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| verifiedrevid = 423355784 |
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| ImageFile = TPPTS.png |
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| ImageFile = TPPTS.png |
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| PIN= Trisodium 3,3′,3′′-phosphanetriyltri(benzene-1-sulfonate) |
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| Name = 3,3′,3′′-Phosphinidynetris(benzenesulfonic acid) trisodium salt |
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| OtherNames = Tris(3-sulfophenyl)phosphine trisodium salt |
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| OtherNames = {{ubl|Trisodium 3-bis(3-sulfonatophenyl)phosphanylbenzenesulfonate|3,3′,3′′-Phosphanetriyltris(benzenesulfonic acid) trisodium salt| Tris(3-sulfophenyl)phosphine trisodium salt}} |
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| Section1 = {{Chembox Identifiers |
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| Section1 = {{Chembox Identifiers |
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| CASNo_Ref = {{cascite|correct|??}} |
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| CASNo = 63995-70-0 |
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| CASNo = 63995-70-0 |
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| PubChem = 4348292 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 3552062 |
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| EINECS = 264-596-6 |
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| SMILES = c1cc(cc(c1)S(=O)(=O))P(c2cccc(c2)S(=O)(=O))c3cccc(c3)S(=O)(=O)... |
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| StdInChI_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChI = 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 |
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| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChIKey = MYAJTCUQMQREFZ-UHFFFAOYSA-K |
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| Section2 = {{Chembox Properties |
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| Section2 = {{Chembox Properties |
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| C=18 | H=12 | O=9 | P=1 | S=3 | Na=3 |
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| Formula = P(C<sub>6</sub>H<sub>4</sub>SO<sub>3</sub>Na)<sub>3</sub> |
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| MolarMass = 568.42 g/mol |
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| Appearance = White microcrystalline solid |
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| Appearance = White microcrystalline solid |
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| Solubility = Soluble in water |
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| Solubility = Soluble |
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| Section3 = {{Chembox Hazards |
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| Section3 = {{Chembox Hazards |
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| RPhrases = {{R36/37/38}} |
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| GHSPictograms = {{GHS07}} |
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| GHSSignalWord = warning |
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| SPhrases = {{S26}} |
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| HPhrases = {{HPhrases|H315|H319|H335}} |
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| PPhrases = {{PPhrases|P302 + P352|P305 + P351 + P338|P337 + P313|P304 + P340|P312|P280|P332 + P313}} |
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| GHS_ref = <ref>GHS: (18 Feb 2021)</ref> |
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'''3,3′,3′′-Phosphanetriyltris(benzenesulfonic acid) trisodium salt''' (abbreviated '''TPPTS'''), is an organic compound that is also known as sodium triphenylphosphine trisulfonate. The compound has the formula P(C<sub>6</sub>H<sub>4</sub>SO<sub>3</sub>Na)<sub>3</sub>. This white solid is an unusual example of a water-soluble ]. Its complexes are also water-soluble.<ref>{{cite book |doi=10.1002/9780470132630.ch3|title=Tris[tris(Sodium m-Sulfonatophenyl)Phosphino]Palladium(0) Enneahydrate|series=Inorganic Syntheses|year=1998|last1=Papadogianakis|first1=G.|last2=Maat|first2=L.|last3=Sheldon|first3=R. A.|chapter=Tris[tris(Sodium m -sulfonatophenyl)-Phosphino]Palladium(0) Enneahydrate |pages=25–29|volume=32|isbn=978-0-470-13263-0 }}</ref> Its complex with ] is used in the industrial production of ].<ref>{{cite book |author1=Herrmann, W.A. |author2=Kohlpaintner, C.W. |chapter=Syntheses of Water-Soluble Phosphines and their Transition Metal Complexes | year = 1998 | title = Inorganic Syntheses | volume = 32 | pages = 8–25 | isbn = 0-471-24921-1 | doi = 10.1002/9780470132630.ch2}}</ref> |
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'''3,3′,3′′-Phosphinidynetris(benzenesulfonic acid) trisodium salt''' (abbreviated '''TPPTS''' when isolated and '''tppts''' as a ]), is an organic compound that is also known as sodium triphenylphosphine trisulfonate. The compound has the formula P(C<sub>6</sub>H<sub>4</sub>SO<sub>3</sub>Na)<sub>3</sub>. This white microcrystalline solid is an unusual example of a water-soluble ]. Its complex with ] is used in the industrial production of ].<ref>{{cite journal | author = Herrmann, W.A.; Kohlpaintner, C.W. | year = 1998 | title = Synthesis of Water-Soluble Phosphines and Their Transition Metal Complexes | journal = ] | volume = 32 | pages = 8–25 | isbn = 0-471-24921-1 | publisher = John Wiley & Sons | location = New York | oclc = 219831361 | doi = 10.1002/9780470132630.ch2}}</ref> |
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==Synthesis== |
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==Synthesis== |
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Tppts is synthesized by ] of ]. The sulfonation occurs at one meta-position of each of the three phenyl rings. The sulfonation agent is ], 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: |
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TPPTS is synthesized by ] of ]. The sulfonation occurs at one meta-position of each of the three phenyl rings. The sulfonation agent is ], a solution of sulfur trioxide in sulfuric acid. Immediately upon dissolving in the oleum, the phosphine is protonated. It is the phosphonium salt that undergoes the sulfonation which explains its meta selectivity: |
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:HP(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub><sup>+</sup> + 3 SO<sub>3</sub> → <sup>+</sup> |
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:HP(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub><sup>+</sup> + 3 SO<sub>3</sub> → <sup>+</sup> |
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:<sup>+</sup> + 4 N(C<sub>8</sub>H<sub>17</sub>)<sub>3</sub> → <sub>3</sub> + <sup>+</sup> |
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:<sub>3</sub> + 3 NaOH → P(C<sub>6</sub>H<sub>4</sub>SO<sub>3</sub>Na)<sub>3</sub> + 3 N(C<sub>8</sub>H<sub>17</sub>)<sub>3</sub> + 3 H<sub>2</sub>O |
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As a ], tppts is stronger than triphenylphosphine. |
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As a ], tppts is stronger than triphenylphosphine. |
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==TPPTS at the origin of two-phase homogeneous catalysis== |
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TPPTS was first synthesized in 1975 by ] who was an engineer at Rhône-Poulenc 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.<ref>E.Kuntz Procédé d’hydroformylation des oléfines FR 2 314 910 (20 06 1975) and FR 2 349 562 (29 04 1976) also published as US 4,248,802</ref> Using TPPTS, allowed him to prepare water-soluble complexes with Rh(I), Ni(0), Pd(0). E.G. Kuntz patented several two-phase homogeneous catalytic reactions: |
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*hydroformylation of propylene with Rh(I) TPPTS,<ref>E.Kuntz Procédé d’hydroformylation des oléfines FR 2 314 910 (20 06 1975) and FR 2 349 562 (29 04 1976) also published as US 4,248,802</ref> later leading to the Ruhrchemie / Rhône-Poulenc process. |
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*hydrocyanation of olefins and dienes with Ni(0) TPPTS.<ref>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</ref> |
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*] of butadiene to 2.7 octadiene -1-ol with Pd(0) TPPTS.<ref>E.Kuntz Procédé de télomérisation de diènes FR 2 366 237 (27 07 1976) also published as US 4,142,060</ref> |
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*The Rh(I) TPPTS catalyst was later used by D.Morel to synthesize geranylacetone from myrcene and farnesylacetone from beta-farnesene which are intermediates in the synthesis of vitamin E.<ref>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</ref> This process was industrialized by Rhône-Poulenc in 1988. |
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The industrial use of TPPTS and homogeneous biphasic catalysis has been reviewed.<ref>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}}</ref><ref>(en) B. Cornils et É.G. Kuntz, « Hydroformylation. Development of commercial biphasic oxo synthesis », Aqueous-Phase Organometallic Catalysis, 1998, p. 271–282.</ref><ref>(en) É.G. Kuntz, « Hydrosoluble ligands for a new technology », Aqueous Organometallic Chemistry and Catalysis, 1995, p. 177-181.</ref><ref>{{cite journal|title=Introducing TPPTS and related ligands for industrial biphasic processes|first1=Boy|last1=Cornils |first2=Emile G. |last2=Kuntz|doi=10.1016/0022-328X(95)05820-F|volume=502|year=1995|page=177-186|journal=Journal of Organometallic Chemistry|issue=1–2 }}</ref> |
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==Uses in hydroformylation== |
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==Uses in hydroformylation== |
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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 ] of ] by Ruhrchemie. Hydroformylation, also known as ], is the reaction of an ] with ] and ]. Traditionally, hydroformylation is catalyzed by rhodium and cobalt complexes in nonaqueous solution.<ref>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}}</ref> |
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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 ] of ] by the Ruhrchemie / Rhône-Poulenc process. Hydroformylation, also known as ], is the reaction of an ] with ] and ]. Traditionally, hydroformylation is catalyzed by rhodium or cobalt complexes in nonaqueous solution<ref>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}}</ref> The industrial use of Tppts and homogeneous biphasic catalysis were mostly ignored in academic research until E.G. Kuntz published a review of its previous work in 1987.<ref> É.G. Kuntz, « Homogeneous catalysis in water », Chemtech, 1987, p. 570-575</ref> Then, from 1990, use of TPPTS was rapidly become popular with thousand of citations in 2004. |
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==References== |
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==References== |