13406-29-6

Basic information

• Product Name: TRIS(4-TRIFLUOROMETHYLPHENYL)PHOSPHINE
• Synonyms: TRIS(P-TRIFLUOROMETHYLPHENYL)BENZENE;TRIS(P-TRIFLUOROMETHYLPHENYL)PHOSPHINE;TRIS(4-TRIFLUOROMETHYLPHENYL)PHOSPHINE;Phosphine, tris(alpha,alpha,alpha-trifluoro-p-tolyl)-;Trisptrifluoromethylphenylphosphineminpaleyellowpowder;Tris(p-trifluoromethylphenyl)phosphine,min.97%;Tris[4-(trifluoromethyl)phenyl]phosphine 98%;Tris[4-(trifluoromethyl)phenyl]phosphine98%
• CAS NO: 13406-29-6
• Molecular Formula: C₂₁H₁₂F₉P
• Molecular Weight: 466.28
• Product Categories: Ligand;organophosphorus ligand;Achiral Phosphine;Aryl Phosphine
• Mol File: 13406-29-6.mol
• Article Data: 17

Chemical Properties

• Melting Point: 70-75 °C
• Boiling Point: 382.8 °C at 760 mmHg
• Flash Point: 185.3 °C
• Appearance: Clear/Liquid
• Vapor Pressure: 1.01E-05mmHg at 25°C
• Storage Temp.: Inert atmosphere,Room Temperature
• Water Solubility: Insoluble in water.
• CAS DataBase Reference: TRIS(4-TRIFLUOROMETHYLPHENYL)PHOSPHINE(CAS DataBase Reference)
• NIST Chemistry Reference: TRIS(4-TRIFLUOROMETHYLPHENYL)PHOSPHINE(13406-29-6)
• EPA Substance Registry System: TRIS(4-TRIFLUOROMETHYLPHENYL)PHOSPHINE(13406-29-6)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-37/39
• WGK Germany: 3
• TSCA: No
• HazardClass: IRRITANT
• Hazardous Substances Data: 13406-29-6(Hazardous Substances Data)

Usage

Chemical Properties

white to light yellow crystal powde

Uses

Tris[4-(trifluoromethyl)phenyl]phosphine is a raw material and intermediate used in organic synthesis, pharmaceuticals and agrochemicals.

InChI:InChI=1/C21H12F9P/c22-19(23,24)13-1-7-16(8-2-13)31(17-9-3-14(4-10-17)20(25,26)27)18-11-5-15(6-12-18)21(28,29)30/h1-12H

Synthetic route

tris(4-trifluoromethylphenyl)phosphine oxide (13406-27-4) → tris(para-trifluoromethyl)phenyl phosphine (13406-29-6)

Conditions	Yield
With diisobutylaluminium hydride In cyclohexane at 72℃; for 14h;	93%
Stage #1: tris(4-trifluoromethylphenyl)phosphine oxide With trityl tetrakis(pentafluorophenyl)borate In (2)H8-toluene at 20℃; Glovebox; Inert atmosphere; Stage #2: With phenylsilane In (2)H8-toluene at 80℃; for 6h; Glovebox; Inert atmosphere; Sealed tube;	92%
With [AlH3(triethylamine)] In hexane at 20℃; for 0.166667h; Inert atmosphere; Schlenk technique;	88 %Chromat.
With hexylsilane; trifluorormethanesulfonic acid In toluene at 70℃; for 24h; Inert atmosphere; Sealed tube; chemoselective reaction;	>= 99 %Spectr.
With 2,6-dimethylpyridine; oxalyl dichloride; hydrogen; tris(2,6-difluorophenyl)borane triethylphosphine oxide In (2)H8-toluene at 130℃; under 3000.3 Torr; for 48h; Reagent/catalyst;	57 %Spectr.

p-trifluoromethylphenyl bromide (402-43-7) → tris(para-trifluoromethyl)phenyl phosphine (13406-29-6)

Conditions	Yield
Stage #1: p-trifluoromethylphenyl bromide With magnesium dihydride In diethyl ether at 20℃; for 1h; Stage #2: With phosphorus trichloride In diethyl ether at 20℃; for 1h;	72%
Stage #1: p-trifluoromethylphenyl bromide With magnesium In diethyl ether for 2h; Reflux; Schlenk technique; Inert atmosphere; Stage #2: With phosphorus trichloride In diethyl ether at 0℃; for 1h; Reflux; Schlenk technique; Inert atmosphere;	63%
With phosphorus trichloride 2) Et2O, reflux, 1h; Yield given. Multistep reaction;

(4-(trifluoromethyl)phenyl)zinc(II) bromide (198345-82-3) → tris(para-trifluoromethyl)phenyl phosphine (13406-29-6)

Conditions	Yield
With phosphorus trichloride In acetonitrile at 20℃; for 2h;	53%

aqueous sodium chloride + p-trifluoromethylphenyl bromide (402-43-7) + phosphorus trichloride (7719-12-2, 52843-90-0) → tris(para-trifluoromethyl)phenyl phosphine (13406-29-6)

Conditions	Yield
With hydrogenchloride; n-butyllithium In diethyl ether; hexane; water	35%

4-(trifluoromethyl)phenylmagnesium bromide (402-51-7) → tris(para-trifluoromethyl)phenyl phosphine (13406-29-6)

Conditions	Yield
With phosphorus trichloride

tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → tris(4-trifluoromethylphenyl)phosphine oxide (13406-27-4)

Conditions	Yield
With dihydrogen peroxide In dichloromethane; water at 20℃; for 3h; Glovebox; Inert atmosphere;	100%
With gold(III) complex supported on cellulose extracted from Carthamus tinctorius immobilized on nanofibrous phosphosilicate; air at 20℃; for 1h; Irradiation;	99%
With dihydrogen peroxide In dichloromethane; water for 0.75h; cooling;	97%

4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane (25015-63-8) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → C27H23BF9O2P

Conditions	Yield
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2 In benzene at 100℃; for 6h; Inert atmosphere; Sealed tube;	100%

7-azido-4-methyl-2H-chromen-2-one + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → 4 -methyl-7-((tris(4-(trifluoromethyl)phenyl)-λ5-phosphanylidene)amino)-2H-chromen-2-one

Conditions	Yield
In tetrahydrofuran at 20℃; for 1h; Inert atmosphere;	100%

dichloro(hydrotris(1-pyrazolyl)borate)(nitrido)osmium(IV) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → (hydrotris(1-pyrazolyl)borate)Os[NP(p-CF3C6H4)3]Cl2

Conditions	Yield
In dichloromethane under inert atm. soln. TpOs(N)Cl2 andphosphine ligand in CH2Cl2 was stirred for 1 h; soln. was concd., hexane was added, ppt. was washed with Et2O and recrystd. from CH2Cl2 and heptane; elem. anal.;	97%

chloro(1,5-cyclooctadiene)rhodium(I) dimer + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6)

Conditions	Yield
In acetone all manipulations under dry N2 atm.; 2 equiv. of P compd. added to soln.of Rh compd., stirred at room temp. (checked for completion by TLC); solvent removed in vac., isolated as crystalline solid; elem. anal.;	97%

copper(l) iodide (7681-65-4) + 2-(diphenylphosphaneyl)-4-methylpyridine (151131-87-2) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6)

Conditions	Yield
In dichloromethane at 20℃; for 12h; Inert atmosphere; Schlenk technique; Darkness;	97%

copper(l) iodide + 2-(diphenylphosphino)pyridine (37943-90-1) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → [(2-(diphenylphosphino)pyridine)(tris(4-trifluoromethylphenyl)phosphine)2Cu2I2]

Conditions	Yield
In dichloromethane at 20℃; for 12h; Inert atmosphere; Schlenk technique; Darkness;	96%

carbon dioxide (124-38-9) + 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (88284-48-4) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → 2-(tris(4-(trifluoromethyl)phenyl)phosphonio)benzoate

Conditions	Yield
With potassium fluoride; 18-crown-6 ether In tetrahydrofuran at 0 - 50℃; under 760.051 Torr; for 36h; Schlenk technique; Sealed tube;	96%

[RhCl(cis-cyclooctene)2]2 (63902-12-5, 12279-09-3) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → C84H48Cl2F36P4Rh2

Conditions	Yield
In toluene at 20℃; Inert atmosphere;	95.1%

+ tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → oxotrichlorobis(tris(p-(trifluoromethyl)phenyl)phosphine)rhenium(V)

Conditions	Yield
In dichloromethane stirring ReOCl3(As(C6H5)3)2 (0.33 mmol) and P(C6H4CF3)2 (0.66 mmol) in CH2Cl2 at room temp. for 27 h; concg. in vac.; addn. of heptane;; pptn.; filtering off, washing with heptane and drying in vac.; elem. anal.;;	95%

tetrafluoroboric acid diethyl ether (67969-82-8) + N-(1-methoxyethyl)phthalimide (22156-23-6) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6)

Conditions	Yield
Stage #1: tetrafluoroboric acid diethyl ether; tris(para-trifluoromethyl)phenyl phosphine In dichloromethane at 0 - 20℃; for 2h; Stage #2: N-(1-methoxyethyl)phthalimide With sodium bromide at 95℃; for 7h;	95%

[osmium(II)dichloride(η6-p-cymene)]2 + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → (p-cymene)OsCl2(P(p-CF3C6H4)3) (212556-61-1)

Conditions	Yield
In dichloromethane inert atmosphere; stirring soln. of Os-complex with 2 equivs. of phosphine for 60 min at room temp.; evapn., washing (hexane), collection (filtration), drying (vac.); elem. anal.;	92%

C12H20ClNOPtS + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → C31H26ClF9NPPt

Conditions	Yield
Inert atmosphere; Schlenk technique;	92%

potassium tetrachloroplatinate(II) (10025-99-7) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → cis-dichlorobis{tris(4-(trifluoromethyl)phenyl)phosphane}platinum(II) (92471-73-3, 92451-53-1)

Conditions	Yield
In ethanol; water addn. of aq. soln. of K2(PtCl4) to hot ethanolic soln. of phosphane; stirring at room temp. for 25 h; filtering, washing with water, ethanol and ether, drying in vac. at room temp.;	91%

tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → bis(4-trifluoromethylphenyl)phosphonium bromide

Conditions	Yield
With phosphorus tribromide; iron (III) bromide In tetrachloromethane at 0 - 80℃; for 10h;	91%

chloro(1,5-cyclooctadiene)(pentamethylcyclopentadiene)ruthenium(II) (92390-26-6) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → (η(5)-C5Me5)RuCl(P(p-CF3C6H4)3)2 (172220-62-1)

Conditions	Yield
In tetrahydrofuran Ar or N2-atmosphere; 2 equivs. of phosphine, stirring overnight; evapn., addn. of hexane, stirring for 20 min, collection (filtration), washing (hexanes), drying (vac.); elem. anal.;	90%
In tetrahydrofuran Ar or N2-atmosphere; 30°C; not sepd., enthalpy of reaction determined;

C18H22Cl2F2N2Pt2 + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → C30H23ClF10NPPt

Conditions	Yield
In dichloromethane at 20℃; for 1.5h;	90%

Fe2(CO)6[μ-SCCHCHC(CH3)CHCS] + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → C33H18F9Fe2O5PS2

Conditions	Yield
With trimethylamine-N-oxide In dichloromethane; acetonitrile at 20℃; for 1h;	90%

iodobenzene (591-50-4) + [RhCl(cis-cyclooctene)2]2 (63902-12-5, 12279-09-3) + cesium pivalate + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → [(p-CF3-C6H4)3P]2 bis(pivalate) rhodium(I)Ph (851530-55-7)

Conditions	Yield
In 1,4-dioxane in dioxane at 120°C;	89%

1,1'-bis-(diphenylphosphino)ferrocene (12150-46-8) + tetrakis(acetonitrile)palladium(II) tetrafluoroborate (21797-13-7) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → [Pd(dppf)(P(p-C6H4CF3)3)][BF4]2

Conditions	Yield
In acetone; benzene for 0.166667h; Inert atmosphere; Glovebox;	88%

(tetrahydrothiophene)gold(I) chloride (39929-21-0) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → [tris(para(trifluoromethyl)phenyl)phosphine]gold(I) chloride (385815-83-8)

Conditions	Yield
In dichloromethane at 20℃; for 1h;	87%
In dichloromethane

copper(l) iodide (7681-65-4) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → C84H48Cu4F36I4P4

Conditions	Yield
In dichloromethane for 12h; Schlenk technique;	87%

(cyclooctadienyl)(cyclopentadienyl)ruthenium chloride + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → (η(5)-C5H5)RuCl(P(p-CF3C6H4)3)2 (172220-60-9)

Conditions	Yield
In tetrahydrofuran Ar or N2-atmosphere; 2 equivs. of phosphine, stirring overnight; evapn., addn. of hexane, stirring for 20 min, collection (filtration), washing (hexanes), drying (vac.); elem. anal.;	86%
In tetrahydrofuran Ar or N2-atmosphere; 30°C; not sepd., enthalpy of reaction determined;

[(η(5)-C5H5)Re(NO)(CO)(MeCN)]BF4 (92269-93-7) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → [(μ5-C5H5)Re(NO)(CO)(P(4-C6H4CF3)3)]BF4 (344800-64-2)

Conditions	Yield
In butanone all manipulations under dry N2 atm.; EtCOMe added to Re complex and the phosphane, refluxed for 46 h; allowed to cool, hexane added, filtered, washed with pentane, dried in vac., elem. anal.;	85%

acetylacetonatodicarbonylrhodium(l) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → Rh(CO)((CH3CO)2CH)(P(C6H4CF3)3) (201140-99-0)

Conditions	Yield
In dichloromethane byproducts: CO; Ar or N2-atmosphere, 30°C; elem. anal.;	85%

hydrogen tetrachloroaurate(III) tetrahydrate + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → [tris(para(trifluoromethyl)phenyl)phosphine]gold(I) chloride (385815-83-8)

Conditions	Yield
With β-thiodiglucol In methanol; dichloromethane; water under N2 or Ar using Schlenk techniques; in the dark; soln. of HAuCl4*4H2O dissolved in H2O/MeOH; cooled; soln. of β-thiodiglucol in MeOH added with stirring; soln. of org. ligand in MeOH/CH2Cl2 added; mixt. stirred overnight; MeOH added; solvent removed (vac.); recrystd. (CH2Cl2/hexane); dried (vac.);	85%

(1,5-cyclooctadiene)dimethylplatinum(II) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → cis-[Me2Pt(P(p-CF3C6H4)3)2] (220556-61-6)

Conditions	Yield
In not given byproducts: cyclooctadiene; 2 equiv. of phosphine; elem. anal.;	84%

1-Iodo-perfluorodecane (423-62-1) + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → (perfluorodecyl)bis(4-(trifluoromethyl)phenyl)phosphine

Conditions	Yield
In chloroform-d1 at 20℃; for 30h; Irradiation; Sealed tube; Inert atmosphere;	84%
at 15 - 25℃; for 30h; Irradiation; Sealed tube; Inert atmosphere;	61 %Spectr.

μ-(1,2-ethanedithilato)diironhexacarbonyl + tris(para-trifluoromethyl)phenyl phosphine (13406-29-6) → C28H16F9Fe2O5PS2

Conditions	Yield
With trimethylamine-N-oxide In dichloromethane; acetonitrile at 20℃; for 1h;	84%

Upstream product

• 402-43-7 p-trifluoromethylphenyl bromide 
• 402-51-7 4-(trifluoromethyl)phenylmagnesium bromide 
• 198345-82-3 (4-(trifluoromethyl)phenyl)zinc(II) bromide 
• 13406-27-4 tris(4-trifluoromethylphenyl)phosphine oxide 
• 7719-12-2 phosphorus trichloride 
• 455-13-0 4-Iodobenzotrifluoride 
• 98-56-6 4-chlorobenzotrifluoride 

Downstream Products

• 13406-18-3 N-phenyl-P,P,P-trisphospha-λ⁵-azene 
• 120360-41-0 methyltris<4-(trifluoromethyl)phenyl>phosphonium tosylate 
• 73116-96-8 4,4,5,5-Tetramethyl-2,2,2-tris-(4-trifluoromethyl-phenyl)-2λ⁵-[1,3,2]dioxaphospholane 
• 13406-27-4 tris(4-trifluoromethylphenyl)phosphine oxide 
• 13406-25-2 4-Trifluormethyl-N--anilin 
• 172220-60-9 (η(5)-C5H5)RuCl(P(p-CF3C6H4)3)2 
• 112088-20-7 {(C₁₀H₈N₂)2{P(C₆H₄CF₃)3}RuCl}⁽¹⁺⁾*ClO₄^(1-)=C₄₁H₂₈Cl₂F₉O₄N₄PRu 
• 121354-22-1 Pd(π-chloranilato)(P(Ph-p-CF3)3)2 
• 117228-43-0 (η-CH3C5H4)Fe(CO){P(p-CF3Ph)3}COMe 
• 117228-09-8 (η-Cp)(CO)(COMe)Fe(P(p-CF3C6H4)3) 
• 92471-73-3 cis-dichlorobis{tris(4-(trifluoromethyl)phenyl)phosphane}platinum(II) 
• 344800-64-2 [(μ5-C5H5)Re(NO)(CO)(P(4-C6H4CF3)3)]BF4 
• 173178-33-1 Cp(*)Ir(CO)[P(p-C₆H₄CF₃)3] 
• 409318-73-6 [CH3(O)Re(η2-o-SCH2C6H4S)((4-CF3C6H4)3P)] 

Relevant articles and documents

A Lewis Base Nucleofugality Parameter, NFB, and Its Application in an Analysis of MIDA-Boronate Hydrolysis Kinetics

The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured. Parameterization of these rates has enabled the development of a nucleofugality scale (NFB), shown to quantify and predict the leaving group ability of a range of other Lewis bases. Additivity observed across a number of series R′3-nRnX (X = P, N; R′ = aryl, alkyl) has allowed the formulation of related substituent parameters (nfPB, nfAB), providing a means of calculating NFB values for a range of Lewis bases that extends far beyond those experimentally derived. The utility of the nucleofugality parameter is explored by the correlation of the substituent parameter nfPB with the hydrolyses rates of a series of alkyl and aryl MIDA boronates under neutral conditions. This has allowed the identification of MIDA boronates with heteroatoms proximal to the reacting center, showing unusual kinetic lability or stability to hydrolysis.

The Trityl-Cation Mediated Phosphine Oxides Reduction

Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C+[B(C6F5)4]? as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes. (Figure presented.).