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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
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{{chembox |
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{{chembox |
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| Watchedfields = changed |
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| Watchedfields = changed |
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| verifiedrevid = 413981325 |
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| verifiedrevid = 470608856 |
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| Name = Thiophosphoryl chloride |
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| Name = Thiophosphoryl chloride |
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| ImageFile = Thiophosphoryl-chloride-2D.png |
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| ImageFile = Thiophosphoryl-chloride-2D.png |
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| ImageSize = 120 |
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| ImageSize = 120 |
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| ImageName = Structural formula of thiophosphoryl chloride |
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| ImageName = Structural formula of thiophosphoryl chloride |
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| ImageFileL1 = Thiophosphoryl-chloride-3D-balls.png |
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| ImageFileL1 = Thiophosphoryl-chloride-3D-balls.png |
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| ImageNameL1 = Ball-and-stick model of thiophosphoryl chloride |
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| ImageSizeL1 = 100 |
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| ImageFileR1 = Thiophosphoryl-chloride-3D-vdW.png |
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| ImageNameL1 = Ball-and-stick model of thiophosphoryl chloride |
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| ImageNameR1 = Space-filling model of thiophosphoryl chloride |
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| ImageFileR1 = Thiophosphoryl-chloride-3D-vdW.png |
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| IUPACName = Phosphorothioic trichloride |
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| ImageSizeR1 = 100 |
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| OtherNames = {{ubl|Phosphoric sulfochloride (1:3)<ref>Thiophosphoryl chloride: trade names</ref>|Phosphorus(V) sulfochloride|Thiophosphoryl chloride}} |
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| ImageNameR1 = Space-filling model of thiophosphoryl chloride |
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|Section1 = {{Chembox Identifiers |
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| IUPACName = Phosphorothioic trichloride |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| OtherNames = Thiophosphoryl chloride |
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| CASNo = 3982-91-0 |
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| Section1 = {{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 18729 |
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| ChemSpiderID = 18729 |
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| EC_number = 223-622-6 |
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| PubChem = 19883 |
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| PubChem = 19883 |
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| RTECS = XN2930000 |
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| UNNumber = 1837 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = II99F8594N |
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| InChI = 1/Cl3PS/c1-4(2,3)5 |
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| InChI = 1/Cl3PS/c1-4(2,3)5 |
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| InChIKey = WQYSXVGEZYESBR-UHFFFAOYAE |
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| InChIKey = WQYSXVGEZYESBR-UHFFFAOYAE |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = WQYSXVGEZYESBR-UHFFFAOYSA-N |
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| StdInChIKey = WQYSXVGEZYESBR-UHFFFAOYSA-N |
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}} |
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| CASNo_Ref = {{cascite|correct|??}} |
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|Section2 = {{Chembox Properties |
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| CASNo = <!-- blanked - oldvalue: 3982-91-0 --> |
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| Formula = {{chem2|PSCl3}} |
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| RTECS = |
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| Cl=3|P=1|S=1 |
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}} |
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| Appearance = Colorless liquid |
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| Section2 = {{Chembox Properties |
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| Formula = Cl<sub>3</sub>PS |
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| Density = 1.67 g/cm<sup>3</sup> |
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| Solubility = Reacts |
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| MolarMass = 169.4 g/mol |
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| SolubleOther = Soluble in ], ], ] and ]. |
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| Appearance = Colorless liquid |
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| MeltingPtC = −35 |
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| Density = 1.67 g/cm<sup>3</sup> |
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| MeltingPt_notes = |
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| Solubility = Reacts |
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| BoilingPtC = 125 |
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| SolubleOther = Soluble in ], ], ] and ]. |
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| BoilingPt_notes = |
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| MeltingPt = −35 °C (987 K) |
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}} |
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| BoilingPt = 125 °C (1685 K) |
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| Section3 = {{Chembox Structure |
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}} |
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| MolShape = ] at the ] atom |
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| Section7 = {{Chembox Hazards |
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| ExternalMSDS = ] |
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| MainHazards = Violent hydrolysis |
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| FlashPt = ?°C |
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| RPhrases = |
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| SPhrases = |
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|Section7 = {{Chembox Hazards |
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| MainHazards = Violent hydrolysis; releasing ] on contact with water,<ref>Thiophosphoryl chloride: main hazards</ref> maybe corrosive to metals and skin |
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| FlashPt = none<ref>Thiophosphoryl chloride: flash point</ref> |
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| GHS_ref=<ref>{{cite web |title=Thiophosphoryl chloride |url=https://pubchem.ncbi.nlm.nih.gov/compound/19883#section=Safety-and-Hazards |website=pubchem.ncbi.nlm.nih.gov |language=en}}</ref> |
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| GHSPictograms = {{GHS05}}{{GHS06}}{{GHS07}} |
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| GHSSignalWord = Danger |
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| HPhrases = {{H-phrases|302|314|330}} |
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| PPhrases = {{P-phrases|260|264|270|271|280|284|301+317|301+330+331|302+361+354|304+340|305+354+338|316|320|321|330|363|403+233|405|501}} |
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}} |
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|Section8 = {{Chembox Related |
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| OtherCompounds = {{ubl|]|]|]|]|]}} |
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}} |
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}} |
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'''Thiophosphoryl chloride''' is an ] with the ] {{chem2|PSCl3|auto=1}}.<ref name = spilling>Spilling, C. D. "Thiophosphoryl Chloride" in Encyclopedia of Reagents for Organic Synthesis John Wiley & Sons, Weinheim, 2001 {{doi| 10.1002/047084289X.rt104}}. Article Online Posting Date: April 15, 2001</ref> It is a colorless pungent smelling liquid that fumes in air. It is synthesized from ] and used to thiophosphorylate organic compounds, such as to produce ]s. |
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==Synthesis== |
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Thiophosphoryl chloride can be generated by several reactions starting from ]. The most common and practical synthesis, hence used in industrial manufacturing, is directly reacting ] with excess ] at 180 °C.<ref name = betterman>{{cite encyclopedia |vauthors=Betterman G, Krause W, Riess G, Hofmann T|title=Phosphorus Compounds, Inorganic |encyclopedia=Ullmann’s Encyclopedia of Industrial Chemistry|year=2005|publisher=Wiley-VCH |location=Weinheim |isbn=3527306730 |doi=10.1002/14356007.a19_527}}</ref> |
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:{{chem2|PCl3 + S → PSCl3}} |
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Using this method, yields can be very high after purification by distillation. Catalysts facilitate the reaction at lower temperatures, but are not usually necessary. |
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Alternatively, it is obtained by combining phosphorus pentasulfide and phosphorus pentachloride.<ref name = martin>Martin, D. R.; Duvall, W. M. “Phosphorus(V) Sulfochloride” Inorganic Syntheses, 1953, Volume IV, p73. {{doi| 10.1002/9780470132357.ch24}}.</ref> |
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:{{chem2|3 PCl5 + P2S5 → 5 PSCl3}} |
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==Structure== |
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Thiophosphoryl chloride has ] and C<sub>3v</sub> ], with the structure {{chem2|S\dPCl3}}. According to ], the phosphorus–sulfur bond length is 189 ] and the phosphorus–chlorine bond length is 201 pm, while the {{chem2|Cl\sP\sCl}} ] is 102°.<ref>{{cite journal | title = Molecular structures of phosphoryl fluoride, phosphoryl chloride, and thiophosphoryl chloride studied by gas electron diffraction | first1 = Kozo | last1 = Kuchitsu | first2 = Tohei | last2 = Moritani | first3 = Yonezo | last3 = Morino | journal = ] | year = 1971 | volume = 10 | issue = 2 | pages = 344–350 | doi = 10.1021/ic50096a025}}</ref> |
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==Reactions== |
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{{chem2|PSCl3}} is soluble in ], ], ], and ].<ref name = spilling/> However, it ] rapidly in ] or ] solutions, such as ] and ], to produce ]s.<ref name = betterman /> In water {{chem2|PSCl3}} reacts, and contingent on the reaction conditions, produces either ], ], and ] or dichlorothiophosphoric acid and hydrochloric acid.<ref name=fee>Fee, D. C.; Gard, D. R.; Yang, C. “Phosphorus Compounds” Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons: New York, 2005 {{doi| 10.1002/0471238961.16081519060505.a01.pub2}}</ref> |
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:{{chem2|PSCl3 + 4 H2O → H3PO4 + H2S + 3 ]}} |
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:{{chem2|PSCl3 + H2O → HO\sP(\dS)Cl2 + HCl}} |
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An intermediate in this process appears to be ].<ref>{{cite book|title=Sulfur in Organic and Inorganic Chemistry|volume=1|editor-first=Alexander|editor-last=Senning|year=1971|publisher=Marcel Dekker|location=New York|lccn=70-154612|isbn=0-8247-1615-9|first=Lucreţia|last=Almasi|chapter=The Sulfur–Phosphorus Bond|page=69}}</ref> |
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{{chem2|PSCl3}} is used to thiophosphorylate organic compounds (to add thiophosphoryl group, P=S, with three free ] at the ] atom, to ]).<ref name ="betterman"/> This conversion is widely applicable for amines and alcohols, as well as ]s, ], and ]s.<ref name = spilling/> Industrially, {{chem2|PSCl3}} is used to produce ], like ].<ref name=fee/> |
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:{{chem2|PSCl3 + 2 CH3CH2OH → (CH3CH2\sO\s)2P(\dS)\sCl + 2 HCl}} |
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:{{chem2|(CH3CH2\sO\s)2P(\dS)\sCl + Na+ → (CH3CH2\sO\s)2P(\dS)\sO\sC6H4\sNO2 + ]}} |
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{{chem2|PSCl3}} reacts with ] ]s to generate ].<ref name = spilling/> For example: |
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:{{chem2|C6H5\sC(\dO)\sN(\sCH3)2 + PSCl3 → C6H5\sC(\dS)\sN(\sCH3)2 + ]}} |
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When treated with ], it give tetramethyldiphosphine disulfide {{chem2|(H3C\s)2P(\dS)\sP(\dS)(\sCH3)2}}.<ref>] "Tetramethylbiphosphine Disulfide" Org. Synth. 1965, volume 45, p. 102. {{doi|10.15227/orgsyn.045.0102}}</ref> |
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==References== |
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{{reflist}} |
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