4731-53-7

Basic information

• Product Name: TRI-N-OCTYLPHOSPHINE
• Synonyms: CYTOP(R) 380;TRIOCTYLPHOSPHINE;TRI-N-OCTYLPHOSPHINE;nsc102529;tl411;trioctyl-phosphin;Cytop? 380 ;TRIOCTYLPHOSPHINE (CYTOP 380) CYTEC QUALITY
• CAS NO: 4731-53-7
• Molecular Formula: C₂₄H₅₁P
• Molecular Weight: 370.64
• EINECS: 225-234-2
• Product Categories: Tertiary Phosphines;Mitsunobu Reaction;Phosphine Ligands;Phosphines (Mitsunobu Reaction);Synthetic Organic Chemistry;Catalysis and Inorganic Chemistry;Phosphine Ligands;Phosphorus Compounds;organophosphorus ligand;Phosphine Compounds;Catalysis and Inorganic Chemistry;Chemical Synthesis;Achiral Phosphine;Alkyl Phosphine
• Mol File: 4731-53-7.mol
• Article Data: 12

Chemical Properties

• Melting Point: 30°C
• Boiling Point: 284-291 °C50 mm Hg(lit.)
• Flash Point: 297 °F
• Appearance: White to off-white/Powder or Crystalline Powder
• Density: 0.831 g/mL at 25 °C(lit.)
• Vapor Pressure: 1.07E-07mmHg at 25°C
• Refractive Index: n20/D 1.468(lit.)
• Water Solubility: Immiscible with water.
• Sensitive: Air Sensitive
• BRN: 1776995
• CAS DataBase Reference: TRI-N-OCTYLPHOSPHINE(CAS DataBase Reference)
• NIST Chemistry Reference: TRI-N-OCTYLPHOSPHINE(4731-53-7)
• EPA Substance Registry System: TRI-N-OCTYLPHOSPHINE(4731-53-7)

Safety Data

• Hazard Codes: C,Xi
• Statements: 34-36/37/38
• Safety Statements: 26-36/37/39-45-37/39
• RIDADR: UN 1760 8/PG 2
• WGK Germany: 2
• RTECS: SZ3450000
• F: 10-13-23
• TSCA: Yes
• HazardClass: 8
• PackingGroup: II
• Hazardous Substances Data: 4731-53-7(Hazardous Substances Data)

Usage

Uses

Tri-n-octylphosphine is used for coating zinc sulfide shells on cadmium-selenium quantum dot core by successive ionic layer adsorption and reaction method. It acts as a precursor to trioctylphosphine oxide. Further, it is used as a solvent for cadmium and selenium precursors. It also serves as a common reagent in the chemical synthesis of nanoparticles. It acts as a precursor to trioctylphosphine oxide.

InChI:InChI=1/C24H51P/c1-4-7-10-13-16-19-22-25(23-20-17-14-11-8-5-2)24-21-18-15-12-9-6-3/h4-24H2,1-3H3

Synthetic route

di-n-octylmagnesium (24219-37-2) → TOP (4731-53-7)

Conditions	Yield
With phosphorus trichloride; iron(III)-acetylacetonate In tetrahydrofuran; n-heptane for 0.5h; Heating;	85%
With phosphorus trichloride	84%

cyanex-921 (78-50-2) → TOP (4731-53-7)

Conditions	Yield
With pinacolboronic acid In acetonitrile at 100℃; for 120h; Inert atmosphere; Glovebox; Sealed tube; Schlenk technique;	57%
With 1,1,3,3-Tetramethyldisiloxane; titanium(IV) isopropylate In various solvent(s) at 100℃; for 10h;
With indium(III) bromide; 1,1,3,3-Tetramethyldisiloxane In toluene at 100℃; for 18h; Inert atmosphere; Sealed tube;

oct-1-ene (111-66-0) → TOP (4731-53-7)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile); phosphan at 80 - 100℃; for 6h;

(Methoxycarbonylamino-methyl)-trioctyl-phosphonium; chloride (62779-16-2) → TOP (4731-53-7)

Conditions	Yield
With sodium methylate In methanol; diethyl ether

1-bromo-octane (111-83-1) → TOP (4731-53-7)

Conditions	Yield
With iodine; magnesium; phosphorus trichloride 1.) ether, reflux, 15 min.; 2.) reflux, 96 h.; Yield given. Multistep reaction;

dichloro-trioctyl-phosphorane → TOP (4731-53-7)

Conditions	Yield
With sodium

1-bromo-octane (111-83-1) + sodium-compound of dioctyl phosphine → TOP (4731-53-7)

lead(II) oleate + trioctylphosphane selenide (20612-73-1) → lead(II) selenide + TOP (4731-53-7)

Conditions	Yield
In further solvent(s) byproducts: tri-n-octylphosphine oxide, oleate anhydride; (C8H17)3PSe injected into soln. of Pb compd. in 1-octadecene; nanocrystals grown at 170°C over 40 min; monitored by (31)P NMR spectra;	A n/a B 0%

TOP (4731-53-7) + carbonic acid dimethyl ester (616-38-6) → 1,1,1-trioctyl-1-methylphosphonium methylcarbonate (1204316-79-9)

Conditions	Yield
In methanol at 140℃; for 20h; Inert atmosphere; Autoclave;	100%
In methanol at 140℃; for 24h; Inert atmosphere; Autoclave;	100%
In methanol at 150℃;	100%

bis(1,5-cyclooctadiene)nickel (0) (1295-35-8) + TOP (4731-53-7) → Ni(COD)(tri-n-octylphosphine)2

Conditions	Yield
In toluene Ni complex reacted with 2 equiv. of tri-n-octylphosphine in toluene;	99%

tetrakis(acetonitrile)copper(I)tetrafluoroborate + TOP (4731-53-7) + 6,6’-diformyl-3,3’-bipyridine (1264748-06-2) + 1,4-phenylenediamine (106-50-3) → ([(H2NC6H4NCH(C5H3N)(C5H3N)CHNC6H4NH2)][Cu(trioctylphosphine)2]2[B(fluoride)4]2)

Conditions	Yield
In dimethyl sulfoxide byproducts: H2O; under inert atm. mixing (H2NC6H4)2, (CHOC5H3N)2, Cu complex, soln. of P compd. in DMSO, sealing, storage at 80°C (12 h);	99%

1-undecen-11-ylbromide (7766-50-9) + TOP (4731-53-7) → trioctyl(undec-10-enyl)phosphonium bromide (1412455-62-9)

Conditions	Yield
In acetonitrile for 18h; Inert atmosphere; Schlenk technique; Reflux;	99%

TOP (4731-53-7) + 4-Vinylbenzyl chloride (1592-20-7) → trioctyl(4-vinylbenzyl)phosphonium chloride

Conditions	Yield
With 2,6-di-tert-butyl-4-methyl-phenol In toluene at 20℃; for 48h; Inert atmosphere;	99%
With 2,6-di-tert-butyl-4-methyl-phenol In toluene at 20℃; for 48h; Inert atmosphere;

Iodoethanol (624-76-0) + TOP (4731-53-7) → (2-hydroxyethyl)tri-n-octylphosphonium iodide

Conditions	Yield
at 60℃; for 5h; Inert atmosphere;	99%

TOP (4731-53-7) → cyanex-921 (78-50-2)

Conditions	Yield
With fluorosulfonylchloride In dichloromethane for 1h; Ambient temperature;	98%
Stage #1: TOP With water; dihydrogen peroxide In toluene at 0 - 20℃; for 12h; Inert atmosphere; Stage #2: In toluene at 20℃; for 4h; Molecular sieve;	90%
In 1,2,4-trimethylbenzene at 25℃; for 1h; Inert atmosphere;
With selenium; octadec-1-ene

TOP (4731-53-7) + ethyl chloromethyl ether (3188-13-4) → tri-n-octylmethoxyethylphosphonium chloride (1273586-10-9)

Conditions	Yield
at 50℃; for 72h; Inert atmosphere;	97%

n-Butyl chloride (109-69-3) + TOP (4731-53-7) → C28H60P(1+)*Cl(1-) (56254-98-9)

Conditions	Yield
at 180℃; under 2250.23 Torr; for 0.5h; Microwave irradiation; Inert atmosphere; neat (no solvent);	97%

1-Chloropentane (543-59-9) + TOP (4731-53-7) → C29H62P(1+)*Cl(1-) (56155-23-8)

Conditions	Yield
at 145℃; for 12h; Inert atmosphere; neat (no solvent);	96%

1-Chlorooctane (111-85-3) + TOP (4731-53-7) → tetraoctylphosphonium chloride (37165-84-7)

Conditions	Yield
at 145℃; for 14h; Inert atmosphere; neat (no solvent);	96%
at 145℃; for 24h; Autoclave;

1-Chloropropane (540-54-5) + TOP (4731-53-7) → C27H58P(1+)*Cl(1-) (56155-22-7)

Conditions	Yield
at 180℃; under 2250.23 Torr; for 0.5h; Microwave irradiation; Inert atmosphere; neat (no solvent);	96%

TOP (4731-53-7) + 4-vinylbenzyl sultone → 4-(trioctylphosphonio)-1-(4-vinylphenyl)butane-2-sulfonate

Conditions	Yield
With 2,6-di-tert-butyl-4-methyl-phenol In toluene at 90℃; for 168h; Inert atmosphere;	96%

1-Chloroheptane (629-06-1) + TOP (4731-53-7) → C31H66P(1+)*Cl(1-) (1352944-92-3)

Conditions	Yield
at 145℃; for 14h; Inert atmosphere; neat (no solvent);	95%

1-Chlorononane (2473-01-0) + TOP (4731-53-7) → C33H70P(1+)*Cl(1-) (1352944-93-4)

Conditions	Yield
at 145℃; for 16h; Inert atmosphere; neat (no solvent);	95%

decyl chloride (1002-69-3) + TOP (4731-53-7) → C34H72P(1+)*Cl(1-) (1352944-94-5)

Conditions	Yield
at 145℃; for 16h; Inert atmosphere; neat (no solvent);	95%

TOP (4731-53-7) + 3-monochloro-1,2-propanediol (96-24-2) → trioctyl(2,3-dihydroxypropyl)phosphonium chloride (688763-75-9)

Conditions	Yield
at 120℃; for 72h; Inert atmosphere; Neat (no solvent);	95%

chloroethane (75-00-3) + TOP (4731-53-7) → ethyl-trioctylphosphonium chloride

Conditions	Yield
at 140℃; under 3000.3 Torr; for 4.5h; Inert atmosphere; Autoclave; neat (no solvent);	94%

1-Chlorohexane (544-10-5) + TOP (4731-53-7) → C30H64P(1+)*Cl(1-) (56255-18-6)

Conditions	Yield
at 145℃; for 12h; Inert atmosphere; neat (no solvent);	94%

(2,2-dimethyl-1,3-dioxolan-4-yl)methyl methanesulfonate (34331-40-3) + TOP (4731-53-7) → CH3O3S(1-)*C30H62O2P(1+) (1353746-15-2)

Conditions	Yield
at 120℃; for 72h; Inert atmosphere; Neat (no solvent);	93%

TOP (4731-53-7) + 1,10-dibromodecane (4101-68-2) → 1,10-di(trioctylphosphonium bromide)decane (53782-85-7)

Conditions	Yield
at 130℃; for 3h; Inert atmosphere; Glovebox; Microwave irradiation;	93%

methylene chloride (74-87-3) + TOP (4731-53-7) → methyltrioctylphosphonium chloride (35675-28-6)

Conditions	Yield
at 140℃; under 3000.3 Torr; for 2.5h; Inert atmosphere; Autoclave; neat (no solvent);	92%
at 100℃; for 12h; Autoclave;

TOP (4731-53-7) + 1-chlorododecane (112-52-7) → trioctyl(dodecyl)phosphonium chloride (1352944-95-6)

Conditions	Yield
at 145℃; for 16h; Inert atmosphere; neat (no solvent);	92%

7-bromoheptanoic acid (30515-28-7) + TOP (4731-53-7) → C31H64O2P(1+)*Br(1-)

Conditions	Yield
In acetonitrile at 80℃; for 48h;	92%

TOP (4731-53-7) + (3-iodopropyl)triethoxysilane (57483-09-7) → trioctyl(3-(triethoxysilyl)propyl)phosphonium iodide

Conditions	Yield
In toluene at 130℃; Inert atmosphere;	92%

TOP (4731-53-7) + solketal tosylate (23737-51-1) → C7H7O3S(1-)*C30H62O2P(1+) (1353746-17-4)

Conditions	Yield
at 120℃; for 48h; Inert atmosphere; Neat (no solvent);	91%

1 ,6-dibromohexane (629-03-8) + TOP (4731-53-7) → 1,6-di(trioctylphosphonium bromide)hexane (103554-07-0)

Conditions	Yield
at 130℃; for 3h; Inert atmosphere; Glovebox; Microwave irradiation;	91%

TOP (4731-53-7) → octylphosphinous dibromide (90224-27-4)

Conditions	Yield
With phosphorus tribromide at 200℃; for 5h;	90%
Multi-step reaction with 2 steps 1: 3 g / PBr3 / 6 h / Heating; nitrogen atmosphere 2: 83 percent / PBr3 / 5 h / 255 - 260 °C View Scheme

TOP (4731-53-7) + 3,3,4,4,5,5,6,6,6-nonafluorohexyliodide (2043-55-2) → C30H55PF9(1+)*I(1-)

Conditions	Yield
at 20℃; for 48h;	90%
Inert atmosphere; Heating;

1,3-propanesultone (1120-71-4) + TOP (4731-53-7) → C27H57O3PS

Conditions	Yield
In toluene at 90℃; for 72h; Inert atmosphere;	90%

Upstream product

• 111-83-1 1-bromo-octane 
• 78-50-2 cyanex-921 
• 20612-73-1 trioctylphosphane selenide 
• 24219-37-2 di-n-octylmagnesium 
• 62779-16-2 (Methoxycarbonylamino-methyl)-trioctyl-phosphonium; chloride 
• 111-66-0 oct-1-ene 

Downstream Products

• 78-50-2 cyanex-921 
• 1005-33-0 4-chlorophenyldichlorophosphine 
• 26508-33-8 iron monophosphide 
• 12032-78-9 manganese phosphide 
• 20612-73-1 trioctylphosphane selenide 
• 1412455-59-4 C₄₇H₈₃P₂⁽¹⁺⁾*C₂F₆NO₄S₂^(1-) 
• 37165-84-7 tetraoctylphosphonium chloride 
• 12134-02-0 cobalt(III) phosphide 
• 12019-57-7 copper phosphide 
• 12019-11-3 copper phosphide 
• 1092969-49-7 (E)-1-cyclopropyl-1-phenyl-2-(1-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)methylene)hexan-1-ol 
• 108083-80-3 Ni(CO)2(C₂₄H₅₁P)2 
• 178264-57-8 ethyl 6-(bromomethyl)-nicotinate 

Relevant articles and documents

On the mechanism of lead chalcogenide nanocrystal formation

On the basis of evidence from 31P NMR spectroscopy, and using PbSe as a model, we propose two simultaneous mechanisms through which monomers are formed in preparations of lead chalcogenide nanocrystals (NCs). In one mechanism, selenium is delivered as a Se2- species, whereas in the other, Se0 reacts with metal already reduced by the organophosphine. This latter mechanism helps explain the sensitivity of NC preparations to the purity of organophosphines and allows the rational modification of batch NC reactions to increase yield. Copyright

METHODS FOR PHOSPHINE OXIDE REDUCTION IN CATALYTIC WITTIG REACTIONS

A method for increasing the rate of phosphine oxide reduction, preferably during a Wittig reaction comprising use of an acid additive is provided. A room temperature catalytic Wittig reaction (CWR) the rate of reduction of the phosphine oxide is increased due to the addition of the acid additive is described. Furthermore, the extension of the CWR to semi-stabilized and non-stabilized ylides has been accomplished by utilization of a masked base and/or ylide-tuning.

Reduction of phosphine oxides to phosphines with the InBr3/TMDS system

An efficient method for the reduction of phosphine oxide derivatives into their corresponding phosphines is described. The system InBr3/TMDS allows the reduction of different secondary and tertiary phosphine oxides as well as aliphatic and aromatic phosphine oxides.