4023-53-4

Basic information

• Product Name: TRIS(2-CYANOETHYL)PHOSPHINE
• Synonyms: TRIS(2-CYANOETHYL)PHOSPHINE;AURORA KA-1114;TRIS(2-CYANOETHYL)PHOSPHINE 92+%;Tris(2-cyanoethyl)phosphine,94%;Tris(2-cyanoethyl)phosphine,min.99%;Tris(2-cyanoethyl)phosphine, min. 99%;3,3',3''-Phosphinetriyltris(propiononitrile);3,3',3''-Phosphinidynetris(propiononitrile)
• CAS NO: 4023-53-4
• Molecular Formula: C₉H₁₂N₃P
• Molecular Weight: 193.19
• EINECS: 223-687-0
• Product Categories: Tertiary Phosphines;organophosphine ligand
• Mol File: 4023-53-4.mol
• Article Data: 4

Chemical Properties

• Melting Point: 97-98°C
• Boiling Point: 235°C 0,9mm
• Flash Point: 235°C/0.9mm
• Appearance: white/crystal
• Vapor Pressure: 1.71E-07mmHg at 25°C
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• Water Solubility: Soluble in DMSO, and DMF. Insoluble in water.
• Sensitive: Air & Moisture Sensitive
• CAS DataBase Reference: TRIS(2-CYANOETHYL)PHOSPHINE(CAS DataBase Reference)
• NIST Chemistry Reference: TRIS(2-CYANOETHYL)PHOSPHINE(4023-53-4)
• EPA Substance Registry System: TRIS(2-CYANOETHYL)PHOSPHINE(4023-53-4)

Safety Data

• Hazard Codes: Xi
• Statements: 20/21/22-36/37/38
• Safety Statements: 36/37/39-45-36-26
• RIDADR: UN3464
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 4023-53-4(Hazardous Substances Data)

Usage

Uses

Tris(2-cyanoethyl)phosphine is used to produce 3,3',3''-phosphanetriyl-tri-propionic acid and hydrochloride by heating. It will need reagent conc. aq. HCl with reaction.

InChI:InChI=1/C9H12N3P/c10-4-1-7-13(8-2-5-11)9-3-6-12/h1-3,7-9H2

Synthetic route

acrylonitrile (107-13-1) → bis(2-cyanoethyl)phosphine (4023-49-8) + tris(2-cyanoethyl)phosphine (4023-53-4) + tris(2-cyanoethyl)phosphine oxide (1439-41-4)

Conditions	Yield
With potassium hydroxide; phosphan In water; acetonitrile for 1h; Ambient temperature;	A 15 % Spectr. B 45% C 15 % Spectr.
With phosphorus; potassium hydroxide In water; acetonitrile at 20 - 70℃; for 0.166667h; Irradiation; sonication;	A 10 % Spectr. B 30 % Spectr. C 60 % Spectr.

acrylonitrile (107-13-1) → tris(2-cyanoethyl)phosphine (4023-53-4)

Conditions	Yield
With potassium hydroxide; phosphan; acetonitrile
With phosphan

acrylonitrile (107-13-1) → bis(2-cyanoethyl)phosphine (4023-49-8) + tris(2-cyanoethyl)phosphine (4023-53-4) + 3-phosphanyl-propionitrile (6783-71-7)

Conditions	Yield
With {(tris(cyanomethyl)phosphine)3platinum}; phosphan In acetonitrile at 20℃; for 1h; Product distribution; Mechanism;
With aluminum oxide; potassium hydroxide; phosphan Product distribution; influence of varying degrees of dryness of solid support;
With phosphan; In acetonitrile

bis(2-cyanoethyl)phosphine (4023-49-8) + acrylonitrile (107-13-1) → tris(2-cyanoethyl)phosphine (4023-53-4)

Conditions	Yield
In acetonitrile

acrylonitrile (107-13-1) + acetonitrile (75-05-8) + phosphine + aqueous KOH-solution → bis(2-cyanoethyl)phosphine (4023-49-8) + tris(2-cyanoethyl)phosphine (4023-53-4) + 3-phosphanyl-propionitrile (6783-71-7)

tris(2-cyanoethyl)phosphine (4023-53-4) + [Pt(C8H12)(C3H4NO)2] (188638-31-5) → [Pt(C3H4NO)2(P(CH2CH2CN)3)2] (188638-33-7)

Conditions	Yield
In dichloromethane pptn. with light petroleum, filtration, washing (light petroleum), drying (vac.); elem. anal.;	100%

tris(2-cyanoethyl)phosphine (4023-53-4) + 3-(perfluorooctyl)propyl iodide (200112-75-0) → tris-(2-cyano-ethyl)-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-undecyl)-phosphonium; iodide

Conditions	Yield
at 130 - 160℃; for 11h;	99.8%

[Fe2(CO)6(μ-PhC=CH2)(μ-PPh2)] + tris(2-cyanoethyl)phosphine (4023-53-4) → Fe2(CO)5(P(CH2CH2CN)3)(HCCHC6H5)P(C6H5)2 (337380-82-2)

Conditions	Yield
In toluene byproducts: CO; (N2); refluxing a soln. of iron complex and phosphine in toluene for 20 min, cooling to room temp.; chromy (deactivated Al2O3, Et2O/light petroleum 2:3); elem. anal.;	98%

bis(benzonitrile)palladium(II) dichloride (15617-18-2, 39958-10-6, 14220-64-5) + tris(2-cyanoethyl)phosphine (4023-53-4) → trans-PdCl2(tris(cyanoethyl)phosphine)2 (204461-54-1, 68494-75-7)

Conditions	Yield
In dichloromethane N2-atmosphere; dropwise addn. of 2 equiv. of phosphine to Pd-complex soln., stirring for 10 min (pptn.); filtration, washing (CH2Cl2), drying (vac.); elem. anal.;	98%

(1,5-cyclooctadiene)dimethylplatinum(II) + tris(2-cyanoethyl)phosphine (4023-53-4) → cis-PtMe2(tris(cyanoethyl)phosphine)2 (204391-74-2)

Conditions	Yield
In acetone N2-atmosphere; dropwise addn. of ligand soln. to 0.5 equiv. of Pt-complex soln., stirring for 10 min; concn., pptn. on Et2O addn., filtration, washing (Et2O), drying (vac.); elem. anal.;	97%

(tetrahydrothiophene)gold(I) chloride (39929-21-0) + tris(2-cyanoethyl)phosphine (4023-53-4) → {tris(2-cyanoethyl)phosphine}gold(I) chloride (148100-44-1)

Conditions	Yield
In dichloromethane; acetonitrile N2; equimolar amounts; stirring for 1 h at room temperature;; precipitation upon addn. of diethyl ether;;	95%

tris(2-cyanoethyl)phosphine (4023-53-4) + bis(4-formylphenyl) azidothiophosphonate (156457-81-7) → C23H22N4O4P2S

Conditions	Yield
In acetonitrile Ambient temperature;	94%

dichloro(1,5-cyclooctadiene)platinum(ll) (12080-32-9) + tris(2-cyanoethyl)phosphine (4023-53-4) → trans-PtCl2(tris(cyanoethyl)phosphine)2 (20699-88-1)

Conditions	Yield
In dichloromethane N2-atmosphere; dropwise addn. of ligand soln. to 0.5 equiv. of Pt-complex soln. (pptn.); filtration, washing (CH2Cl2), drying (vac.);	93%

tris(2-cyanoethyl)phosphine (4023-53-4) + [PdCl(η(3)-allyl)]2 → PdCl(tris(cyanoethyl)phosphine)(η(3)-allyl)

Conditions	Yield
In acetone N2-atmosphere; stirring stoich. amts. for 10 min; concn., pptn. on Et2O addn., filtration, washing (Et2O), drying (vac.); elem. anal.;	93%

di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium (12092-47-6) + tris(2-cyanoethyl)phosphine (4023-53-4) → RhCl(tris(cyanoethyl)phosphine)(COD) (204391-82-2)

Conditions	Yield
In acetone N2-atmosphere; stirring Rh-complex with 2 equiv. of phosphine for 15 min; concn., pptn. on Et2O addn.; elem. anal.;	93%

tris(2-cyanoethyl)phosphine (4023-53-4) + trans-PdCl2(tris(cyanoethyl)phosphine)2 (204461-54-1, 68494-75-7) → Pd(tris(cyanoethyl)phosphine)3 (200437-22-5)

Conditions	Yield
With LiOMe In methanol; ethanol N2-atmosphere; addn. of 4 equiv. of 0.1 M LiOMe (in MeOH) to EtOH, then addn. of 1 equiv. of Pd-complex and 2 equiv. phosphine, refluxing for 2 h (pptn.); filtration, washing (Et2O), drying (vac.); elem. anal.;	92%

tris(2-cyanoethyl)phosphine (4023-53-4) + 3-bromo-1,2-naphthoquinone (7474-83-1) → tris(2-cyanoethyl)phosphine oxide (1439-41-4) + 3-bromo-1,2-dihydroxynaphthalene (61978-07-2)

Conditions	Yield
With water In dichloromethane for 24h; Inert atmosphere;	A 92% B 80%

chloro-trimethyl-silane (75-77-4) + tetrakis(acetato)dimolybdenum(II) (14221-06-8, 744215-74-5) + tris(2-cyanoethyl)phosphine (4023-53-4) → [Mo2Cl4(tris(β-cyanoethyl)phosphine)2]x

Conditions	Yield
In toluene N2-atmosphere; dropwise addn. of excess Me3SiCl to stoich. mixt. of Mo-compd. and ligand, stirring at room temp. for >= 2 d (pptn.); collection (filtration), washing (PhMe, 40°C; hexanes at room temp.; Et2O), drying (vac., room temp., >=12 h); elem. anal.;	90%
In tetrahydrofuran N2-atmosphere; dropwise addn. of excess Me3SiCl to stoich. mixt. of Mo-compd. and ligand, stirring at room temp. for >= 2 d (pptn.); collection (filtration), washing (PhMe, 40°C; hexanes at room temp.; Et2O), drying (vac., room temp., >=12 h);	90%
In benzene N2-atmosphere; dropwise addn. of excess Me3SiCl to stoich. mixt. of Mo-compd. and ligand, stirring at room temp. for >= 2 d (pptn.); collection (filtration), washing (PhMe, 40°C; hexanes at room temp.; Et2O), drying (vac., room temp., >=12 h);	90%

nickel(II) chloride hexahydrate + cobalt(II) chloride hexahydrate + tris(2-cyanoethyl)phosphine (4023-53-4) → [Ni0.5Co0.5Cl2(P(CH2CH2CN)3)2]x + [Ni0.5Co0.5Cl2(P(CH2CH2CN)3)2]x + [Ni0.5Co0.5Cl2(P(CH2CH2CN)3)2]x

Conditions	Yield
In ethanol; acetone EtOH:acetone:triethyl orthoformate=6:5:1, equimolar amts. of metal salts, excess of ligand, ambient temp. (pptn., then dissoln. of Ni-complex, crystn. of mixt. of products on slow evapn.); mixt. of products not separated;	A 8% B 90% C 2%

tris(2-cyanoethyl)phosphine (4023-53-4) + {Co(CNC(CH3)3)4H2O}(2+)*2(ClO4)(1-)={Co(CNC(CH3)3)4H2O}(ClO4)2 → {Co(CNC(CH3)3)3(P(C2H4CN)3)2}(1+)*(ClO4)(1-)={Co(CNC(CH3)3)3(P(C2H4CN)3)2}(ClO4) (101190-22-1)

Conditions	Yield
In acetonitrile at 0°C;; recrystallization from methylene dichloride and ether, elem. anal.;	89%

tris(2-cyanoethyl)phosphine (4023-53-4) → tris-(2-carboxyethyl)-phosphine hydrochloride (51805-45-9)

Conditions	Yield
With hydrogenchloride for 2h; Heating;	88%

tris(2-cyanoethyl)phosphine (4023-53-4) + tris(bicyclo[2.2.1]heptene)platinum(0) → {(tris(cyanomethyl)phosphine)3platinum} (132199-05-4)

Conditions	Yield
In acetone; toluene N2-atmosphere; dropwise addn. of 3 equiv. of phosphine (in Me2CO) to Pt-complex soln. (in PhMe, pptn.), stirring for 3 h; filtration, dissoln. in Me2CO, pptn. on PhMe addn.; elem. anal.;	86%

tris(2-cyanoethyl)phosphine (4023-53-4) + silver nitrate → bis[tris(2-cyanoethyl)phosphine]silver(I) nitrate (172915-72-9)

Conditions	Yield
In ethanol; acetonitrile addn. of AgNO3 (in hot MeCN) to 2 equiv. of ligand (in warm EtOH); crystn. on slow cooling (in dark); elem. anal.;	85%

tetrakis(acetonitrile)copper(I)tetrafluoroborate + tris(2-cyanoethyl)phosphine (4023-53-4) + Tris(pyrazolyl)methane (80510-03-8) → [Cu{tris(pyrazol-1-yl)methane}(tris(2-cyanoethyl)phosphine)][BF4]

Conditions	Yield
Stage #1: tetrakis(acetonitrile)copper(I)tetrafluoroborate; tris(2-cyanoethyl)phosphine In acetonitrile for 0.0833333h; Schlenk technique; Inert atmosphere; Stage #2: Tris(pyrazolyl)methane In acetonitrile for 4h; Schlenk technique; Inert atmosphere;	85%

{Ni(η-CH3C5H4)((C6H5)2PCH2CH2P(C6H5)2)}NCS + tris(2-cyanoethyl)phosphine (4023-53-4) → {Ni(η-CH3C5H4)((C6H5)2PCH2CH2P(C6H5)2)(P(CH2CH2CN)3)}NCS

Conditions	Yield
In acetone addn. of phosphine soln. to stirred Ni complex soln. under N2; stirring, 4h; concentratin; addn. of hexane; pptn.; filtration; washing (Et2O); elem. anal.;	84%

tetrachloronitridotechnatate(VI) tetra-n-butylammonium + tris(2-cyanoethyl)phosphine (4023-53-4) → (Bu4N){TcNCl3(tri(2-cyanoethyl)phosphine)}

Conditions	Yield
In acetone refluxing (1 h); pptn. on concn., addn. of MeOH and cooling; elem. anal.;	83%

copper(l) iodide (7681-65-4) + tris(2-cyanoethyl)phosphine (4023-53-4) → [CuI(tris(2-cyanoethyl)phosphine)]n

Conditions	Yield
In acetonitrile for 0.333333h; Reflux; Inert atmosphere;	83%

tetrakis(actonitrile)copper(I) hexafluorophosphate (64443-05-6) + tris(2-cyanoethyl)phosphine (4023-53-4) → [Cu(tris(2-cyanoethyl)phosphine)2]n(PF6)n

Conditions	Yield
In acetonitrile for 1h; Reflux; Inert atmosphere;	83%

di(rhodium)tetracarbonyl dichloride + tris(2-cyanoethyl)phosphine (4023-53-4) → trans-RhCl(CO)(tris(cyanoethyl)phosphine)2 * 0.5 Me2CO

Conditions	Yield
In acetone N2-atmosphere; stirring Rh-complex with 4 equiv. of phosphine for 40 min; evapn.; elem. anal.;	82%

chloro(1,5-cyclooctadiene)iridium(I) dimer + tris(2-cyanoethyl)phosphine (4023-53-4) → IrCl(tris(cyanoethyl)phosphine)(COD) (204391-83-3)

Conditions	Yield
In acetone N2-atmosphere; stirring Ir-complex with 2 equiv. of phosphine for 15 min; concn., pptn. on Et2O addn.; elem. anal.;	82%

dichloro(1,5-cyclooctadiene)platinum(ll) (12080-32-9) + tris(2-cyanoethyl)phosphine (4023-53-4) → PtCl2(CO)P(CH2CH2CN)3 (111046-55-0)

Conditions	Yield
With carbon monoxide In chloroform CO was bubbled through a soln. of Pt-complex in CHCl3 for 1 h, a soln. of the phosphine in hot CHCl3 was added dropwise over 30 min with stirring; ppt. was washed with CHCl3, recrystd. from acetone-propan-2-ol; elem. anal.;	81%

[RuCl(η(5)-C5H4Me)(PPh3)2] (55272-36-1) + tris(2-cyanoethyl)phosphine (4023-53-4) → (C5H4CH3)RuCl(P(CH2CH2CN)3)2

Conditions	Yield
In acetone N2 atmosphere; refluxing (1 h); concn. of aoln., pptn. (addn. of chloroform); elem. anal.;	79%
In toluene N2 atmosphere; refluxing (1.5 h), pptn.; dissolution (acetone), repptn. (addn. of chloroform); elem. anal.;	79%

Upstream product

• 107-13-1 acrylonitrile 
• 4023-49-8 bis(2-cyanoethyl)phosphine 
• 75-05-8 acetonitrile 

Downstream Products

• 1439-41-4 tris(2-cyanoethyl)phosphine oxide 
• 6783-73-9 tris(2-cyanoethyl)phosphine sulphide 
• 5961-85-3 tris(2-carboxyethyl)phosphine 
• 10310-38-0 hexakis-P-(2-cyano-ethyl)-P,P'-ethanediyl-di-phosphonium; dibromide 
• 1896-59-9 Tris-(2'-cyano-ethyl)-methyl-phosphonium 
• 122530-83-0 TcCl₄(tri(2-cyanoethyl)phosphine)2 
• 98703-39-0 Mo(P(C₆H₅)3)(P(CH₂CH₂CN)3)(((C₆H₅)2PCH₂)2) 
• 204391-78-6 Pd(tris(cyanoethyl)phosphine)2(η(2)-dibenzylideneacetone) 
• 15909-92-9 bis(2-cyanoethyl)phenylphosphine 
• 61978-07-2 3-bromo-1,2-dihydroxynaphthalene 
• 1185728-03-3 6,6'-dibromo-1,1'-2,2'-tetrahydroxy-4,4'-binaphthyl 
• 959428-44-5 [(P(C₂H₄CN)3)2PdCl(C₆H₂(CHNCH₂C₆H₅)2C(CH₃)3)] 
• 869286-57-7 [Pt(P(C2H4CN)3)(η3-2-(2-Ph2PC6H4N=CH)-3-MeO-C6H3O)]ClO4 
• 869286-59-9 [Pt(P(C2H4CN)3)(η3-2-(2-Ph2PC6H4N=CH)-5-MeO-C6H3O)]ClO4 

Relevant articles and documents

Dual Radical/Polar Pudovik Reaction: Application Field of New Activation Methods

The Pudovik reaction (addition of organophosphorus compounds containing a labile P-H bond with alkenes and alkynes) can progess via a radical or (and) ionic mechanism. A comparative and systematic study including various reagents and different activation methods (heating, photochemical or ultrasonic irradiation, and dry medium supported reactions) is presented. Photolysis is the most efficient method for the radical processes, but in a few examples, ultrasonic irradiation can be more appropriate since the reaction time is shorter and ultrasound did not induce side-reactions (in particular Z/E isomerization). Dry medium process on basic solid support is the best anionic activation (yield, time, selectivity, purification facilities). Ultrasound, by its mechanical effects, can contribute to increase yield compared to the classical thermal method under these basic conditions. All the activation methods are efficient whatever the unsaturated substrates for the phosphine reactivity, whereas the appropriate activation method is exclusively determined by the nature of the unsaturated system for the thiophosphine (or phosphine oxide) reactivity.

Alkylation of phosphine PH3 generated from red phosphorus

The generation of phosphine PH3 by alkaline hydrolysis of red phosphorus is realized. The subsequent alkylation of PH3 by terminal alkenes and alkynes in basic media leading to the corresponding aliphatic and vinylic phosphine derivatives can occur by two-steps or one-pot reaction by a Michael-like reaction mechanism.