Sulfuryl chloride
Structure and dimensions of sulfuryl chloride
Ball-and-stick model of sulfuryl chloride
Names
IUPAC name
Sulfuryl chloride
Other names
Sulfonyl chloride
Sulfuric chloride
Sulfur dichloride dioxide
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.029.314 Edit this at Wikidata
EC Number
  • 232-245-6
2256
RTECS number
  • WT4870000
UNII
UN number 1834
  • InChI=1S/Cl2O2S/c1-5(2,3)4 checkY
    Key: YBBRCQOCSYXUOC-UHFFFAOYSA-N checkY
  • InChI=1/Cl2O2S/c1-5(2,3)4
    Key: YBBRCQOCSYXUOC-UHFFFAOYAD
  • ClS(Cl)(=O)=O
Properties
SO2Cl2
Molar mass 134.9698 g mol−1
Appearance Colorless liquid with a pungent odor. Yellows upon standing.
Density 1.67 g cm−3 (20 °C)
Melting point −54.1 °C (−65.4 °F; 219.1 K)
Boiling point 69.4 °C (156.9 °F; 342.5 K)
hydrolyzes
Solubility miscible with benzene, toluene, chloroform, CCl4, glacial acetic acid
1.4437 (20 °C)[1]
Hazards
GHS labelling:
GHS05: CorrosiveGHS07: Exclamation mark
Danger
H314, H335
P260, P261, P264, P271, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P312, P321, P363, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazard W: Reacts with water in an unusual or dangerous manner. E.g. sodium, sulfuric acid
3
0
2
W
Flash point Not flammable
Related compounds
Related sulfuryl halides
 Sulfuryl fluoride
Related compounds
 Thionyl chloride
Chlorosulfonic acid
Sulfuric acid
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 ?)

Sulfuryl chloride is an inorganic compound with the formula SO2Cl2. At room temperature, it is a colorless liquid with a pungent odor. Sulfuryl chloride is not found in nature, as can be inferred from its rapid hydrolysis.

Sulfuryl chloride is commonly confused with thionyl chloride, SOCl2. The properties of these two sulfur oxychlorides are quite different: sulfuryl chloride is a source of chlorine whereas thionyl chloride is a source of chloride ions. An alternative IUPAC name is sulfuroyl dichloride.

Structure

Sulfur is tetrahedral in SO2Cl2 and the oxidation state of the sulfur atom is +6, as in sulfuric acid.

Synthesis

SO2Cl2 is prepared by the reaction of sulfur dioxide and chlorine in the presence of a catalyst, such as activated carbon.[2]

SO2 + Cl2 → SO2Cl2

The product can be purified by fractional distillation.

Legacy routes

Sulfuryl chloride was first prepared in 1838 by the French chemist Henri Victor Regnault.[3]

Legacy routes include oxidation of thionyl chloride:

SOCl2 + HgO → ClSSCl + HgCl2 + SO2Cl2
2 SOCl2 + MnO2 → SO2 + MnCl2 + SO2Cl2

Reactions

Sulfuryl chloride reacts with water, releasing hydrogen chloride gas and sulfuric acid:

2 H2O + SO2Cl2 → 2 HCl + H2SO4

For sulfuryl chloride, this happens at room temperature, but the related sulfuryl fluoride does not hydrolyse at temperatures up to 150 °C.

SO2Cl2 will also decompose when heated to or above 100 °C, about 30 °C above its boiling point.

Upon standing, SO2Cl2 decomposes to sulfur dioxide and chlorine, which gives the older samples a slightly yellowish color.[2]

SO2Cl2 can be used as a source of chlorine in alkane chlorination, initiated by chemicals (usually a peroxide) or light:[4]

CH4 + SO2Cl2 → CH3Cl + SO2 + HCl

Uses

Sulfuryl chloride is used as a source of Cl2. Because it is a pourable liquid, it is considered more convenient than Cl2 to dispense. It is used as a reagent in the conversion of C−H to C−Cl adjacent to activating substituents such as carbonyls and sulfoxides. It also chlorinates alkanes, alkenes, alkynes, aromatics, ethers (such as tetrahydrofuran) and epoxides. Such reactions occur under free radical conditions using an initiator such as AIBN. It can also be used to convert thiols or disulfides into their corresponding sulfenyl chlorides, though sulfinyl chlorides result from thiols in some cases.[5] SO2Cl2 can also convert alcohols to alkyl chlorides. In industry, sulfuryl chloride is most used in producing pesticides.

Sulfuryl chloride can also be used to treat wool to prevent shrinking.

Precautions

Sulfuryl chloride is toxic, corrosive, and acts as a lachrymator. It releases hydrogen chloride upon contact with water, as well as donor solvents such as dimethyl sulfoxide and dimethylformamide.

See also

References

  1. ^ Patnaik, P. (2002). Handbook of Inorganic Chemicals. McGraw-Hill. ISBN 978-0-07-049439-8.[page needed]
  2. ^ a b F. Fehér (1963). "Sulfuryl Chloride". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 1. NY, NY: Academic Press. pp. 382–384.
  3. ^ Regnault, Victor (1838). "Sur l'acide chlorosulfurique et la sulfamide" [On sulfuryl chloride and sulfamide]. Annales de Chimie et de Physique. Série 2 (in French). 69: 170–184.
  4. ^ Roberts JD, Caserio MC. "Practical Halogenations and Problems of Selectivity". Basic Principles of Organic Chemistry.
  5. ^ Page, P. C. B.; Wilkes, R. D.; Reynolds, D. (1995). "Alkyl Chalcogenides: Sulfur-based Functional Groups". In Ley, Steven V. (ed.). Synthesis: Carbon with One Heteroatom Attached by a Single Bond. Comprehensive Organic Functional Group Transformations. Elsevier. pp. 113–276. ISBN 9780080423234.

Further reading

Categories