Chlorobenzene

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.[3]

Chlorobenzene
Chlorobenzene
Chlorobenzene
Names
Preferred IUPAC name
Chlorobenzene
Other names
Phenyl chloride
Identifiers
3D model (JSmol)
Abbreviations PhCl
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.003.299
KEGG
RTECS number
  • CZ0175000
UNII
Properties
C6H5Cl
Molar mass 112.56 g/mol
Appearance colorless liquid
Odor almond-like[1]
Density 1.11 g/cm3, liquid
Melting point −45 °C (−49 °F; 228 K)
Boiling point 131 °C (268 °F; 404 K)
0.5 g l−1 in water at 20 °C
Solubility in other solvents soluble in most organic solvents
Vapor pressure 9 mmHg[1]
−69.97·10−6 cm3/mol
Hazards
Safety data sheet See: data page
R-phrases (outdated) R10 R20 R51/53
S-phrases (outdated) S24/25 S61
NFPA 704 (fire diamond)
Flammability code 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g. gasolineHealth code 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformReactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
2
0
Flash point 29 °C (84 °F; 302 K)
Explosive limits 1.3%-9.6%[1]
Lethal dose or concentration (LD, LC):
2290 mg/kg (rat, oral)
2250 mg/kg (rabbit, oral)
2300 mg/kg (mouse, oral)
2250 mg/kg (guinea pig, oral)[2]
8000 ppm (cat, 3 hr)[2]
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 75 ppm (350 mg/m3)[1]
REL (Recommended)
 none[1]
IDLH (Immediate danger)
 1000 ppm[1]
Related compounds
Related Halobenzenes
 Fluorobenzene
Bromobenzene
Iodobenzene
Related compounds
 benzene
1,4-dichlorobenzene
Supplementary data page
Refractive index (n),
Dielectric constant (εr), etc.
Thermodynamic
data
 Phase behaviour
solid–liquid–gas
UV, IR, NMR, MS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is YN ?)
Infobox references

Uses

Historical

The major use of chlorobenzene is as an intermediate in the production of commodities such as herbicides, dyestuffs, and rubber. Chlorobenzene is also used as a high-boiling solvent in many industrial applications as well as in the laboratory.[4] Chlorobenzene is nitrated on a large scale to give a mixture of 2-nitrochlorobenzene and 4-nitrochlorobenzene, which are separated. These mononitrochlorobenzenes are converted to related 2-nitrophenol, 2-nitroanisole, bis(2-nitrophenyl)disulfide, and 2-nitroaniline by nucleophilic displacement of the chloride, with respectively sodium hydroxide, sodium methoxide, sodium disulfide, and ammonia. The conversions of the 4-nitro derivative are similar.[5]

Chlorobenzene once was used in the manufacture of certain pesticides, most notably DDT, by reaction with chloral (trichloroacetaldehyde), but this application has declined with the diminished use of DDT. At one time, chlorobenzene was the main precursor for the manufacture of phenol:[6]

C6H5Cl + NaOH → C6H5OH + NaCl

The reaction also has a byproduct of salt. The reaction is known as the Dow process, with the reaction carried out at 350 °C using fused sodium hydroxide without solvent. Labeling experiments show that the reaction proceeds via elimination/addition, through benzyne as the intermediate.

Production

It was first described in 1851. Chlorobenzene is manufactured by chlorination of benzene in the presence of a catalytic amount of Lewis acid such as ferric chloride, sulfur dichloride, and anhydrous aluminium chloride:[3]

The catalyst enhances the electrophilicity of the chlorine. Because chlorine is electronegative, C6H5Cl exhibits somewhat decreased susceptibility to further chlorination. Industrially the reaction is conducted as a continuous process to minimize the formation of dichlorobenzenes.

Laboratory routes

Chlorobenzene is producible from aniline via benzenediazonium chloride, otherwise known as the Sandmeyer reaction.

Safety

Chlorobenzene exhibits "low to moderate" toxicity as indicated by its LD50 of 2.9 g/kg.[4] The Occupational Safety and Health Administration has set a permissible exposure limit at 75 ppm (350 mg/m3) over an eight-hour time-weighted average for workers handling chlorobenzene.[7]

Toxicology and biodegradation

Chlorobenzene can persist in soil for several months, in air for about 3.5 days, and in water for less than one day. Humans may be exposed to this agent via breathing contaminated air (primarily via occupational exposure), consuming contaminated food or water, or by coming into contact with contaminated soil (typically near hazardous waste sites). However, because it has only been found at 97 out of 1,177 NPL hazardous waste sites, it is not considered a widespread environmental contaminant. The bacterium Rhodococcus phenolicus degrades chlorobenzene as sole carbon sources.[8]

Upon entering the body, typically via contaminated air, chlorobenzene is excreted both via the lungs and the urinary system.

On other planets

In 2015, the SAM science team announced that the Curiosity rover reported evidence of higher concentrations of chlorobenzene in a sedimentary rock, named "Cumberland", on Mars.[9] The team speculated that the chlorobenzene might have been produced when the sample was heated in the instrument sampling chamber. The heating would have triggered a reaction of organics in the Martian soil, which is known to contain perchlorate.

See also

References
  1. NIOSH Pocket Guide to Chemical Hazards. "#0121". National Institute for Occupational Safety and Health (NIOSH).
  2. "Chlorobenzene". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  3. U. Beck, E. Löser "Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons" Ullmann's Encyclopedia of Industrial Chemistry, 2012, Wiley-VCH, Weinheim. doi:10.1002/14356007.o06_o03
  4. Rossberg, Manfred; Lendle, Wilhelm; Pfleiderer, Gerhard; Tögel, Adolf; Dreher, Eberhard-Ludwig; Langer, Ernst; Rassaerts, Heinz; Kleinschmidt, Peter; Strack, Heinz; Cook, Richard; Beck, Uwe; Lipper, Karl-August; Torkelson, Theodore R.; Löser, Eckhard; Beutel, Klaus K.; Mann, Trevor (2006). "Chlorinated Hydrocarbons". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a06_233.pub2. ISBN 3527306730.
  5. Gerald Booth (2007). "Nitro Compounds, Aromatic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a17_411. ISBN 978-3527306732. Missing or empty |title= (help)
  6. Weber, Manfred; Weber, Markus; Kleine-Boymann, Michael (2004). "Phenol". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a19_299.pub2. ISBN 3527306730.
  7. CDC - NIOSH Pocket Guide to Chemical Hazards
  8. Rehfuss, M.; Urban, J. (2005). "Rhodococcus phenolicus sp. nov., a novel bioprocessor isolated actinomycete with the ability to degrade chlorobenzene, dichlorobenzene and phenol as sole carbon sources". Systematic and Applied Microbiology. 28 (8): 695–701. doi:10.1016/j.syapm.2005.05.011. PMID 16261859. Erratum: Rehfuss, M. (2006). "Erratum to "Rhodococcus phenolicus sp. nov., a novel bioprocessor isolated actinomycete with the ability to degrade chlorobenzene, dichlorobenzene and phenol as sole carbon sources" [Systematic and Applied Microbiology 28 (2005) 695–701]". Systematic and Applied Microbiology. 29 (2): 182. doi:10.1016/j.syapm.2005.11.005.
  9. Freissinet, C.; et al. (2015). "Organic molecules in the sheepbed mudstone, gale crater, mars". Journal of Geophysical Research: Planets. 120 (3): 495–514. Bibcode:2015JGRE..120..495F. doi:10.1002/2014JE004737. PMC 4672966. PMID 26690960.
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