Perchloromethyl mercaptan

Last updated
Perchloromethyl mercaptan
Perchloromethyl mercaptan.svg
Perchloromethyl mercaptan molecule spacefill.png
Names
Preferred IUPAC name
Trichloromethyl thiohypochlorite
Other names
Trichloromethane sulfenyl chloride

Trichloromethyl sulfur chloride

Clairsit
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.008.948 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 209-840-4
PubChem CID
RTECS number
  • PB0370000
UNII
UN number 1670
  • InChI=1S/CCl4S/c2-1(3,4)6-5 Yes check.svgY
    Key: RYFZYYUIAZYQLC-UHFFFAOYSA-N Yes check.svgY
  • InChI=1S/CCl4S/c2-1(3,4)6-5
  • ClC(Cl)(Cl)SCl
Properties
CCl4S
Molar mass 185.87 g·mol−1
AppearanceOily, yellow liquid
Odor disagreeable, acrid odor
Density 1.72 g/cm3
Melting point −44 °C (−47 °F; 229 K)
Boiling point 147 to 148 °C (297 to 298 °F; 420 to 421 K)
Insoluble, reacts
log P 3.47 (estimated)
Vapor pressure 0.4 kPa (at 20 °C)
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-skull.svg GHS-pictogram-exclam.svg
Danger
H301, H311, H312, H314, H330, H335
P260, P261, P264, P270, P271, P280, P284, P301+P310, P301+P330+P331, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P310, P312, P320, P321, P322, P330, P361, P363, P403+P233, P405, P501
NFPA 704 (fire diamond)
3
0
2
Lethal dose or concentration (LD, LC):
82.6 mg/kg (rat, oral) [1]
11 ppm (rat, 1 hr)
16 ppm (rat, 1 hr)
9 ppm (mouse, 3 hr)
38 ppm (mouse, 2 hr)
11 ppm (rat, 1 hr) [1]
388 ppm (human, 10 min)
46 ppm (mouse, 10 min) [1]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 0.1 ppm (0.8 mg/m3) [2]
REL (Recommended)
TWA 0.1 ppm (0.8 mg/m3) [2]
IDLH (Immediate danger)
10 ppm [2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Perchloromethyl mercaptan is the organosulfur compound with the formula CCl3SCl. It is mainly used as an intermediate for the synthesis of dyes and fungicides (captan, folpet). It is a colorless oil, although commercial samples are yellowish. It is insoluble in water but soluble in organic solvents. It has a foul, unbearable, acrid odor. Perchloromethyl mercaptan is the original name. The systematic name is trichloromethanesulfenyl chloride, because the compound is a sulfenyl chloride, not a mercaptan. [3]

Contents

History

It was used as a chemical warfare agent by the French in the 1915 battle of Champagne. Shortly thereafter, wartime use was abandoned due to the clear warning properties, the decomposition in the presence of iron and steel, and the easy removal of the vapor by charcoal. [4]

Preparation

The method to prepare perchloromethyl mercaptan was first described by Rathke in 1873 [3] and is still used. Carbon disulfide is chlorinated using an iodine catalyst. The following equations operate most efficiently at temperatures below about 30 °C

CS2 + 3 Cl2 → CCl3SCl + SCl2
2 CS2 + 5 Cl2 → 2 CCl3SCl + S2Cl2

At higher temperatures, the chlorination gives carbon tetrachloride and additional sulfur chlorides. [5] The formation of byproducts can be suppressed by performing the reaction in the presence of diketones. [6] Another byproduct is thiophosgene. The more volatile byproducts such as carbon tetrachloride and sulfur dichloride can be removed by distillation. The separation of perchloromethyl mercaptan from S2Cl2 by distillation is challenging since their boiling points are very close. Another byproduct that forms is hexachloroethane. Innovations in the basic Rathke method have been reported. [6]

Reactivity

The compound slowly hydrolyzes: [6]

CSCl4 + 2 H2O → CO2 + 4 HCl + 1⁄8 S8

The compound is corrosive to most metals. It reacts with iron, evolving carbon tetrachloride. Perchloromethyl mercaptan is oxidized by nitric acid to trichloromethanesulfonyl chloride (Cl3CSO2Cl), a white solid. [4]

Toxicity

AnimalOralInhalation IntraperitonealIntravenousSkinEyes
Rat82,6 mg/kg11 ppm/1h25 mg/kg
Mouse40 mg/kg296 g/m3/2h10 mg/kg56 mg/kg
Rabbit1410 mg/kg
Guinea Pig500 μL/kg50 μg/24h [7]

When it is heated or in a fire, it will emit toxic and corrosive gases. It is also very toxic by inhalation or skin absorption. [3]

At least two mechanisms could account for the toxicity of perchloromethyl mercaptan, as hypothesized by Althoff (1973). The first mechanism is a reaction between perchloromethyl mercaptan and biological functional groups such as hydroxyl, sulfhydryl, amino and carboxyl groups. This results in an inactivation of key enzymes. A second general pathway reaction is the hydrolysis to give hydrochloric acid. [3]

Related Research Articles

<span class="mw-page-title-main">Carbon tetrachloride</span> Chemical compound

Carbon tetrachloride, also known by many other names (such as tetrachloromethane, also recognised by the IUPAC, carbon tet in the cleaning industry, Halon-104 in firefighting, and Refrigerant-10 in HVACR) is an organic compound with the chemical formula CCl4. It is a colourless liquid with a "sweet" smell that can be detected at low levels. It is practically incombustible at lower temperatures. It was formerly widely used in fire extinguishers, as a precursor to refrigerants and as a cleaning agent, but has since been phased out because of environmental and safety concerns. Exposure to high concentrations of carbon tetrachloride (including vapor) can affect the central nervous system and degenerate the liver and kidneys. Prolonged exposure can be fatal.

Tetrachloroethylene, also known under the systematic name tetrachloroethene, or perchloroethylene, and many other names (and abbreviations such as "perc" or "PERC", and "PCE"), is a chlorocarbon with the formula Cl2C=CCl2. It is a colorless liquid widely used for dry cleaning of fabrics, hence it is sometimes called "dry-cleaning fluid". It also has its uses as an effective automotive brake cleaner. It has a sweet odor detectable by most people at a concentration of 1 part per million (1 ppm). Worldwide production was about 1 million metric tons (980,000 long tons; 1,100,000 short tons) in 1985.

<span class="mw-page-title-main">Carbon disulfide</span> Neurotoxic compound with formula S=C=S


Carbon disulfide is a neurotoxic, colorless, volatile liquid with the formula CS2 and structure S=C=S. The compound is used frequently as a building block in organic chemistry as well as an industrial and chemical non-polar solvent. It has an "ether-like" odor, but commercial samples are typically contaminated with foul-smelling impurities. It is of comparable toxicity to carbon monoxide.

<span class="mw-page-title-main">Dichloromethane</span> Chemical compound

Dichloromethane is an organochlorine compound with the formula CH2Cl2. This colorless, volatile liquid with a chloroform-like, sweet odour is widely used as a solvent. Although it is not miscible with water, it is slightly polar, and miscible with many organic solvents.

<span class="mw-page-title-main">1,1,1-Trichloroethane</span> Chemical compound

The organic compound 1,1,1-trichloroethane, also known as methyl chloroform, is a chloroalkane. This colorless, sweet-smelling liquid was once produced industrially in large quantities for use as a solvent. It is regulated by the Montreal Protocol as an ozone-depleting substance and its use is being rapidly phased out.

<span class="mw-page-title-main">Phosphorus pentachloride</span> Chemical compound

Phosphorus pentachloride is the chemical compound with the formula PCl5. It is one of the most important phosphorus chlorides, others being PCl3 and POCl3. PCl5 finds use as a chlorinating reagent. It is a colourless, water-sensitive and moisture-sensitive solid, although commercial samples can be yellowish and contaminated with hydrogen chloride.

<span class="mw-page-title-main">Chlorobenzene</span> Aromatic organochlorine compound

Chlorobenzene is an aromatic organic compound with the chemical formula C6H5Cl. This colorless, flammable liquid is a common solvent and a widely used intermediate in the manufacture of other chemicals.

<span class="mw-page-title-main">Sulfuryl chloride</span> Chemical compound

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.

<span class="mw-page-title-main">Hafnium tetrachloride</span> Chemical compound

Hafnium(IV) chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a catalyst.

<span class="mw-page-title-main">Thiophenol</span> Chemical compound

Thiophenol is an organosulfur compound with the formula C6H5SH, sometimes abbreviated as PhSH. This foul-smelling colorless liquid is the simplest aromatic thiol. The chemical structures of thiophenol and its derivatives are analogous to phenols except the oxygen atom in the hydroxyl group (-OH) bonded to the aromatic ring is replaced by a sulfur atom. The prefix thio- implies a sulfur-containing compound and when used before a root word name for a compound which would normally contain an oxygen atom, in the case of 'thiol' that the alcohol oxygen atom is replaced by a sulfur atom.

<span class="mw-page-title-main">Sulfur dichloride</span> Chemical compound

Sulfur dichloride is the chemical compound with the formula SCl2. 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.

1,1-Dichloroethene, commonly called 1,1-dichloroethylene or vinylidene chloride or 1,1-DCE, is an organochloride with the molecular formula C2H2Cl2. It is a colorless liquid with a sharp odor. Like most chlorocarbons, it is poorly soluble in water, but soluble in organic solvents. 1,1-DCE was the precursor to the original clingwrap, Saran, for food, but this application has been phased out.

<span class="mw-page-title-main">Chromyl chloride</span> Chemical compound

Chromyl chloride is the inorganic compound with the formula CrO2Cl2. It is a reddish brown compound that is a volatile liquid at room temperature, which is unusual for transition metal complexes.

<span class="mw-page-title-main">Sulfur tetrafluoride</span> Chemical compound

Sulfur tetrafluoride is the chemical compound with the formula SF4. It is a colorless corrosive gas that releases dangerous HF upon exposure to water or moisture. Despite these unwelcome characteristics, this compound is a useful reagent for the preparation of organofluorine compounds, some of which are important in the pharmaceutical and specialty chemical industries.

<span class="mw-page-title-main">Disulfur dichloride</span> Chemical compound

Disulfur dichloride is the inorganic compound of sulfur and chlorine with the formula S2Cl2.

<span class="mw-page-title-main">Thiophosgene</span> Chemical compound

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.

<span class="mw-page-title-main">Hexachlorobutadiene</span> Chemical compound

Hexachlorobutadiene, Cl2C=C(Cl)C(Cl)=CCl2, is a colorless liquid at room temperature that has an odor similar to that of turpentine. It is a chlorinated aliphatic diene with niche applications but is most commonly used as a solvent for other chlorine-containing compounds.

<span class="mw-page-title-main">Sulfenyl chloride</span> Chemical group (R–S–Cl)

In organosulfur chemistry, a sulfenyl chloride is a functional group with the connectivity R−S−Cl, where R is alkyl or aryl. Sulfenyl chlorides are reactive compounds that behave as sources of RS+. They are used in the formation of RS−N and RS−O bonds. According to IUPAC nomenclature they are named as alkyl thiohypochlorites, i.e. esters of thiohypochlorous acid.

<span class="mw-page-title-main">Chloroacetaldehyde</span> Chemical compound

Chloroacetaldehyde is an organic compound with the formula ClCH2CHO. Like some related compounds, it is highly electrophilic reagent and a potentially dangerous alkylating agent. The compound is not normally encountered in the anhydrous form, but rather as the hemiacetal (ClCH2CH(OH))2O.

<span class="mw-page-title-main">Octachloropropane</span> Chemical compound

Octachloropropane or perchloropropane is the chemical compound with elemental formula C3Cl8 and structural formula Cl3C−CCl2−CCl3. Its molecule has a simple chain of three carbon atoms connected by single bonds, with chlorine atoms filling their remaining bonds. It is a chlorocarbon, specifically the third simplest perchloroalkane. It can be described as a derivative of propane C3H8, with all hydrogen atoms replaced by chlorine.

References

  1. 1 2 3 "Perchloromethyl mercaptan". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  2. 1 2 3 NIOSH Pocket Guide to Chemical Hazards. "#0489". National Institute for Occupational Safety and Health (NIOSH).
  3. 1 2 3 4 Committee on Acute Exposure Guideline Levels, Committee on Toxicology, National Research Council, (2011), Acute Exposure Guideline Levels for Selected Airborne Chemicals.
  4. 1 2 Sosnovsky, George "The chemistry of trichloromethanesulfenyl chloride" Chemical Reviews 1958, volume 58, 509-40. doi : 10.1021/cr50021a003
  5. ↑ 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
  6. 1 2 3 Greco, C., (1978), Production of perchloromethyl mercaptan, Stauffer ChemicalCompany, Westport, Conn.
  7. ↑ Catalog of Chemical Suppliers, Custom Synthesis Companies and Equipment Manufactures.
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