| Revision as of 12:32, 16 September 2011 editCheMoBot (talk | contribs)Bots141,565 edits Updating {{chembox}} (no changed fields - added verified revid - updated 'DrugBank_Ref', 'UNII_Ref', 'ChEMBL_Ref', 'ChEBI_Ref', 'KEGG_Ref') per Chem/Drugbox validation (report errors or [[user← Previous edit |
Latest revision as of 14:27, 12 November 2024 edit undo134.126.58.234 (talk) →Conversion of alcohols to alkyl chlorides: Corrected SN2 to SN1. |
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{{Use dmy dates|date=February 2022}} |
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{{chembox |
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| Verifiedfields = changed |
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| verifiedrevid = 450795552 |
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| Watchedfields = changed |
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| Name = Phosphorus trichloride |
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| verifiedrevid = 450796811 |
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| ImageFile = Phosphorus-trichloride-2D-dimensions.png |
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| ImageName = Phosphorus trichloride |
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| Name = Phosphorus trichloride |
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| ImageFile1 = Phosphorus-trichloride-3D-vdW.png |
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| ImageFile = Phosphorus-trichloride-2D-dimensions.png |
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| ImageName1 = Phosphorus trichloride |
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| ImageName = Phosphorus trichloride |
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| ImageFile2 = Phosphorus trichloride 25ml.jpg |
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| ImageFile1 = Phosphorus-trichloride-3D-vdW.png |
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| ImageName1 = Phosphorus trichloride |
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| ImageSize2 = 250px |
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| IUPACName = Phosphorus trichloride |
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| ImageFile2 = Phosphorus trichloride 25ml.jpg |
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| ImageSize2 = 250px |
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| OtherNames = Phosphorus(III) chloride<br/>Phosphorous chloride |
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| IUPACName = Phosphorus trichloride |
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| Section1 = {{Chembox Identifiers |
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| SystematicName = Trichlorophosphane |
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| CASNo = 7719-12-2 |
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| OtherNames = Phosphorus(III) chloride<br/>Phosphorous chloride |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| Section1 = {{Chembox Identifiers |
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| EINECS = 231-749-3 |
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| PubChem = 24387 |
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| CASNo = 7719-12-2 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| UNII_Ref = {{fdacite|changed|FDA}} |
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| UNII = M97C0A6S8U |
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| EINECS = 231-749-3 |
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| PubChem = 24387 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 22798 |
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| ChemSpiderID = 22798 |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 30334 |
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| ChEBI = 30334 |
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| SMILES = ClP(Cl)Cl |
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| SMILES = ClP(Cl)Cl |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI=1S/Cl3P/c1-4(2)3 |
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| StdInChI=1S/Cl3P/c1-4(2)3 |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = FAIAAWCVCHQXDN-UHFFFAOYSA-N |
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| StdInChIKey = FAIAAWCVCHQXDN-UHFFFAOYSA-N |
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| RTECS = TH3675000 |
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| RTECS = TH3675000 |
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| UNNumber = 1809 |
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| UNNumber = 1809 |
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}} |
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}} |
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| Section2 = {{Chembox Properties |
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| Section2 = {{Chembox Properties |
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| Formula = PCl<sub>3</sub> |
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| Formula = PCl<sub>3</sub> |
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| MolarMass = 137.33 g/mol |
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| MolarMass = 137.33 g/mol |
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| Appearance = colourless liquid |
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| Appearance = Colorless to yellow fuming liquid<ref name=PGCH/> |
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| Odor = unpleasant, acrid, like ]<ref name=PGCH/> |
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| Solubility = ] |
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| Solubility = ] |
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| Solvent = other solvents |
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| Solvent = other solvents |
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| SolubleOther = soluble in ], ], ], ], halogenated ] |
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| SolubleOther = soluble{{vague|date=February 2013}} in ], ], ], ], ], halogenated ] <br/> reacts with ] |
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| MeltingPt = -93.6 °C (179.6 K) |
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| MeltingPtC = -93.6 |
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| BoilingPt = 76.1 °C (349.3 K) |
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| Density = 1.574 g/cm<sup>3</sup> |
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| BoilingPtC = 76.1 |
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| Density = 1.574 g/cm<sup>3</sup> |
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| Dipole = 0.97 ] |
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| Dipole = 0.97 ] |
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| RefractIndex = 1.516 (14 °C) |
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| RefractIndex = 1.5122 (21 °C) |
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| Viscosity = 0.65 cP (0 °C) <br/> 0.438 cP (50 °C) |
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| SurfaceTension = 0.0291 N/m |
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| VaporPressure = 13.3 kPa |
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| MagSus = −63.4·10<sup>−6</sup> cm<sup>3</sup>/mol |
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}} |
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}} |
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| Section4 = {{Chembox Thermochemistry |
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| Section4 = {{Chembox Thermochemistry |
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| DeltaHf = −319.7 kJ/mol |
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| DeltaHf = −319.7 kJ/mol |
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}} |
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}} |
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| Section7 = {{Chembox Hazards |
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| Section7 = {{Chembox Hazards |
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| MainHazards = Highly toxic,<ref>Phosphorus trichloride toxicity</ref> corrosive |
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| ExternalMSDS = |
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| ExternalSDS = |
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| EUIndex = 015-007-00-4 |
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| GHSPictograms = {{GHS06}} {{GHS08}} {{GHS05}} |
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| EUClass = Toxic ('''T''')<br/>Harmful ('''Xn''')<br/>Corrosive ('''C''') |
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| GHSSignalWord = Danger |
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| RPhrases = {{R14}}, {{R26/28}}, {{R35}}, {{R48/20}} |
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| GHS_ref = <ref name ="Sigma">{{Sigma-Aldrich|id=310115|name=Phosphorus trichloride|access-date=28/1/2020}}</ref> |
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| SPhrases = {{S1/2}}, {{S7/8}}, {{S26}}, {{S36/37/39}}, {{S45}} |
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| HPhrases = {{H-phrases|300|301|330|314|373}} |
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| NFPA-H = 4 |
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| PPhrases = {{P-phrases|260|273|284|305+351+338|304+340+310|303+361+353}} |
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| NFPA-F = 0 |
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| NFPA-R = 2 |
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| NFPA-H = 4 |
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| NFPA-O = W |
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| NFPA-F = 0 |
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| NFPA-R = 2 |
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| FlashPt = |
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| LD50 = 550 mg/kg |
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| NFPA-S = W |
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| FlashPt = |
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| LD50 = 18 mg/kg (rat, oral)<ref name=IDLH>{{IDLH|7719122|Phosphorus trichloride}}</ref> |
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| IDLH = 25 ppm<ref name=PGCH>{{PGCH|0511}}</ref> |
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| LC50 = 104 ppm (rat, 4 hr)<br/>50 ppm (guinea pig, 4 hr)<ref name=IDLH/> |
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| REL = TWA 0.2 ppm (1.5 mg/m<sup>3</sup>) ST 0.5 ppm (3 mg/m<sup>3</sup>)<ref name=PGCH/> |
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| PEL = TWA 0.5 ppm (3 mg/m<sup>3</sup>)<ref name=PGCH/> |
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}} |
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}} |
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| Section8 = {{Chembox Related |
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| Section8 = {{Chembox Related |
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| Function = phosphorus chlorides |
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| OtherFunction_label = phosphorus chlorides |
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| OtherFunctn = ]<br/>]<br/>] |
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| OtherFunction = ]<br/>]<br/>] |
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| OtherCpds = ]<br/>]<br/>] |
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| OtherCompounds = ]<br/>]<br/>] |
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}} |
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}} |
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}} |
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}} |
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'''Phosphorus trichloride''' is a ] of ] and ], having ] PCl<sub>3</sub>. Its shape is trigonal pyramidal. It is the most important of the three ]. It is an important ], being used for the manufacture of organophosphorus compounds for a wide variety of applications. It has a <sup>31</sup>P NMR signal at around +220 ppm. |
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'''Phosphorus trichloride''' is an ] with the ] PCl<sub>3</sub>. A colorless liquid when pure, it is an important ], being used for the manufacture of ]s and other ]s. It is toxic and reacts readily with water to release ]. |
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==Chemical properties== |
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The ] in PCl<sub>3</sub> is often considered to have the +3 ] and the ] atoms are considered to be in the −1 oxidation state. Most of its reactivity is consistent with this description. |
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===Redox reactions=== |
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== History == |
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Phosphorus trichloride was first prepared in 1808 by the French chemists ] and ] by heating ] (Hg<sub>2</sub>Cl<sub>2</sub>) with ].<ref>{{cite journal|last1=Gay-Lussac|last2=Thénard|title=Extrait de plusieurs notes sur les métaux de la potasse et de la soude, lues à l'Institut depuis le 12 janvier jusqu'au 16 mai|journal=Gazette Nationale, Ou le Moniteur Universel|date=27 May 1808|volume=40|issue=148|pages=581–582|url=https://books.google.com/books?id=GRROAAAAcAAJ&pg=PA581|trans-title=Extracts from several notes on the metals potassium and sodium, read at the Institute from the 12th of January to the 16th of May|language=fr}} From p. 582: ''"Seulement ils ont rapporté qu'en traitant le mercure doux par le phosphure, dans l'espérance d'avoir de l'acide muriatique bien sec, il ont trouvé une liqueur nouvelle très limpide, sans couleur, répandant de fortes vapeurs, s'enflammant spontanément lorsqu'on en imbibe le papier joseph; laquelle ne paraît être qu'une combinaison de phosphore, d'oxigène et d'acide muriatique, et par conséquent analogue à cette qu'on obtient en traitant le soufre par le gas acide muriatique oxigèné."'' (Only they reported that by treating calomel with phosphorus, in the hope of obtaining very dry hydrogen chloride, they found a new, very clear liquid, colorless, giving off strong vapors, spontaneously igniting when one soaks filter paper in it; which seems to be only a compound of phosphorus, oxygen, and hydrochloric acid, and thus analogous to what one obtains by treating sulfur with chlorine gas.)</ref> Later during the same year, the English chemist ] produced phosphorus trichloride by burning phosphorus in chlorine gas.<ref>{{cite journal|last1=Davy|first1=Humphry|title=The Bakerian Lecture. An account of some new analytical researches on the nature of certain bodies, particularly the alkalies, phosphorus, sulphur, carbonaceous matter, and the acids hitherto undecomposed; with some general observations on chemical theory|journal=Philosophical Transactions of the Royal Society of London|date=1809|volume=99|pages=39–104|url=https://babel.hathitrust.org/cgi/pt?id=mdp.39015034564347;view=1up;seq=53|doi=10.1098/rstl.1809.0005|s2cid=98814859}} On pp. 94–95, Davy mentioned that when he burned phosphorus in chlorine gas ("oxymuriatic acid gas"), he obtained a clear liquid (phosphorus trichloride) and a white solid (phosphorus pentachloride).</ref> |
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PCl<sub>3</sub> is a precursor to other phosphorus compounds, undergoing ] to ] (PCl<sub>5</sub>), ] (PSCl<sub>3</sub>), or ] (POCl<sub>3</sub>). |
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==Preparation== |
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If an ] is passed through a mixture of PCl<sub>3</sub> vapour and ] gas, a rare chloride of phosphorus is formed, diphosphorus tetrachloride (P<sub>2</sub>Cl<sub>4</sub>). |
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World production exceeds one-third of a million ]s.<ref>{{Greenwood&Earnshaw2nd}}</ref> Phosphorus trichloride is prepared industrially by the reaction of ] with ], using phosphorus trichloride as the solvent. In this continuous process PCl<sub>3</sub> is removed as it is formed in order to avoid the formation of PCl<sub>5</sub>. |
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===PCl<sub>3</sub> as an electrophile=== |
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:P<sub>4</sub> + 6 Cl<sub>2</sub> → 4 PCl<sub>3</sub> |
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Phosphorus trichloride is the precursor to ]s that contain one or more P(III) atoms, most notably phosphites and phosphonates. These compounds do not usually contain the chlorine atoms found in PCl<sub>3</sub>. |
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==Structure and spectroscopy== |
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It has a trigonal pyramidal shape. Its <sup>31</sup>P ] spectrum exhibits a singlet around +220 ppm with reference to a phosphoric acid standard.{{fact|date=February 2022}} |
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==Reactions== |
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PCl<sub>3</sub> reacts rapidly and ]ally with ] to form ], H<sub>3</sub>PO<sub>3</sub> and ]: |
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The ] in PCl<sub>3</sub> is often considered to have the +3 ] and the ] atoms are considered to be in the −1 oxidation state. Most of its reactivity is consistent with this description.<ref>{{Cite web |title=Phosphorus trichloride (PCl3) |url=https://www.simply.science/images/content/chemistry/metals_and_non_metals/nitrogen_family/conceptmap/Phosphorus_chloride.html |access-date=2023-02-15 |website=www.simply.science}}</ref> |
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===Oxidation=== |
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PCl<sub>3</sub> is a precursor to other phosphorus compounds, undergoing ] to ] (PCl<sub>5</sub>), ] (PSCl<sub>3</sub>), or ] (POCl<sub>3</sub>). |
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===PCl<sub>3</sub> as an electrophile=== |
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PCl<sub>3</sub> reacts vigorously with ] to form ] (H<sub>3</sub>PO<sub>3</sub>) and ]: |
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:PCl<sub>3</sub> + 3 H<sub>2</sub>O → H<sub>3</sub>PO<sub>3</sub> + 3 HCl |
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:PCl<sub>3</sub> + 3 H<sub>2</sub>O → H<sub>3</sub>PO<sub>3</sub> + 3 HCl |
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A large number of similar substitution reactions are known, the most important of which is the formation of ]s by reaction with ]s or ]. For example, with ], ] is formed: |
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Phosphorus trichloride is the precursor to ]s. It reacts with ] to give ]: |
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:3 PhOH + PCl<sub>3</sub> → P(OPh)<sub>3</sub> + 3 HCl |
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:{{chem2|1=3 PhOH + PCl3 → P(OPh)3 + 3 HCl (Ph = C6H5)}} |
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]s such as ethanol react similarly in the presence of a ] such as a tertiary amine:<ref>{{OrgSynth | author = A. H. Ford-Moore | author2 = B. J. Perry | name-list-style=amp | title = Triethyl Phosphite | collvol = 4 | collvolpages = 955 | year = 1963 | prep = CV4P0955}}</ref> |
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:{{chem2|PCl3 + 3 EtOH + 3 R<sub>3</sub>N → P(OEt)3 + 3 R3NH(+)Cl(-)}} |
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With one equivalent of alcohol and in the absence of base, the first product is alkoxyphosphorodichloridite:<ref>{{cite journal |doi=10.1039/JR9530001920|title=394. Interaction of phosphorus trichloride with alcohols and with hydroxy-esters |year=1953 |last1=Gerrard |first1=W. |last2=Isaacs |first2=M. J. D. |last3=Machell |first3=G. |last4=Smith |first4=K. B. |last5=Wyvill |first5=P. L. |journal=Journal of the Chemical Society (Resumed) |page=1920 }}</ref> |
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:{{chem2|PCl3 + EtOH → PCl2(OEt) + HCl}} |
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In the absence of base, however, with excess alcohol, phosphorus trichloride converts to ]:<ref>{{cite book|chapter=Diethyl phosphite|author=Malowan, John E.|title=Inorganic Syntheses|year=1953|volume=4|pages=58–60|doi=10.1002/9780470132357.ch19|isbn=9780470132357}}</ref><ref name='CSSP488'>{{cite journal|last = Pedrosa|first = Leandro|year = 2011|url = http://cssp.chemspider.com/488|title = Esterification of Phosphorus Trichloride with Alcohols; Diisopropyl phosphonate|journal = ChemSpider Synthetic Pages|pages=488|doi = 10.1039/SP488|publisher = Royal Society of Chemistry|doi-access = free}}</ref> |
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where "Ph" stands for ] group, -C<sub>6</sub>H<sub>5</sub>. ]s such as ethanol react similarly in the presence of a ] such as a tertiary amine:<ref>{{OrgSynth | author = A. H. Ford-Moore and B. J. Perry | title = Triethyl Phosphite | collvol = 4 | collvolpages = 955 | year = 1963 | prep = CV4P0955}}</ref> |
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:PCl<sub>3</sub> + 3 EtOH → (EtO)<sub>2</sub>P(O)H + 2 HCl + EtCl |
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Secondary ]s (R<sub>2</sub>NH) form ]s. For example, ], (Et<sub>2</sub>N)<sub>2</sub>PCl, is obtained from ] and PCl<sub>3</sub>. ]s (RSH) form P(SR)<sub>3</sub>. An industrially relevant reaction of PCl<sub>3</sub> with amines is phosphonomethylation, which employs ]: |
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:PCl<sub>3</sub> + 3 EtOH + 3 R<sub>3</sub>N → P(OEt)<sub>3</sub> + 3 R<sub>3</sub>NH<sup>+</sup>Cl<sup>−</sup> |
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: R<sub>2</sub>NH + PCl<sub>3</sub> + CH<sub>2</sub>O → (HO)<sub>2</sub>P(O)CH<sub>2</sub>NR<sub>2</sub> + 3 HCl |
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The herbicide ] is also produced this way. |
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The reaction of PCl<sub>3</sub> with ]s and ]s is a useful method for the preparation of organic ]s with the formula R<sub>3</sub>P (sometimes called phosphanes) such as ], Ph<sub>3</sub>P. |
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Of the many related compounds can be prepared similarly, triisopropyl phosphite is an example (b.p. 43.5 °C/1.0 mm; CAS# 116-17-6). |
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:{{chem2|3 RMgBr + PCl3 -> R3P + 3 MgBrCl}} |
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In the absence of base, however, the reaction produces ] and an ], according to the following stoichiometry: |
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Triphenylphosphine is produced industrially by the reaction between phosphorus trichlorid, ], and sodium:<ref name= Corbridge>{{cite book | author = Corbridge, D. E. C. | title = Phosphorus: An Outline of its Chemistry, Biochemistry, and Technology | year = 1995 | edition = 5th | publisher = Elsevier | location = Amsterdam | isbn = 0-444-89307-5}}</ref> |
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:{{chem2|PCl3 + 3 PhCl + 6 Na -> PPh3 + 6 NaCl}}, where Ph = {{chem2|C6H5}} |
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Under controlled conditions or especially with bulky R groups, similar reactions afford less substituted derivatives such as ]. |
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:PCl<sub>3</sub> + 3 C<sub>2</sub>H<sub>5</sub>OH → 3 C<sub>2</sub>H<sub>5</sub>Cl + H<sub>3</sub>PO<sub>3</sub><ref name = "testing">Clark, Jim (2008). . Retrieved October 9, 2008.</ref> |
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===Conversion of alcohols to alkyl chlorides=== |
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Alternatively, under certain conditions the dialkyl ] (dialkyl phosphite) may be isolated, as well as some alkyl chloride:<ref name='CSSP488'>{{cite journal|last = Pedrosa|first = Leandro|year = 2011|url = http://cssp.chemspider.com/488|title = Esterification of Phosphorus Trichloride with Alcohols; Diisopropyl phosphonate|journal = ChemSpider Synthetic Pages|pages=488|doi = 10.1039/SP488|publisher = Royal Society of Chemistry}}</ref> |
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Phosphorus trichloride is commonly used to convert primary and secondary alcohols to the corresponding chlorides.<ref>{{cite book |doi=10.1002/9780470771259.ch11|chapter=Displacement of Hydroxyl Groups |title=The Hydroxyl Group (1971) |year=1971 |last1=Brown |first1=Geoffrey W. |series=PATai's Chemistry of Functional Groups |pages=593–639 |isbn=9780470771259 }}</ref> As discussed above, the reaction of alcohols with phosphorus trichloride is sensitive to conditions. The mechanism for the ROH →RCl conversion involves the reaction of HCl with phosphite esters: |
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:{{chem2|P(OR)3 + HCl <-> HP(OR)3(+)Cl(-)}} |
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:{{chem2|HP(OR)3(+)Cl(-) -> RCl + HOP(OR)2}}. |
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:{{chem2| HOP(OR)2 + HCl <-> H2OP(OR)2(+)Cl(-)}} |
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:PCl<sub>3</sub> + 3 <sup>i</sup>PrOH → <sup>i</sup>Pr<sub>2</sub>PH=O + <sup>i</sup>PrCl + 2 HCl(g) where <sup>i</sup>Pr = ], (CH<sub>3</sub>)<sub>2</sub>CH- |
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:{{chem2|H2OP(OR)2(+)Cl(-) -> RCl + (HO)2P(OR)}} |
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:{{chem2| (HO)2P(OR) + HCl <-> H(HO)2P(OR)(+)Cl(-)}} |
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]s, R<sub>2</sub>NH, form P(NR<sub>2</sub>)<sub>3</sub>, and ]s (RSH) form P(SR)<sub>3</sub>. An industrially relevant reaction of PCl<sub>3</sub> with amines is phosphonomethylation, which employs ]: |
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:{{chem2|H(HO)2P(OR)(+)Cl(-) -> RCl + (HO)3P}} |
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: R<sub>2</sub>NH + PCl<sub>3</sub> + CH<sub>2</sub>O → (HO)<sub>2</sub>P(O)CH<sub>2</sub>NR<sub>2</sub> + 3 HCl |
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The first step proceeds with nearly ideal stereochemistry but the final step far less so owing to an SN1 pathway. |
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Aminophosphonates are widely used as sequestring and antiscale agents in water treatment. The large volume herbicide ] is also produced this way. The reaction of PCl<sub>3</sub> with ]s and ]s is a useful method for the preparation of organic ]s with the formula R<sub>3</sub>P (sometimes called phosphanes) such as ], Ph<sub>3</sub>P. |
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===Redox reactions=== |
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:3 PhMgBr + PCl<sub>3</sub> → Ph<sub>3</sub>P + 3 MgBrCl |
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Phosphorus trichloride undergoes a variety of redox reactions:<ref name= Corbridge/> |
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:{{chem2|3PCl3 + 2 CrO3 -> 3POCl3 + Cr2O3 }} |
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Under controlled conditions PCl<sub>3</sub> can be used to prepare PhPCl<sub>2</sub> and Ph<sub>2</sub>PCl. |
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:{{chem2|PCl3 + SO3 -> POCl3 + SO2}} |
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:{{chem2|3 PCl3 + SO2 -> 2POCl3 + PSCl3}} |
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===PCl<sub>3</sub> as a nucleophile=== |
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===PCl<sub>3</sub> as a nucleophile=== |
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Phosphorus trichloride has a lone pair, and therefore can act as a ], for example with the ]s BBr<sub>3</sub><ref>{{cite journal | author = R. R. Holmes | journal = Journal of Inorganic and Nuclear Chemistry | volume = 12 | issue = 3-4 | pages = 266–275 | year = 1960 | doi = 10.1016/0022-1902(60)80372-7 | title = An examination of the basic nature of the trihalides of phosphorus, arsenic and antimony,}}</ref> it forms a 1:1 adduct, Br<sub>3</sub>B<sup>−</sup>−<sup>+</sup>PCl<sub>3</sub>. Metal complexes such as Ni(PCl<sub>3</sub>)<sub>4</sub> are known. This Lewis basicity is exploited in one useful route to organophosphorus compounds using an ] chloride and ]: |
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Phosphorus trichloride has a lone pair, and therefore can act as a ],<ref>{{cite journal | author = R. R. Holmes | journal = Journal of Inorganic and Nuclear Chemistry | volume = 12 | issue = 3–4 | pages = 266–275 | year = 1960 | doi = 10.1016/0022-1902(60)80372-7 | title = An examination of the basic nature of the trihalides of phosphorus, arsenic and antimony}}</ref> e.g., forming a 1:1 adduct Br<sub>3</sub>B-PCl<sub>3</sub>. Metal complexes such as Ni(PCl<sub>3</sub>)<sub>4</sub> are known, again demonstrating the ligand properties of PCl<sub>3</sub>. |
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:PCl<sub>3</sub> + RCl + AlCl<sub>3</sub> → RPCl{{su|b=3|p=+}} + AlCl{{su|b=4|p=−}} |
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This Lewis basicity is exploited in the ] to prepare alkylphosphonyl dichlorides (RP(O)Cl<sub>2</sub>) and alkyl] esters (RP(O)(OR')<sub>2</sub>). Alkylation of phosphorus trichloride is effected in the presence of ] give the alkyltrichlorophosphonium salts, which are versatile intermediates:<ref name = Svara>{{ Ullmann | author = Svara, J. | author2 = Weferling, N. | author3 = Hofmann, T. | title = Phosphorus Compounds, Organic | doi = 10.1002/14356007.a19_545.pub2}}</ref> |
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:PCl<sub>3</sub> + RCl + AlCl<sub>3</sub> → RPCl{{su|b=3|p=+}} + AlCl{{su|b=4|p=−}} |
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The RPCl{{su|b=3|p=+}} product can then be decomposed with water to produce an alkylphosphonic dichloride RP(=O)Cl<sub>2</sub>. |
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The RPCl{{su|b=3|p=+}} product can then be decomposed with water to produce an alkylphosphonic dichloride RP(=O)Cl<sub>2</sub>. |
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===PCl<sub>3</sub> as a ligand=== |
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==Preparation== |
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PCl<sub>3</sub>, like the more popular ], is a ligand in ]. One example is Mo(CO)<sub>5</sub>PCl<sub>3</sub>.<ref>{{cite journal |doi=10.1021/om020311d|title=Nature of the Metal−Ligand Bond in M(CO)<sub>5</sub>PX<sub>3</sub> Complexes (M = Cr, Mo, W; X = H, Me, F, Cl): Synthesis, Molecular Structure, and Quantum-Chemical Calculations|year=2002|last1=Frenking|first1=Gernot|last2=Wichmann|first2=Karin|last3=Fröhlich|first3=Nikolaus|last4=Grobe|first4=Joseph|last5=Golla|first5=Winfried|last6=Van|first6=Duc Le|last7=Krebs|first7=Bernt|last8=Läge|first8=Mechtild|journal=Organometallics|volume=21|issue=14|pages=2921–2930}}</ref> |
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World production exceeds one-third of a million ]s.<ref>{{Greenwood&Earnshaw2nd}}</ref> Phosphorus trichloride is prepared industrially by the reaction of ] with a ]ing solution of white ] in phosphorus trichloride, with continuous removal of PCl<sub>3</sub> as it is formed. |
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==Uses== |
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:P<sub>4</sub> + 6 Cl<sub>2</sub> → 4 PCl<sub>3</sub> |
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PCl<sub>3</sub> is important indirectly as a precursor to ], ] and ], which are used in many applications, including ]s, ]s, ]s, ]s, and ]s. |
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For example, oxidation of PCl<sub>3</sub> gives ], which is used for the manufacture of ] and ], which find application as ]s and ]s for ]. They are also used to make ]s such as ]. Phosphonates include the ] ]. |
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Industrial production of phosphorus trichloride is controlled under the ], where it is listed in ]. In the laboratory it may be more convenient to use the less toxic red phosphorus.<ref>{{cite journal | author = M. C. Forbes, C. A. Roswell, R. N. Maxson | journal = ] | volume = 2 | pages = 145–7 | year = 1946 | doi = 10.1002/9780470132333.ch42 | title = Phosphorus(III) Chloride}}</ref> It is sufficiently inexpensive that it would not be synthesized for laboratory use. |
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PCl<sub>3</sub> is the precursor to ] for the ], and ]s which may be used as industrial intermediates, or used in the ], both important methods for making ]s. It can be used to make ] (TOPO), used as an extraction agent, although TOPO is usually made via the corresponding phosphine. |
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==Uses== |
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PCl<sub>3</sub> is important indirectly as a precursor to ], ] and ]. which in turn enjoy many applications in ]s, ]s, ]s, ]s, and ]s. |
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PCl<sub>3</sub> is also used directly as a ] in ]. It is used to convert primary and secondary ]s into ]s, or ]s into ]s, although ] generally gives better yields than PCl<sub>3</sub>.<ref>{{cite book | author = L. G. Wade Jr. | title = Organic Chemistry | edition = 6th | page = 477 | publisher = Pearson/Prentice Hall | location = Upper Saddle River, New Jersey, USA | year = 2005}}</ref> |
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For example oxidation of PCl<sub>3</sub> gives ], which is used for the manufacture of ] and ], which find application as ]s and ]s for ]. They are also used to make ]s such as ]. Phosphonates include the ] ]. |
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==Safety== |
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PCl<sub>3</sub> is the precursor to ] for the ], and ]s which may be used as industrial intermediates, or used in the ], both important methods for making ]s. It can be used to make ] (TOPO), used as an extraction agent, although TOPO is usually made via the corresponding phosphine. |
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* 600 ] is lethal in just a few minutes.<ref>{{cite book | author = A. D. F. Toy | title = The Chemistry of Phosphorus | publisher = Pergamon Press | location = Oxford, UK | year = 1973}}</ref> |
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* 25 ppm is the US ] "]" level<ref></ref> |
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* 0.5 ppm is the US ] "]" over a time-weighted average of 8 hours.<ref></ref> |
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* 0.2 ppm is the US ] "]" over a time-weighted average of 8 hours.<ref></ref> |
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* Under ] ], PCl<sub>3</sub> is classified as ] and '']'' , and the ] R14, R26/28, R35 and R48/20 are obligatory. |
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Industrial production of phosphorus trichloride is controlled under the ], where it is listed in ], as it can be used to produce ].<ref>{{cite book |author1=M. C. Forbes |author2=C. A. Roswell |author3=R. N. Maxson |title=Inorganic Syntheses |chapter=Phosphorus(III) Chloride | journal = ] | volume = 2 | pages = 145–7 | doi = 10.1002/9780470132333.ch42 |date=2007 |isbn=9780470132333 }}</ref> |
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PCl<sub>3</sub> is also used directly as a ] in ]. It is used to convert primary and secondary ]s into ]s, or ]s into ]s, although ] generally gives better yields than PCl<sub>3</sub>.<ref>L. G. Wade, Jr., ''Organic Chemistry'', 6th ed., p. 477, Pearson/Prentice Hall, Upper Saddle River, New Jersey, USA, 2005.</ref> |
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==Precautions== |
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==See also== |
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*] |
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PCl<sub>3</sub> is toxic, with a concentration of 600 ] being lethal in just a few minutes.<ref>A. D. F. Toy, ''The Chemistry of Phosphorus'', Pergamon Press, Oxford, UK, 1973.</ref> PCl<sub>3</sub> is classified as ] and '']'' under ] ], and the ] R14, R26/28, R35 and R48/20 are obligatory. |
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*] |
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*] |
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==References== |
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==References== |
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{{reflist}} |
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{{Reflist}} |
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<!-- Dead note "2": ''Handbook of Chemistry and Physics'', 71st edition, CRC Press, Ann Arbor, Michigan, 1990. --> |
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<!-- Dead note "2": ''Handbook of Chemistry and Physics'', 71st edition, CRC Press, Ann Arbor, Michigan, 1990. --> |
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<!-- Dead note "3": J. March, ''Advanced Organic Chemistry'', 4th ed., p. 723, Wiley, New York, 1992. --> |
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<!-- Dead note "3": J. March, ''Advanced Organic Chemistry'', 4th ed., p. 723, Wiley, New York, 1992. --> |
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{{DEFAULTSORT:Phosphorus Trichloride}} |
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