998-40-3 Usage
Description
Tributylphosphine is an organic compound with the chemical formula (C4H9)3P. It is a colorless, oily liquid with a strong, unpleasant odor. As a phosphine, it has a wide range of applications in various chemical reactions and processes.
Uses
Used in Organic Synthesis:
Tributylphosphine is used as a 1,4-addition catalyst, enabling the thioetherification of alcohols using disulfides. It also serves as an acylation catalyst, aiding in the formation of esters from carboxylic acids and alcohols.
Used in Suzuki Reaction:
In the field of cross-coupling reactions, Tributylphosphine acts as a catalyst in the Suzuki reaction, facilitating the formation of carbon-carbon bonds between aryl or vinyl halides and boronic acids or esters.
Used in Domino Reactions:
Tributylphosphine is commonly used as a catalyst for domino reactions involving activated conjugated dienes and β,γ-unsaturated-α-ketoesters. These reactions are crucial for the synthesis of complex organic molecules.
Used in [3+2]-Cycloadditions:
As a catalyst, Tributylphosphine is employed in [3+2]-cycloadditions, a type of reaction that leads to the formation of five-membered rings from threeand two-atom components.
Used in Umpolung Addition Reactions:
Tributylphosphine plays a role in umpolung addition reactions, where it reverses the polarity of a functional group, allowing for the formation of new chemical bonds.
Used in Reductive Carbonylation:
In reductive carbonylation processes, Tributylphosphine acts as a catalyst, enabling the conversion of halides or pseudo-halides into carboxylic acids or their derivatives under carbon monoxide and hydrogen pressure.
Used in Allylation Reactions:
Tributylphosphine is utilized as a catalyst in allylation reactions, which involve the formation of carbon-carbon bonds through the reaction of allyl compounds with various electrophiles.
Synthesis Reference(s)
Tetrahedron Letters, 25, p. 2493, 1984 DOI: 10.1016/S0040-4039(01)81213-2
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.
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.]
Check Digit Verification of cas no
The CAS Registry Mumber 998-40-3 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 9,9 and 8 respectively; the second part has 2 digits, 4 and 0 respectively.
Calculate Digit Verification of CAS Registry Number 998-40:
(5*9)+(4*9)+(3*8)+(2*4)+(1*0)=113
113 % 10 = 3
So 998-40-3 is a valid CAS Registry Number.
InChI:InChI=1/C12H27P/c1-4-7-10-13(11-8-5-2)12-9-6-3/h4-12H2,1-3H3
998-40-3Relevant articles and documents
Sato, M.,Sato, F.,Yoshida, T.
, p. 415 - 419 (1971)
Kinetics and mechanism of the reaction of bis-μ-diethylphosphidobis(tetracarbonylmanganese) with tri-n-butylphosphine
Basato, Marino
, p. 173 - 180 (1993)
The dinuclear phosphido-bridged manganese complex undergoes thermal CO substitution by PnBu3 in decalin to give nBu3)> and nBu3P)(OC)3Mn(μ-PEt2)2Mn(CO)3(PnBu3)>.A kinetic study of the first CO/PnBu3 exchange indicates that all substitutions for the forward and reverse reactions occur via a dissociative mechanism.The rate of CO dissociation is rather low (k = 6.27 * 10-5 s-1 at 130 deg C), mainly as a consequence of a high activation enthalpy (ΔH* = 165 kJ mol-1).The discriminating ability ofthe resulting coordinatively unsaturated intermediate is only slightly in favour of attack of the more basic PnBu3 compared to CO, as indicated by the values of the competition rate ratio nBu3) = 0.36-0.47>.This behaviour is compared with that of the isostructural chromium complex and discussed in the light of the electronic and structural features related to the metal-metal distance in the two complexes (Mn-Mn = 3.675 Angstroem, Cr-Cr = 2.905 Angstroem, for the μ-PMe2 derivatives).
Sato, M.,Sato, F.,Yoshida, T.
, p. C49 - C50 (1971)
Reductive conversion of phosphoryl P(O) compounds to trivalent organophosphines R3P
Zhang, Jian-Qiu,Han, Li-Biao
supporting information, (2021/02/20)
By introducing trimethylsilyl chloride (TMSCl), the pentavalent phosphoryl P(V) compounds such as triphenylphosphine oxides, secondary phosphine oxides etc., were readily converted to the corresponding R2P(OTMS) intermediates, that can further react efficiently with an electrophile R'X or with a nucleophile R'Li to produce the corresponding trivalent phosphines R2PR’. Chiral phosphines could also be obtained stereospecifically by this strategy.
Reversing Lewis acidity from bismuth to antimony
Balasubramaniam, Selvakumar,Jemmis, Eluvathingal D.,Kumar, Sandeep,Sharma, Deepti,Venugopal, Ajay
supporting information, p. 8889 - 8892 (2021/09/10)
Investigations on the boundaries between the neutral and cationic models of (Mesityl)2EX (E = Sb, Bi and X = Cl?, OTf?) have facilitated reversing the Lewis acidity from bismuth to antimony. We use this concept to demonstrate a higher efficiency of (Mesityl)2SbOTf(Mesityl)2BiOTf in the catalytic reduction of phosphine oxides to phosphines. The experiments supported with computations described herein will find use in designing new Lewis acids relevant to catalysis.
Convergent synthesis of polysubstituted furans via catalytic phosphine mediated multicomponent reactions
Fan, Xia,Chen, Rongshun,Han, Jie,He, Zhengjie
supporting information, (2019/12/25)
Tri- or tetrasubstituted furans have been prepared from terminal activated olefins and acyl chlorides or anhydrides by a multicomponental convergent synthesis mode. Instead of stoichiometric nBu3P, only catalytic nBu3P or nBu3P=O is needed to furnish the furans in modest to excellent yields with a good functional group tolerance under the aid of reducing agent silane. This synthetic method features a silane-driven catalytic intramolecular Wittig reaction as a key annulation step and represents the first successful application of catalytic Wittig reaction in multicomponent cascade reaction.