Herstellung von hydrolysestabilen Ammoniumsalzen sulfonierter Phosphite und deren Einsatz als Cokatalysatoren in der rhodiumkatalysierten Hydroformylierung

Abstract

Hydrolytic Stable Ammonium Salts of Sulfonated Organic Phosphites and their Use as Cocatalysts in the Rhodium‐catalyzed Hydroformylation of Olefins Ammonium salts of sulfonated organic phosphites, which are resistant to hydrolysis, have been prepared by transesterification of triphenylphosphite with mono‐ammonium salt of p‐hydroxyphenylsulfonic acid in yields between 66 and 76%. A mixture containing triisooctylammonium salts of sulfonated triphenylphosphite [TPPp‐SO3HN(i‐octyl)3] was submitted to a test for stability to hydrolysis. The time required for hydrolysis of 7.4% of the TPPp‐SO3HN(i‐octyl)3 was 3 hours under drastic conditions. Triphenylphosphite was in the same test hydrolyzed quantitatively within three hours. Tetradec‐1‐ene was hydroformylated by means of the catalytic systems consisting of rhodium‐2‐ethylhexanoate with either TPPp‐SO3HN(i‐octyl)3, triphenylphosphite (TPPp) or triphenylphosphine (TPP) at 125°C, 0.6 MPa and a rhodium concentration of 50 ppm. Higher reaction selectivities for linear aldehydes were achieved with the rhodium/TPPp‐SO3HN(i‐octyl)3 catalytic system. Reaction rates increased with the Rh/TPPp‐SO3HN(i‐octyl)3 catalyst at lower temperature (110°C). Using this catalyst at 110°C, higher yields are achieved than with the Rh/TPP or Rh/TPPp catalysts. Hex‐1‐ene was hydroformylated by using the catalytic systems Rh4(CO)12 with TPPp‐SO3HN(i‐octyl)3, Rh4(CO)12 TPP or Rh4 (CO)12 with TPPp at 125°C, 2,5 MPa and a rhodium concentration of 20 ppm. This confirms the above experiments which indicated that higher linear: branched aldehyde ratios were obtained with the rhodium/TPPp‐SO3HN(i‐octyl)3 catalyst.

A water-soluble phosphite derived from sulfonated calix[4]arene. The remarkable stability of its rhodium complexes and two phase hydroformylation studies

“…The hydrophilic phosphite L c was made according to the route shown in Scheme 1. Treatment of the rigorously dried trioctylammonium salt of the commercially available calix [4]arene tetrasulfonic acid with P(NMe 2 ) 3 in CH 2 Cl 2 followed by bubbling gaseous NHMe 2 through the solution gave a white precipitate which was assigned to the six-coordinate phosphorus species 1 ( 31 P NMR in D 2 O, d À124.5 1 J(PH) 730 Hz) from the close similarity of its 31 P NMR data to the analogous nonsulfonated species. 6 Solid 1 could be stored for weeks without change but in water, 1 converted over a period of 1 hour to phosphite L c as shown by its characteristic 31 P chemical shift of 113.5 ppm (cf.…”

“…1,2 Triaryl phosphites are excellent ancillary ligands for Rh-catalysed hydroformylation 3 but the kinetic instability of P-OR bonds to hydrolysis would appear to preclude making water-soluble sulfonated phosphites with any useful lifetime. Indeed Fell et al 4 showed that a mixture of sulfonated triphenylphosphites (TPOPS) (as tri-isooctylammonium salts) completely decompose in aqueous acetone after 24 h and Karakhanov et al 5 also reported that a polyether phosphite rapidly decomposed in the presence of water.…”

“…Phosphite ligands derived from calix [4]arene have been extensively studied [6][7][8] and we reported 7 that phosphites L a and L b are stable to hydrolysis under conditions in which P(OPh) 3 is rapidly hydrolysed. We now report the synthesis of phosphite L c derived from sulfonated calix [4]arene and show that its complexes are sufficiently stable in water to allow their application in two-phase catalysis.…”

“…

The reaction of tetrasulfonated calix [4]arene (trioctylammonium salt) with P(NMe 2 ) 3 followed by treatment with gaseous NMe 2 H gave a zwitterionic six-coordinate phosphorus(V) species 1 containing a P(H)(NHMe 2 ) group which can be stored for months without decomposition. In water, 1 loses NHMe 2 and rearranges to form the water soluble phosphite L c .

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Design of Ionic Phosphites for Catalytic Hydrocyanation Reaction of 3‐Pentenenitrile in Ionic Liquids†

“…[16] A cationic phosphinite obtained by reaction of trimethyloxonium tetrafluoroborate with an aminophosphinite (Scheme 3) was prepared in situ and directly reacted with rhodium in a reaction of catalytic asymmetric hydrogenation. [21] The only cationic phosphite described in the literature was obtained by reaction of methyl iodide with the tris-[3-(N,N-dimethylamino)-phenyl] phosphite to form the ammonium compound (Scheme 4). [25] This compound was not characterized further than the determination of its melting point.…”