Chemistry:Sulfur dichloride

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Sulfur dichloride
Structure and dimensions of the sulfur dichloride molecule
Ball-and-stick model of sulfur dichloride
Space-filling model of sulfur dichloride
Names
IUPAC name
  • Dichlorosulfane
  • Sulfur dichloride
  • Sulfur(II) chloride
Other names
  • Chloro thiohypobromite
  • Dichloro sulfide
  • Sulphur chloride
Identifiers
3D model (JSmol)
ChemSpider
EC Number
  • 234-129-0
RTECS number
  • WS4500000
UNII
UN number 1828
Properties
SCl
2
Molar mass 102.96 g·mol−1
Appearance Cherry-red liquid
Odor Pungent
Density 1.621 g/cm3
Melting point −121.0 °C (−185.8 °F; 152.2 K)
Boiling point 59 °C (138 °F; 332 K) (decomposes)
Insoluble, reacts slowly
−49.4·10−6 cm3/mol
1.5570
Structure
C2v
Bent
Hazards
Safety data sheet ICSC 1661
GHS pictograms GHS05: CorrosiveGHS07: HarmfulGHS09: Environmental hazard
GHS Signal word Danger
H314, H335, H400
P260, P261, P264, P271, P273, P280, P301+330+331, P303+361+353, P304+340, P305+351+338, P310, P312, P321, P363, P391, P403+233, P405, P501
NFPA 704 (fire diamond)
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilHealth code 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasReactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no codeNFPA 704 four-colored diamond
1
3
1
234 °C (453 °F; 507 K)
Related compounds
Related
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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Infobox references
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Sulfur dichloride is the chemical compound with the formula SCl
2
. This cherry-red liquid is the simplest sulfur chloride and one of the most common, and it is used as a precursor to organosulfur compounds. It is a highly corrosive and toxic substance, and it reacts on contact with water to form chlorine-containing acids.

Chlorination of sulfur

SCl
2
is produced by the chlorination of either elemental sulfur or disulfur dichloride.[1] The process occurs in a series of steps, some of which are:

S
8
+ 4 Cl
2
→ 4 S
2
Cl
2
; ΔH = −58.2 kJ/mol
S
2
Cl
2
+ Cl
2
↔ 2 SCl
2
; ΔH = −40.6 kJ/mol

The addition of Cl
2
to S
2
Cl
2
has been proposed to proceed via a mixed valence intermediate Cl
3
S–SCl
. SCl
2
undergoes even further chlorination to give SCl
4
, but this species is unstable at near room temperature. It is likely that several S
n
Cl
2
exist where n > 2.

Disulfur dichloride, S
2
Cl
2
, is the most common impurity in SCl
2
. Separation of SCl
2
from S
2
Cl
2
is possible via distillation with PCl
3
to form an azeotrope of 99% purity, however sulfur dichloride loses chlorine slowly at room temperature and reverts to disulfur dichloride. Pure samples may be stored in sealed glass ampules which develop a slight positive pressure of chlorine, halting the decomposition.

Use of SCl
2
in chemical synthesis

SCl
2
is used in organic synthesis. It adds to alkenes to give chloride-substituted thioethers. Illustrative is its addition to 1,5-cyclooctadiene to give a bicyclic thioether[2] A well tested method for the production of the mustard gas bis(2-chloroethyl)sulfide, is the addition of ethylene to sulfur dichloride:[3]

SCl
2
+ 2 C
2
H
4
→ (ClC
2
H
4
)
2
S

SCl
2
is also a precursor to several inorganic sulfur compounds. Treatment with fluoride salts gives SF
4
via the decomposition of the intermediate sulfur difluoride. With H
2
S
, SCl
2
reacts to give "lower" sulfanes such as S
3
H
2
.

Reaction with ammonia affords sulfur nitrides related to S
4
N
4
. Treatment of SCl
2
with primary amines gives sulfur diimides. One example is di-t-butylsulfurdiimide.[4]

Safety considerations

References

  1. F. Fehér "Dichloromonosulfane" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 370.
  2. Bishop, Roger (1992). "9-Thiabicyclo[3.3.1]nonane-2,6-dione". Organic Syntheses 70: 120. http://www.orgsyn.org/demo.aspx?prep=cv9p0692. ; Collective Volume, 9, pp. 692 
  3. R. J. Cremlyn “An Introduction to Organosulfur Chemistry” John Wiley and Sons: Chichester (1996). ISBN:0-471-95512-4.
  4. Kresze, G.; Wucherpfennig, W. (1967). "New Methods of Preparative Organic Chemistry V: Organic Syntheses with Imides of Sulfur Dioxide". Angewandte Chemie International Edition in English 6 (2): 149–167. doi:10.1002/anie.196701491. PMID 4962859.