Chlorobenzene

The major use of chlorobenzene is as a precursor for further intermediates such as nitrophenols, nitroanisole, chloroaniline, and phenylenediamines, which are used in the production of herbicides, dyestuffs, chemicals for rubber, and pharmaceuticals.{{Ullmann |author1=Uwe Beck |author2=Eckhard Löser |title=Chlorinated Benzenes and other Nucleus-Chlorinated Aromatic Hydrocarbons |date=2012 |DOI: 10.1002/14356007.o06_o03}}

It is also used as a high-boiling solvent in industrial and laboratory applications, for materials such as oils, waxes, resins, and rubber.{{Cite book |doi=10.1002/14356007.a06_233.pub2 |title=Ullmann's Encyclopedia of Industrial Chemistry |year=2006|last1=Rossberg|first1=Manfred|last2=Lendle|first2=Wilhelm|last3=Pfleiderer|first3=Gerhard|last4=Tögel|first4=Adolf|last5=Dreher|first5=Eberhard-Ludwig|last6=Langer|first6=Ernst|last7=Rassaerts|first7=Heinz|last8=Kleinschmidt|first8=Peter|last9=Strack|first9=Heinz|last10=Cook|first10=Richard|last11=Beck|first11=Uwe|last12=Lipper|first12=Karl-August|last13=Torkelson|first13=Theodore R.|last14=Löser|first14=Eckhard|last15=Beutel|first15=Klaus K.|last16=Mann|first16=Trevor|isbn=3527306730|chapter=Chlorinated Hydrocarbons }}

Chlorobenzene is nitrated on a large scale to give a mixture of 2-nitrochlorobenzene and 4-nitrochlorobenzene, which are separated and used as intermediates in production of other chemicals. 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.{{cite encyclopedia|author=Gerald Booth|chapter=Nitro Compounds, Aromatic|encyclopedia=Ullmann's Encyclopedia of Industrial Chemistry|year=2007|publisher=Wiley-VCH|location=Weinheim|doi=10.1002/14356007.a17_411|isbn=978-3527306732}}

Chlorobenzene once was used in the manufacture of 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:{{Cite book |doi=10.1002/14356007.a19_299.pub2 |title=Ullmann's Encyclopedia of Industrial Chemistry |chapter=Phenol |year=2004 |last1=Weber |first1=Manfred |last2=Weber |first2=Markus |last3=Kleine-Boymann |first3=Michael |isbn=3527306730}}

:C₆H₅Cl + NaOH → C₆H₅OH + NaCl

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.

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 aluminium chloride:{{cite book|doi=10.1002/14356007.o06_o03 |chapter=Chlorinated Benzenes and Other Nucleus-Chlorinated Aromatic Hydrocarbons |title=Ullmann's Encyclopedia of Industrial Chemistry |date=2011 |last1=Beck |first1=Uwe |last2=Löser |first2=Eckhard |isbn=978-3-527-30385-4 }}

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

Chlorobenzene could be produced from aniline via benzenediazonium chloride, otherwise known as the Sandmeyer reaction.

Chlorobenzene exhibits "low to moderate" toxicity as indicated by its {{LD50}} of 2.9 g/kg. 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.[https://www.cdc.gov/niosh/npg/npgd0121.html CDC - NIOSH Pocket Guide to Chemical Hazards]

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, dichlorobenzene and phenol as sole carbon sources.{{Cite journal | last1 = Rehfuss | first1 = M. | last2 = Urban | first2 = J. | doi = 10.1016/j.syapm.2005.05.011 | title = Rhodococcus phenolicus sp. nov., a novel bioprocessor isolated actinomycete with the ability to degrade chlorobenzene, dichlorobenzene and phenol as sole carbon sources | journal = Systematic and Applied Microbiology | volume = 28 | issue = 8 | pages = 695–701 | year = 2005 | pmid = 16261859}} Erratum: {{Cite journal | last1 = Rehfuss | first1 = M. | title = 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] | doi = 10.1016/j.syapm.2005.11.005 | journal = Systematic and Applied Microbiology | volume = 29 | issue = 2 | page = 182| year = 2006 | doi-access = free }}

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

Chlorobenzene has been detected in a sedimentary rock on Mars.{{Cite journal |last=Freissinet |first=C. |last2=Glavin |first2=D. P. |last3=Mahaffy |first3=P. R. |last4=Miller |first4=K. E. |last5=Eigenbrode |first5=J. L. |last6=Summons |first6=R. E. |last7=Brunner |first7=A. E. |last8=Buch |first8=A. |last9=Szopa |first9=C. |last10=Archer |first10=P. D. |last11=Franz |first11=H. B. |last12=Atreya |first12=S. K. |last13=Brinckerhoff |first13=W. B. |last14=Cabane |first14=M. |last15=Coll |first15=P. |display-authors=1 |year=2015 |title=Organic molecules in the Sheepbed Mudstone, Gale Crater, Mars |url=https://agupubs.onlinelibrary.wiley.com/doi/10.1002/2014JE004737 |journal=Journal of Geophysical Research: Planets |volume=120 |issue=3 |pages=495–514 |bibcode=2015JGRE..120..495F |doi=10.1002/2014JE004737 |issn=2169-9097 |pmc=4672966 |pmid=26690960 |doi-access=free |first16=P. G. |last16=Conrad |first17=D. J. |last17=Des Marais |first18=J. P. |last18=Dworkin |first19=A. G. |last19=Fairén |first20=P. |last20=François |first21=J. P. |last21=Grotzinger |first22=S. |last22=Kashyap |first23=I. L. |last23=ten Kate |first24=L. A. |last24=Leshin |first25=C. A. |last25=Malespin |first26=M. G. |last26=Martin |first27=F. J. |last27=Martin-Torres |first28=A. C. |last28=McAdam |first29=D. W. |last29=Ming |first30=R. |last30=Navarro-González |first31=A. A. |last31=Pavlov |first32=B. D. |last32=Prats |first33=S. W. |last33=Squyres |first34=A. |last34=Steele |first35=J. C. |last35=Stern |first36=D. Y. |last36=Sumner |first37=B. |last37=Sutter |first38=M.-P. |last38=Zorzano |author39=the MSL Science Team}} It was 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.

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Category:Halogenated solvents

Category:Chlorobenzenes

Category:Aromatic solvents

Category:Phenyl compounds

Category:Substances discovered in the 19th century