3115-68-2

Basic information

• Product Name: Tetrabutylphosphonium bromide
• Synonyms: Tetranbutylphosphoniumbromidewhitextl;TETRABUTYLPHOSPHONIUM BROMIDE, FOR IPC;Tetra-n-butylphosphoniumbromide,98%;HISHICOLIN PX-4B;tetrabutylphosphonium;Tetra-n-butylphosphonium bromide, typically 95%;Tetrabutylphosphanium bromide;TETRABUTYLPHOSPHONIUM BROMIDE
• CAS NO: 3115-68-2
• Molecular Formula: Br*C₁₆H₃₆P
• Molecular Weight: 339.33
• EINECS: 221-487-8
• Product Categories: Phosphonium Salts;Quaternary phosphonium salts;Ammonium, Phosphonium, Sulfonium Salts (Ionic Liquids);Ionic Liquids;Phosphonium Compounds;Synthetic Organic Chemistry;Phosphonium Salts;Greener Alternatives: Catalysis;Phase Transfer Catalysts;organophosphorus compound
• Mol File: 3115-68-2.mol
• Article Data: 7

Chemical Properties

• Melting Point: 100-103 °C(lit.)
• Flash Point: 290 °C
• Appearance: white/crystal
• Density: 1.8[at 20℃]
• Vapor Pressure: 0.018Pa at 25℃
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• Water Solubility: ca 70 g/100 mL
• Sensitive: Hygroscopic
• Stability: hygroscopic
• BRN: 4160474
• CAS DataBase Reference: Tetrabutylphosphonium bromide(CAS DataBase Reference)
• NIST Chemistry Reference: Tetrabutylphosphonium bromide(3115-68-2)
• EPA Substance Registry System: Tetrabutylphosphonium bromide(3115-68-2)

Safety Data

• Hazard Codes: Xn,T,Xi
• Statements: 21/22-36/37/38-24-20/21/22
• Safety Statements: 26-37/39-45-36/37/39-28A-36
• RIDADR: UN 3464 6.1/PG 3
• WGK Germany: 3
• RTECS: TA2417000
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 3115-68-2(Hazardous Substances Data)

Usage

Chemical Properties

Tetrabutylphosphonium bromide is WHITE TO CREAM CRYSTALLINE POWDER

Uses

Different sources of media describe the Uses of 3115-68-2 differently. You can refer to the following data:
1. Tetrabutylphosphonium bromide is a useful synthetic reagent used in proteomics research.
2. Tetra-n-butylphosphonium bromide is used as a phase-transfer catalyst at high temperatures, at which nitrogen analogues tend to undergo elimination e.g. as catalyst for the dealkoxycarbonylation of malonates and -keto esters by heating in stearic acid. used as an ionic liquid solvent in the regioselective O-alkylation of C/O ambident nucleophiles. It is a synthetic reagent used in proteomics research.
3. Tetrabutylphosphonium bromide (TBPB) is a quaternary salt which can be used:As a medium to disperse ruthenium catalyst for the synthesis of ethylene glycol from synthesis gas via ruthenium melt catalysis.As a catalyst supported on silica or alumina for the halogen exchange reaction to synthesize alkyl bromide from alkyl chloride.To synthesize various ionic liquids on mixing with different proportions of 1,3-dimethylurea for capturing NO gas.As a hydrogen-bond acceptor along with levulinic acid as a hydrogen-bond donor for the preparation of deep eutectic solvents to separate toluene from toluene/n-hexane mixtures.To prepare ionic semiclathrate hydrates.

Flammability and Explosibility

Nonflammable

InChI:InChI=1/C16H36P.BrH/c1-5-9-13-17(14-10-6-2,15-11-7-3)16-12-8-4;/h5-16H2,1-4H3;1H/q+1;/p-1

Synthetic route

1-bromo-butane (109-65-9) → tetrabutyl phosphonium bromide (3115-68-2)

Conditions	Yield
With samarium(III) chloride; phosphorous In acetonitrile at 50℃; electrosynthesis;	10%

1-bromo-butane (109-65-9) + n-butyl magnesium bromide (693-03-8) → tetrabutyl phosphonium bromide (3115-68-2)

Conditions	Yield
With P

1-bromo-butane (109-65-9) + tributylphosphine (998-40-3) → tetrabutyl phosphonium bromide (3115-68-2)

tetrabutyl phosphonium bromide (3115-68-2) → tetrabutylphosphonium fluoride dihydrofluoride

Conditions	Yield
With potassium hydrogen bifluoride In dichloromethane for 0.5h; Ambient temperature;	100%

tetrabutyl phosphonium bromide (3115-68-2) → tetra-n-butylphosphonium tetrafluoroborate

Conditions	Yield
With triethyloxonium fluoroborate In dichloromethane at 20℃; for 0.5h;	100%
With trimethyl phosphite; tetrafluoroboric acid at 0 - 60℃; for 15h; Inert atmosphere; neat (no solvent);	94%
With sodium tetrafluoroborate In water	93%
With sodium tetrafluoroborate In dichloromethane at 120℃; for 24h; Inert atmosphere; Schlenk technique; Glovebox;	90%

cis-dibromobis(trimethylphosphite-κP)platinum (31299-31-7, 77519-93-8) + tetrabutyl phosphonium bromide (3115-68-2) → tetrabutylphosphonium cis-dibromo(dimethylphosphonato)(trimethylphosphite)platinum(II) (1478658-04-6)

Conditions	Yield
In acetonitrile at 70℃; for 2h;	100%

2H(1+)*C6B2N6(2-)*2H2O + tetrabutyl phosphonium bromide (3115-68-2) → 2C16H36P(1+)*C6B2N6(2-)

Conditions	Yield
In water	99%

sodium tetrafluoroborate (13755-29-8) + tetrabutyl phosphonium bromide (3115-68-2) → tetra-n-butylphosphonium tetrafluoroborate

Conditions	Yield
In pentan-1-ol	98.6%

tetrabutyl phosphonium bromide (3115-68-2) + phenyl chloroformate (1885-14-9) + carbonic acid dimethyl ester (616-38-6) → bis(phenyl) carbonate (102-09-0)

Conditions	Yield
	98%

methyl phenyl carbonate (13509-27-8) + tetrabutyl phosphonium bromide (3115-68-2) + phenyl chloroformate (1885-14-9) → bis(phenyl) carbonate (102-09-0)

Conditions	Yield
	98%

potassium trifluoromethansulfonate (2926-27-4) + tetrabutyl phosphonium bromide (3115-68-2) → tetra-n-butylphosphonium trifluoromethanesulfonate (126991-62-6)

Conditions	Yield
In water	98%

methyl phenyl carbonate (13509-27-8) + tetrabutyl phosphonium bromide (3115-68-2) + benzoyl chloride (98-88-4) → benzoic acid phenyl ester (93-99-2)

Conditions	Yield
	97%

triphenyl(p-tolyl)borate potassium salt + tetrabutyl phosphonium bromide (3115-68-2) → tetrabutylphosphonium triphenyl(p-tolyl)borate

Conditions	Yield
In 1,2-dichloro-ethane for 1h;	97%

methyl phenyl carbonate (13509-27-8) + tetrabutyl phosphonium bromide (3115-68-2) + chloroacetic acid ethyl ester (105-39-5) → phenoxyacetic acid ethyl ester (2555-49-9)

Conditions	Yield
	96%

trifluorormethanesulfonic acid (1493-13-6) + tetrabutyl phosphonium bromide (3115-68-2) → tetra-n-butylphosphonium trifluoromethanesulfonate (126991-62-6)

Conditions	Yield
With trimethyl phosphite at 0 - 60℃; for 15h; Inert atmosphere; neat (no solvent);	96%

methyl (S)-2-(benzyloxycarbonlamino)-3-(p-toluenesulfonyl)propionate (1492-52-0) + tetrabutyl phosphonium bromide (3115-68-2) + potassium carbonate (584-08-7) + thiophenol (108-98-5) → N-benzyloxycarbonyl-S-phenyl-L-cysteine methyl ester (153277-33-9)

Conditions	Yield
In water; toluene	94.6%

2-bromo-N-(4-chlorophenyl)butanamide (90841-17-1) + tetrabutyl phosphonium bromide (3115-68-2) → N-(4-chloro)phenyl-2-hydroxy butyramide (72468-65-6)

Conditions	Yield
With sodium hydroxide; sodium formate In water; toluene	94%

bis[bis(pentafluoroethyl)phosphinyl]imide (916079-45-3) + tetrabutyl phosphonium bromide (3115-68-2) → tetra(n-butyl)phosphonium bis[bis(pentafluoroethyl)phosphinyl]azanide

Conditions	Yield
In water at 20℃;	94%
In water at 20℃;	86%

ethene (74-85-1) + tetrabutyl phosphonium bromide (3115-68-2) + platinum(II) bromde → [nBu4P][PtBr3(C2H4)] (1184173-10-1)

Conditions	Yield
In toluene at 150℃; under 18751.9 Torr; for 15h; Autoclave;	94%
In toluene pptd. (Et2O);

sodium tungstate (VI) dihydrate (10213-10-2) + tetraoxo-μ-oxobis(pentamethylcyclopentadienyl)ditungsten(VI) + tetrabutyl phosphonium bromide (3115-68-2) → P(C4H9)4(1+)*(C5(CH3)5)W6O18(1-)=P(C4H9)4(C5(CH3)5)W6O18

Conditions	Yield
With HNO3 In methanol; water byproducts: H2O; (C5(CH3)5)W2O5 in methanol was mixed with an aq. soln. of Na2WO4*2H2O, aq. HNO3 was added, stirring for 2 h, bromide salt in water was added; ppt. was filtered off, washed with small portions of water, methanol anddiethyl ether, dried under vac. at 70°C; elem. anal.;	94%

propyl methanesulfonate (1912-31-8) + tetrabutyl phosphonium bromide (3115-68-2) → propyl bromide (106-94-5) + tetrabutylphosphonium methanesulfonate (98342-59-7)

Conditions	Yield
In benzene at 80℃;	A n/a B 93%

tetrabutyl phosphonium bromide (3115-68-2) + 2-methylsulfanyl-6,7,8,9-tetrahydro-1,2,4-triazolo[5,1-b]quinazoline-5(10H)-one (124005-47-6) → 2-methylthio-6,7,8,9-tetrahydro-1,2,4-triazolo[5,1-b]quinazolin-5(10H)-one tetrabutylphosphonium salt

Conditions	Yield
With sodium hydroxide In chloroform at 20℃; for 0.0833333h;	93%

potassium hexabromoplatinate(IV) + tetrabutyl phosphonium bromide (3115-68-2) → tetrabutylphosphonium hexabromoplatinate

Conditions	Yield
In acetone	93%

gold-colored oil + 1-butanethiol (109-79-5) + ethylphosphonothioic dichloride (993-43-1) + tetrabutyl phosphonium bromide (3115-68-2) → S-n-butyl ethylphosphonodithioic chloride (17162-58-2)

Conditions	Yield
With sodium carbonate In diethyl ether	92.5%

sodium molybdate dihydrate (7631-95-0) + tetraoxo-μ-oxobis(pentamethylcyclopentadienyl)dimolybdenum(VI) + tetrabutyl phosphonium bromide (3115-68-2) → P(C4H9)4(1+)*(C5(CH3)5)Mo6O18(1-)=P(C4H9)4(C5(CH3)5)Mo6O18

Conditions	Yield
With HNO3 In methanol; water byproducts: H2O; (C5(CH3)5)Mo2O5 in methanol was mixed with an aq. soln. of Na2MoO4*2H2O,aq. HNO3 was added, stirring for 2 h, bromide salt in water was added; ppt. was filtered off, washed with small portions of water, methanol anddiethyl ether, dried under vac. at 70°C; elem. anal.;	92%

silver(I) tungstate + tetrabutyl phosphonium bromide (3115-68-2) → 2C16H36P(1+)*O4W(2-)

Conditions	Yield
In water for 0.166667h;	92%

potassium tetracyanoborate + tetrabutyl phosphonium bromide (3115-68-2) → tetra-n-butylphosphonium tetracyanidoborate (916730-42-2)

Conditions	Yield
In acetonitrile for 0.25h;	91%
In acetonitrile byproducts: KBr; solns. of K(B(CN)4) (1.624 mmol) and P(C4H9)4Br mixed, stireed for 15 min; centrifuged, solvent evapd., ppt. washed (Et2O), dried at room temp. (under vac.), recrystd. from CH3CN; elem. anal.;	91%

sodium metavanadate + tetrabutyl phosphonium bromide (3115-68-2) → [tris(tetrabutylphosphonium)] decavanadateH3

Conditions	Yield
With nitric acid In water for 0.0833333h; pH=4.5;	91%

silver(I) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (160298-76-0) + tetrabutyl phosphonium bromide (3115-68-2) → C16H36P(1+)*C32H12BF24(1-)

Conditions	Yield
In dichloromethane at 25℃; for 0.166667h; Darkness; Schlenk technique;	91%

tetrabutyl phosphonium bromide (3115-68-2) → tetrabutylphosphonium nitrate

Conditions	Yield
With trimethyl phosphite; nitric acid at 0 - 60℃; for 15h; Inert atmosphere; neat (no solvent);	90%

tetrabutyl phosphonium bromide (3115-68-2) + bis(trifluoromethane)sulfonimide lithium (90076-65-6) → tetrabutylphosphonium bis(trifluoromethanesulfonyl)amide

Conditions	Yield
In dichloromethane at 120℃; for 24h; Inert atmosphere; Schlenk technique; Glovebox;	90%
In water for 2h;

K[cis-PF2(CN)4] + tetrabutyl phosphonium bromide (3115-68-2) → [(n-Bu4)P][cis-PF2(CN)4]

Conditions	Yield
In dichloromethane; water at 20℃; for 1h;	90%

phosphoric acid O,O'-bis-(3-pentadecyl-phenyl) ester + tetrabutyl phosphonium bromide (3115-68-2) → C42H70O4P(1-)*C16H36P(1+)

Conditions	Yield
With potassium hydroxide In hexane; water at 20℃; for 6h;	90%

Upstream product

• 109-65-9 1-bromo-butane 
• 693-03-8 n-butyl magnesium bromide 
• 998-40-3 tributylphosphine 

Downstream Products

• 220689-12-3 tetrabutylphosphonium nonafluorobutane-1-sulfonate 
• 123-09-1 4-chlorophenyl methyl sulfide 
• 813-75-2 1,3-difluoro-2,2-difluoropropane 
• 56758-54-4 1,2,2-trifluoro-3-chloropropane 
• 423-55-2 1-perfluorooctyl bromide 
• 102-09-0 bis(phenyl) carbonate 
• 13326-10-8 benzyl methyl carbonate 
• 113959-87-8 1-(3-trifluoromethyl)-anilino-2-butanone hydrochloride 
• 113940-11-7 N-(t-butyl)carboxy-1-(3-trifluoromethyl)anilino-2-butanone 
• 2555-49-9 phenoxyacetic acid ethyl ester 
• 2486-07-9 2,4-dinitrophenyl phenyl ether 
• 1493-27-2 ortho-nitrofluorobenzene 
• 68121-46-0 (3,5-dichlorophenyl)(methyl)sulfane 
• 7642-18-4 (Z)-pent-1-en-1-ylbenzene 

Relevant articles and documents

Phosphonium-phosphates/thiophosphates: Ionic liquids or liquid ion pairs? NMR spectroscopic classification

Structurally unique ionic liquids phosphonium-phosphate and phosphonium-thiophosphate, having both phosphorus based counter ions, in which the anionic part is represented by di-aryl phosphate or di-aryl thiophosphate and cations been tetraalkylphosphonium groups, behave differently in terms of their NMR behaviour. While phosphonium-phosphates show significant changes in its 1H, 13C and 31P NMR chemical shifts vis. á vis. corresponding chemical shifts for a physical mixture of tetraalkylphosphonium bromide and di-aryl phosphate, phosphonium-thiophosphates behave almost similarly in terms of NMR with their synthetic precursors, hence indicating phosphate-phosphonium interaction has a significant covalent component resembling more to a liquid ion pair while thiophosphate-phosphonium interaction is principally ionic in nature. Translational diffusion behavior studied by PFGSE-NMR experiments and ionic conductivities of these ionic liquids in chloroform solution corroborated the hypothesis. The effect of variable alkyl chain length in phosphonium cation is effectively observed in the extent of ion association. Results of this study may provide insight into the solution state behavior of these ionic liquids, would help to classify those in terms of their strength of ion association and thus potential application thereof.

Coordination Catalysis in Organic Electrosynthesis. Electrochemical Phosphorylation of Organic Halides in the Presence of Samarium Dichloride

The feasibility was demonstrated for arylation (or alkylation) of white phosphorus under the action of electrochemically generated Sm(II).

Process for the preparation of substantially fluorinated alkyl bromides

According to the process according to the invention, substantially fluorinated alkyl bromides, preferably perfluoroalkyl bromides, are prepared by reaction of substantially fluorinated alkyl iodides with organic bromine compounds in which the bromine atom is bound covalently to a carbon atom or a nitrogen atom.