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Thiophosgene

Names
IUPAC name Carbonothioyl dichloride
Other names Thiophosgene; Thiocarbonyl chloride; Carbonothioic dichloride
Identifiers
CAS Number	463-71-8
3D model (JSmol)	Interactive image
ChEBI	CHEBI:29366
ChemSpider	9645
ECHA InfoCard	100.006.675
PubChem CID	10040
RTECS number	XN2450000
UNII	067FQP576P
CompTox Dashboard (EPA)	DTXSID2060046
InChI InChI=1S/CCl2S/c2-1(3)4Key: ZWZVWGITAAIFPS-UHFFFAOYSA-N InChI=1/CCl2S/c2-1(3)4Key: ZWZVWGITAAIFPS-UHFFFAOYAH
SMILES ClC(Cl)=S
Properties
Chemical formula	CSCl2
Molar mass	114.97 g·mol
Appearance	Red liquid
Odor	Persistent, choking odor
Density	1.50 g/cm
Boiling point	70 to 75 °C (158 to 167 °F; 343 to 348 K)
Solubility in water	Decomposes
Solubility in other solvents	Reacts with amines and alcohols, soluble in polar organic solvents
Magnetic susceptibility (χ)	-50.6·10 cm/mol
Refractive index (nD)	1.558
Structure
Molecular shape	planar, sp, C2v
Hazards
Occupational safety and health (OHS/OSH):
Main hazards	Highly toxic
Flash point	62 °C (144 °F; 335 K)
Related compounds
Related compounds	Phosgene Thiocarbonyl fluoride Thiocarbonyl bromide Sulfur dichloride Thionyl chloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). Y verify (what is  ?) Infobox references

Thiophosgene is a red liquid with the formula CSCl₂. It is a molecule with trigonal planar geometry. There are two reactive C–Cl bonds that allow it to be used in diverse organic syntheses.

Preparation

Typically, CSCl₂ is prepared in a two-step process from carbon disulfide. In the first step, carbon disulfide is chlorinated to give trichloromethanesulfenyl chloride (CCl₃SCl), a rare sulfenyl chloride:

CS₂ + 3 Cl₂ → CCl₃SCl + S₂Cl₂

The chlorination must be controlled as excess chlorine converts trichloromethanesulfenyl chloride into carbon tetrachloride. Steam distillation separates the trichloromethanesulfenyl chloride and hydrolyzes the disulfur dichloride. Reduction of trichloromethanesulfenyl chloride with, e.g., tin or dihydroanthracene produces thiophosgene:

CCl₃SCl + M → CSCl₂ + MCl₂

An alternative one-step reaction is

CCl₄ + H₂S → SCCl₂ + 2 HCl

Reactions

CSCl₂ is mainly used to prepare compounds with the connectivity CSX₂ where X = OR, NHR. Such reactions proceed via intermediate such as CSClX. Under certain conditions, one can convert primary amines into isothiocyanates. CSCl₂ also serves as a dienophile to give, after reduction 5-thiacyclohexene derivatives. Thiophosgene is also known as the appropriate reagent in Corey-Winter synthesis for stereospecific conversion of 1,2-diols into alkenes.

It forms a head-to-tail dimer upon irradiation with UV light:

2 CSCl₂ → S₂(CCl₂)₂

Unlike thiophosgene monomer, a red liquid, the photodimer, an example of a 1,3-dithietane, is a colourless solid. Swarts fluorination of the dimer and then cracking is the principal route to thiocarbonyl fluoride.

Thiophosgene decomposes at 200 °C or above to form carbon disulfide and carbon tetrachloride. It has also been observed decomposing to hydrogen sulfide, hydrogen chloride, and carbonyl sulfide gases via contact with human tissue.

Toxicology and safety

CSCl₂ is considered highly toxic. Inhalation of the substance can cause irritation of respiratory system, burns, delayed pulmonary edema and death.

See also

• Phosgene
• Carbonyl fluoride
• Sulfur dichloride

References

1. Manchiu D. S. Lay, Mitchell W. Sauerhoff And Donald R. Saunders "Carbon Disulfide" in Ullmann's Encyclopedia Of Industrial Chemistry, 2000, Wiley-VCH, Weinheim. doi:10.1002/14356007.a05_185
2. Dyson, G. M. (1926). "Thiophosgene". Organic Syntheses. 6: 86. doi:10.15227/orgsyn.006.0086.
3. K. T. Potts, C. Sapino (1972). "Thiocarbonyl halides". In S. Patai (ed.). Acyl Halides. PATAI'S Chemistry of Functional Groups. pp. 349–380. doi:10.1002/9780470771273.ch11. ISBN 978-0-470-77127-3.
4. Graham-Otto's Ausführliches Lehrbuch der Chemie (in German; 1881). Germany: Vieweg.
5. Pascual, Roxana Martinez "Thiophosgene" Synlett 2015, vol. 26, pp. 1776-1777.doi:10.1055/s-0034-1380659
6. Sharma, S. (1978). "Thiophosgene in Organic Synthesis". Synthesis. 1978 (11): 803–820. doi:10.1055/s-1978-24896.
7. B. Krebs H. Beyer (1969). "Die Kristall- und Molekelstruktur des dimeren Thiophosgens". Z. Anorg. Allg. Chem. 365 (3–4): 199–210. doi:10.1002/zaac.19693650315.
8. Potts, K. T.; Sapino, C. (1972). "Thiocarbonyl halides". In Patai, Saul (ed.). The Chemistry of Acyl Halides. The Chemistry of Functional Groups. Wiley. pp. 354–355. doi:10.1002/9780470771273.ch11. ISBN 978-0-471-66936-4.
9. U.S. Coast Guard, Department of Transportation (1999). CHRIS - Hazardous Chemical Data. Commandant Instruction 16465.12C. Washington, D.C.: U.S. Government Printing Office — via Cameo Chemicals. As cited in "Thiophosgene" PubChem compound record.
10. "Thiophosgene".
11. US National Library of Medicine (2020). Hazardous Substances Databank entry, as summarized on "Thiophosgene" PubChem compound record.

Further reading

• Holleman, Arnold Frederik; Wiberg, Egon (2001), Wiberg, Nils (ed.), Inorganic Chemistry, translated by Eagleson, Mary; Brewer, William, San Diego/Berlin: Academic Press/De Gruyter, ISBN 0-12-352651-5

• Inorganic carbon compounds
• Inorganic sulfur compounds
• Thiochlorides
• Thiocarbonyl compounds