Chlorodiphenylphosphine

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Chlorodiphenylphosphine
Ph2PCl.png
Chlorodiphenylphosphine-3D-balls.png
Names
Preferred IUPAC name
Diphenylphosphinous chloride [1]
Other names
chlorodiphenylphosphine
p-chlorodiphenylphosphine
diphenyl phosphine chloride
diphenylchlorophosphine
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.012.813 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 214-093-2
PubChem CID
UNII
  • InChI=1S/C12H10ClP/c13-14(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H Yes check.svgY
    Key: XGRJZXREYAXTGV-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C12H10ClP/c13-14(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H
    Key: XGRJZXREYAXTGV-UHFFFAOYAM
  • ClP(c1ccccc1)c2ccccc2
Properties
C12H10ClP
Molar mass 220.63776 g mol−1
Appearanceclear to light yellow liquid
Density 1.229 g cm−3
Boiling point 320 ˚C
Reacts
Solubility Reacts with alcohols
highly soluble in benzene, THF, and ethers
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-exclam.svg
Danger
H290, H302, H314, H412
P234, P260, P264, P270, P273, P280, P301+P312, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P330, P363, P390, P404, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Chlorodiphenylphosphine is an organophosphorus compound with the formula (C6H5)2PCl, abbreviated Ph2PCl. It is a colourless oily liquid with a pungent odor that is often described as being garlic-like and detectable even in the ppb range. It is useful reagent for introducing the Ph2P group into molecules, which includes many ligands. [2] Like other halophosphines, Ph2PCl is reactive with many nucleophiles such as water and easily oxidized even by air.

Contents

Synthesis and reactions

Chlorodiphenylphosphine is produced on a commercial scale from benzene and phosphorus trichloride (PCl3). Benzene reacts with phosphorus trichloride at extreme temperatures around 600 °C to give dichlorophenylphosphine (PhPCl2) and HCl. Redistribution of PhPCl2 in the gas phase at high temperatures results in chlorodiphenylphosphine. [2] [3]

2 PhPCl2 → Ph2PCl + PCl3

Alternatively such compounds are prepared by redistribution reactions starting with triphenylphosphine and phosphorus trichloride.

PCl3 + 2 PPh3 → 3 Ph2PCl

Chlorodiphenylphosphine hydrolyzes to give diphenylphosphine oxide. Reduction with sodium affords tetraphenyldiphosphine:

2 Ph2PCl + 2 Na → [Ph2P]2 + 2 NaCl

With ammonia and elemental sulfur, it converts to the thiophosphorylamide: [4]

Ph2PCl + 2 NH3 + S → Ph2P(S)NH2 + NH4Cl

Uses

Chlorodiphenylphosphine, along with other chlorophosphines, is used in the synthesis of various phosphines. A typical route uses Grignard reagents: [3]

Ph2PCl + MgRX → Ph2PR + MgClX

The phosphines produced from reactions with Ph2PCl are further developed and used as pesticides (such as EPN), stabilizers for plastics (Sandostab P-EPQ), various halogen compound catalysts, flame retardants (cyclic phosphinocarboxylic anhydride), as well as UV-hardening paint systems (used in dental materials) making Ph2PCl an important intermediate in the industrial world. [2] [3]

Precursor to diphenylphosphido derivatives

Chlorodiphenylphosphine is used in the synthesis of sodium diphenylphosphide via its reaction with sodium metal in refluxing dioxane. [5]

Ph2PCl + 2 Na → Ph2PNa + NaCl

Diphenylphosphine can be synthesized in the reaction of Ph2PCl and LiAlH4, the latter usually used in excess. [6]

4 Ph2PCl + LiAlH4 → 4 Ph2PH + LiCl + AlCl3

Both Ph2PNa and Ph2PH are also used in the synthesis of organophosphine ligands.

Characterization

The quality of chlorodiphenylphosphine is often checked by 31P NMR spectroscopy. [7]

Compound31P chemical shift

(ppm vs 85% H3PO4)

PPh3-6
PPh2Cl81.5
PPhCl2165
PCl3218

Related Research Articles

<span class="mw-page-title-main">Organolithium reagent</span> Chemical compounds containing C–Li bonds

In organometallic chemistry, organolithium reagents are chemical compounds that contain carbon–lithium (C–Li) bonds. These reagents are important in organic synthesis, and are frequently used to transfer the organic group or the lithium atom to the substrates in synthetic steps, through nucleophilic addition or simple deprotonation. Organolithium reagents are used in industry as an initiator for anionic polymerization, which leads to the production of various elastomers. They have also been applied in asymmetric synthesis in the pharmaceutical industry. Due to the large difference in electronegativity between the carbon atom and the lithium atom, the C−Li bond is highly ionic. Owing to the polar nature of the C−Li bond, organolithium reagents are good nucleophiles and strong bases. For laboratory organic synthesis, many organolithium reagents are commercially available in solution form. These reagents are highly reactive, and are sometimes pyrophoric.

<span class="mw-page-title-main">Phosphorus trichloride</span> Chemical compound

Phosphorus trichloride is an inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic and reacts readily with water to release hydrogen chloride.

<span class="mw-page-title-main">Triphenylphosphine</span> Chemical compound

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is versatile compound that is widely used as a reagent in organic synthesis and as a ligand for transition metal complexes, including ones that serve as catalysts in organometallic chemistry. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

Organophosphorus chemistry is the scientific study of the synthesis and properties of organophosphorus compounds, which are organic compounds containing phosphorus. They are used primarily in pest control as an alternative to chlorinated hydrocarbons that persist in the environment. Some organophosphorus compounds are highly effective insecticides, although some are extremely toxic to humans, including sarin and VX nerve agents.

<span class="mw-page-title-main">Indium(III) chloride</span> Chemical compound

Indium(III) chloride is the chemical compound with the formula InCl3 which forms a tetrahydrate. This salt is a white, flaky solid with applications in organic synthesis as a Lewis acid. It is also the most available soluble derivative of indium. This is one of three known indium chlorides.

Organophosphines are organophosphorus compounds with the formula PRnH3−n, where R is an organic substituent. These compounds can be classified according to the value of n: primary phosphines (n = 1), secondary phosphines (n = 2), tertiary phosphines (n = 3). All adopt pyramidal structures. Organophosphines are generally colorless, lipophilic liquids or solids. The parent of the organophosphines is phosphine (PH3).

<span class="mw-page-title-main">Thiophosphoryl chloride</span> Chemical compound

Thiophosphoryl chloride is an inorganic compound with the chemical formula PSCl3. It is a colorless pungent smelling liquid that fumes in air. It is synthesized from phosphorus chloride and used to thiophosphorylate organic compounds, such as to produce insecticides.

<span class="mw-page-title-main">Diphosphines</span>

Diphosphines, sometimes called bisphosphanes, are organophosphorus compounds most commonly used as bidentate phosphine ligands in inorganic and organometallic chemistry. They are identified by the presence of two phosphino groups linked by a backbone, and are usually chelating. A wide variety of diphosphines have been synthesized with different linkers and R-groups. Alteration of the linker and R-groups alters the electronic and steric properties of the ligands which can result in different coordination geometries and catalytic behavior in homogeneous catalysts.

<span class="mw-page-title-main">Triethyl phosphite</span> Chemical compound

Triethyl phosphite is an organophosphorus compound, specifically a phosphite ester, with the formula P(OCH2CH3)3, often abbreviated P(OEt)3. It is a colorless, malodorous liquid. It is used as a ligand in organometallic chemistry and as a reagent in organic synthesis.

<span class="mw-page-title-main">Trimethyl phosphite</span> Chemical compound

Trimethyl phosphite is an organophosphorus compound with the formula P(OCH3)3, often abbreviated P(OMe)3. It is a colorless liquid with a highly pungent odor. It is the simplest phosphite ester and finds used as a ligand in organometallic chemistry and as a reagent in organic synthesis. The molecule features a pyramidal phosphorus(III) center bound to three methoxy groups.

<span class="mw-page-title-main">Diphenylphosphine</span> Chemical compound

Diphenylphosphine, also known as diphenylphosphane, is an organophosphorus compound with the formula (C6H5)2PH. This foul-smelling, colorless liquid is easily oxidized in air. It is a precursor to organophosphorus ligands for use as catalysts.

<span class="mw-page-title-main">1,3-Bis(diphenylphosphino)propane</span> Chemical compound

1,3-Bis(diphenylphosphino)propane (dppp) is an organophosphorus compound with the formula Ph2P(CH2)3PPh2. The compound is a white solid that is soluble in organic solvents. It is slightly air-sensitive, degrading in air to the phosphine oxide. It is classified as a diphosphine ligand in coordination chemistry and homogeneous catalysis.

<span class="mw-page-title-main">Chlorodiisopropylphosphine</span> Chemical compound

Chlorodiisopropylphosphine is an organophosphorus compound with the formula [(CH3)2CH]2PCl. It is a colorless liquid that reacts with water and oxygen. The compound is used to prepare tertiary phosphines and phosphinite ligands.

<span class="mw-page-title-main">Diphenylphosphine oxide</span> Chemical compound

Diphenylphosphine oxide is an organophosphorus compound with the formula (C6H5)2P(O)H. It is a white solid that soluble in polar organic solvents.

<span class="mw-page-title-main">Diethylphosphite</span> Chemical compound

Diethyl phosphite is the organophosphorus compound with the formula (C2H5O)2P(O)H. It is a popular reagent for generating other organophosphorus compounds, exploiting the high reactivity of the P-H bond. Diethyl phosphite is a colorless liquid. The molecule is tetrahedral.

In organophosphorus chemistry, an aminophosphine is a compound with the formula R3−nP(NR2)n where R = H or an organic substituent, and n = 0, 1, 2. At one extreme, the parent H2PNH2 is lightly studied and fragile, but at the other extreme tris(dimethylamino)phosphine (P(NMe2)3) is commonly available. Intermediate members are known, such as Ph2PN(H)Ph. These compounds are typically colorless and reactive toward oxygen. They have pyramidal geometry at phosphorus.

Phosphinous acids are usually organophosphorus compounds with the formula R2POH. They are pyramidal in structure. Phosphorus is in the oxidation state III. Most phosphinous acids rapidly convert to the corresponding phosphine oxide, which are tetrahedral and are assigned oxidation state V.

1,2-Bis(dichlorophosphino)ethane is an organophosphorus compound with the formula (CH2PCl2)2. A colorless liquid, it is a precursor to chelating diphosphines.

<span class="mw-page-title-main">Bis(diethylamino)chlorophosphine</span> Chemical compound

Bis(diethylamino)chlorophosphine is an organophosphorus compound with the formula (Et2N)2PCl (Et = ethyl). A colorless liquid, it serves as a masked source of PCl2+.

In chemistry, phosphorochloridites are a class of organophosphorus compound with the formula (RO)2PCl (R = organic substituent). They are pyramidal in shape, akin to regular phosphites (P(OR)3). They are usually colorless and sensitive toward hydrolysis and, to some extent, oxidation to the corresponding phosphorochloridates ((RO)2P(O)Cl).

References

  1. International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. p. 926. doi:10.1039/9781849733069. ISBN   978-0-85404-182-4.
  2. 1 2 3 Quin, L. D. A Guide to Organophosphorus Chemistry; Wiley IEEE: New York, 2000; pp 44-69. ISBN   0-471-31824-8
  3. 1 2 3 Svara, J.; Weferling, N.; Hofmann, T. "Phosphorus Compounds, Organic," In 'Ullmann's Encyclopedia of Industrial Chemistry, 7th ed.; Wiley-VCH: 2008; doi : 10.1002/14356007.a19_545.pub2; Accessed: February 18, 2008.
  4. Lin, Shaoquan; Otsuka, Yasunari; Yin, Liang; Kumagai, Naoya; Shibasaki, Masakatsu (2017). "Catalytic Enantioselective Addition of Diethyl Phosphite to N-Thiophosphinoyl Ketimines: Preparation of (R)-Diethyl (1-Amino-1-phenylethyl)phosphonate". Organic Syntheses. 94: 313–331. doi: 10.15227/orgsyn.094.0313 .
  5. Roy, Jackson W; Thomson, RJ; MacKay, M.F. (1985). "The Stereochemistry of Organometallic Compounds. XXV. The Stereochemistry of Displacements of Secondary Methanesulfonate and p-Toluene-sulfonate esters by Diphenylphosphide Ions. X-ray Crystal Structure of (5α-Cholestan-3α-yl)diphenylphosphine Oxide". Australian Journal of Chemistry . 38 (1): 111–18. doi:10.1071/CH9850111.
  6. Stepanova, Valeria A.; Dunina, Valery V.; Smoliakova, Irina P. (2009). "Reactions of Cyclopalladated Complexes with Lithium Diphenylphosphide". Organometallics . 28 (22): 6546–6558. doi:10.1021/om9005615.
  7. O. Kühl "Phosphorus-31 NMR Spectroscopy" Springer, Berlin, 2008. ISBN   978-3-540-79118-8