6737-42-4

Basic information

• Product Name: 1,3-Bis(diphenylphosphino)propane
• Synonyms: 1,3-BIS(DIPHENYLPHOSPHINE)PROPANE;1,3-BIS(DIPHENYLPHOSPHINO)PROPANE;DPPP;TRIMETHYLENEBIS(DIPHENYLPHOSPHINE);[3-(Diphenylphosphino)propyl](diphenyl)phosphine;1,3-Propanediylbis(diphenylphosphine);Bis(1,3-diphenylphosphino)propane;Phosphine, 1,3-propanediylbis[diphenyl-
• CAS NO: 6737-42-4
• Molecular Formula: C₂₇H₂₆P₂
• Molecular Weight: 412.44
• EINECS: 229-791-2
• Product Categories: Phosphines;Ligand;API intermediates;Phosphine Ligands;Synthetic Organic Chemistry;organophosphine ligand;API intermediate;Achiral Phosphine;Aryl Phosphine
• Mol File: 6737-42-4.mol
• Article Data: 33

Chemical Properties

• Melting Point: 63-65 °C(lit.)
• Boiling Point: 529.667 °C at 760 mmHg
• Flash Point: 235°C
• Appearance: White to light yellow-beige/Granules or Powder
• Vapor Pressure: 9E-11mmHg at 25°C
• Storage Temp.: Store below +30°C.
• Water Solubility: insoluble
• Sensitive: Air Sensitive
• BRN: 2821785
• CAS DataBase Reference: 1,3-Bis(diphenylphosphino)propane(CAS DataBase Reference)
• NIST Chemistry Reference: 1,3-Bis(diphenylphosphino)propane(6737-42-4)
• EPA Substance Registry System: 1,3-Bis(diphenylphosphino)propane(6737-42-4)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-37/39-36
• WGK Germany: 3
• F: 10-23
• TSCA: Yes
• Hazardous Substances Data: 6737-42-4(Hazardous Substances Data)

Usage

Chemical Properties

white to light yellow crystal powde

Uses

Different sources of media describe the Uses of 6737-42-4 differently. You can refer to the following data:
1. suzuki reaction
2. 1,3-Bis(diphenylphosphino)propane is used as a bidentate ligand in coordination chemistry and form complex dichloro(1,3-bis(diphenylphosphino)propane)nickel by reacting with nickel(II) chloride. This complex is used as a catalyst for Kumada coupling reaction. It also acts as a ligand for palladium(II) catalysts which is useful for the co-polymerization of carbon monoxide and ethylene to get polyketones. Further, it is employed in palladium-catalyzed arylation under Heck reaction and Suzuki reaction. In addition to this, it serves as a catalyst for Negishi coupling and Sonogashira coupling reactions.

InChI:InChI=1/C27H26P2/c1-5-14-24(15-6-1)28(25-16-7-2-8-17-25)22-13-23-29(26-18-9-3-10-19-26)27-20-11-4-12-21-27/h1-12,14-21H,13,22-23H2

Synthetic route

methanol (67-56-1) + (propane-1,3-diyl)bis(diphenylphosphane)-borane(1:2) (100809-49-2) → Trimethyl borate (121-43-7) + 1,3-bis-(diphenylphosphino)propane (6737-42-4)

Conditions	Yield
In toluene at 100℃; Inert atmosphere;	A n/a B 98%

1,3-chlorobromopropane (109-70-6) → 1,3-bis-(diphenylphosphino)propane (6737-42-4)

Conditions	Yield
Stage #1: chloro-diphenylphosphine With sodium In dibutyl ether at 105℃; for 2h; Stage #2: 1.3-chlorobromopropane In dibutyl ether at 105℃; for 2h;	95%

(propane-1,3-diyl)bis(diphenylphosphane)-borane(1:2) (100809-49-2) + ethanol (64-17-5) → triethyl borate (150-46-9) + 1,3-bis-(diphenylphosphino)propane (6737-42-4)

Conditions	Yield
Inert atmosphere; Reflux;	A n/a B 94%

1,3-bis(diphenylphosphoryl)propane (16524-41-7) → 1,3-bis-(diphenylphosphino)propane (6737-42-4)

Conditions	Yield
With diisobutylaluminium hydride In toluene at 150℃; for 12h; Inert atmosphere;	93%
With 1,1,3,3-Tetramethyldisiloxane; titanium(IV) isopropylate In various solvent(s) at 100℃; for 7h;	91%
With diethoxymethylane; Bis(p-nitrophenyl) phosphate In toluene at 110℃; Inert atmosphere; chemoselective reaction;	82%
With indium(III) bromide; 1,1,3,3-Tetramethyldisiloxane In toluene at 100℃; for 22h; Inert atmosphere; Sealed tube;	80%
With hexylsilane; trifluorormethanesulfonic acid In toluene at 70℃; for 24h; Inert atmosphere; Sealed tube; chemoselective reaction;	72 %Spectr.

1,3-dibromo-propane (109-64-8) + diphenylphosphane (829-85-6) → 1,3-bis-(diphenylphosphino)propane (6737-42-4)

Conditions	Yield
With cesium hydroxide; 4 Angstroem MS In N,N-dimethyl-formamide at 23℃; for 45h;	83%
With cesium hydroxide; 4 A molecular sieve In N,N-dimethyl-formamide at 23℃; for 45h;	83%
With tert-butylimino-tris(dimethylamino)phosphorane In tetrahydrofuran; diethyl ether for 24h; Ambient temperature;	60%

C21H14N2O8 (1273415-58-9) + chloro-diphenylphosphine (1079-66-9) → 1,3-bis-(diphenylphosphino)propane (6737-42-4)

Conditions	Yield
With [Ir(ppy)2bpy]PF6; N-ethyl-N,N-diisopropylamine In 1,2-dichloro-ethane at 22℃; for 8h; Irradiation;	82%

phenylmagnesium bromide (100-58-3) → 1,3-bis-(diphenylphosphino)propane (6737-42-4)

Conditions	Yield
Multi-step reaction with 2 steps 1: sodium triflate / tetrahydrofuran / 2.25 h / 0 °C / Inert atmosphere; Reflux 2: diisobutylaluminium hydride / toluene / 12 h / 150 °C / Inert atmosphere View Scheme

n-butyllithium (109-72-8, 29786-93-4) + 1,3-dibromo-propane (109-64-8) + diphenylphosphane (829-85-6) → diphenyl(3-bromopropyl)phosphine + 1,3-bis-(diphenylphosphino)propane (6737-42-4)

Conditions	Yield
Stage #1: n-butyllithium; diphenylphosphane In tetrahydrofuran; hexane at 20℃; for 0.833333h; Inert atmosphere; Stage #2: 1,3-dibromo-propane In tetrahydrofuran; hexane at 20℃; for 0.333333h; Inert atmosphere; Overall yield = 396.6 mg;

latter phosphonate + 1,3-bis-(diphenylphosphino)propane (6737-42-4) + dimethyl 1-octen-2-yl-phosphonate (174781-89-6) → dimethyl (E)-octenylphosphonate

Conditions	Yield
In palladium diacetate	100%
In 1,3-bis(dimethylphosphino)propane	85%

(bicyclo[2.2.1]hepta-2,5-diene)tetracarbonylmolybdenum(0) (12146-37-1, 124717-04-0) + 1,3-bis-(diphenylphosphino)propane (6737-42-4) → tetracarbonyl-1,3-bis(diphenylphosphino)propane-molybdenum(0) (15553-68-1) + bicyclo[2.2.1]hepta-2,5-diene (121-46-0)

Conditions	Yield
In tetrahydrofuran reaction in a calorimeter under argon;	A 100% B n/a

[Rh(dppp)(CO)2]2 + 1,3-bis-(diphenylphosphino)propane (6737-42-4) + hydrogen (1333-74-0) → RhH(CO)(C6H5)2PCH2CH2CH2P(C6H5)2(C6H5)2P(CH2)3P(C6H5)2 (81524-37-0)

Conditions	Yield
In dichloromethane-d2 total pressure: 1 atm; 1.0-6.0 h; room temperature; dpp:Rh2 ratio=6.2:1;; no isolation; NMR-spectroscopic characterization;;	100%
In dichloromethane-d2 total pressure: 1 atm; 10 h; room temperature; dpp:Rh2 ratio=19.8:1;; no isolation; NMR-spectroscopic characterization;;	80%
In dichloromethane-d2 total pressure: 1 atm; 0.2 h; room temperature; dpp:Rh2 ratio=6.2:1; about 20-25 % unknown hydrides;; no isolation; NMR-spectroscopic characterization;;	60%
With carbon monoxide In dichloromethane-d2 total pressure: 1 atm; 0.2 h; room temperature; dpp:Rh2 ratio=6.1:1;H2:CO=1:1; about 20-25 % unknown hydrides detected;; no isolation; NMR-spectroscopic characterization;;	14%

chloromethyl(1,5-cyclooctadiene)palladium(II) + 1,3-bis-(diphenylphosphino)propane (6737-42-4) → [PdCl(CH3)(bis(diphenylphosphino)propane)] (139168-06-2)

Conditions	Yield
In dichloromethane under N2 at room temp. in darkness, 1:1 mixt., stirred for 1.5 h; pptd., filtered, washed (ether), dried (vac.), NMR;	100%

chlorobis(1,3-diphenylphosphinopropane)-exo-nido-[10-hydroorthocarborane-5,6,10-tris(hydrido)]ruthenium + 1,3-bis-(diphenylphosphino)propane (6737-42-4) → bis(1,3-diphenylphosphinopropane)chlororuthenium(II) nido-7,8-dicarbaundecaborate dichloromethane

Conditions	Yield
In benzene benzene added to equimolar mixt. of Ru-carborane-complex and (PPh2)2(CH2)3, stirred at 22°C for 2-3 h; ppt. filtered off, washed (C6H6), recrystd. (CH2Cl2-hexane); elem. anal.;	100%

chlorobis(1,3-diphenylphosphinopropane)-exo-nido-[7,8-dimethyl-10-hydroorthocarborane-5,6,10-tris(hydrido)]ruthenium(II) semidichloromethane + 1,3-bis-(diphenylphosphino)propane (6737-42-4) → bis(1,3-diphenylphosphinopropane)chlororuthenium(II) nido-7,8-dimethyl-7,8-dicarbaundecaborate dichloromethane

Conditions	Yield
In benzene benzene added to equimolar mixt. of Ru-carborane-complex and (PPh2)2(CH2)3, stirred at 22°C for 2-3 h; ppt. filtered off, washed (C6H6), recrystd. (CH2Cl2-hexane); elem. anal.;	100%

Pt(Sn(CH3)3)2(P(CH3C6H4)3)2 + 1,3-bis-(diphenylphosphino)propane (6737-42-4) → Pt(Sn(CH3)3)2(C6H5)2P(CH2)3P(C6H5)2

Conditions	Yield
	99%

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + 1,3-bis-(diphenylphosphino)propane (6737-42-4) → [1,3-bis(diphenylphosphino)propane]dichloridepalladium(II) (59831-02-6)

Conditions	Yield
In dichloromethane for 2h; Inert atmosphere;	99%

1,3-bis-(diphenylphosphino)propane (6737-42-4) + N-(2-cyclopropylideneethyl)-4-methyl-N-(prop-2-yn-1-yl)benzenesulfonamide + cobalt(II) bromide → C42H44CoNO2P2S

Conditions	Yield
With zinc(II) iodide; zinc In acetonitrile at 20 - 25℃; for 2h; Inert atmosphere; Sealed tube;	99%

2-trifluoromethanesulfonyloxy-8-acetylaminonaphthalene (168901-50-6) + 1,3-bis-(diphenylphosphino)propane (6737-42-4) + palladium diacetate (3375-31-3) → 8-acetylamino-2-naphthoic acid, methyl ester

Conditions	Yield
With dimethyl sulfoxide; triethylamine In methanol	98.5%

hydrogenchloride (7647-01-0) + 1,3-bis-(diphenylphosphino)propane (6737-42-4) + palladium (7440-05-3) → bis(diphenylphosphino)propanepalladium(II) dichloride (59831-02-6)

Conditions	Yield
Stage #1: hydrogenchloride; palladium With nitric acid In water Stage #2: 1,3-bis-(diphenylphosphino)propane In water; N,N-dimethyl-formamide at 50℃; for 1h;	98.1%

di(pyridin-2-yl)amine (1202-34-2) + 1,3-bis-(diphenylphosphino)propane (6737-42-4) + silver perchlorate → [Ag2(bis(2-pyridyl)amine)2(dppp)(ClO4)2] (936008-61-6)

Conditions	Yield
In acetonitrile stoich. mixt. in CH3CN stirred for 12 h at room temp.; evapd., washed (Et2O), elem. anal.;	98%

2,2':6,2''-terpyridine (1148-79-4) + 1,3-bis-(diphenylphosphino)propane (6737-42-4) + silver perchlorate → [Ag2(2,2':6',6''-terpyridyl)2(dppp)][ClO4]2

Conditions	Yield
In acetonitrile stoich. mixt. in CH3CN stirred for 12 h at room temp.; evapd., washed (Et2O), elem. anal.;	98%

(C8H12)Pt(CH3C(O)NCH2COO) (142316-59-4) + 1,3-bis-(diphenylphosphino)propane (6737-42-4) → ((C6H5)2P(CH2)3P(C6H5)2)Pt(CH3C(O)NCH2COO) (142316-57-2)

Conditions	Yield
In dichloromethane N2; stirred for 20 min at room temp.; evapd. to dryness under reduced pressure, crystd. from CH2Cl2/light petroleum; NMR;	98%

(C8H12)Pt(CH3C(O)NCH(CH2C6H5)COO) + 1,3-bis-(diphenylphosphino)propane (6737-42-4) → ((C6H5)2P(CH2)3P(C6H5)2)Pt(CH3C(O)NCH(CH2C6H5)COO)*H2O

Conditions	Yield
In dichloromethane N2; stirred for 15 min at room temp.; evapd. to dryness under reduced pressure, crystd. from CH2Cl2/light petroleum; NMR;	98%

cis-dichloro(dimethylaminomethylene)(triphenylarsine)platinum(II) + 1,3-bis-(diphenylphosphino)propane (6737-42-4) → [1,3-bis(diphenylphosphino)propane](dimethylaminomethylene)(chloro)platinum(II) chloride - H2O (2/1)

Conditions	Yield
With H2O In chloroform-d1 CDCl3; evapd., the residue was washed with pentane, crystd. from CH2Cl2-hexane (elem. anal.);	98%

1,3-bis-(diphenylphosphino)propane (6737-42-4) + nickel(II) acetate tetrahydrate (6018-89-9) + Thiosalicylic acid (147-93-3) → [Ni(SC6H4CO2)(C27H26P2)] (195049-36-6)

Conditions	Yield
With pyridine In methanol dissoln. of the Ni salt and the ligand in MeOH with warming, addn. of thiosalicylic acid, then pyridine, short reflux; filtration, washing (cold MeOH; Et2O), drying, recrystn. (CH2Cl2/Et2O); elem. anal.;	98%

[(COD)Rh(μ-,kappa.O,O'-HCO2)]2 (125979-15-9) + 1,3-bis-(diphenylphosphino)propane (6737-42-4) → Rh(η(3)-cyclooctenyl)(Ph2P(CH2)3PPh2) (177283-23-7)

Conditions	Yield
In tetrahydrofuran Ar-atmosphere; slow addn. of 1 equiv. of phosphine to Rh-complex soln. at -78°C, stirring for 20 min, slow warming to room temp., stirring for 30 min; solvent removal, drying (vac., 1 d);	98%

nickel(II) chloride hexahydrate + dimercaptomaleonitrile disodium salt hydrate + 1,3-bis-(diphenylphosphino)propane (6737-42-4) → (maleonitriledithilato)(1,3-bis(diphenylphosphino)propane)nickel(II) (635315-48-9)

Conditions	Yield
In acetone mixt. of solids NiCl2*6H2O (1 mmol) and Ph2PCH2CH2CH2P(Ph)2 (0.41 g) in acetone stirred for 1 h; pptd. by H2O addn. with stirring; ppt. filtered off; washed (H2O, EtOH, Et2O); dried at room temp.; elem. anal.;	98%

potassium tetrachloroplatinate(II) (10025-99-7) + 1,3-bis-(diphenylphosphino)propane (6737-42-4) → {1,3-bis(diphenylphosphino)propane}platinumCl2 (59329-00-9)

Conditions	Yield
With hydrogenchloride In ethanol; water at 90℃; for 3h;	98%

Upstream product

• 142-28-9 1,3-Dichloropropane 
• 603-35-0 triphenylphosphine 
• 67-56-1 methanol 
• 100809-49-2 (propane-1,3-diyl)bis(diphenylphosphane)-borane(1:2) 
• 64-17-5 ethanol 
• 109-72-8 n-butyllithium 
• 109-64-8 1,3-dibromo-propane 
• 829-85-6 diphenylphosphane 
• 1273415-58-9 C₂₁H₁₄N₂O₈ 
• 1079-66-9 chloro-diphenylphosphine 
• 100-58-3 phenylmagnesium bromide 
• 4559-70-0 Diphenylphosphine oxide 
• 7439-93-2 lithium 
• 109-70-6 1.3-chlorobromopropane 

Downstream Products

• 133508-95-9 dibromure d'hexaphenyl-1,1,5,5,9,12 dioxo-9,12 diphosphona-9,12 diphosphonia-1,5 cyclopentadecane 
• 133508-96-0 dibromure d'hexaphenyl-1,1,5,5,9,13 dioxo-9,13 diphospha-9,13 diphosphonia-1,5 cyclohexadecane 
• 87664-38-8 C₂₇H₂₆O₆P₂S₂ 
• 591-51-5 phenyllithium 
• 60778-68-9 1,3-bis(lithiumphenylphosphido)propane 
• 28240-66-6 1,3-bis(phenylphosphano)propane 
• 1552-12-1 1,5-cis,cis-cyclooctadiene 
• 357408-93-6 methyl 4-[(2S)-2-(N-benzyl-N-((2S)-2-hydroxy-3-phenoxypropyl)amino]-3-hydroxypropyl]benzoate 
• 332179-55-2 4-(7-{2-[tert-Butoxycarbonyl-(tetrahydro-pyran-4-yl)-amino]-ethylamino}-2,5-dimethyl-pyrazolo[1,5-a]pyrimidin-3-yl)-3,5-dichloro-benzoic acid methyl ester 
• 255051-21-9 4-[2-methylsulfinyl-4-methoxycarbonylphenyl]-N-Cbz-piperidine 
• 275384-21-9 methyl 3-(2-chloro-4-(1-propoxy)benzyl)-2-ethyl-3H-imidazo[4,5-b]pyridine-5-carboxylate 
• 301690-23-3 2,2-dimethyl-4-(4-methoxyphenyl)-5-{4-(methylsulfonyl)phenyl}-3(2H)-furanone 
• 169759-10-8 methyl (R)-3-(N,N-dicyclobutylamino)-8-fluoro-3,4-dihydro-2H-1-benzopyran-5-carboxylate 

Relevant articles and documents

Catalytic Cleavage of Unactivated C(aryl)-P Bonds by Chromium

We describe here the coupling to transform aryl phosphine derivatives by the cleavage of unactivated C(aryl)-P bonds with chromium catalysis, allowing us to achieve the reaction with alkyl bromides and arylmagnesium reagents under mild conditions. Mechani

Decarboxylative Phosphine Synthesis: Insights into the Catalytic, Autocatalytic, and Inhibitory Roles of Additives and Intermediates

Phosphines are among the most widely used ligands, catalysts, and reagents. Current synthetic approaches to phosphines are dominated by nucleophilic displacement reactions with organometallic reagents. Here, we report a radical-based approach to phosphines that proceeds by a cross-electrophile coupling of chlorophosphines and redox-active esters. The reaction allows for the synthesis of a broad range of substituted phosphines that were not readily attainable with the present methods. Our experimental and DFT computational studies also clarified the catalytic, autocatalytic, and inhibitory roles of additives and intermediates, as well as the mechanistic details of the photocatalytic and zinc-mediated redox modes that can have implications for the mechanistic interpretation of other cross-electrophile coupling reactions.

Organocatalyzed Reduction of Tertiary Phosphine Oxides

A novel selective catalytic reduction method of tertiary phosphine oxides to the corresponding phosphines has been developed. Notably, the reaction proceeds smoothly with low catalyst loadings of 1-5 mol% even at low temperature (70 C). Under the optimized conditions various phosphine oxides could be selectively reduced and the desired phosphines were usually obtained in excellent yields above 90%. Furthermore, we have developed a one-pot reaction sequence for the preparation of valuable phosphinborane adducts. Simple addition of BH3THF subsequent to the reduction step gave the desired adducts in yields up to 99%.