Thiophosgene

Thiophosgene
Thiophosgene
Thiophosgene
Thiophosgene
Thiophosgene
Names
IUPAC name
Carbonothioyl dichloride
Other names
Thiophosgene; Thiocarbonyl chloride; Carbonothioic dichloride
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.006.675 Edit this at Wikidata
RTECS number
  • XN2450000
UNII
  • InChI=1S/CCl2S/c2-1(3)4 checkY
    Key: ZWZVWGITAAIFPS-UHFFFAOYSA-N checkY
  • InChI=1/CCl2S/c2-1(3)4
    Key: ZWZVWGITAAIFPS-UHFFFAOYAH
  • ClC(Cl)=S
Properties
CSCl2
Molar mass 114.97 g·mol−1
Appearance Red liquid
Odor Persistent, choking odor
Density 1.50 g/cm3
Boiling point 70 to 75 °C (158 to 167 °F; 343 to 348 K)
Decomposes
Solubility in other solvents Reacts with amines and alcohols, soluble in polar organic solvents
-50.6·10−6 cm3/mol
1.558
Structure
planar, sp2, C2v
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Highly toxic
Flash point 62 °C (144 °F; 335 K)
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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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.[1]

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[2] or dihydroanthracene[3] produces thiophosgene:

CCl3SCl + M → CSCl2 + MCl2

An alternative one-step reaction is[4]

CCl4 + H2S → SCCl2 + 2 HCl

Reactions

CSCl2 is mainly used to prepare compounds with the connectivity CSX2 where X = OR, NHR.[5] 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.[6]

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.[7] Swarts fluorination of the dimer and then cracking is the principal route to thiocarbonyl fluoride.[8]

Thiophosgene decomposes at 200 °C or above to form carbon disulfide and carbon tetrachloride.[9] It has also been observed decomposing to hydrogen sulfide, hydrogen chloride, and carbonyl sulfide gases via contact with human tissue.[10][failed verification]

Toxicology and safety

CSCl2 is considered highly toxic. Inhalation of the substance can cause irritation of respiratory system, burns, delayed pulmonary edema and death.[11]

See also

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