2501-94-2

Basic information

• Product Name: T-BUTYLPHOSPHINE
• Synonyms: TERT-BUTYLPHOSPHINE;T-BUTYLPHOSPHINE;(1,1-dimethylethyl)-phosphin;(1,1-dimethylethyl)phosphine;1,1-Dimethylethylphosphine;tert-Butyl-phosphane;tert-C4H9PH2;Tertiarybutylphosphine
• CAS NO: 2501-94-2
• Molecular Formula: C₄H₁₁P
• Molecular Weight: 90.1
• Product Categories: Primary Phosphines;Organics;organophosphorus ligand
• Mol File: 2501-94-2.mol
• Article Data: 18

Chemical Properties

• Melting Point: -85 °C
• Boiling Point: 54°C
• Flash Point: °C
• Appearance: colorless/liquid
• Density: 0.7
• Vapor Pressure: 125mmHg at 25°C
• Sensitive: air sensitive
• CAS DataBase Reference: T-BUTYLPHOSPHINE(CAS DataBase Reference)
• NIST Chemistry Reference: T-BUTYLPHOSPHINE(2501-94-2)
• EPA Substance Registry System: T-BUTYLPHOSPHINE(2501-94-2)

Safety Data

• Statements: 17-26-34
• Safety Statements: 9-43-45
• RIDADR: 2845
• HazardClass: 4.2
• PackingGroup: I
• Hazardous Substances Data: 2501-94-2(Hazardous Substances Data)

Usage

General Description

T-Butylphosphine is a chemical compound with the formula (CH3)3C–P. It is a colorless, flammable gas that is used as a ligand in organometallic chemistry and catalysis. T-butylphosphine is a strong reducing agent and is generally stable at room temperature and pressure, but can decompose violently when heated or in the presence of certain oxidizing agents. The compound is commonly used in the synthesis of pharmaceuticals and in the production of polymers and fine chemicals. T-butylphosphine is also used in the semiconductor industry for the production of electronic and optoelectronic devices.

InChI:InChI=1/C4H11P/c1-4(2,3)5/h5H2,1-3H3

Synthetic route

(dimethylamino)dibromoborane (7360-64-7) + lithium tert-butylphosphide (67877-34-3, 112215-24-4) → 1,3-di-tert-butyl-2,4-bis(dimethylamino)-1,2,3,4-diphosphadiboretane (122501-55-7, 112438-33-2) + tert-butylphosphine (2501-94-2)

Conditions	Yield
In pentane under N2 or Ar or in vac., cooled to -45°C, addn. of LiPHtBu in pentane, warmed to ambient temp.; filtration of insolubles, from filtrate evapn. of volatiles; elem. anal.;	A 95% B n/a

dichlorodimethylaminoborane (1113-31-1) + lithium tert-butylphosphide (67877-34-3, 112215-24-4) → 1,3-di-tert-butyl-2,4-bis(dimethylamino)-1,2,3,4-diphosphadiboretane (122501-55-7, 112438-33-2) + tert-butylphosphine (2501-94-2)

Conditions	Yield
In pentane byproducts: LiCl; under N2 or Ar or in vac., cooled to -45°C, addn. of LiPHtBu in pentane, warmed to ambient temp.; filtration of insolubles, from filtrate evapn. of volatiles; elem. anal.;	A 95% B n/a

C4H11AlCl3P → tert-butylphosphine (2501-94-2)

Conditions	Yield
With triethylamine In toluene	88%

tert-butyldichlorophosphine (25979-07-1) → tert-butylphosphine (2501-94-2)

Conditions	Yield
With lithium aluminium tetrahydride In butyl diglyme at 20 - 100℃;	82%
With lithium aluminium tetrahydride at 20℃; for 3h; Schlenk technique; Inert atmosphere;	82%
With lithium aluminium tetrahydride In diethylene glycol dimethyl ether at -78℃;	80%
With lithium aluminium tetrahydride In dibutyl ether
With lithium aluminium tetrahydride

tert-butyldifluorophosphine (29149-32-4) → tert-butylphosphine (2501-94-2)

Conditions	Yield
With ethyl trimethylsilyl ether at 20℃; for 1h;	65%

S-ethyl tert-butylthiophosphinite (105414-84-4) + acetyl chloride (75-36-5) + sodium thioethylate (811-51-8) → ethyl thioacetate (625-60-5) + tert-butylphosphine (2501-94-2) + S,S-diethyl tert-butyldithiophosphonite (78187-17-4) + tert-butyldichlorophosphine (25979-07-1)

Conditions	Yield
for 20h; Ambient temperature; sealed;	A 51% B 24% C n/a D n/a

isobutene (115-11-7) → tert-butylphosphine (2501-94-2)

Conditions	Yield
With phosphan; toluene-4-sulfonic acid at 110℃; for 14h;	37%

1,4-dipotassium-1,2,3,4-tetra-t-butyl-tetraphosphane (7621-12-7) → tert-butylphosphine (2501-94-2)

Conditions	Yield
With water In 1,4-dioxane

t-Butylfluorphosphan → tert-butylphosphine (2501-94-2) + tert-butyldifluorophosphine (29149-32-4) + C8H19FP2

Conditions	Yield
Ambient temperature;

t-Butyl-t-butylaminophosphan → tert-butylphosphine (2501-94-2) + (CH3)3CP[HNC(CH3)3]2 (228703-72-8) + C12H29NP2

Conditions	Yield
Ambient temperature;

tert-butylbis(trimethylsilyl)phosphine (42491-33-8) → tert-butylphosphine (2501-94-2) + tert-butyl(trimethylsilyl)phosphine (67033-70-9)

Conditions	Yield
With trans-Crotonaldehyde other reagent: mesityl oxide;

methanesulfonic acid (75-75-2) + n-heptane (142-82-5) + isobutene (115-11-7) + phosphine → tert-butylphosphine (2501-94-2) + di-tert-butylphosphine

Conditions	Yield
at 60℃; under 24271.8 - 25742.8 Torr;
at 60℃; under 24271.8 - 25742.8 Torr;

1,2-Di-tert-butyldiphosphane (90600-97-8) → tert-butylphosphine (2501-94-2) + tert-Butyldiphosphan (82240-49-1) + 1,2-Di-tert-butyltriphosphan + PH3, P3H5

Conditions	Yield
With diphosphane In 1,2-dimethoxyethane at 60℃; for 1h; THF; Title compound not separated from byproducts;
With diphosphane In 1,2-dimethoxyethane at 60℃; for 1h; THF; Yield given. Title compound not separated from byproducts;

tris(tert-butylphosphino)phosphane → tert-butylphosphine (2501-94-2) + 1,2-Di-tert-butyldiphosphane (90600-97-8) + higher tert-butylphosphanes

Conditions	Yield
at -30℃; Mechanism; disproportination and decomposition studies;

(Et2P(CH2)2PEt2)Ni(η-Me3SiPPCMe3) (115713-55-8) → bis{1,2-bis(diethylphosphino)ethane}nickel(0) (54910-60-0) + (((C2H5)2PCH2CH2P(C2H5)2)Ni)2P2 (96555-93-0) + Methoxytrimethylsilane (1825-61-2) + tert-butylphosphine (2501-94-2) + 1,2-Di-tert-butyldiphosphane (90600-97-8)

Conditions	Yield
With methanol In toluene excess CH3OH, reaction proceeds slowly at 0°C and rapidly at 20°C; observed by NMR-spectroscopy;

((C6H11)2PCH2CH2P(C6H11)2)Ni(HPPC(CH3)3) (115713-56-9) → ((C6H11)2PCH2CH2P(C6H11)2Ni)2P2 (96555-95-2) + tert-butylphosphine (2501-94-2)

Conditions	Yield
In toluene 5 d at 80°C;

tert-butylphosphine trimethylaluminum complex → tert-butylphosphine (2501-94-2) + trimethylaluminum (75-24-1)

Conditions	Yield
In gas above 298 K;

tert-butyldichlorophosphine (25979-07-1) → 1,2,3,4-Tetra-tert-butyl-tetraphosphetane (79082-91-0, 5995-07-3) + tert-butylphosphine (2501-94-2) + 1,2-Di-tert-butyldiphosphane (90600-97-8)

Conditions	Yield
With triethylsilane; gallium(III) trichloride In chlorobenzene at 100℃; for 168h;

tert-butyldichlorophosphine (25979-07-1) → 1,2,3,4-Tetra-tert-butyl-tetraphosphetane (79082-91-0, 5995-07-3) + tert-butylphosphine (2501-94-2)

Conditions	Yield
With triethylsilane; gallium(III) trichloride In chlorobenzene at 100℃; for 168h;

tert-butylphosphine (2501-94-2) → t-butylphosphine-borane

Conditions	Yield
With borane-THF In tetrahydrofuran; hexane at 0℃; for 1h;	99%

tert-butylphosphine (2501-94-2) + borane tetrahydrofuran → tert-butylphosphine-borane (162053-46-5)

Conditions	Yield
In tetrahydrofuran; hexane (Ar); transferring of soln. of t-BuPH2 in hexane to flask via syringe, slowly addn. of BH3-THF complex in THF at 0°C , stirring for 1 h at this temp.; removal of solvents under vac., distn. in vac.;	99%

tris(3,4,5-trifluorophenyl)borane (148892-97-1) + tert-butylphosphine (2501-94-2) → tris(3,4,5-trifluorophenyl)boron-tert-butylphosphine adduct (184044-79-9)

Conditions	Yield
In light petroleum (inert atmosphere); stirring (48 h); decantation, drying (vac.), further material from the supernatant; no reliable elemental analysis;	99%

tert-butylphosphine (2501-94-2) + tris(pentafluorophenyl)borate (1109-15-5) → tris(pentafluorophenyl)boron-tert-butylphosphine adduct (184044-76-6)

Conditions	Yield
In light petroleum (inert atmosphere); stirring (48 h); decantation, drying (vac.), further material from the supernatant; no reliable elemental analysis;	99%

tert-butylphosphine (2501-94-2) + tris(2,6-difluorophenyl)borane triethylphosphine oxide (146355-09-1) → tris(2,6-difluorophenyl)boron-tert-butylphosphine adduct (184044-78-8)

Conditions	Yield
In light petroleum (inert atmosphere); stirring (48 h); decantation, drying (vac.), further material from the supernatant; no reliable elemental analysis;	99%

tert-butylphosphine (2501-94-2) + diborane (19287-45-7) → tert-butylphosphine-borane (162053-46-5)

Conditions	Yield
In tetrahydrofuran at 0 - 20℃;	99%

tricarbonylcyclopentadienylmolybdenum(II) chloride (12128-23-3) + tert-butylphosphine (2501-94-2) → cis-dicarbonyl(chloro)(η5-cyclopentadienyl)(tert-butylphosphine)molybdenum(II)

Conditions	Yield
In methyl cyclohexane under N2; equimolar mixt. of Mo complex and ligand in methylcyclohexaneheated at 70°C for 1 h; cooled to room temp.; concd. in vac.; crystd. at 0°C; filtered; washed with pentane; dried in vac.; elem. anal.;	98%

pentamethylcyclopentadienyl tantalum(V) tetrachloride + tert-butylphosphine (2501-94-2) → C5(CH3)5TaCl4(PH2C(CH3)3) (406943-02-0)

Conditions	Yield
In toluene in dry Ar atmosphere C5(CH3)5TaCl4 suspended in toluene, equimolar amt. of PH2C(CH3)3 added, stirred at room temp. until clear soln. obtained; solvent removed to dryness, residue extd. with-pentane, cooled to 5 °C, crystn.; elem. anal.;	96%

tert-butylphosphine (2501-94-2) + pivalaldehyde (630-19-3) → C9H21OP (1246895-41-9)

Conditions	Yield
With trifluoroacetic acid at 80℃;	96%

tert-butylphosphine (2501-94-2) + benzaldehyde (100-52-7) → t-butylbenzylphosphine oxide

Conditions	Yield
With trifluoroacetic acid at 80℃;	95%

tert-butylphosphine (2501-94-2) + 1,5-dihydro-benzo[e][1,3,2]dioxathiepine 3,3-dioxide (187879-67-0) → 2-tert-butyl-1,3-dihydro-isophosphindole 2-oxide (104229-83-6)

Conditions	Yield
Multistep reaction;	94%
With n-butyllithium; dihydrogen peroxide; sodium sulfate In tetrahydrofuran	94%

pentamethylcyclopentadienyl niobium(V) tetrachloride (80432-35-5) + tert-butylphosphine (2501-94-2) → C5(CH3)5NbCl4(PH2C(CH3)3) (499219-54-4)

Conditions	Yield
In toluene; pentane in dry Ar atmosphere C5(CH3)5NbCl4 suspended in toluene, equimolar amt. of PH2C(CH3)3 added, stirred at room temp. until clear soln. obtained; solvent removed to dryness, residue extd. with-pentane, cooled to 5 °C, crystn.; elem. anal.;	94%

tert-butylphosphine (2501-94-2) + di-tert-butyldichloromethylenediphosphine (78463-57-7, 74399-62-5, 74399-57-8) + tert-butyldichlorophosphine (25979-07-1) → 1,2,3,4-Tetra-tert-butyl-[1,2,3,4]tetraphospholane

Conditions	Yield
In toluene at 60℃; for 12h;	93%

mesytaldehyde (487-68-3) + tert-butylphosphine (2501-94-2) → C14H23OP (1246895-43-1)

Conditions	Yield
With trifluoroacetic acid at 80℃;	93%

[(η(5)-cyclopentadienyl)Fe(CO)3] tetrafluoroborate + tert-butylphosphine (2501-94-2) → [(tert-butyl)phosphane]dicarbonyl(η(5)-cyclopentadienyl)iron(II) tetrafluoroborate (215736-16-6)

Conditions	Yield
In acetonitrile byproducts: CO; N2-atmosphere; stirring Fe-complex with slight excess of phosphine (70°C, 20 h); concn. (vac.), pptn. on ether addn., filtration, drying (vac.); elem. anal.;	91%
In acetonitrile byproducts: CO; N2 atmosphere, mixing of cooled soln. of Fe complex (0°C) with phosphane, stirring (60°C, 10 h); reduction of volume (vacuum), pptn. (ether), filtration, washing (ether), drying (vacuum); elem. anal.;	85%

methyl 4,6-O-benzylidene-2,3-anhydro-α-D-mannopyranoside (3150-16-1) + tert-butylphosphine (2501-94-2) → (methyl 3-deoxy-4,6-oxo-benzylidene-α-D-pyranopyranoside)-3-tert-butylphosphine

Conditions	Yield
Stage #1: tert-butylphosphine In tetrahydrofuran; hexane at -78 - 20℃; for 2h; Schlenk technique; Inert atmosphere; Stage #2: methyl 4,6-O-benzylidene-2,3-anhydro-α-D-mannopyranoside In tetrahydrofuran for 6h; Schlenk technique;	90%

bis(diethylamino)chlorophosphine (685-83-6) + tert-butylphosphine (2501-94-2) → 1,1,3,3-Tetrakis(diethylamino)-2-tert-butyl-triphosphan

Conditions	Yield
With n-butyllithium 1.) Et2O, n-hexane, reflux, 0.5 h, 2.) n-pentane, -78 deg C, 1 h;	89%

(η5-cyclopentadienyl)Re(NO)(P(C6H5)3)(CF3SO3) (92695-35-7) + tert-butylphosphine (2501-94-2) → Re(C5H5)(P(C6H5)3)(PH2C(CH3)3)(NO)(1+)*OSO2CF3(1-)={Re(C5H5)(P(C6H5)3)(PH2C(CH3)3)(NO)}OSO2CF3

Conditions	Yield
In benzene addn. of P(t-Bu)H2 to complex in a Schlenk tube with stirring, react. time 3 h; addn. of hexane, ppt. filtered, washed with hexane, dissolved in THF, slowly addn. of ether, ppt. filtered, dried under oil pump vac.; elem. anal.;	89%

Re(C5H5)(P(C6H5)3)(OSO2CF3)(NO) + tert-butylphosphine (2501-94-2) → Re(C5H5)(P(C6H5)3)(PH2C(CH3)3)(NO)(1+)*OSO2CF3(1-)={Re(C5H5)(P(C6H5)3)(PH2C(CH3)3)(NO)}OSO2CF3

Conditions	Yield
In benzene addn. of P(t-Bu)H2 to complex in a Schlenk tube with stirring, react. time 3 h; addn. of hexane, ppt. filtered, washed with hexane, dissolved in THF, slow addn. of ether by vapor diffusion, ppt. filtered, dried under oil pump vac., pure by 1H- and 31P-NMR;	88%

tert-butylphosphine (2501-94-2) + bis(diphenylphosphino)methane (28240-64-4) + tert-butyldichlorophosphine (25979-07-1) → 2,3-Di-tert-butyl-1,4-diphenyl-[1,2,3,4]tetraphospholane

Conditions	Yield
In toluene at 60 - 80℃; for 12h;	86%

chloro-trimethyl-silane (75-77-4) + tert-butylphosphine (2501-94-2) → tert-butylbis(trimethylsilyl)phosphine (42491-33-8)

Conditions	Yield
Stage #1: tert-butylphosphine With n-butyllithium In diethyl ether at -78 - 20℃; for 2.25h; Inert atmosphere; Schlenk technique; Glovebox; Stage #2: chloro-trimethyl-silane In diethyl ether at -78 - 20℃;	86%

2-chloroacetylenephosphonic acid dimethyl ester (19519-59-6) + tert-butylphosphine (2501-94-2) → dimethyl <(tert-butylphosphino)ethynyl>phosphonate

Conditions	Yield
	85%

diiron nonacarbonyl (15321-51-4) + tert-butylphosphine (2501-94-2) → Fe(CO)4{PH2(C(CH3)3)} (85737-35-5)

Conditions	Yield
In diethyl ether byproducts: Fe(CO)5; strirring at room temp. for 24 h in dark; filtration, removing Fe(CO)5, distn.; elem. anal.;	84%

tert-butylphosphine (2501-94-2) + (5aS,9aS)-octahydrobenzo[e][1,3,2]dioxathiepine 3,3-dioxide (1252080-10-6) → (3aS,7aS)-2-(tert-butyl)octahydro-1H-isophosphindole 2-sulfide (1252080-12-8)

Conditions	Yield
Stage #1: tert-butylphosphine With n-butyllithium In tetrahydrofuran; octane; hexane at -78 - 20℃; for 1h; Inert atmosphere; Stage #2: (5aS,9aS)-octahydrobenzo[e][1,3,2]dioxathiepine 3,3-dioxide In tetrahydrofuran; octane; hexane at -78 - 20℃; for 4h; Inert atmosphere; Further stages;	81%
Stage #1: tert-butylphosphine With n-butyllithium In tetrahydrofuran; octane; hexane at -78 - 20℃; Stage #2: (5aS,9aS)-octahydrobenzo[e][1,3,2]dioxathiepine 3,3-dioxide With n-butyllithium In tetrahydrofuran; octane; hexane at -78 - 20℃; Stage #3: With sulfur In tetrahydrofuran; octane; hexane; water at 20℃; for 2h; optical yield given as %ee;	81%

tert-butylphosphine (2501-94-2) + di-tert-butylantimony chloride (4718-00-7) → C12H28PSb

Conditions	Yield
Stage #1: tert-butylphosphine With n-butyllithium In hexane; pentane at 0℃; Schlenk technique; Inert atmosphere; Stage #2: di-tert-butylantimony chloride In hexane; pentane at -20 - 20℃; Schlenk technique; Inert atmosphere;	81%

tert-butylphosphine (2501-94-2) + dimesitylfluoroborane (436-59-9) → (Mes)2BP(H)(C(CH3)3) (118496-13-2)

Conditions	Yield
In diethyl ether 0°C, stirring for 1 h at room temp.;	80%

Upstream product

• 29149-32-4 tert-butyldifluorophosphine 
• 115-11-7 isobutene 
• 75-75-2 methanesulfonic acid 
• 142-82-5 n-heptane 
• 90600-97-8 1,2-Di-tert-butyldiphosphane 
• 1113-31-1 dichlorodimethylaminoborane 
• 67877-34-3 lithium tert-butylphosphide 
• 25979-07-1 tert-butyldichlorophosphine 
• 115713-56-9 ((C₆H₁₁)2PCH₂CH₂P(C₆H₁₁)2)Ni(HPPC(CH₃)3) 
• 115713-55-8 (Et2P(CH2)2PEt2)Ni(η-Me3SiPPCMe3) 
• 7360-64-7 (dimethylamino)dibromoborane 
• 42491-33-8 tert-butylbis(trimethylsilyl)phosphine 
• 105414-84-4 S-ethyl tert-butylthiophosphinite 
• 75-36-5 acetyl chloride 

Downstream Products

• 34557-54-5 methane 
• 75-28-5 Isobutane 
• 115-11-7 isobutene 
• 12063-98-8 gallium phosphide 
• 12032-78-9 manganese phosphide 
• 22398-80-7 indium(III) phosphide 
• 118496-19-8 {Li(Et₂O)2P(t-Bu)B(C₆H₂(CH(CH₃)3)2)} 
• 118496-13-2 (Mes)2BP(H)(C(CH₃)3) 
• 131054-66-5 {osmium(Cl)(PH₂CMe₃)(CO)2(PPh₃)2}perchlorate 
• 153367-55-6 ((CO)2Ni(PH(CF₃)CF₂PH(C(CH₃)3)))2 
• 184044-79-9 tris(3,4,5-trifluorophenyl)boron-tert-butylphosphine adduct 
• 184044-76-6 tris(pentafluorophenyl)boron-tert-butylphosphine adduct 
• 184044-78-8 tris(2,6-difluorophenyl)boron-tert-butylphosphine adduct 
• 1246895-43-1 C₁₄H₂₃OP 

Relevant articles and documents

Synthesis and characterization of bridged dimeric and trimeric Group 13/15 complexes containing primary phosphidotBu)PH>- and arsenido tBu)AsH>- units

Addition of the primary phosphine tBuPH2 or the primary arsine tBuAsH2 to tBu3M (M = Ga, Al) followed by heating or photolysis affords the complexes tBu2M(μ-E(tBu)H)>n (1; M = Ga, E = P; n = 2; 2, M = Al, E = P, n = 2; 3, M = Ga, E = As, n = 3; 4, M = Al, E = As, n = 3).For each compound, the degree of association was assessed on the basis of 1H, 31P, 13C NMR and mass spectroscopy.The anti-isomer of 1 (1a) was also characterized by X-ray crystallography.Crystal data for 1a; C24H56Ga2P2, monoclinic, space group C2/m, a 17.124(7), b 11.755(7), c 8.700(3) Angstroem, V 1561.94(15) Angstroem3, Z = 4, Dcalc 1.157 g cm-3, μ(MoKα) 18.3 cm-1.A total of 1501 unique reflections was measured over the range 3.0 2θ 50.0 deg (θ-2θ scan mode) and 1263 of these with I above 3?(I) were used in the refinement to afford final R and Rw values of 0.059 and 0.070, respectively.

A Simple Strategy for the Preparation of P-Chirogenic Trost Ligands with Different Absolute Configurations

P-chirogenic compounds are useful ligands and organocatalysts in asymmetric synthesis. However, the lack of preparative methods and their configurational instability have significantly hampered their development. Herein, we report a simple strategy for the preparation of enantiomerically pure P,C-chirogenic diphosphines. Amidation of the borane adducts of rac-phosphinobenzoic acids with enantiomerically pure trans-1,2-diaminocyclohexane afforded a 1:2:1 mixture of the diastereomers (C*,C*,Rp,Rp), (C*,C*,Rp,Sp), and (C*,C*,Sp,Sp), which were separated by column chromatography on silica gel. The prepared (C*,C*,Rp,Rp) and (C*,C*,Sp,Sp) stereoisomers were identical to those obtained from the enantiopure phosphines, which were synthesized by a multi-step route using chiral auxiliaries. Hence, this simple, short and convenient route towards P,C-chirogenic diphosphines obviates the use of chiral auxiliaries and enables the access to diphosphines with differently configured P-stereocenters.

Exploring the Reactivity of Donor-Stabilized Phosphenium Cations: Lewis Acid-Catalyzed Reduction of Chlorophosphanes by Silanes

Phosphane-stabilized phosphenium cations react with silanes to effect either reduction to primary or secondary phosphanes, or formation of P-P bonded species depending upon counteranion. This operates for in situ generated phosphenium cations, allowing catalytic reduction of P(III)-Cl bonds in the absence of strong reducing agents. Anion and substituent dependence studies have allowed insight into the competing mechanisms involved.