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

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

Used in Catalyst Applications:
4-(DIMETHYLAMINO)PHENYLDIPHENYLPHOSPHINE is used as a catalyst in the following reactions for the specified reasons:
1. Preparation of dicyano(aryl)cyclohexenecarboxylic acid esters via regioselective annulation: It facilitates the selective formation of the desired product by stabilizing intermediates and enhancing the reaction rate.
2. Diastereoselective cycloaddition of styrenyl allenoates: The catalyst aids in controlling the stereochemistry of the reaction, leading to the preferential formation of specific diastereomers.
3. Interfacial carbonylation of methylbenzyl bromide: It promotes the carbonylation reaction at the interface, enhancing the yield and selectivity of the desired product.
4. Hydroformylation of octene: The catalyst plays a crucial role in the hydroformylation process, selectively producing the desired aldehyde with high efficiency.
5. Reducing agent for selectivity of disulfide-internally linked peptide-nucleic acid cleavage: It selectively reduces disulfide bonds in the presence of peptide-nucleic acid, enabling controlled and specific cleavage reactions.

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

• 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 
• 1079-66-9 chloro-diphenylphosphine 
• 121-69-7 N,N-dimethyl-aniline 
• 29972-74-5 (4-dimethylamino-phenyl)-phosphonous acid dichloride 

Downstream Products

• 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 
• 1041-99-2 4-diphenylthiophosphinoyl-N,N-dimethyl-aniline 
• 882-33-7 diphenyldisulfane 
• 797-72-8 [4-(dimethylamino)phenyl]diphenylphosphane oxide 
• 74-87-3 methylene chloride 
• 100-61-8 N-methylaniline 
• 829-85-6 diphenylphosphane 
• 71-43-2 benzene 
• 252650-89-8 Mo(CO)4(P(C₆H₅)2(C₆H₄N(CH₃)2))2 
• 2067-89-2 Diphenyl-benzyl-<4-dimethylaminophenyl>-phosphoniumbromid 

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.

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.).

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.

A preparation method of compound phosphine benzene apperception (by machine translation)

The invention relates to a method for preparing phosphine benzene apperception compound, the bromine compound is made with the magnesium reaction of Grignard reagent, then using four (triphenylphosphine) palladium-catalyzed bromophenylacetic compound phosphine chlorination reaction with the Grignard reagent. The specific method is, under the protection of inert gas, the bromo compound is made with the magnesium chips and organic solvent Grignard reagent, reflux 2 the [...] 10 hours; joined four at room temperature (triphenylphosphine) palladium, stirring 10 minutes to 3 hours, chlorinated room temperature instillment phosphine composition, reflux reaction the 1 [...] 10 hours; in the ice water bath in the fluid adds by drops full and weak acid to the reaction under weak alkali salt-water solution, liquid, organic phase exsolution, alcohol solvent crystallization, filtering to obtain compound phosphine benzene. The preparation method of this invention not only greatly improves manufacturing yield, and after treatment is simple, the process of repeated washing with ammonia water, the manufacturing process is simplified, is beneficial for large-scale industrial production. (by machine translation)

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

Electrosynthesis of triorganylphosphines from organic halides and chlorophosphines, catalyzed by nickel complexes

The possibility of cross coupling of organic halides and chlorophosphines under the action of electrochemically generated Ni(0) complexes of 2,2′-bipy is shown. The final triorganylphosphines are formed by several pathways, including reaction of the σ complex of ArNiX with chlorophosphine and electron transfer-induced reductive elimination of Ph2PArNiX, leading to the cross-coupling product.

Nickel-catalysed electrochemical coupling between mono- or di-chlorophenylphosphines and aryl or heteroaryl halides

Nickel-catalysed electrochemical cross-coupling between aryl- or heteroaryl-halides and chlorodiphenylphosphine or dichlorophenylphosphine affords tertiary phosphines in good to high yields.

Syntheses and Spectroscopic Investigations of Substituted cis- and trans-Dichlorobis(triphenylphospane)platinum(II) Compounds

Compounds of the type cis- and trans-dichlorobis(triphenylphosphane)platinum(II) (3) with substituents of different electronic character in the phenyl rings bonded to phosphorus have been synthesized.The coupling constants 1J and the chloro-platinum valence vibrational frequencies are demonstrated to be criteria for unambiguous discrimination between cis- and trans-configurations at platinum; a linear correlation exists between the sum of the ?-constants of the sustituents at the triphenylphosphane and the coupling constants 1J.

PHOSPHORORGANISCHE VERBINDUNGEN 102. TERTIAERE PHOSPHINE MIT o-DIALKYLAMINOPHENYL- UND ORTHO-DIALKYLAMINOBENZYLGRUPPEN

N,N-dialkylarylamines and N,N-dialkylbenzylamines are lithiated with n-butyllithium (n-BuLi) under the assistance of tetramethylethylenediamine (TMEDA) in the ortho-position.According the Eqs. (1) and (4) triarylphosphines (30-50percent) are obtained. 1-(N,N-dimethylamino)-naphthalene and N,N-dimethyl-1-(1-naphthyl)-ethylamine 18 are lithiated in the 8-position.In N,N-dimethyl-1-(2-naphthyl)-ethylamine 19 the 1- and 3-position is lithiated in nearly equal amount.Experiments to introduce lithium twice into the model compounds 28-30 are without success.