Tributylphosphine

Chemical properties

Clear liquid

The Uses of Tributylphosphine

Tributylphosphine is usually used as catalyst for Domino reactions of activated conjugated dienes with β,γ-unsaturated-α-ketoesters, [3+2]-Cycloadditions,Umpolung addition reactions,Reductive carbonylation, Allylation reactions.

The Uses of Tributylphosphine

To a solution of the bromide (1.2 g, 4.7 mmol) in dry DMF (36 mL) degassed with N2 was added Pd(PPh3)4 (270 mg, 0.23 mmol) and the stannane (1.85 g, 5.6 mmol). The mixture was flushed with N2 for 5 min, then stirred at 80 C overnight. After cooling, the mixture was partitioned between EtOAc and brine. The org layer was washed with brine (2x), dried, and concentrated to give 3.5 g of a yellow oil. The material was purified by Prep LC (80 g silica, 5-10% EtOAc/heptane) to provide the product as a colorless oil. [900 mg, 88%]

The Uses of Tributylphosphine

1,4-addition catalyst; used with disulfides for the thioetherification of alcohols; acylation catalyst; used to prepare active esters.

The Uses of Tributylphosphine

suzuki reaction

Synthesis Reference(s)

Tetrahedron Letters, 25, p. 2493, 1984 DOI: 10.1016/S0040-4039(01)81213-2

General Description

Tributylphosphane is a colorless to yellowish liquid with a strong garlic-like odor. Tributylphosphane is insoluble in water. Tributylphosphane is liable to heat and ignite spontaneously in air. If involved in a fire phosphine gas, a highly flammable and toxic gas, will evolve. Tributylphosphane is irritating to mucous membranes.

Air & Water Reactions

Highly flammable. May ignite on contact with air or moist air. Insoluble in water.

Reactivity Profile

Organophosphates, such as Tributylphosphane, are susceptible to formation of highly toxic and flammable phosphine gas in the presence of strong reducing agents such as hydrides. Partial oxidation by oxidizing agents may result in the release of toxic phosphorus oxides.

Health Hazard

Fire will produce irritating, corrosive and/or toxic gases. Inhalation of decomposition products may cause severe injury or death. Contact with substance may cause severe burns to skin and eyes. Runoff from fire control may cause pollution.

Fire Hazard

Flammable/combustible material. May ignite on contact with moist air or moisture. May burn rapidly with flare-burning effect. Some react vigorously or explosively on contact with water. Some may decompose explosively when heated or involved in a fire. May re-ignite after fire is extinguished. Runoff may create fire or explosion hazard. Containers may explode when heated.

Purification Methods

Fractionally distil it under reduced pressure in an inert atmosphere (N2) through an 8inch gauze-packed column (b 110-111o/10mm) and redistil it in a vacuum, then seal it in thin glass ampoules. It is easily oxidised by air to tri-n-butylphosphine oxide, b 293-296o/745mm. It has a characteristic odour, it is soluble in EtOH, Et2O, and *C6H6 but is insoluble in H2O and less easily oxidised by air than the lower molecular weight phosphines. It forms complexes, e.g. with CS2 (1:1) m 65.5o (from EtOH). [Davies & Jones J Chem Soc 33 1929, Chernick & Skinner J Chem Soc 1401 1956, Beilstein 4 IV 3436.]