| Revision as of 00:56, 15 February 2011 editKupirijo (talk | contribs)Extended confirmed users9,131 editsm →Reactions: parathion← Previous edit |
Latest revision as of 17:12, 5 November 2024 edit undoCitation bot (talk | contribs)Bots5,433,757 edits Misc citation tidying. | Use this bot. Report bugs. | #UCB_CommandLine |
| (63 intermediate revisions by 27 users not shown) |
| Line 1: |
Line 1: |
|
{{chembox |
|
{{chembox |
|
|
| Verifiedfields = changed |
| ⚫ |
| verifiedrevid = 400864590 |
|
|
|
| Watchedfields = changed |
| ⚫ |
| Name = Thiophosphoryl chloride |
|
|
⚫ |
| verifiedrevid = 470608856 |
| ⚫ |
| ImageFile = Thiophosphoryl-chloride-2D.png |
|
|
⚫ |
| Name = Thiophosphoryl chloride |
| ⚫ |
| ImageSize = 120 |
|
|
⚫ |
| ImageFile = Thiophosphoryl-chloride-2D.png |
| ⚫ |
| ImageName = Structural formula of thiophosphoryl chloride |
|
|
⚫ |
| ImageSize = 120 |
| ⚫ |
| ImageFileL1 = Thiophosphoryl-chloride-3D-balls.png |
|
|
⚫ |
| ImageName = Structural formula of thiophosphoryl chloride |
|
| ImageSizeL1 = 100 |
|
|
⚫ |
| ImageFileL1 = Thiophosphoryl-chloride-3D-balls.png |
|
| ImageNameL1 = Ball-and-stick model of thiophosphoryl chloride |
|
| ImageNameL1 = Ball-and-stick model of thiophosphoryl chloride |
|
| ImageFileR1 = Thiophosphoryl-chloride-3D-vdW.png |
|
| ImageFileR1 = Thiophosphoryl-chloride-3D-vdW.png |
|
| ImageSizeR1 = 100 |
|
|
| ImageNameR1 = Space-filling model of thiophosphoryl chloride |
|
| ImageNameR1 = Space-filling model of thiophosphoryl chloride |
|
| IUPACName = Phosphorothioic trichloride |
|
| IUPACName = Phosphorothioic trichloride |
|
| OtherNames = Thiophosphoryl chloride |
|
| OtherNames = {{ubl|Phosphoric sulfochloride (1:3)<ref>Thiophosphoryl chloride: trade names</ref>|Phosphorus(V) sulfochloride|Thiophosphoryl chloride}} |
|
| Section1 = {{Chembox Identifiers |
|
|Section1 = {{Chembox Identifiers |
|
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
|
| CASNo_Ref = {{cascite|correct|CAS}} |
|
⚫ |
| CASNo = 3982-91-0 |
|
|
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
|
| ChemSpiderID = 18729 |
|
| ChemSpiderID = 18729 |
|
|
| EC_number = 223-622-6 |
|
| PubChem = 19883 |
|
| PubChem = 19883 |
|
⚫ |
| RTECS = XN2930000 |
|
|
| UNNumber = 1837 |
|
|
| UNII_Ref = {{fdacite|correct|FDA}} |
|
|
| UNII = II99F8594N |
|
| InChI = 1/Cl3PS/c1-4(2,3)5 |
|
| InChI = 1/Cl3PS/c1-4(2,3)5 |
|
| InChIKey = WQYSXVGEZYESBR-UHFFFAOYAE |
|
| InChIKey = WQYSXVGEZYESBR-UHFFFAOYAE |
| Line 24: |
Line 31: |
|
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
|
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
|
| StdInChIKey = WQYSXVGEZYESBR-UHFFFAOYSA-N |
|
| StdInChIKey = WQYSXVGEZYESBR-UHFFFAOYSA-N |
|
⚫ |
}} |
| ⚫ |
| CASNo = 3982-91-0 |
|
|
⚫ |
|Section2 = {{Chembox Properties |
| ⚫ |
| RTECS = |
|
|
|
| Formula = {{chem2|PSCl3}} |
| ⚫ |
}} |
|
|
|
| Cl=3|P=1|S=1 |
| ⚫ |
| Section2 = {{Chembox Properties |
|
|
⚫ |
| Appearance = Colorless liquid |
|
| Formula = Cl<sub>3</sub>PS |
|
|
| MolarMass = 169.4 g/mol |
|
| Density = 1.67 g/cm<sup>3</sup> |
|
|
| Solubility = Reacts |
| ⚫ |
| Appearance = Colorless liquid |
|
|
⚫ |
| SolubleOther = Soluble in ], ], ] and ]. |
|
| Density = 1.67 g/cm<sup>3</sup> |
|
|
| Solubility = Reacts |
|
| MeltingPtC = −35 |
|
|
| MeltingPt_notes = |
| ⚫ |
| SolubleOther = Soluble in ], ], ] and ]. |
|
|
|
| BoilingPtC = 125 |
|
| MeltingPt = -35 °C (987 K) |
|
|
|
| BoilingPt_notes = |
|
| BoilingPt = 125 °C (1685 K) |
|
|
}} |
|
}} |
|
| Section7 = {{Chembox Hazards |
|
| Section3 = {{Chembox Structure |
|
|
| MolShape = ] at the ] atom |
|
| ExternalMSDS = ] |
|
|
⚫ |
}} |
|
| MainHazards = Violent hydrolysis |
|
|
|
|Section7 = {{Chembox Hazards |
|
| FlashPt = ?°C |
|
|
|
| MainHazards = Violent hydrolysis; releasing ] on contact with water,<ref>Thiophosphoryl chloride: main hazards</ref> maybe corrosive to metals and skin |
|
| RPhrases = |
|
|
|
| FlashPt = none<ref>Thiophosphoryl chloride: flash point</ref> |
|
| SPhrases = |
|
|
|
| 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> |
| ⚫ |
}} |
|
|
|
| GHSPictograms = {{GHS05}}{{GHS06}}{{GHS07}} |
|
|
| GHSSignalWord = Danger |
|
|
| HPhrases = {{H-phrases|302|314|330}} |
|
|
| 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}} |
|
|
}} |
|
|
|Section8 = {{Chembox Related |
|
|
| OtherCompounds = {{ubl|]|]|]|]|]}} |
|
|
}} |
|
}} |
|
}} |
|
|
|
|
|
'''Thiophosphoryl chloride''' is an ] with the ] PSCl<sub>3</sub>. <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> |
|
'''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. |
|
Thiophosphoryl chloride, PSCl<sub>3</sub>, is a fuming, colorless liquid with a pungent odor. It is synthesized from ] and used to thiophosphorylate organic compounds, such as to produce ]s. |
|
|
|
|
|
|
==Synthesis== |
|
==Synthesis== |
|
Thiophosporyl 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 sulfur at 180 °C. <ref name = betterman> Betterman, G.; Krause, W.; Riess, G.; Hofmann, T. “Phosphorus Compounds, Inorganic” Ullman’s Encyclopedia of Industrial Chemistry. John Wiley & Sons: New York, 2005. {{DOI| 10.1002/14356007.a19_527}}.</ref> |
|
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> |
|
|
|
|
|
:PCl<sub>3</sub> + S → PSCl<sub>3</sub> |
|
:{{chem2|PCl3 + S → PSCl3}} |
|
|
|
|
|
Using this method, yields can be very high after purification by distillation. Catalysts can further the reaction at lower temperatures, but are not necessary. |
|
Using this method, yields can be very high after purification by distillation. Catalysts facilitate the reaction at lower temperatures, but are not usually necessary. |
|
Alternatively, the reaction of phosphorus pentasulfide and phosphorus pentachloride also affords thiophosporyl chloride in yields around 70%. <ref name = martin> Martin, D. R.; Duvall, W. M. “Phosphorus (V) Sulfochloride” Inorganic Syntheses, Volume IV. McGraw-Hill, 1953. {{DOI| 10.1002/9780470132357.ch24}}. </ref> |
|
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> |
|
|
|
|
|
|
:{{chem2|3 PCl5 + P2S5 → 5 PSCl3}} |
|
:3 PCl<sub>5</sub> + P<sub>2</sub>S<sub>5</sub> → 5 PSCl<sub>3</sub> |
|
|
|
|
|
|
==Structure== |
|
|
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> |
|
|
|
|
|
==Reactions== |
|
==Reactions== |
|
PSCl<sub>3</sub> is soluble in ], ], ], and ].<ref name = spilling/> However, it hydrolyzes rapidly in basic or ] solutions, such as alcohols and amines, to produce ]s.<ref name = betterman>/ In water PSCl<sub>3</sub> reacts, and contingent on the reaction conditions, produces either ], ], and ] or dichlorothiophosphoric acid and hydrochloric acid. <refname=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> |
|
{{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> |
|
|
:{{chem2|PSCl3 + 4 H2O → H3PO4 + H2S + 3 ]}} |
|
|
:{{chem2|PSCl3 + H2O → HO\sP(\dS)Cl2 + HCl}} |
|
|
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> |
|
|
|
|
|
|
{{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/> |
|
:PSCl<sub>3</sub> + 4 H<sub>2</sub>O → H<sub>3</sub>PO<sub>4</sub> + H<sub>2</sub>S + 3 HCl |
|
|
|
|
|
|
:PSCl<sub>3</sub> + H<sub>2</sub>O → HOP(S)Cl<sub>2</sub> + HCl |
|
:{{chem2|PSCl3 + 2 CH3CH2OH → (CH3CH2\sO\s)2P(\dS)\sCl + 2 HCl}} |
|
|
:{{chem2|(CH3CH2\sO\s)2P(\dS)\sCl + Na+ → (CH3CH2\sO\s)2P(\dS)\sO\sC6H4\sNO2 + ]}} |
|
|
|
|
|
⚫ |
{{chem2|PSCl3}} reacts with ] ]s to generate ].<ref name = spilling/> For example: |
|
PSCl<sub>3</sub> is used to ], or add P=S, organic compounds.<ref name = betterman/> This conversion is widely applicable for amines and alcohols, as well as amino alcohols, diols, and diamines.<ref name = spilling/> Industrially, PSCl<sub>3</sub> is primarily used to produce insecticides, like ].<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> |
|
|
|
|
|
|
|
:{{chem2|C6H5\sC(\dO)\sN(\sCH3)2 + PSCl3 → C6H5\sC(\dS)\sN(\sCH3)2 + ]}} |
|
:PSCl<sub>3</sub> + 2 C<sub>2</sub>H<sub>5</sub>OH → (C<sub>2</sub>H<sub>5</sub>O)<sub>2</sub>PSCl + 2 HCl |
|
|
:(C<sub>2</sub>H<sub>5</sub>O)<sub>2</sub>PSCl + NaOC<sub>6</sub>H<sub>4</sub>NO<sub>2</sub> → (C<sub>2</sub>H<sub>5</sub>O)<sub>2</sub>PSOC<sub>6</sub>H<sub>4</sub>NO<sub>2</sub> + NaCl |
|
|
|
|
|
|
|
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> |
| ⚫ |
PSCl<sub>3</sub> reacts with ] to generate ].<ref name = spilling/> For example: |
|
|
|
|
|
:C<sub>6</sub>H<sub>5</sub>C(O)N(CH<sub>3</sub>)<sub>2</sub> + PSCl<sub>3</sub> → C<sub>6</sub>H<sub>5</sub>C(S)N(CH<sub>3</sub>)<sub>2</sub> + POCl<sub>3</sub> |
|
|
|
|
|
|
==References== |
|
==References== |
|
{{reflist}} |
|
{{reflist}} |
|
|
|
|
|
|
] |
|
] |
|
] |
|
] |
|
] |
|
|
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|