Thiophosphoryl Chloride

Thiophosphoryl chloride
Names
	IUPAC name Phosphorothioic trichloride
	Other names Thiophosphoryl chloride, Phosphoric sulfochloride (1:3); Phosphorus(V) sulfochloride
Identifiers
CAS Number	3982-91-0 ;
3D model (JSmol)	Interactive image;
ChemSpider	18729 ;
EC Number	223-622-6;
PubChem CID	19883;
RTECS number	XN2930000;
UNII	II99F8594N ;
UN number	1837
	InChI InChI=1S/Cl3PS/c1-4(2,3)5 Key: WQYSXVGEZYESBR-UHFFFAOYSA-N ; InChI=1/Cl3PS/c1-4(2,3)5 Key: WQYSXVGEZYESBR-UHFFFAOYAE;
	SMILES P(=S)(Cl)(Cl)Cl;
Properties
Chemical formula	Cl3PS
Molar mass	169.4 g/mol
Appearance	Colorless liquid
Density	1.67 g/cm3
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.
Hazards
Main hazards	Violent hydrolysis; releasing HCl on contact with water, maybe corrosive to metals and skin
Safety data sheet	Magnesium chloride MSDS
GHS pictograms
GHS Signal word	Danger
GHS hazard statements	H302, H314, H330
GHS precautionary statements	P260, P264, P270, P271, P280, P284, P301+317Script error: No such module "Preview warning".Category:GHS errors, P301+330+331, P302+361+354Script error: No such module "Preview warning".Category:GHS errors, P304+340, P305+354+338Script error: No such module "Preview warning".Category:GHS errors, P316Script error: No such module "Preview warning".Category:GHS errors, P320, P321, P330, P363, P403+233, P405, P501
Flash point	none
Related compounds
Related compounds	Phosphoryl chloride; Thiophosphoryl fluoride; Thiophosphoryl bromide; Thiophosphoryl iodide; Phosphorothioic chloride difluoride;
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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	Infobox references

Thiophosphoryl chloride is an inorganic compound with the formula PSCl₃.^[5] 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.^[6]

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.^[7]

3 PCl₅ + P₂S₅ → 5 PSCl₃

Structure

Thiophosphoryl chloride has tetrahedral molecular geometry and C_3v molecular symmetry. According to gas electron diffraction, the phosphorus–sulfur bond length is 1.89 Å and the phosphorus–chlorine bond length is 2.01 Å, while the Cl–P–Cl bond angle is 102°.^[8]

Reactions

PSCl₃ is soluble in benzene, carbon tetrachloride, chloroform, and carbon disulfide.^[5] However, it hydrolyzes rapidly in basic or hydroxylic solutions, such as alcohols and amines, to produce thiophosphates.^[6] 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.^[9]

PSCl₃ + 4 H₂O → H₃PO₄ + H₂S + 3 HCl

PSCl₃ + H₂O → HOP(S)Cl₂ + HCl

PSCl₃ is used to thiophosphorylate (add P=S to) organic compounds.^[6] This conversion is widely applicable for amines and alcohols, as well as amino alcohols, diols, and diamines.^[5] Industrially, PSCl₃ is used to produce insecticides, like parathion.^[9]

PSCl₃ + 2 C₂H₅OH → (C₂H₅O)₂PSCl + 2 HCl

(C₂H₅O)₂PSCl + NaOC₆H₄NO₂ → (C₂H₅O)₂PSOC₆H₄NO₂ + NaCl

PSCl₃ reacts with tertiary amides to generate thioamides.^[5] For example:

C₆H₅C(O)N(CH₃)₂ + PSCl₃ → C₆H₅C(S)N(CH₃)₂ + POCl₃

When treated with methylmagnesium iodide, it give tetramethyldiphosphine disulfide ([Me₂P(S)].₂.^[10]

References

↑ Thiophosphoryl chloride: trade names
↑ Thiophosphoryl chloride: main hazards
↑ Thiophosphoryl chloride: flash point
↑ "Thiophosphoryl chloride" (in en). https://pubchem.ncbi.nlm.nih.gov/compound/19883#section=Safety-and-Hazards.
↑ ^5.0 ^5.1 ^5.2 ^5.3 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.
↑ ^6.0 ^6.1 ^6.2 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. .
↑ Martin, D. R.; Duvall, W. M. “Phosphorus(V) Sulfochloride” Inorganic Syntheses, 1953, Volume IV, p73. doi: 10.1002/9780470132357.ch24.
↑ Kuchitsu, Kozo; Moritani, Tohei; Morino, Yonezo (1971). "Molecular structures of phosphoryl fluoride, phosphoryl chloride, and thiophosphoryl chloride studied by gas electron diffraction". Inorg. Chem. 10 (2): 344–350. doi:10.1021/ic50096a025.
↑ ^9.0 ^9.1 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
↑ G. W. Parshall "Tetramethylbiphosphine Disulfide" Org. Synth. 1965, volume 45, p. 102. doi:10.15227/orgsyn.045.0102

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Original source: https://en.wikipedia.org/wiki/Thiophosphoryl chloride. Read more

[1] Thiophosphoryl chloride: trade names

[2] Thiophosphoryl chloride: main hazards

[3] Thiophosphoryl chloride: flash point

[4] "Thiophosphoryl chloride" (in en). https://pubchem.ncbi.nlm.nih.gov/compound/19883#section=Safety-and-Hazards.

[spilling-5] 5.0 ^5.1 ^5.2 ^5.3 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.

[betterman-6] 6.0 ^6.1 ^6.2 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. .

[martin-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". Inorg. Chem. 10 (2): 344–350. doi:10.1021/ic50096a025.

[fee-9] 9.0 ^9.1 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] G. W. Parshall "Tetramethylbiphosphine Disulfide" Org. Synth. 1965, volume 45, p. 102. doi:10.15227/orgsyn.045.0102