Thiophosphoryl chloride

| Ball-and-stick model of thiophosphoryl chloride | Space-filling model of thiophosphoryl chloride

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Names
IUPAC name

Phosphorothioic trichloride

Other names

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

Identifiers

CAS Number

* 3982-91-0 Y

3D model (JSmol)

* Interactive image

ChemSpider |

* 18729 Y

ECHA InfoCard | 100.021.476
EC Number |

* 223-622-6

PubChem CID

* 19883

RTECS number |

* XN2930000

UNII |

* II99F8594N Y

UN number | 1837

CompTox Dashboard (EPA)

* DTXSID3063253

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

| PSCl3
Molar mass | 169.38 g·mol−1
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.
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,[2] maybe corrosive to metals and skin
GHS labelling:[4]

Pictograms

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[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

Chemical compound

Thiophosphoryl chloride is an inorganic compound with the chemical 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[edit]

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[edit]

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°.[8]

## Reactions[edit]

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 → HO−P(=S)Cl2 \+ HCl

PSCl3 is used to thiophosphorylate organic compounds (to add thiophosphoryl group, P=S, with three free valences at the P atom, to organic compounds).[6] This conversion is widely applicable for amines and alcohols, as well as aminoalcohols, diols, and diamines.[5] Industrially, PSCl3 is used to produce insecticides, like parathion.[9]

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.[5] 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.[10]

## References[edit]

1. ^ Thiophosphoryl chloride: trade names
2. ^ Thiophosphoryl chloride: main hazards
3. ^ Thiophosphoryl chloride: flash point
4. ^ "Thiophosphoryl chloride". pubchem.ncbi.nlm.nih.gov.
5. ^ a b c d 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. ^ a b c 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. ^ a b 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

*[CID]: Compound ID
*[EPA]: U.S. Environmental Protection Agency
*[H302]: H302: Harmful if swallowed
*[H314]: H314: Causes severe skin burns and eye damage
*[H330]: H330: Fatal if inhaled
*[P260]: P260: Do not breathe dust/fume/gas/mist/vapours/spray.
*[P264]: P264: Wash ... thoroughly after handling.
*[P270]: P270: Do not eat, drink or smoke when using this product.
*[P271]: P271: Use only outdoors or in a well-ventilated area.
*[P280]: P280: Wear protective gloves/protective clothing/eye protection/face protection.
*[P284]: P284: Wear respiratory protection.
*[P301+P317]: P301+P317: IF SWALLOWED: IF SWALLOWED: Get medical help.
*[P301+P330+P331]: P301+P330+P331: IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
*[P302+P361+P354]: P302+P361+P354: IF ON SKIN: Take off Immediately all contaminated clothing. Immediately rinse with water for several minutes.
*[P304+P340]: P304+P340: IF INHALED: Remove victim to fresh air and keep at rest in a position comfortable for breathing.
*[P305+P354+P338]: P305+P354+P338: IF IN EYES: Immediately rinse with water for several minutes. Remove contact lenses if present and easy to do. Continue rinsing.
*[P316]: P316: Get immediate emergency medical help.
*[P320]: P320: Specific treatment is urgent (see ... on this label).
*[P321]: P321: Specific treatment (see ... on this label).
*[P330]: P330: Rinse mouth.
*[P363]: P363: Wash contaminated clothing before reuse.
*[P403+P233]: P403+P233: Store in a well ventilated place. Keep container tightly closed.
*[P405]: P405: Store locked up.
*[P501]: P501: Dispose of contents/container to ...