TPPTS

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TPPTS
TPPTS.png
Names
Preferred IUPAC name
Trisodium 3,3′,3′′-phosphanetriyltri(benzene-1-sulfonate)
Other names
  • Trisodium 3-bis(3-sulfonatophenyl)phosphanylbenzenesulfonate
  • 3,3′,3′′-Phosphanetriyltris(benzenesulfonic acid) trisodium salt
  • Tris(3-sulfophenyl)phosphine trisodium salt
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.058.706 Edit this at Wikidata
  • InChI=1S/C18H15O9PS3.3Na/c19-29(20,21)16-7-1-4-13(10-16)28(14-5-2-8-17(11-14)30(22,23)24)15-6-3-9-18(12-15)31(25,26)27;;;/h1-12H,(H,19,20,21)(H,22,23,24)(H,25,26,27);;;/q;3*+1/p-3 ☒N
    Key: MYAJTCUQMQREFZ-UHFFFAOYSA-K ☒N
  • c1cc(cc(c1)S(=O)(=O)[O-])P(c2cccc(c2)S(=O)(=O)[O-])c3cccc(c3)S(=O)(=O)[O-].[Na+].[Na+].[Na+]
Properties
C18H12Na3O9PS3
Molar mass 568.41 g·mol−1
Appearance White microcrystalline solid
Soluble
Hazards
GHS labelling:[1]
GHS07: Exclamation mark
Signal word
 Warning
H315, H319, H335
P280, P302+P352, P304+P340, P305+P351+P338, P312, P332+P313, P337+P313
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N  (what is checkY☒N ?)
Infobox references

3,3′,3′′-Phosphanetriyltris(benzenesulfonic acid) trisodium salt (abbreviated TPPTS when isolated and tppts as a ligand), is an organic compound that is also known as sodium triphenylphosphine trisulfonate. The compound has the formula P(C6H4SO3Na)3. This white solid is an unusual example of a water-soluble phosphine. Its complexes are also water-soluble.[2] Its complex with rhodium is used in the industrial production of butyraldehyde.[3]

Synthesis[]

TPPTS is synthesized by sulfonation of triphenylphosphine. The sulfonation occurs at one meta-position of each of the three phenyl rings. The sulfonation agent is oleum, a solution of sulfur trioxide in sulfuric acid. The resulting trisulfonic acid is then treated with triisooctylamine and sodium hydroxide. Immediately upon dissolving in the reaction medium, the phosphine is protonated. It is the phosphonium salt that undergoes the sulfonation:

HP(C6H5)3+ + 3 SO3 → [HP(C6H4SO3H)3]+
[HP(C6H4SO3H)3]+ + 4 N(C8H17)3 → [HN(C8H17)3]3[P(C6H4SO3)3] + [HN(C8H17)3]+
[HN(C8H17)3]3[P(C6H4SO3)3] + 3 NaOH → P(C6H4SO3Na)3 + 3 N(C8H17)3 + 3 H2O

As a Lewis base, tppts is stronger than triphenylphosphine.

TPPTS at the origin of two-phase homogeneous catalysis[]

TPPTS was synthesized in 1975 by E.G Kuntz with the aim of carrying out a two-phase homogeneous catalysis in which the aqueous phase catalyst could be easily separated from the reaction products and recycled.[4] Using TPPTS, water-soluble complexes were reported for Rh(I), Ni(0), Pd(0). Several patents were issued:

  • hydroformylation of propylene,[5] leading to the Ruhrchemie process.
  • hydrocyanation of olefins and dienes.[6]
  • telomerization of butadiene to 2.7 octadiene -1-ol by Pd.[7]
  • synthesis of geranylacetone from myrcene and of farnesylacetone from beta-farnesene which are intermediates in the synthesis of vitamin E.[8] This process was industrialized by Rhône-Poulenc in 1988.

The industrial use of Tppts and homogeneous biphasic catalysis has been reviewed.[9]

Uses in hydroformylation[]

Complexes of Tppts are very soluble in water, which is the basis of its industrial application. Tppts-based rhodium catalysts were introduced in 1984 for a two-phase hydroformylation of propene by Rhône-Poulenc / Ruhrchemie (Patent's inventor society / Patent's exploiting society) . Hydroformylation, also known as oxo synthesis, is the reaction of an alkene with carbon monoxide and hydrogen. Traditionally, hydroformylation is catalyzed by rhodium and cobalt complexes in nonaqueous solution [10]

References[]

  1. ^ GHS: Alfa Aesar 039538 (18 Feb 2021)
  2. ^ Papadogianakis, G.; Maat, L.; Sheldon, R. A. (1998). "Tris[tris(Sodium m-Sulfonatophenyl)Phosphino]Palladium(0) Enneahydrate". Inorganic Syntheses. 32: 25–29. doi:10.1002/9780470132630.ch3.
  3. ^ Herrmann, W.A.; Kohlpaintner, C.W. (1998). "Synthesis of Water-Soluble Phosphines and Their Transition Metal Complexes". Inorganic Syntheses. 32: 8–25. doi:10.1002/9780470132630.ch2. ISBN 0-471-24921-1.
  4. ^ E.Kuntz Procédé d’hydroformylation des oléfines FR 2 314 910 (20 06 1975) also published as US 4,248,802
  5. ^ E.Kuntz Procédé d’hydroformylation des oléfines FR 2 314 910 (20 06 1975) also published as US 4,248,802
  6. ^ E.Kuntz Procédé d’hydrocyanation de composés organiques insaturés comportant au moins une double liaison éthylénique FR 2 338 253 (13 01 1976) also published as US 4,087,452
  7. ^ E.Kuntz Procédé de télomérisation de diènes FR 2 366 237 (27 07 1976) also published as US 4,142,060
  8. ^ D. Morel Procédé d’addition sélective d’un composé à méthylène actif sur un diène conjugué substitué et nouveaux composés résultants FR 2 486 525 (10 07 1980) also published as US 4,460,786
  9. ^ Cornils, B.; Kuntz, E. G. (2004). "Development of the commercial biphasic oxo synthesis". Aqueous-Phase Organometallic Catalysis (2nd Edition). pp. 351–363.
  10. ^ Boy Cornils, Richard W. Fischer, Christian Kohlpaintner "Butanals" in Ullmann's Encyclopedia of Industrial Chemistry, 2000, Wiley-VCH, Weinheim. doi:10.1002/14356007.a04_447
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