molecular formula C12H27OP B122868 Tributylphosphine oxide CAS No. 814-29-9

Tributylphosphine oxide

Cat. No.: B122868
CAS No.: 814-29-9
M. Wt: 218.32 g/mol
InChI Key: MNZAKDODWSQONA-UHFFFAOYSA-N
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Description

Tributylphosphine oxide is an organophosphorus compound with the chemical formula C12H27OP. It is a phosphine oxide derivative, characterized by the presence of three butyl groups attached to a phosphorus atom, which is further bonded to an oxygen atom. This compound is known for its utility in various chemical reactions and industrial applications due to its unique chemical properties.

Scientific Research Applications

Tributylphosphine oxide has a wide range of applications in scientific research:

Safety and Hazards

Tributylphosphine oxide is a severe eye irritant . Inhalation may cause corrosive injuries to the upper respiratory tract and lungs . It is also harmful if swallowed, in contact with skin, or if inhaled .

Future Directions

Tributylphosphine oxide has been used as a probe molecule in solid-state nuclear magnetic resonance (NMR) techniques to assess the chemistry of defects in solid acid catalysts . This suggests potential future applications in the field of materials science and catalysis .

Mechanism of Action

Target of Action

Tributylphosphine oxide (TBPO) is an organophosphorus compound . It primarily targets carbon-fluorine bonds in organic molecules . The compound’s role is to act as a catalyst, facilitating the breaking of these bonds and enabling the substitution of hydrogen or an amine .

Mode of Action

TBPO interacts with its targets through a process known as oxidative addition . This process involves the breaking of the carbon-fluorine bonds in the target molecules . TBPO then passes the fluoride to a silane in exchange for a hydride or amide . This process is similar to what a typical metal catalyst does .

Biochemical Pathways

The biochemical pathways affected by TBPO involve the generation of phosphine-centered radical species . These species are generated from various tertiary phosphines via phosphine–oxidant charge transfer processes, photoredox catalysis, and electrochemical oxidations . The activation modes and reactions associated with these processes can give rise to many unprecedented activation modes and reactions .

Pharmacokinetics

It’s known that tbpo is a solid at room temperature and has a molecular weight of 21832 . It’s soluble in organic solvents such as methanol . These properties may influence its absorption, distribution, metabolism, and excretion (ADME) properties, and thus its bioavailability.

Result of Action

The result of TBPO’s action is the transformation of the target molecules. Specifically, it enables the breaking of carbon-fluorine bonds and the substitution of hydrogen or an amine . This transformation can be used in various applications, such as the synthesis of new compounds .

Action Environment

The action of TBPO is influenced by environmental factors. For instance, the compound reacts slowly with atmospheric oxygen, and rapidly with other oxidizing agents, to give the corresponding phosphine oxide . Because this reaction is so fast, TBPO is usually handled under an inert atmosphere . Additionally, the compound is sensitive to high temperatures and light, which can cause it to decompose .

Preparation Methods

Synthetic Routes and Reaction Conditions: Tributylphosphine oxide is typically synthesized through the oxidation of tributylphosphine. The reaction involves the exposure of tributylphosphine to oxygen, resulting in the formation of this compound: [ 2 \text{P(CH}_2\text{CH}_2\text{CH}_2\text{CH}_3)_3 + \text{O}_2 \rightarrow 2 \text{O=P(CH}_2\text{CH}_2\text{CH}_2\text{CH}_3)_3 ]

Industrial Production Methods: In industrial settings, this compound is produced by the controlled oxidation of tributylphosphine using air or oxygen. The reaction is typically carried out under an inert atmosphere to prevent over-oxidation and ensure the purity of the product .

Types of Reactions:

    Oxidation: As mentioned, tributylphosphine undergoes oxidation to form this compound.

    Alkylation: Tributylphosphine can be easily alkylated to form various phosphonium salts.

Common Reagents and Conditions:

    Oxidizing Agents: Oxygen or air is commonly used for the oxidation of tributylphosphine.

    Alkylating Agents: Benzyl chloride and other alkyl halides are used for alkylation reactions.

Major Products:

    Oxidation: this compound.

    Alkylation: Phosphonium salts such as tributyl(phenylmethyl)phosphonium chloride.

Comparison with Similar Compounds

    Triphenylphosphine oxide: Another phosphine oxide with three phenyl groups instead of butyl groups.

    Trioctylphosphine oxide: A similar compound with three octyl groups.

    Tri-n-butylphosphine: The precursor to tributylphosphine oxide, which lacks the oxygen atom.

Uniqueness: this compound is unique due to its specific combination of butyl groups and the presence of the phosphine oxide functional group. This combination imparts distinct chemical properties, making it particularly useful in certain catalytic and synthetic applications .

Properties

IUPAC Name

1-dibutylphosphorylbutane
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InChI

InChI=1S/C12H27OP/c1-4-7-10-14(13,11-8-5-2)12-9-6-3/h4-12H2,1-3H3
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InChI Key

MNZAKDODWSQONA-UHFFFAOYSA-N
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URL https://pubchem.ncbi.nlm.nih.gov
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Canonical SMILES

CCCCP(=O)(CCCC)CCCC
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Molecular Formula

C12H27OP
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DSSTOX Substance ID

DTXSID2061149
Record name Tributylphosphine oxide
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Molecular Weight

218.32 g/mol
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Physical Description

White crystalline powder; Hygroscopic; [Acros Organics MSDS]
Record name Tributylphosphine oxide
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CAS No.

814-29-9
Record name Tributylphosphine oxide
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Record name TRIBUTYLPHOSPHINE OXIDE
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Synthesis routes and methods I

Procedure details

A solution of (5)-tert-butyl 2-((S)-1,2-bis(tert-butyldimethylsilyloxy)ethyl)aziridine-1-carboxylate (0.740 g, 1.7 mmol) and 1H-imidazole (0.35 g, 5.1 mmol) in 3 mL toluen was thoroughly degassed and treated with tributylphosphine (0.42 ml, 1.7 mmol). The reaction mixture was heated to reflux and allowed to stir for 3 hours. NaH (60% dispersion in mineral oil) (0.069 g, 2.9 mmol) was added and the reaction mixture was allowed to stir at 110° C. overnight. The reaction mixture was quenched with saturated NH4Cl solution and diluted with EtOAc. The reaction mixture was washed with water then brine. The organics were dried over MgSO4 and concentrated in vacuo. Purification of the crude residue by column chromatography gave tert-butyl (2S,3S)-3,4-bis(tert-butyldimethylsilyloxy)-1-(1H-imidazol-1-yl)butan-2-ylcarbamate with tributylphosphine oxide as the major impurity. This material was used without further purification.
Name
(5)-tert-butyl 2-((S)-1,2-bis(tert-butyldimethylsilyloxy)ethyl)aziridine-1-carboxylate
Quantity
0.74 g
Type
reactant
Reaction Step One
Quantity
0.35 g
Type
reactant
Reaction Step One
Quantity
3 mL
Type
solvent
Reaction Step One
Quantity
0.42 mL
Type
reactant
Reaction Step Two
Name
Quantity
0.069 g
Type
reactant
Reaction Step Three

Synthesis routes and methods II

Procedure details

A one gram quantity of Co(acetate)2. 4H2O and 9 grams triphenylphosphine oxide were charged to an autoclave with 100 cc methanol and 30 cc methylnaphthalene. The reactor was pressured to 3200 psi with an approximately equimolar mixture of hydrogen and carbon monoxide and heated to 180° C. with stirring. The reaction was allowed to proceed for 5 hours. The reactor was cooled and vented, and the reaction product was analyzed and shown to contain ethanol (21.3%), methyl acetate (9.8%), dimethylacetal (15.9%) and acetic acid (5.1%). The products were distilled and the cobalt remained in a soluble form in the distillation residue which consisted primarily of methylnaphthalene. The absence of a solid coating or precipitate on the distillation flask was noted. The distillation residue was returned to the reactor with additional methanol, and found to display high catalytic activity under carbonylation conditions as employed in this example. Thus it is demonstrated that the catalyst can be retained in soluble form by use of phosphine oxide stabilizer, and recycled in a form suitable for use upon application of carbonylation conditions. Similar results to the foregoing can be obtained if tributylphosphine oxide or other tertiary phosphine oxides are substituted for the triphenylphosphine oxide.
Quantity
0 (± 1) mol
Type
solvent
Reaction Step One
[Compound]
Name
Co(acetate)2
Quantity
0 (± 1) mol
Type
reactant
Reaction Step Two
Quantity
9 g
Type
reactant
Reaction Step Three
Quantity
30 mL
Type
reactant
Reaction Step Three
Quantity
100 mL
Type
solvent
Reaction Step Three
Quantity
0 (± 1) mol
Type
reactant
Reaction Step Four
Quantity
0 (± 1) mol
Type
reactant
Reaction Step Four
Quantity
0 (± 1) mol
Type
reactant
Reaction Step Five
[Compound]
Name
dimethylacetal
Quantity
0 (± 1) mol
Type
reactant
Reaction Step Six
Quantity
0 (± 1) mol
Type
solvent
Reaction Step Seven

Synthesis routes and methods III

Procedure details

116.5 g (1 mol) chlorosulfonic acid was placed in an apparatus as described in Example 4 and reacted therein within 60 minutes with 208 g (1 mol) tributylphosphane at 18°-20° C. while cooling with ice. Towards the end of the reaction when cooling was stopped, the reaction temperature rose to 34° C. The whole was stripped at 70° C. under a pressure of 0.5 millibar. This was accompanied by a violent exothermal reaction. The temperature rose up to 140° C. The material was stripped once again at 80° C. under a pressure of 1 millibar. 263 g tributylphosphane oxide was obtained in the form of a HCl-adduct (determined by elementary analysis and 31P -NMR-spectroscopy). 90% P was in the form of a tributylphosphane oxide HCl-adduct.
Name
Quantity
0 (± 1) mol
Type
reactant
Reaction Step One
Quantity
116.5 g
Type
reactant
Reaction Step Two
Quantity
208 g
Type
reactant
Reaction Step Three

Retrosynthesis Analysis

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Strategy Settings

Precursor scoring Relevance Heuristic
Min. plausibility 0.01
Model Template_relevance
Template Set Pistachio/Bkms_metabolic/Pistachio_ringbreaker/Reaxys/Reaxys_biocatalysis
Top-N result to add to graph 6

Feasible Synthetic Routes

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Customer
Q & A

Q1: How does Tributylphosphine oxide interact with metal ions?

A1: this compound exhibits strong complexation with various metal ions. This interaction stems from the electron-donating nature of the oxygen atom in the phosphoryl group (P═O) of TBPO, which readily coordinates with electron-deficient metal centers. [, , , , , ]

Q2: What is the role of this compound in synergistic extraction systems?

A2: this compound often acts as a synergist in combination with other extractants, enhancing the extraction efficiency of metal ions. This synergistic effect arises from the formation of ternary complexes involving the metal ion, the primary extractant, and TBPO. [, , , , , ]

Q3: How does the presence of this compound affect the extraction of uranium?

A3: Studies demonstrate that TBPO effectively extracts uranium from nitric acid solutions. The extraction efficiency is influenced by factors like nitric acid concentration, the presence of other salts, and the specific ionic liquid used as a diluent. []

Q4: What is the molecular formula and weight of this compound?

A4: The molecular formula of this compound is C12H27OP, and its molecular weight is 218.33 g/mol.

Q5: How is infrared spectroscopy used to characterize this compound and its complexes?

A5: Infrared (IR) spectroscopy provides insights into the strength of hydrogen bonds formed by TBPO with other molecules. Specifically, shifts in the P═O stretching band upon complexation with hydrogen bond donors, like substituted phenols, are indicative of the hydrogen bond strength. []

Q6: What is the stability of this compound under different conditions?

A6: this compound exhibits high stability under various conditions, including exposure to high radiation doses. [] This stability makes it suitable for applications like nuclear fuel reprocessing.

Q7: How does this compound influence the reactions of tin enolates with α-halogeno carbonyls?

A7: this compound serves as an effective additive in controlling the regioselectivity of tin enolate reactions with α-halogeno carbonyls. Depending on its concentration and the presence of other additives, TBPO can promote the formation of either 1,4-diketones or β-keto oxiranes. []

Q8: How are computational methods employed to study this compound?

A8: Density functional theory (DFT) calculations are used to predict the adsorption structures, 31P NMR chemical shifts, and hydrogen bond characteristics of TBPO and its complexes with various molecules. [, ]

Q9: How does the structure of this compound impact its synergistic extraction ability?

A9: The butyl groups in TBPO influence its solubility in organic solvents, which in turn affects its extraction capabilities. Modifications to the alkyl chain length can lead to variations in extraction efficiency and selectivity for specific metal ions. [, ]

Q10: How does this compound contribute to the stability of nanoparticles?

A10: TBPO acts as a capping ligand in the synthesis of TiO2 nanoparticles, preventing aggregation and enhancing their stability. Its ability to form complexes with the TiO2 surface through the phosphoryl group is crucial for this stabilization. [, ]

Q11: What analytical techniques are employed to study this compound?

A11: Various techniques are utilized to analyze TBPO and its complexes. These include:

  • Gas Chromatography (GC): Used to identify and quantify low-molecular-weight components in silicone oils, potentially including TBPO as a heat-decomposition product. []
  • Nuclear Magnetic Resonance (NMR) Spectroscopy: Primarily 31P NMR, provides information on complexation, adduct formation, and hydrogen bonding interactions involving TBPO. [, , , , , , ]
  • Infrared (IR) Spectroscopy: Characterizes the P═O group and its involvement in hydrogen bonding with other molecules. []
  • Electrospray Ionization Mass Spectrometry (ESI-MS): Identifies the composition of extracted species and complexes formed by TBPO. []
  • Ultraviolet-Visible (UV-Vis) Spectroscopy: Investigates the electronic transitions and complex formation of TBPO with metal ions. []
  • X-ray Powder Diffraction (XRD): Determines the crystalline structure of materials, including TiO2 nanoparticles synthesized using TBPO. []
  • Transmission Electron Microscopy (TEM): Visualizes the size and morphology of nanoparticles stabilized by TBPO. []
  • Fluorometry: Used to determine trace amounts of elements, like uranium, after extraction using TBPO. []
  • Atomic Absorption Spectrometry (AAS): Measures the concentration of metal ions, particularly after preconcentration using TBPO-based extraction methods. [, ]

Q12: How does the choice of solvent affect the extraction properties of this compound?

A12: The solubility of TBPO and its metal complexes varies depending on the solvent used. This solubility difference influences the extraction efficiency and selectivity. For example, using TBPO in ionic liquids for metal extraction can significantly impact the phase behavior and extraction mechanism. [, ]

Q13: What research tools and resources are essential for studying this compound?

A13: A combination of experimental and computational techniques is crucial for a comprehensive understanding of TBPO. Essential resources include:

    Q14: What are the emerging cross-disciplinary applications of this compound?

    A14: TBPO's versatile nature makes it valuable in various fields. Research highlights its role in:

    • Analytical Chemistry: As an extractant for preconcentrating metal ions and separating lanthanides. [, , , , , ]
    • Materials Science: As a stabilizing agent for nanoparticle synthesis, particularly in the production of TiO2 nanoparticles for applications like solar cells and photocatalysis. [, ]
    • Organic Synthesis: As an additive for controlling regioselectivity in reactions involving tin enolates and α-halogeno carbonyls. []

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