observe the reduction of the central ion of a catalyst complex to the metallic state. In many cases this leads to a loss of catalytic activity, however, in certain systems an active and selective catalyst mixture is formed. Such is the case when a solution of RhCU in water methanol = 1 1 is refluxed in the presence of three equivalents of TPPTS. Evaporation to dryness gives a brown solid which is an active catalyst for the hydrogenation of a wide range of olefins in aqueous solution or in two-phase reaction systems. This solid contains a mixture of Rh(I)-phosphine complexes, TPPTS oxide and colloidal rhodium. Patin and co-workers developed a preparative scale method for biphasic hydrogenation of olefins [61], some of the substrates and products are shown on Scheme 3.3. The reaction is strongly influenced by steric effects. 

It is to be mentioned that water-soluble phosphine complexes of rhodium(I), such as [RhCl(TPPMS)3], [RhCl(TPPTS)3], [RhCl(PTA)3], either preformed, or prepared in situ, catalyze the hydrogenation of unsaturated aldehydes at the C=C bond [187, 204, 205]. As an example, at 80 °C and 20 bar H2, in 0.3-3 h cinnamaldehyde and crotonaldehyde were hydrogenated to the corresponding saturated aldehydes with 93 % and 90 % conversion, accompanied with 95.7 % and 95 % selectivity, respectively. Using a water/toluene mixture as reaction medium allowed recycling of the catalyst in the aqueous phase with no loss of activity. 

A water-soluble diphosphine ligand with large bite angle was prepared by controlled sulfonation of XANTHPHOS. The rhodium complex of the resulting (2,7-bis(S03Na)-XANTHPHOS (51) showed a catalytic activity in propene hydroformylation comparable to Rh/TPPTS (TOF 310 vs 500 h" at 120 °C, 9 bar propene and 10 bar CO/H2 = 1/1) [70]. The regioselectivity... 

Diarylethenes, 1,1-diarylallylalcohols and aryl vinyl ethers were succesfully hydroformylated in water/toluene or water/cyclohexane biphasic mixtures with a catalyst prepared in situ from[ RhCl(COD) 2] and TPPTS (Scheme 4.15). Yields of the desired linear aldehyde product were around 80%. This method was applied for the synthesis of the neuroleptics Fluspirilen and Penfluridol (Scheme 4.16) and for other pharmaceutically active compounds containing the 4,4-bis(p-fluorophenyl)butyl group [153]. 

Carbonylation of bromobenzene (Scheme 5.7) with [Pd(TPPTS)3] required still higher temperatures (150 T). The possible acyl intermediates of such reactions [PdBr(C6H5CO) Ph3)2] and [PdBr(C6H5CO)(TPPTS)2] were synthetized and characterized [26]. Bromobenzene was also carbonylated to benzoic acid in water/toluene using a catalyst prepared from [PdCl2(COD)j and 27 in the presence of NEt3 [21]. 

The reaction is catalyzed by palladium complexes either pre-formed, as [Pd(TPPMS)3] [13], or prepared in situ from (usually) [Pd(OAc)2] and various phosphines [21,23-27], TPPTS being one of the most frequently used [14]. Other precursors, e.g. [ PdCl(T -C3H5) 2] and so-caUed ligandless (phosphine-free) Pd-catalysts can also be effective. In fact, in several cases a phosphine inhibition was observed [23]. The solvent can be only slightly aqueous (5 % water in CH3CN, [14]) or neat water [26]. In the latter case a biphasic reaction mixture (e.g. with toluene) facilitates catalyst separation albeit on the expense of the reaction rate. A short selection of the reactions studied in aqueous solvents is shown on Scheme 6.9. 

Scheme 6.11) [30,31]- The catalyst was prepared from [PdCU] and the phosphonato-phosphine Ph2P-C6H4-PO(ONa)2 in water/ethyleneglycol and a mixture of NaOAc and Na2C03 served as base. Similar results were obtained with the Pd/TPPTS catalyst in a biphasic reaction mixture. 

In water-heptane biphasic systems, allylic alcohols underwent rearrangement to the corresponding carbonyl compounds with a catalyst prepared in situ from RhCU.aq and TPPTS. The reactions proceeded very fast (TOP up to 2500 h ) and in most cases provided the carbonyl products quantitatively. The industrially interesting geraniol was isomerized mostly to citronelM, albeit octatrienes and tricyclene were also produced. With an increase of the pH of the aqueous phase the yield of isomerization decreased somewhat (from 48 % to 40 %), however the selectivity towards the... 

In the presence of a large excess of cyanide, the catalyst prepared from [Ni(COD)2] and TPPTS was also active in the hydrocyanation of allylbenzene however, at low cyanide/nickel ratios isomerization to propenylbenzene became the main reaction path (Scheme 9.9) [5]. 

Optimization of reaction conditions was carried out with the hydrosoluble complex [(7i-allyl)Pd(TPPTS)2]Cl prepared from [(7i-allyl)PdCl]2 and two equivalent of TPPTS per Pd [54]. As low DS are expected, 1 is used as the limiting reactant (0.3 equiv./glucose unit). When the amount of co-solvent decreases, the conversion of 1 is lower but the catalyst is still active even in pure water (DS = 0.02) (Table 12) [53]. 

In a 100-mL Schlenk tube equipped with a magnetic stirrer, 1.95 equiv (4.83 g) of the sodium salt of tris(3-sulfonatophenyl)phosphine (TPPTS) dissolved in a minimum amount of water (ca. 5 mL) are added at room temperature to the solution of [NH2Me2] [Rh(CO)2Cl2] prepared as described in Section 21.K. The reaction is fast, with significant CO evolution. After 15 min, an IR spectmm of the solution shows a single vco band at 1982 cm. The yellow product is precipitated by adding 50 mL of cold ethanol, then collected by filtration on a Buchner funnel, washed with 150 mL of ethanol, and dried under vacuum. Yield 3.81 g (71%). 

A breakthrough in the hydroformylation of propene was achieved following the synthesis of the water soluble ligand tppts for the preparation of the RhH(CO)(tppts)3 catalyst345 which formed the basis for the development of the Ruhrchemie/Rhone-Poulenc two phase process. This process operates under mild reaction conditions giving excellent n/i ratios and easy separation of products from the catalyst by decantation with virtually no catalyst leaching. 

Typical reaction conditions of the RCH/RP process37,38,336 are T=120°C P=50 bar / =1.01 P/Rh=50-100 aqueous/organic phase=6 concentration of rhodium 10-1000 ppm pH of the aqueous phase 4-10. The RhH(CO)(tppts)3 catalyst345 is prepared in situ from rhodium-2-ethylhexanoate, for example, by addition of tppts in water. The process engineering is enormously simplified in comparison to classical oxo plants. Figure 1 shows the flowsheet of the RCH/RP oxo process.38,424... 

More recently, a palladium TPPTS complex was shown5,6 to catalyze carbonylations in aqueous media. The original method1 of preparation of... 

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