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{{chembox {{chembox
| Verifiedfields = changed
| Watchedfields = changed | Watchedfields = changed
| verifiedrevid = 413981325 | verifiedrevid = 470608856
| Name = Thiophosphoryl chloride | Name = Thiophosphoryl chloride
| ImageFile = Thiophosphoryl-chloride-2D.png | ImageFile = Thiophosphoryl-chloride-2D.png
| ImageSize = 120 | ImageSize = 120
| ImageName = Structural formula of thiophosphoryl chloride | ImageName = Structural formula of thiophosphoryl chloride
| ImageFileL1 = Thiophosphoryl-chloride-3D-balls.png | ImageFileL1 = Thiophosphoryl-chloride-3D-balls.png
⚫ | ImageNameL1 = Ball-and-stick model of thiophosphoryl chloride
| ImageSizeL1 = 100
⚫ | ImageFileR1 = Thiophosphoryl-chloride-3D-vdW.png
⚫ | ImageNameL1 = Ball-and-stick model of thiophosphoryl chloride
⚫ | ImageNameR1 = Space-filling model of thiophosphoryl chloride
⚫ | ImageFileR1 = Thiophosphoryl-chloride-3D-vdW.png
⚫ | IUPACName = Phosphorothioic trichloride
| ImageSizeR1 = 100
| OtherNames = {{ubl|Phosphoric sulfochloride (1:3)<ref>Thiophosphoryl chloride: trade names</ref>|Phosphorus(V) sulfochloride|Thiophosphoryl chloride}}
⚫ | ImageNameR1 = Space-filling model of thiophosphoryl chloride
⚫ |Section1 = {{Chembox Identifiers
⚫ | IUPACName = Phosphorothioic trichloride
⚫ | CASNo_Ref = {{cascite|correct|CAS}}
⚫ | OtherNames = Thiophosphoryl chloride
⚫ | CASNo = 3982-91-0
⚫ | Section1 = {{Chembox Identifiers
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | 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 25: Line 31:
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} | StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = WQYSXVGEZYESBR-UHFFFAOYSA-N | StdInChIKey = WQYSXVGEZYESBR-UHFFFAOYSA-N
⚫ }}
⚫ | CASNo_Ref = {{cascite|correct|??}}
⚫ |Section2 = {{Chembox Properties
⚫ | CASNo = 3982-91-0
| Formula = {{chem2|PSCl3}}
⚫ | RTECS =
| Cl=3|P=1|S=1
⚫ }}
⚫ | Appearance = Colorless liquid
⚫ | Section2 = {{Chembox Properties
| Formula = Cl<sub>3</sub>PS | Density = 1.67 g/cm<sup>3</sup>
⚫ | Solubility = Reacts
| MolarMass = 169.4 g/mol
⚫ | SolubleOther = Soluble in ], ], ] and ].
⚫ | Appearance = Colorless liquid
| MeltingPtC = −35
| Density = 1.67 g/cm<sup>3</sup>
| MeltingPt_notes =
⚫ | Solubility = Reacts
| BoilingPtC = 125
⚫ | SolubleOther = Soluble in ], ], ] and ].
| BoilingPt_notes =
| MeltingPt = −35&nbsp;°C (987 K)
⚫ }}
| BoilingPt = 125&nbsp;°C (1685 K)
⚫ | Section3 = {{Chembox Structure
⚫ }}
| MolShape = ] at the ] atom
⚫ | Section7 = {{Chembox Hazards
⚫ }}
| ExternalMSDS = ]
|Section7 = {{Chembox Hazards
| MainHazards = Violent hydrolysis
| MainHazards = Violent hydrolysis; releasing ] on contact with water,<ref>Thiophosphoryl chloride: main hazards</ref> maybe corrosive to metals and skin
| FlashPt = ?°C
⚫ | FlashPt = none<ref>Thiophosphoryl chloride: flash point</ref>
| RPhrases =
| 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>
| SPhrases =
| 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&nbsp;°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&nbsp;°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&ndash;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}}


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Latest revision as of 17:12, 5 November 2024

Thiophosphoryl chloride
Structural formula of thiophosphoryl chloride
Ball-and-stick model of thiophosphoryl chloride
Ball-and-stick model of thiophosphoryl chloride
Space-filling model of thiophosphoryl chloride
Space-filling model of thiophosphoryl chloride
Names
IUPAC name Phosphorothioic trichloride
Other names
  • Phosphoric sulfochloride (1:3)
  • Phosphorus(V) sulfochloride
  • Thiophosphoryl chloride
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.021.476 Edit this at Wikidata
EC Number
  • 223-622-6
PubChem CID
RTECS number
  • XN2930000
UNII
UN number 1837
CompTox Dashboard (EPA)
InChI
  • InChI=1S/Cl3PS/c1-4(2,3)5Key: WQYSXVGEZYESBR-UHFFFAOYSA-N
  • InChI=1/Cl3PS/c1-4(2,3)5Key: WQYSXVGEZYESBR-UHFFFAOYAE
SMILES
  • P(=S)(Cl)(Cl)Cl
Properties
Chemical formula PSCl3
Molar mass 169.38 g·mol
Appearance Colorless liquid
Density 1.67 g/cm
Melting point −35 °C (−31 °F; 238 K)
Boiling point 125 °C (257 °F; 398 K)
Solubility in water Reacts
Solubility Soluble in benzene, chloroform, CS2 and CCl4.
Structure
Molecular shape Tetrahedral at the P atom
Hazards
Occupational safety and health (OHS/OSH):
Main hazards Violent hydrolysis; releasing HCl on contact with water, maybe corrosive to metals and skin
GHS labelling:
Pictograms GHS05: CorrosiveGHS06: ToxicGHS07: Exclamation mark
Signal word Danger
Hazard statements H302, H314, H330
Precautionary statements P260, P264, P270, P271, P280, P284, P301+P317, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P316, P320, P321, P330, P363, P403+P233, P405, P501
Flash point none
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). ☒N verify (what is  ?) Infobox references
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.

Synthesis

Thiophosphoryl chloride can be generated by several reactions starting from phosphorus trichloride. The most common and practical synthesis, hence used in industrial manufacturing, is directly reacting phosphorus trichloride with excess sulfur at 180 °C.

PCl3 + S → PSCl3

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, it is obtained by combining phosphorus pentasulfide and phosphorus pentachloride.

3 PCl5 + P2S5 → 5 PSCl3

Structure

Thiophosphoryl chloride has tetrahedral molecular geometry and C3v molecular symmetry, with the structure S=PCl3. According to gas electron diffraction, the phosphorus–sulfur bond length is 189 pm and the phosphorus–chlorine bond length is 201 pm, while the Cl−P−Cl bond angle is 102°.

Reactions

PSCl3 is soluble in benzene, carbon tetrachloride, chloroform, and carbon disulfide. However, it hydrolyzes rapidly in basic or hydroxylic solutions, such as alcohols and amines, to produce thiophosphates. In water PSCl3 reacts, and contingent on the reaction conditions, produces either phosphoric acid, hydrogen sulfide, and hydrochloric acid or dichlorothiophosphoric acid and hydrochloric acid.

PSCl3 + 4 H2O → H3PO4 + H2S + 3 HCl
PSCl3 + H2O → HO−P(=S)Cl2 + HCl

An intermediate in this process appears to be tetraphosphorus nonasulfide.

PSCl3 is used to thiophosphorylate organic compounds (to add thiophosphoryl group, P=S, with three free valences at the P atom, to organic compounds). This conversion is widely applicable for amines and alcohols, as well as aminoalcohols, diols, and diamines. Industrially, PSCl3 is used to produce insecticides, like parathion.

PSCl3 + 2 CH3CH2OH → (CH3CH2−O−)2P(=S)−Cl + 2 HCl
(CH3CH2−O−)2P(=S)−Cl + Na[O−C6H4−NO2] → (CH3CH2−O−)2P(=S)−O−C6H4−NO2 + NaCl

PSCl3 reacts with tertiary amides to generate thioamides. For example:

C6H5−C(=O)−N(−CH3)2 + PSCl3 → C6H5−C(=S)−N(−CH3)2 + POCl3

When treated with methylmagnesium iodide, it give tetramethyldiphosphine disulfide (H3C−)2P(=S)−P(=S)(−CH3)2.

References

  1. Thiophosphoryl chloride: trade names
  2. Thiophosphoryl chloride: main hazards
  3. Thiophosphoryl chloride: flash point
  4. "Thiophosphoryl chloride". pubchem.ncbi.nlm.nih.gov.
  5. ^ 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
  6. ^ Betterman G, Krause W, Riess G, Hofmann T (2005). "Phosphorus Compounds, Inorganic". Ullmann’s Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_527. ISBN 3527306730.
  7. Martin, D. R.; Duvall, W. M. “Phosphorus(V) Sulfochloride” Inorganic Syntheses, 1953, Volume IV, p73. doi:10.1002/9780470132357.ch24.
  8. Kuchitsu, Kozo; Moritani, Tohei; Morino, Yonezo (1971). "Molecular structures of phosphoryl fluoride, phosphoryl chloride, and thiophosphoryl chloride studied by gas electron diffraction". Inorganic Chemistry. 10 (2): 344–350. doi:10.1021/ic50096a025.
  9. ^ 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
  10. Almasi, Lucreţia (1971). "The Sulfur–Phosphorus Bond". In Senning, Alexander (ed.). Sulfur in Organic and Inorganic Chemistry. Vol. 1. New York: Marcel Dekker. p. 69. ISBN 0-8247-1615-9. LCCN 70-154612.
  11. G. W. Parshall "Tetramethylbiphosphine Disulfide" Org. Synth. 1965, volume 45, p. 102. doi:10.15227/orgsyn.045.0102
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