739-58-2

Basic information

• Product Name: 4-(DIMETHYLAMINO)PHENYLDIPHENYLPHOSPHINE
• Synonyms: 4-(DIPHENYLPHOSPHINO)-N,N-DIMETHYLANILINE;4-(DIMETHYLAMINO)TRIPHENYLPHOSPHINE;4-(DIMETHYLAMINO)PHENYLDIPHENYLPHOSPHINE;4-(DIMETHYLAMINO)PHENYLDIPHENYLPHOSPHINE 95+%;4-(Diphenylphosphanyl)-N,N-dimethylaniline;4-(Dimethylamino)triphenylphosphine 4-(Diphenylphosphino)-N,N-dimethylaniline;TricyclohexylphosphoniuM;4-(DiMethylaMino)phenyldiphenylphosphine SynonyMs 4-(Diphenylphosphanyl)-N,N-diMethylaniline
• CAS NO: 739-58-2
• Molecular Formula: C₂₀H₂₀NP
• Molecular Weight: 305.35
• EINECS: 228-193-9
• Product Categories: Mitsunobu Reaction;Phosphine Ligands;Phosphines (Mitsunobu Reaction);Synthetic Organic Chemistry;Achiral Phosphine;Aryl Phosphine
• Mol File: 739-58-2.mol
• Article Data: 9

Chemical Properties

• Melting Point: 151-154 °C(lit.)
• Boiling Point: 417.5 °C at 760 mmHg
• Flash Point: 206.3 °C
• Appearance: white/solid
• Vapor Pressure: 3.52E-07mmHg at 25°C
• Storage Temp.: Inert atmosphere,Room Temperature
• PKA: 4.20±0.12(Predicted)
• Sensitive: air sensitive
• BRN: 916331
• CAS DataBase Reference: 4-(DIMETHYLAMINO)PHENYLDIPHENYLPHOSPHINE(CAS DataBase Reference)
• NIST Chemistry Reference: 4-(DIMETHYLAMINO)PHENYLDIPHENYLPHOSPHINE(739-58-2)
• EPA Substance Registry System: 4-(DIMETHYLAMINO)PHENYLDIPHENYLPHOSPHINE(739-58-2)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• TSCA: No
• Hazardous Substances Data: 739-58-2(Hazardous Substances Data)

Usage

Uses

Catalyst for:Preparation of dicyano(aryl)cyclohexenecarboxylic acid esters via regioselective annulationDiastereoselective cycloaddition of styrenyl allenoatesInterfacial carbonylation of methylbenzyl bromideHydroformylation of octeneReducing agent for selectivity of disulfide-internally linked peptide-nucleic acid cleavage

InChI:InChI=1/C20H20NP/c1-21(2)17-13-15-20(16-14-17)22(18-9-5-3-6-10-18)19-11-7-4-8-12-19/h3-16H,1-2H3

Synthetic route

4-bromo-N,N-dimethylaniline (586-77-6) + chloro-diphenylphosphine (1079-66-9) → 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2)

Conditions	Yield
Stage #1: 4-bromo-N,N-dimethylaniline With magnesium In tetrahydrofuran for 10h; Inert atmosphere; Reflux; Stage #2: chloro-diphenylphosphine With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran at 20℃; for 11h; Reflux; Inert atmosphere;	96%
With tetrabutylammonium tetrafluoroborate; (2,2'-bipyridine)nickel(II) dibromide In N,N-dimethyl-formamide electrochemical coupling;	70%
With tetrabutylammonium tetrafluoroborate; (2,2'-bipyridine)nickel(II) dibromide In N,N-dimethyl-formamide Electrolysis;	70%

(4-(dimethylamino)phenyl)diphenylphosphine oxide (797-72-8) → 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2)

Conditions	Yield
With 1,3-diphenyl-disiloxane In toluene at 110℃; Sealed tube; chemoselective reaction;	89%

diphenylphosphane (829-85-6) + 4-cyano-N,N-dimethylaniline (1197-19-9) → 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2)

Conditions	Yield
With bis(1,5-cyclooctadiene)nickel(0); 8-quinolinol; potassium tert-butylate In 1,4-dioxane at 90℃; for 16h; Catalytic behavior; Schlenk technique; Inert atmosphere;	70%

(4-dimethylamino-phenyl)-phosphonous acid dichloride (29972-74-5) → 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2)

Conditions	Yield
With sodium; chlorobenzene; benzene ueber mehrere Stufen;

(4-dimethylamino-phenyl)-phosphonous acid dichloride (29972-74-5) + phenylmagnesium bromide → 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2)

Conditions	Yield
In diethyl ether

N,N-dimethyl-aniline (121-69-7) + chloro-diphenylphosphine (1079-66-9) → 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2)

Conditions	Yield
With pyridine; aluminium trichloride In benzene

4-bromo-N,N-dimethylaniline (586-77-6) + Diphenylphosphinic chloride (1499-21-4) → 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: magnesium; iodine / tetrahydrofuran / 1.5 h / 60 °C 1.2: 18 h / 0 - 23 °C 2.1: 1,3-diphenyl-disiloxane / toluene / 110 °C / Sealed tube View Scheme

chloro(dimethylsulfide) gold(I) (29892-37-3) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → [(4-dimethylaminophenyl)diphenylphosphine]gold(I) chloride (137008-26-5)

Conditions	Yield
In tetrahydrofuran byproducts: (CH3)2S; under N2; dropwise addn. of soln. of phosphane to suspension of Au-compd. at 0°C, stirred for 15 min, warmed to room temp.; concd., pptn. by addn. of pentane, dried (high vac.); elem. anal.;	97%
byproducts: (CH3)2S; according to: D. B. Dyson, R. V. Parish, C. A. McAuliffe, R. Fields, Hyperfine interact. 40 (1988) 327.;	97.5%

silver thiocyanate (1701-93-5) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → C82H80Ag2N6P4S2

Conditions	Yield
In acetonitrile Reflux;	92%

[Fe2(CO)6{μ-SCH2CH(CH2CH3)S}] + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → [Fe2(CO)5{Ph2P(4-C6H4NMe2)}{μ-SCH2CH(CH2CH3)S}]

Conditions	Yield
With trimethylamine-N-oxide In dichloromethane; acetonitrile at 20℃; for 1h;	91%

iron(III) chloride (7705-08-0) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → mer-[iron(III)(chloride)3(4-(dimethylamino)phenyldiphenylphosphine)3]

Conditions	Yield
In acetonitrile PPh2(p-C6H4NMe2) (0.66 mmol) soln. added dropwise to FeCl3 (0.22 mmol) soln., refluxed under N2 for 1 h, cooled; solvent evapd., solid mass washed with ether and hexane, dried under vac., recrystd. from CH3CN;	86%

(1,2,5,6-η4-cycloocta-1,5-diene)bis(4-methoxyphenyl)platinum(II) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → cis-bis({4-(dimethylamino)phenyl}diphenylphosphane)bis(4-methoxyphenyl)platinum(II)

Conditions	Yield
In dichloromethane dropping of soln. of phosphane derivative to soln. of Pt complex then stirring at 0°C for 4 h; evapg. of solvent, hydrolysing with ice water, sepg., extg. of aq. layer with C6H6 then CH2Cl2, washing with H2O, drying over MgSO4, evapg. to dryness, dissolving in CH2Cl2 then pptg. with acetone; elem. anal.;	84.5%

copper(l) iodide (7681-65-4) + acetonitrile (75-05-8) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → [Cu4I4(4-(diphenylphosphino)-N,N-dimethylaniline)4]*CH3CN

Conditions	Yield
at 20℃; for 6h;	79.69%

Rh6(μ3-CO)4(CO)11(NCCH3) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → Rh6(CO)15(4-(dimethylamino)phenyldiphenylphosphine)

Conditions	Yield
In dichloromethane byproducts: Rh6(CO)16; (Ar); addn. of phosphine deriv. to CH2Cl2 soln. of rhodium compd., stirring for few mins; evapn., dissolving in CH2Cl2, addn. of hexane, chromy. (silica gel, CH2Cl2/hexane (1/2)), evapn., NMR and MS;	78%

potassium tetrachloroplatinate(II) (10025-99-7) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → trans-dichlorobis{(4-(dimethylamino)phenyl)diphenylphosphane}platinum(II) (92451-52-0, 92471-71-1)

Conditions	Yield
In xylene addn. of finelly grinded K2(PtCl4) to soln. of phosphane derivative; refluxing of suspension for 25 h under N2;; filtering, washing with ethanol/water (1:1), drying in desiccator above silica gel; elem. anal.;	73%

1,3-(μ-propanedithiolato)diironhexacarbonyl + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → pentacarbonyl(propane-1,3-dithiolato)-4-(dimethylamino)phenyldiphenylphosphino diiron(I)

Conditions	Yield
With trimethylamine-N-oxide In dichloromethane; acetonitrile at 20℃; for 1h;	73%

μ-(1,2-ethanedithilato)diironhexacarbonyl + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → (μ-SCH2CH2S-μ)Fe2(CO)5(4-(dimethylamino)phenyldiphenylphosphine)

Conditions	Yield
With trimethylamine-N-oxide In dichloromethane; acetonitrile at 20℃; for 1h;	71%

Fe2(CO)6[μ-SCCHCHC(CH3)CHCS] + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → [Fe2(CO)5(Ph2P(4‑C6H4NMe2)){μ‑SC6H3(CH3)S}]

Conditions	Yield
With trimethylamine-N-oxide dihydrate In dichloromethane; acetonitrile at 20℃; for 1h;	70%

bis(piperidyl)tetracarbonylmolybdenum(0) (65337-26-0, 59967-36-1) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → Mo(CO)4(P(C6H5)2(C6H4N(CH3)2))2 (252650-89-8)

Conditions	Yield
In dichloromethane (N2); reflux (15 min); filtration, concn., addn. of MeOH, left in a freezer (overnight), filtration, drying in air, purifn. by dissoln. in hot MeOH and crystn. at -20°C; elem. anal.;	62%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → Ru3*9CO*3P(C6H5)2(C6H4N(CH3)2) = [Ru3(CO)9(P(C6H5)2(C6H4N(CH3)2))3]

Conditions	Yield
In toluene (N2); reflux (30 min); chromy. (SiO; light petroleum/CH2Cl2); elem. anal.;	53%

4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) + methyl iodide (74-88-4) → (4-dimethylamino-phenyl)-methyl-diphenyl-phosphonium; hydroxide

Conditions	Yield
laesst auf das Jodid in heisser alkoholischer Loesung Silberoxyd einwirken;

4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → (4-(dimethylamino)phenyl)diphenylphosphine oxide (797-72-8)

Conditions	Yield
With iron(III) chloride
With dihydrogen peroxide In water; acetone at 5 - 10℃; for 0.25h;
With dihydrogen peroxide In dichloromethane for 0.5h;

4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → 4-diphenylthiophosphinoyl-N,N-dimethyl-aniline (1041-99-2)

Conditions	Yield
With sulfur In toluene at 25℃; Rate constant; Mechanism;
With carbon disulfide; sulfur

benzyl bromide (100-39-0) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → Diphenyl-benzyl-<4-dimethylaminophenyl>-phosphoniumbromid (2067-89-2)

chloroacetic acid ethyl ester (105-39-5) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → Diphenyl-<4-dimethylaminophenyl>-aethoxycarbonylmethyl-phosphoniumbromid

allyl bromide (106-95-6) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → Allyl-diphenyl-<4-dimethylaminophenyl>-phosphoniumbromid

chloroacetone (78-95-5) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → Diphenyl-<4-dimethylaminophenyl>-acetonyl-phosphoniumbromid

Phenyl azide (622-37-7) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → N--anilin (13406-16-1)

Conditions	Yield
In benzene at 25℃; Rate constant;

diazodiphenylmethane (908093-98-1) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → Benzophenon-p-dimethylaminophenyl-diphenyl-phosphazin (13271-40-4)

Conditions	Yield
In benzene

2-chloroethanal (107-20-0) + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → Formylmethyl-diphenyl-<4-dimethylaminophenyl>-phosphoniumbromid

2-<2-<4-(bromomethyl)phenyl>ethenyl>-1,3-benzothiazole (58702-55-9) + 2'-methoxy-(1,1'-biphenyl)-2-diazonium tetrafluoroborate + 4-(N,N-Dimethylamino)triphenylphosphine (739-58-2) → 2-(4-{[(4-dimethylamino-phenyl)-diphenyl-phosphonio]-methyl}-styryl)-3-methyl-benzothiazolium; diperchlorate

Conditions	Yield
(i) CH2Cl2, (ii) /BRN= 916331/, DMF, (iii) aq. NaClO4, EtOH; Multistep reaction;

Upstream product

• 121-69-7 N,N-dimethyl-aniline 
• 1079-66-9 chloro-diphenylphosphine 
• 586-77-6 4-bromo-N,N-dimethylaniline 
• 1499-21-4 Diphenylphosphinic chloride 
• 797-72-8 [4-(dimethylamino)phenyl]diphenylphosphane oxide 
• 829-85-6 diphenylphosphane 
• 1197-19-9 4-cyano-N,N-dimethylaniline 
• 29972-74-5 (4-dimethylamino-phenyl)-phosphonous acid dichloride 

Downstream Products

• 797-72-8 [4-(dimethylamino)phenyl]diphenylphosphane oxide 
• 1041-99-2 4-diphenylthiophosphinoyl-N,N-dimethyl-aniline 
• 2067-89-2 Diphenyl-benzyl-<4-dimethylaminophenyl>-phosphoniumbromid 
• 13406-16-1 N--anilin 
• 13271-40-4 Benzophenon-p-dimethylaminophenyl-diphenyl-phosphazin 
• 13271-47-1 -p-dimethylaminophenyl-diphenyl-phosphazin 
• 13271-45-9 -p-dimethylaminophenyl-diphenyl-phosphazin 
• 13271-44-8 -p-dimethylaminophenyl-diphenyl-phosphazin 
• 24764-34-9 Diphenyl-(4-dimethylamino-phenyl)-<2,7-dibrom-fluorenyliden-(9)>-phosphoran 
• 882-33-7 diphenyldisulfane 
• 14474-87-4 4-Nitro-N--anilin 
• 13406-23-0 4-Trifluormethyl-N--anilin 
• 74-87-3 methylene chloride 
• 100-61-8 N-methylaniline 

Relevant articles and documents

[4-(N,N-dimethylamino)phenyl]diphenylphosphine oxide and its partial oxides: An isomorphous crystal series

The title compound [4-(N,N-dimethylamino)phenyl]diphenylphosphine oxide (1) has been synthesized and its single-crystal X-ray structure determined. The structures of two 'partial' oxides of the parent compound, (2) and (3) (50% and 25% oxidized), isolated from the intermediate phosphine reaction product have also been determined, yielding an unusual isomorphous crystal series. An apparent P-O bond shortening with increasing oxidation is also observed across the series (1)-(3) (1.480(4), 1.351(4), 1.280(4) A respectively) and is considered an artifact of the structure refinement. The packing in the crystals shows primary one-dimensional chains with weak head-to-tail associations between the oxide oxygen (three-centre) and two hydrogen atoms from separate methyl groups of the N-substituted amine (range C-H...O 3.115(4)-3.356(8) A), extended into a sheet structure by peripheral inter-chain C-H (aromatic)...O (oxide) associations.

Chemoselective Reduction of Phosphine Oxides by 1,3-Diphenyl-Disiloxane

Reduction of phosphine oxides to the corresponding phosphines represents the most straightforward method to prepare these valuable reagents. However, existing methods to reduce phosphine oxides suffer from inadequate chemoselectivity due to the strength of the P=O bond and/or poor atom economy. Herein, we report the discovery of the most powerful chemoselective reductant for this transformation to date, 1,3-diphenyl-disiloxane (DPDS). Additive-free DPDS selectively reduces both secondary and tertiary phosphine oxides with retention of configuration even in the presence of aldehyde, nitro, ester, α,β-unsaturated carbonyls, azocarboxylates, and cyano functional groups. Arrhenius analysis indicates that the activation barrier for reduction by DPDS is significantly lower than any previously calculated silane reduction system. Inclusion of a catalytic Br?nsted acid further reduced the activation barrier and led to the first silane-mediated reduction of acyclic phosphine oxides at room temperature.

Nickel-catalysed P-C bond formation via P-H/C-CN cross coupling reactions

Nickel-catalysed P-H/C-CN cross coupling reactions take place efficiently under mild reaction conditions affording the corresponding sp2C-P bonds. This transformation provides a convenient method for the preparation of arylphosphines and arylphosphine oxides from the readily available P-H compounds and arylnitriles. This journal is