Thiophosphoryl chloride

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Names
IUPAC name

Phosphorothioic trichloride

Other names

Thiophosphoryl chloride, Phosphoric sulfochloride (1:3);[1] Phosphorus(V) sulfochloride

Identifiers

CAS Number

* 3982-91-0 Y

3D model (JSmol)

* Interactive image

ChemSpider |

* 18729 Y

EC Number |

* 223-622-6

PubChem CID

* 19883

RTECS number |

* XN2930000

UNII |

* II99F8594N Y

UN number | 1837

InChI

* InChI=1S/Cl3PS/c1-4(2,3)5 Y

Key: WQYSXVGEZYESBR-UHFFFAOYSA-N Y

* 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,[2] 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[3]
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).

N verify (what is YN ?)
Infobox references

Tracking categories (test):

* SizeSet

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.

## Contents

* 1 Synthesis
* 2 Structure
* 3 Reactions
* 4 References

## 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 C3v 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

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.
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.
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. .
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.
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

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*[CID]: Compound ID
*[H302]: Harmful if swallowed
*[H314]: Causes severe skin burns and eye damage
*[H330]: Fatal if inhaled
*[P260]: Do not breathe dust/fume/gas/mist/vapours/spray
*[P264]: Wash … thoroughly after handling
*[P270]: Do not eat, drink or smoke when using this product
*[P271]: Use only outdoors or in a well-ventilated area
*[P280]: Wear protective gloves/protective clothing/eye protection/face protection
*[P284]: Wear respiratory protection
*[P301+330+331]: IF SWALLOWED: Rinse mouth. Do NOT induce vomiting
*[P304+340]: IF INHALED: Remove victim to fresh air and keep at rest in a position comfortable for breathing
*[P320]: Specific treatment is urgent (see … on this label)
*[P321]: Specific treatment (see … on this label)
*[P330]: Rinse mouth
*[P363]: Wash contaminated clothing before reuse
*[P403+233]: Store in a well ventilated place. Keep container tightly closed
*[P405]: Store locked up
*[P501]: Dispose of contents/container to …