131211-27-3

Basic information

• Product Name: DI-1-ADAMANTYLPHOSPHINE
• Synonyms: DI-1-ADAMANTYLPHOSPHINE;Di-1-adamantylphosphine,min.97%;Bis(adamant-1-yl)phosphine, Bis(tricyclo[3.3.1.13,7]dec-1-yl)phosphine;Di-1-adamantylphosphine, min. 97%;Bis(1-adamantyl)phosphine, 98%;Di-1-adamantylphosphine 97%;Bis(adamant-1-yl)phosphine;Diadamantylphosphine
• CAS NO: 131211-27-3
• Molecular Formula: C₂₀H₃₁P
• Molecular Weight: 302.43
• Product Categories: organophosphine ligand;P-H;Achiral Phosphine;Alkyl Phosphine
• Mol File: 131211-27-3.mol
• Article Data: 14

Chemical Properties

• Melting Point: 181-185 °C
• Boiling Point: 407.8±12.0 °C(Predicted)
• Appearance: white/Powder
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• Sensitive: air sensitive
• CAS DataBase Reference: DI-1-ADAMANTYLPHOSPHINE(CAS DataBase Reference)
• NIST Chemistry Reference: DI-1-ADAMANTYLPHOSPHINE(131211-27-3)
• EPA Substance Registry System: DI-1-ADAMANTYLPHOSPHINE(131211-27-3)

Safety Data

• Hazard Codes: T
• Statements: 23/24/25-36/37/38
• Safety Statements: 36/37/39-45
• RIDADR: UN 2811 6.1/PG 3
• WGK Germany: 3
• HazardClass: 6.1
• PackingGroup: Ⅲ
• Hazardous Substances Data: 131211-27-3(Hazardous Substances Data)

Usage

Appearance

White Powder

Uses

Di-1-adamantylphosphine is a useful research chemical.

Synthetic route

1-(1-adamantyl)chlorophosphinoyladamantane (126683-99-6) → di-1-adamantylphosphine (131211-27-3)

Conditions	Yield
With lithium aluminium tetrahydride In tetrahydrofuran for 16h; Ambient temperature;	94.3%
With trichlorosilane In toluene for 264h; Ambient temperature;	93%
With lithium aluminium tetrahydride In tetrahydrofuran at -10 - 20℃; for 14h;	90%

di-1-adamantylchlorophosphane (157282-19-4) → di-1-adamantylphosphine (131211-27-3)

Conditions	Yield
With lithium aluminium tetrahydride In diethyl ether at 20℃; for 4h;	70%

(1-adamantyl)magnesium chloride (97580-87-5) → di-1-adamantylphosphine (131211-27-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: 69 percent / diethyl ether / Heating 2: 70 percent / LiAlH4 / diethyl ether / 4 h / 20 °C View Scheme

(1-adamantyl)dichlorophosphine (23906-91-4) → di-1-adamantylphosphine (131211-27-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: 69 percent / diethyl ether / Heating 2: 70 percent / LiAlH4 / diethyl ether / 4 h / 20 °C View Scheme

adamantane (281-23-2) + Fe(CO)5 → di-1-adamantylphosphine (131211-27-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) PCl3, AlCl3, 2.) H2O / 1.) reflux, 6 h, 2.) chloroform 2: 94.3 percent / LiAlH4 / tetrahydrofuran / 16 h / Ambient temperature View Scheme

adamantane (281-23-2) → di-1-adamantylphosphine (131211-27-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: 95 percent / phosphorus trichloride, aluminum chloride / 5 h / Heating 2: 62 percent / LiAlH4 / diethyl ether / 3 h / Heating View Scheme
Multi-step reaction with 2 steps 1: phosphorus trichloride; aluminum (III) chloride / 6.17 h / Reflux 2: lithium aluminium tetrahydride / tetrahydrofuran / 20 h / -10 - 20 °C View Scheme
Multi-step reaction with 2 steps 1.1: aluminum (III) chloride; phosphorus trichloride / Reflux 1.2: Cooling with ice 2.1: lithium aluminium tetrahydride / tetrahydrofuran / 1 h / 0 - 20 °C / Inert atmosphere View Scheme

bis(1-adamantyl)phosphine oxide (131266-79-0) → di-1-adamantylphosphine (131211-27-3)

Conditions	Yield
With copper(II) trifluoromethanesulfonate; 1,1,3,3-Tetramethyldisiloxane In toluene at 100℃; for 9h; Inert atmosphere;
With diethoxymethylane; Bis(p-nitrophenyl) phosphate In toluene at 110℃; Inert atmosphere; chemoselective reaction;	99 %Spectr.

di-1-adamantylphosphine (131211-27-3) → di-1-adamantylchlorophosphane (157282-19-4)

Conditions	Yield
With tetrachloromethane at 50℃; for 16h;	100%
With tetrachloromethane at 50℃; for 24h;	98%
With 1,8-diazabicyclo[5.4.0]undec-7-ene In toluene for 16h; Ambient temperature;	93.7%
With phosgene; 1,8-diazabicyclo[5.4.0]undec-7-ene In toluene at -10℃;	67%
Multi-step reaction with 2 steps 1: phosgen / toluene / Ambient temperature 2: Et3N / toluene / a) 60 deg C, 4 h, b) reflux, 3 h View Scheme

benzyl bromide (100-39-0) + di-1-adamantylphosphine (131211-27-3) → di(1-adamantyl)benzylphosphonium hydrobromide

Conditions	Yield
In toluene Glovebox; Schlenk technique; Inert atmosphere; Reflux;	100%
In toluene Glovebox; Schlenk technique; Inert atmosphere; Reflux;	100%
In toluene at 90℃; for 14h;	92%

di-1-adamantylphosphine (131211-27-3) → C20H30P(1-)*Li(1+)

Conditions	Yield
With n-butyllithium In tetrahydrofuran; hexane at 20℃; for 3h;	100%

di-1-adamantylphosphine (131211-27-3) → bis(1-adamantyl)phosphine oxide (131266-79-0)

Conditions	Yield
With dihydrogen peroxide In toluene for 1h; Ambient temperature;	99.3%
With oxygen In tetrahydrofuran for 6h;	90%
Multi-step reaction with 2 steps 1: toluene / 16 h / Ambient temperature 2: H2O / CH2Cl2 / 72 h / Ambient temperature View Scheme
Multi-step reaction with 2 steps 1: 93.7 percent / COCl2, DBU / toluene / 16 h / Ambient temperature 2: 84.5 percent / H2O, DBU / CH2Cl2 / 72 h / Ambient temperature View Scheme
With oxygen

borane-THF (14044-65-6) + di-1-adamantylphosphine (131211-27-3) → di-adamantan-1-yl-phosphane; compound with borane

Conditions	Yield
In tetrahydrofuran at 20℃; for 16h;	98%

BH3-THP (92348-80-6) + di-1-adamantylphosphine (131211-27-3) → [di-1-adamantylphosphine]trihydroboron (512185-48-7)

Conditions	Yield
for 5h;	98%

3-bromo-4-morpholinobenzonitrile (1207541-01-2) + di-1-adamantylphosphine (131211-27-3) → C31H41N2OP

Conditions	Yield
With 1,1'-bis(diisopropylphosphino)ferrocene; palladium diacetate; sodium t-butanolate In toluene at 110℃; Inert atmosphere;	98%

di-1-adamantylphosphine (131211-27-3) + 2-Bromoethyl methyl ether (6482-24-2) → di(1-adamantyl)-2-methoxyethylphosphonium bromide

Conditions	Yield
at 80℃; for 8h;	95%

di-1-adamantylphosphine (131211-27-3) → bromo-di(1-adamantyl)phosphine

Conditions	Yield
With carbon tetrabromide In dichloromethane for 0.0833333h; Inert atmosphere;	95%
Multi-step reaction with 2 steps 1: Br2 / toluene / 0 °C 2: Et3N / toluene / 1 h / Heating View Scheme

1-{[dimethyl(1,1-dimethylethyl)silyl]oxy}-4-iodobutane (92511-12-1) + di-1-adamantylphosphine (131211-27-3) → di-adamantan-1-yl-[4-(tert-butyl-dimethyl-silanyloxy)-butyl]-phosphane; hydriodide

Conditions	Yield
In toluene at 90℃; for 14h;	94%

[(1,3-bis-(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene)PdCl(μ-Cl)]2 + di-1-adamantylphosphine (131211-27-3) → [(1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)Pd(Cl)2(PH(C10H15)2]

Conditions	Yield
In not given by a react. of Pd-contg. compd. with a ligand (2 equivs.) at room temp. for 1 h; (31)P NMR spectra monitoring;	94%

C32H20BrF12N + di-1-adamantylphosphine (131211-27-3) → C52H50F12NP

Conditions	Yield
Stage #1: C32H20BrF12N With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate In toluene at 24℃; for 0.25h; Inert atmosphere; Schlenk technique; Stage #2: di-1-adamantylphosphine In toluene at 120℃; for 16h; Inert atmosphere;	94%

di-1-adamantylphosphine (131211-27-3) + methyl iodide (74-88-4) → di(1-adamantyl)methylphosphonium iodide

Conditions	Yield
In toluene for 24h; Ambient temperature;	93%
In dibutyl ether at 20℃; for 24h;	90%

1-iodo-butane (542-69-8) + di-1-adamantylphosphine (131211-27-3) → di(1-adamantyl)-N-butylphosphine hydroiodide

Conditions	Yield
In dibutyl ether at 130℃; for 8h;	93%

di-1-adamantylphosphine (131211-27-3) + 4-(monomethyl polyethylene glycol 2000)-CH2C6H4CH2Br → 4-(monomethyl polyethylene glycol 2000)-CH2C6H4CH2P(1-Ad)2*HBr

Conditions	Yield
In toluene at 90℃; for 14h;	92%

di-1-adamantylphosphine (131211-27-3) + (2-bromophenoxy)-triisopropylsilane (378787-34-9) → OTips-DalPhos (1384966-55-5)

Conditions	Yield
With 1,1'-bis(diisopropylphosphino)ferrocene; palladium diacetate; sodium t-butanolate In toluene at 110℃; for 12h; Concentration; Inert atmosphere; Sealed tube;	91%
With 1,1'-bis(diisopropylphosphino)ferrocene; palladium diacetate; sodium t-butanolate In toluene at 110℃; for 12h; Inert atmosphere; Sealed vial;	83%

1,8-bis(bromomethyl)-3,6-di-tert-butyl-9H-carbazole (1421060-68-5) + di-1-adamantylphosphine (131211-27-3) → 1,8-bis(di-1-adamantylphosphinomethyl)-3,6-di-tert-butyl-9H-carbazole

Conditions	Yield
In acetone for 24h; Schlenk technique; Inert atmosphere; Reflux;	90%

di-μ-chlorobis[2-[(dimethylamino)methyl]phenyl-C,N]dipalladium(II) + di-1-adamantylphosphine (131211-27-3) → chloro-{[2-(N,N-dimethylamino)methyl]phenyl-C,N}(di-1-adamantylphosphine-P)palladium

Conditions	Yield
With caesium carbonate In dichloromethane at 20℃; for 0.5h; Solvent; Temperature; Schlenk technique; Glovebox; Inert atmosphere;	90%

2-(2-bromo-4,5-dimethoxyphenyl)-1,3-dioxolane (103477-58-3) + di-1-adamantylphosphine (131211-27-3) → (2-(1,3-dioxolan-2-yl)-4,5-dimethoxyphenyl)di((3S,5S,7S)-adamant-an-1-yl)phosphane

Conditions	Yield
With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate In toluene at 110℃; for 10h; Inert atmosphere;	90%

4-bromo-N,N-dimethylaniline (586-77-6) + di-1-adamantylphosphine (131211-27-3) + trifluoroacetic acid (76-05-1) → di(1-adamantyl)-4-(N,N-dimethyl)amino-phenyl-phosphane trifluoroacetic acid

Conditions	Yield
Stage #1: 4-bromo-N,N-dimethylaniline; di-1-adamantylphosphine With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate In toluene at 100℃; Inert atmosphere; Stage #2: trifluoroacetic acid In water; acetonitrile	89.6%

di-1-adamantylphosphine (131211-27-3) + 1-bromomethyl-4-bromobenzene (589-15-1) → di-adamantan-1-yl-(4-bromo-benzyl)-phosphane; hydrobromide

Conditions	Yield
In toluene at 90℃; for 14h;	89%

trimethylsilylazide (4648-54-8) + di-1-adamantylphosphine (131211-27-3) → di-1-adamantylphosphinsaeure-(N-trimethylsilylamid)-N-trimethylsilylimid

Conditions	Yield
In toluene for 72h; Heating;	88.9%

4-(2-bromopyridin-3-yl)morpholine (54231-45-7) + di-1-adamantylphosphine (131211-27-3) → C29H41N2OP

Conditions	Yield
With 1,1'-bis(diisopropylphosphino)ferrocene; palladium diacetate; sodium t-butanolate In toluene at 110℃; Inert atmosphere;	88%

C14H15BrN4 + di-1-adamantylphosphine (131211-27-3) → N-(2-(diadamantylphosphino)phenyl)-2-(piperazin-1-yl)pyrimidine

Conditions	Yield
With palladium diacetate; sodium t-butanolate In toluene at 110℃; Inert atmosphere; Schlenk technique; Sealed tube;	88%

C33H19BrF15N + di-1-adamantylphosphine (131211-27-3) → C53H49F15NP

Conditions	Yield
Stage #1: C33H19BrF15N With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate In toluene at 24℃; for 0.25h; Inert atmosphere; Schlenk technique; Stage #2: di-1-adamantylphosphine In toluene at 120℃; for 14h; Inert atmosphere;	88%

di-1-adamantylphosphine (131211-27-3) → C20H30IP*HI

Conditions	Yield
With iodine In tetrachloromethane at 0℃; for 2h;	87.7%

4-(2-bromo-5-methylphenyl)morpholine + di-1-adamantylphosphine (131211-27-3) → C31H44NOP

Conditions	Yield
With 1,1'-bis(diisopropylphosphino)ferrocene; palladium diacetate; sodium t-butanolate In toluene at 110℃; Inert atmosphere;	87%

4-bromopyridin (1120-87-2) + di-1-adamantylphosphine (131211-27-3) + trifluoroacetic acid (76-05-1) → di(1-adamantantyl)-4-pyridyl-phosphane trifluoroacetic acid

Conditions	Yield
Stage #1: 4-bromopyridin; di-1-adamantylphosphine With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate In toluene at 100℃; Inert atmosphere; Stage #2: trifluoroacetic acid In water; acetonitrile	87%

1-Adamantanecarbonyl chloride (2094-72-6) + di-1-adamantylphosphine (131211-27-3) → Di-1-adamantyl-(1-adamantoyl)phosphin

Conditions	Yield
With triethylamine In toluene for 336h; Ambient temperature;	86.6%

Upstream product

• 126683-99-6 1-(1-adamantyl)chlorophosphinoyladamantane 
• 157282-19-4 di-1-adamantylchlorophosphane 
• 97580-87-5 (1-adamantyl)magnesium chloride 
• 23906-91-4 (1-adamantyl)dichlorophosphine 
• 281-23-2 adamantane 
• 131266-79-0 bis(1-adamantyl)phosphine oxide 

Downstream Products

• 131266-79-0 bis(1-adamantyl)phosphine oxide 
• 157282-19-4 di-1-adamantylchlorophosphane 
• 175167-66-5 2-(Di-adamantan-1-yl-phosphinoyl)-1,1,1,3,3,3-hexafluoro-propan-2-ol 
• 321921-71-5 catacxium A 
• 395116-70-8 di(1-adamantyl)benzylphosphane 
• 554432-03-0 di-adamantan-1-yl-[4-(tert-butyl-dimethyl-silanyloxy)-phenyl]-phosphane 
• 220466-27-3 n-butyl trans-4-trifluoromethylcinnamate 
• 622-97-9 1-ethenyl-4-methylbenzene 
• 4714-21-0 E-1-methyl-4-styryl-benzene 
• 33534-88-2 2-(4-methylphenyl)malononitrile 
• 613-37-6 4-methoxylbiphenyl 
• 620-93-9 di-p-tolylamine 
• 152776-83-5 (C₁₀H₁₅)2PHNi(CO)3 
• 126683-99-6 1-(1-adamantyl)chlorophosphinoyladamantane 

Relevant articles and documents

CYCLOPENTADIENYL/ADAMANTYL PHOSPHINIMINE TITANIUM COMPLEXES

Provided in this disclosure are titanium complexes that contain 1) a cyclopentadienyl ligand; 2) an adamantyl-phosphinimine ligand; and 3) at least one activatable ligand. The use of such a complex, in combination with an activator, as an olefin polymerization catalyst is demonstrated. The catalysts are effective for the copolymerization of ethylene with an alpha olefin (such as 1-butene, 1-hexene or 1-octene) and enable the production of high molecular weight copolymers (Mw greater than 25,000) at high productivity under solution polymerization conditions.

A Bulky Three-Hindered Quadrant Bisphosphine Ligand: Synthesis and Application in Rhodium-Catalyzed Asymmetric Hydrogenation of Functionalized Alkenes

A bulky three-hindered quadrant bisphosphine ligand, di-1-adamantylphosphino(tert-butylmethylphosphino)methane, named BulkyP*, has been synthesized via a convergent short pathway with chromatography-free procedures. The ligand is a crystalline solid and can be readily handled in air. Its rhodium(I) complex exhibits very high enantioselectivities and catalytic activities in the asymmetric hydrogenation of functionalized alkenes.

Catalyst system

The present invention provides a catalyst system capable of catalyzing the carbonylation of an ethylenically unsaturated compound, which system is obtainable by combining: a) a metal of Group VIB or Group VIIIB or a compound thereof,b) a bidentate phosphine, arsine or stibine ligand, andc) an acid, wherein the ligand is present in at least a 2:1 molar excess compared to the metal or the metal in the metal compound, and that the acid is present in at least a 2:1 molar excess compared to the ligand, a process for the carbonylation of an ethylenically unsaturated compound, a reaction medium, and use of the system.