Surfactant phosphines

Monflier, E. Bourdauducq, P. Couturier, J.L. Kervennal, J. Mortreux, A. (1995) Highly efficient telomerization of butadiene into octadienol in a micellar system a judicious choice of the phosphine/surfactant combination, Appl Catal A - Gen., 131,167-78. 

The industrially used homogeneous catalysts for the hydroformylation of higher molecular olefins into aldehydes, which are hydrogenated to the corresponding surfactant alcohols, are cobalt carbonyl [47] or cobalt carbonylItert-phosphine complexes [48]. 

There are many parallels between phosphates and sulfates of aliphatic alcohols. Both types of surfactants contain ester bonds undergoing hydrolysis in acid solutions. In that case the starting materials are received once more. By dry heating of the salts above a temperature of 140°C destruction will occur forming the corresponding alkenes and an inorganic acid salt. In the same way as sulfonic and sulfinic acids are formed by C-S bonds, C-P bonds lead to phosphonic and phosphinic acids. 

Colorless phosphate ester surfactants were also prepared by treating P4O,0 with an organic OH-containing compound in the presence of a phosphinic acid color inhibitor, e.g., bis(hydroxymethyl)phosphinic acid color inhibitor. Thus, 558 parts dodecanol containing 2.4 parts of phosphinic acid color inhibitor was treated with 142 parts P4O10 at 100-135°C. The phosphate ester surfactant had a VCS color value of 1, whereas a sample prepared without the color inhibitor had a VCS color value of 5. Twenty-eight similar surfactants were prepared using various alcohols and alcohol-alkylene oxide condensates [22]. 

Hydroaminomethylation of alkenes occurred to give both n- and /. so aliphatic amines catalyzed by [Rh(cod)Cl]2 and [Ir(cod)Cl]2 with TPPTS in aqueous NH3 with CO/H2 in an autoclave. The ratio of n-and /.soprimary amines ranged from 96 4 to 84 16.178 The catalytic hydroaminomethylation of long-chain alkenes with dimethylamine can be catalyzed by a water-soluble rhodium-phosphine complex, RhCl(CO) (Tppts)2 [TPPTS P(m-C6H4S03Na)3], in an aqueous-organic two-phase system in the presence of the cationic surfactant cetyltrimethy-lammonium bromide (CTAB) (Eq. 3.43). The addition of the cationic surfactant CTAB accelerated the reaction due to the micelle effect.179... 

The effect of surfactant on enantioselective hydrogenation has been thoroughly investigated. Rhodium complexes of phosphinated glucopyranosides were used for hydrogenation of prochiral dehydroaminoacid derivatives in aqueous systems in the presence of sodium dodecylsulfate (SDS)... 

Oheme and co-workers investigated335 in an aqueous micellar system the asymmetric hydrogenation of a-amino acid precursors using optically active rhodium-phosphine complexes. Surfactants of different types significantly enhance both activity and enantioselectivity provided that the concentration of the surfactants is above the critical micelle concentration. The application of amphiphilized polymers and polymerized micelles as surfactants facilitates the phase separation after the reaction. Table 2 shows selected hydrogenation results with and without amphiphiles and with amphiphilized polymers for the reaction in Scheme 61.335... 

Greater durability of the colloidal Pd/C catalysts was also observed in this case. The catalytic activity was found to have declined much less than a conventionally manufactured Pd/C catalyst after recycling both catalysts 25 times under similar conditions. Obviously, the lipophilic (Oct)4NCl surfactant layer prevents the colloid particles from coagulating and being poisoned in the alkaline aqueous reaction medium. Shape-selective hydrocarbon oxidation catalysts have been described, where active Pt colloid particles are present exclusively in the pores of ultramicroscopic tungsten heteropoly compounds [162], Phosphine-free Suzuki and Heck reactions involving iodo-, bromo-or activated chloroatoms were performed catalytically with ammonium salt- or poly(vinylpyrroli-done)-stabilized palladium or palladium nickel colloids (Equation 3.9) [162, 163],... 

Fluorinated phosphinic and phosphonic acid derivatives Perfluoro derivatives of alkyl phosphonic acid CnF2n+1-P(0)(0H)2 and alkyl phosphinic acid CnF2n+i(CmF2m+1)-P(0)0H (n = m or n m) shown with their general structural formulae in Fig. 2.11.29(1) and (II) were examined by negative ESI- and APCI-FIA-MS. These anionic surfactant compounds contained perfluoro alkyl chains [2,22,25]. By analogy with their behaviour in the TSI-FIA-MS(—) process [25], the phosphonic acid formed [M — H] ions at m/z 399 and 499... 

The surface tensions of some fatty-acid phosphates have been determined228 and the surfactant properties of perfluoroalkanesulphonamidoalkanephosphonic acid and corresponding phosphinic acid derivatives studied.229... 

The use of surfactants in hydrogenation and hydroformylation immediately followed the practical implementation of the original idea of aqueous biphasic catalysis [57, 118]. Not only the effect of well-known tenzides (SDS, CTAB, etc.) was studied, but new amphiphilic phosphine... 

Amphiphilic tertiary phosphines have their phosphorus donor atom located somewhere in the hydrophobic part of the molecule and should have at least one long alkyl or alkyl-aryl chain carrying a polar head group (Scheme 4. 10). Some of them, such as the sulfonated derivatives, are quite well soluble in water, others, such as Ph2P(CH) COOH (n = 3, 5, 7, 9, 11) are practically insoluble, however, can be easily solubilized with common surfactants (SDS, CTAB etc.). 

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