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m Previous odor described as, "it smells like BEEF." Changed to the description found here: https://pubs.acs.org/doi/10.1021/op970002c
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{{chembox
{{chembox
| Watchedfields = changed
| Watchedfields = changed
| verifiedrevid = 445098555
| verifiedrevid = 445098555
| Name = Thiophosgene
| Name = Thiophosgene
| ImageFile_Ref = {{chemboximage|correct|??}}
| ImageFile_Ref = {{chemboximage|correct|??}}
| ImageFileL1_Ref = {{chemboximage|correct|??}}
| ImageFileL1_Ref = {{chemboximage|correct|??}}
| ImageFileL1 = Thiophosgene-2D.png
| ImageFile =
| ImageFileL1 = Thiophosgene-2D.png
| ImageSizeL1 = 126px
| ImageSizeL1 = 126px
| ImageNameL1 = Thiophosgene
| ImageNameL1 = Thiophosgene
| ImageFileR1 = Thiophosgene-3D-vdW.png
| ImageFileR1 = Thiophosgene-3D-vdW.png
| ImageSizeR1 = 116px
| ImageSizeR1 = 116px
| ImageNameR1 = Thiophosgene
| ImageNameR1 = Thiophosgene
| IUPACName = Carbonothioyl dichloride
| IUPACName = Carbonothioyl dichloride
| OtherNames = Thiophosgene; Thiocarbonyl chloride; Carbonothioic dichloride
| OtherNames = Thiophosgene; Thiocarbonyl chloride; Carbonothioic dichloride
| SystematicName =
|Section1={{Chembox Identifiers
| Section1 = {{Chembox Identifiers
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = 067FQP576P
| UNII = 067FQP576P
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| RTECS = XN2450000
| RTECS = XN2450000
}}
}}
|Section2={{Chembox Properties
| Section2 = {{Chembox Properties
| Formula = CSCl<sub>2</sub>
| Formula = CSCl<sub>2</sub>
| MolarMass = 114.98 g/mol
| MolarMass = 114.98 g/mol
| Appearance = Red liquid
| Appearance = Red liquid
| Odor = It smells like BEEF
| Odor = Persistent, choking odor
| Density = 1.50 g/cm<sup>3</sup>
| Density = 1.50 g/cm<sup>3</sup>
| Solubility = Decomposition
| Solubility = Decomposition
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| MagSus = -50.6·10<sup>−6</sup> cm<sup>3</sup>/mol
| MagSus = -50.6·10<sup>−6</sup> cm<sup>3</sup>/mol
}}
}}
|Section3={{Chembox Structure
| Section3 = {{Chembox Structure
| MolShape = planar, sp<sup>2</sup>, C<sub>2v</sub>
| MolShape = planar, sp<sup>2</sup>, C<sub>2v</sub>
| Dipole =
| Dipole =
}}
}}
| Section4 =
⚫
|Section7={{Chembox Hazards
| Section5 =
| Section6 =
⚫
| Section7 = {{Chembox Hazards
| ExternalSDS =
| ExternalSDS =
| MainHazards = Highly toxic
| MainHazards = Highly toxic
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| SPhrases =
| SPhrases =
}}
}}
|Section8={{Chembox Related
| Section8 = {{Chembox Related
| OtherCompounds = [[Phosgene]]<br/> [[Thiocarbonyl fluoride]] <br/> [[Thiocarbonyl bromide]] <br/> [[Sulfur dichloride]]<br/>[[Thionyl chloride]]
| OtherCompounds = [[Phosgene]]<br/> [[Thiocarbonyl fluoride]] <br/> [[Thiocarbonyl bromide]] <br/> [[Sulfur dichloride]]<br/>[[Thionyl chloride]]
}}
}}

Revision as of 18:29, 21 October 2020

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 114.98 g/mol
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)
Decomposition
Solubility in other solvents polar organic solvents
rxn with amines and alcohols
-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
 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 [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

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 of CSCl2

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

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, a rare sulfenyl chloride, and hydrolyzes the sulfur monochloride. Reduction of trichloromethanesulfenyl chloride produces thiophosgene:

CCl3SCl + M → CSCl2 + MCl2

Typically, tin is used for the reducing agent M.[2]

Reactions

CSCl2 is mainly used to prepare compounds with the connectivity CSX2 where X = OR, NHR.[3] 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 olefins.[4]

It forms a head-to-tail dimer upon irradiation with UV light:[5]

2 CSCl2 → S2(CCl2)2

Unlike thiophosgene monomer, a red liquid, the photodimer, an example of a 1,3-dithietane, is a colorless solid.

Safety considerations

CSCl2 is considered highly toxic.[citation needed]

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" (PDF). Organic Syntheses. 6: 86. doi:10.15227/orgsyn.006.0086; Collected Volumes, vol. 1, p. 506.
  3. ^ Pascual, Roxana Martinez "Thiophosgene" Synlett 2015, vol. 26, pp. 1776-1777. doi:10.1055/s-0034-1380659
  4. ^ Sharma, S. (1978). "Thiophosgene in Organic Synthesis". Synthesis. 1978 (11): 803–820. doi:10.1055/s-1978-24896.
  5. ^ "Die Kristall‐ und Molekelstruktur des dimeren Thiophosgens". Z. anorg. allg. Chem. 365: 199–210. 1969. doi:10.1002/zaac.19693650315. {{cite journal}}: Unknown parameter |authors= ignored (help)

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
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