Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
Hydrolytic Stable Ammonium Salts of Sulfonated Organic Phosphites and their Use as Cocatalysts in the Rhodium-catalyzed Hydroformylation of OlefinsAmmonium 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.
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