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Toluene

Topic: Chemistry

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Toluene
Toluol.svg
Toluene-from-xtal-3D-balls.png
Sample of toluene
Names
Preferred IUPAC name
Toluene[2]
Systematic IUPAC name
Methylbenzene
Other names
Methyl benzene[1]
Methylcyclohexa-1,3,5-triene
Benzylane
Phenylmethane
Toluol
Anisen
Identifiers
3D model (JSmol)
Abbreviations PhMe
MePh
BnH
Tol
ChEBI
ChEMBL
ChemSpider
DrugBank
KEGG
RTECS number
  • XS5250000
UNII
Properties
C
6H
5CH
3
Molar mass 92.141 g·mol−1
Appearance Colorless liquid[3]
Odor sweet, pungent, benzene-like[4]
Density 0.8623 g/mL (25 °C)[1]
Melting point −95.0 °C (−139.0 °F; 178.2 K)[1]
Boiling point 110.60 °C (231.08 °F; 383.75 K)[1]
0.54 g/L (5 °C)
0.519 g/L (25 °C)
0.63 g/L (45 °C)
1.2 g/L (90 °C)[5]
log P 2.73[6]
Vapor pressure 2.8 kPa (20 °C)[4]
−66.1·10−6 cm3/mol[7]
Thermal conductivity 0.1310 W/(m·K) (25 °C)[8]
1.4941 (25 °C)[1]
Viscosity 0.560 mPa·s (25 °C)[9]
Structure
0.375 D[10]
Thermochemistry[11]
157.3 J/(mol·K)
12.4 kJ/mol
3.910 MJ/mol
Hazards
Main hazards highly flammable
Safety data sheet SIRI.org
GHS pictograms GHS02: FlammableGHS08: Health hazardGHS07: Harmful
GHS Signal word Danger
H225, H361d, H304, H373, H315, H336
P210, P240, P301+310, P302+352, P308+313, P314, P403+233
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 codeNFPA 704 four-colored diamond
3
2
0
Flash point 4 °C (39 °F; 277 K)[12]
480[12] °C (896 °F; 753 K)
Explosive limits 1.1–7.1%[12]
50 mL/m3, 190 mg/m3
Lethal dose or concentration (LD, LC):
>26700 ppm (rat, 1 h)
400 ppm (mouse, 24 h)[13]
55,000 ppm (rabbit, 40 min)[13]
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 200 ppm C 300 ppm 500 ppm (10-minute maximum peak)[4]
REL (Recommended)
 TWA 100 ppm (375 mg/m3) ST 150 ppm (560 mg/m3)[4]
IDLH (Immediate danger)
 500 ppm[4]
Related compounds
benzene
xylene
naphthalene
Related compounds
 methylcyclohexane
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is ☑Y☒N ?)
Infobox references
Tracking categories (test):

Toluene (/ˈtɒl.juiːn/), also known as toluol (/ˈtɒl.ju.ɒl, -ɔːl, -oʊl/), is a substituted aromatic hydrocarbon[15] with the chemical formula C
6H
5CH
3, often abbreviated as PhCH
3, where Ph stands for phenyl group. It is a colorless, water-insoluble liquid with the odor associated with paint thinners. It is a mono-substituted benzene derivative, consisting of a methyl group (CH3) attached to a phenyl group by a single bond. As such, its systematic IUPAC name is methylbenzene. Toluene is predominantly used as an industrial feedstock and a solvent.

As the solvent in some types of paint thinner, permanent markers, contact cement and certain types of glue, toluene is sometimes used as a recreational inhalant[16] and has the potential of causing severe neurological harm.[17][18]

History

The compound was first isolated in 1837 through a distillation of pine oil by Pierre Joseph Pelletier and Filip Neriusz Walter, who named it rétinnaphte.[19][20] In 1841, Henri Étienne Sainte-Claire Deville isolated a hydrocarbon from balsam of Tolu (an aromatic extract from the tropical Colombian tree Myroxylon balsamum), which Deville recognized as similar to Walter's rétinnaphte and to benzene; hence he called the new hydrocarbon benzoène.[21][22][23] In 1843, Jöns Jacob Berzelius recommended the name toluin.[24] In 1850, French chemist Auguste Cahours isolated from a distillate of wood a hydrocarbon which he recognized as similar to Deville's benzoène and which Cahours named toluène.[25][26]

Chemical properties

The distance between carbon atoms in the toluene ring is 0.1399 nm. The C-CH3 bond is longer at 0.1524 nm, while the average C-H bond length is 0.111 nm.[27]

Ring reactions

Toluene reacts as a normal aromatic hydrocarbon in electrophilic aromatic substitution.[28][29][30] Because the methyl group has greater electron-releasing properties than a hydrogen atom in the same position, toluene is more reactive than benzene toward electrophiles. It undergoes sulfonation to give p-toluenesulfonic acid, and chlorination by Cl2 in the presence of FeCl3 to give ortho and para isomers of chlorotoluene.

Nitration of toluene gives mono-, di-, and trinitrotoluene, all of which are widely used. Dinitrotoluene is the precursor to toluene diisocyanate, a precursor to polyurethane foam. Trinitrotoluene (TNT) is an explosive.

Complete hydrogenation of toluene gives methylcyclohexane. The reaction requires a high pressure of hydrogen and a catalyst.

Side chain reactions

The C-H bonds of the methyl group in toluene are benzylic, therefore they are weaker than C-H bonds in simpler alkanes. Reflecting this weakness, the methyl group in toluene undergoes a variety of free radical reactions. For example, when heated with N-bromosuccinimide (NBS) in the presence of AIBN, toluene converts to benzyl bromide. The same conversion can be effected with elemental bromine in the presence of UV light or even sunlight.

Toluene may also be brominated by treating it with HBr and H2O2 in the presence of light.[31]

C6H5CH3 + Br2 → C6H5CH2Br + HBr

Benzoic acid and benzaldehyde are produced commercially by partial oxidation of toluene with oxygen. Typical catalysts include cobalt or manganese naphthenates.[32] Related but laboratory-scale oxidations involve the use of potassium permanganate to yield benzoic acid and chromyl chloride to yield benzaldehyde (Étard reaction).

toluene oxidation

The methyl group in toluene undergoes deprotonation only with very strong bases; its pKa is estimated to be approximately 41.[33]

Miscibility

Toluene is miscible (soluble in all proportions) with ethanol, benzene, diethyl ether, acetone, chloroform, glacial acetic acid and carbon disulfide, but immiscible with water.[34]

Production

Toluene occurs naturally at low levels in crude oil and is a byproduct in the production of gasoline by a catalytic reformer or ethylene cracker. It is also a byproduct of the production of coke from coal. Final separation and purification is done by any of the distillation or solvent extraction processes used for BTX aromatics (benzene, toluene, and xylene isomers).[15]

Other preparative routes

Toluene can be prepared by a variety of methods. For example, benzene reacts with methanol in presence of a solid acid to give toluene:[15]

[math]\ce{ C6H6 + CH3OH ->[t^o]C6H5CH3 + H2O }[/math]

Uses

Toluene is one of the most abundantly produced chemicals. Its main uses are (1) as a precursor to benzene and xylenes, (2) as a solvent for thinners, paints, lacquers, adhesives, and (3) as an additive for gasoline.[15]

Precursor to benzene and xylenes

Toluene is converted to benzene via hydrodealkylation:

C6H5CH3 + H2 → C6H6 + CH4

Its transalkylation gives a mixture of benzene and xylenes.

Solvent

It is widely used in the paint, dye, rubber, chemical, glue, printing, and pharmaceutical industries as a solvent.[35] Nail polish, paintbrush cleaners, and stain removers may contain toluene. Manufacturing of explosives (TNT) uses it as well. Toluene is also found in cigarette smoke and car exhaust. If not in contact with air, toluene can remain unchanged in soil or water for a long time.[36]

Toluene is a common solvent, e.g. for paints, paint thinners, silicone sealants,[37] many chemical reactants, rubber, printing ink, adhesives (glues), lacquers, leather tanners, and disinfectants.[15]

Fuel

Toluene is an octane booster in gasoline fuels for internal combustion engines as well as jet fuel and turbocharged engines in Formula One.[38]

In Australia in 2003, toluene was found to have been illegally combined with petrol in fuel outlets for sale as standard vehicular fuel. Toluene incurs no fuel excise tax, while other fuels are taxed at more than 40%, providing a greater profit margin for fuel suppliers. The extent of toluene substitution has not been determined.[39][40]

Niche applications

In the laboratory, toluene is used as a solvent for carbon nanomaterials, including nanotubes and fullerenes, and it can also be used as a fullerene indicator. The color of the toluene solution of C60 is bright purple. Toluene is used as a cement for fine polystyrene kits (by dissolving and then fusing surfaces) as it can be applied very precisely by brush and contains none of the bulk of an adhesive. Toluene can be used to break open red blood cells in order to extract hemoglobin in biochemistry experiments. Toluene has also been used as a coolant for its good heat transfer capabilities in sodium cold traps used in nuclear reactor system loops. Toluene had also been used in the process of removing the cocaine from coca leaves in the production of Coca-Cola syrup.[41]

Toxicology and metabolism

The environmental and toxicological effects of toluene have been extensively studied.[42]

Toluene is irritating to the eyes, skin, and respiratory tract. It is absorbed slowly through the skin. It can cause systemic toxicity by inhalation or ingestion. Inhalation is the most common route of exposure. Symptoms of toluene poisoning include central nervous system effects (headache, dizziness, drowsiness, ataxia, euphoria, tremors, hallucinations, seizures, and coma), chemical pneumonitis, respiratory depression, ventricular arrhythmias, nausea, vomiting, and electrolyte imbalances.[35]

Inhalation of toluene in low to moderate levels can cause tiredness, confusion, weakness, drunken-type actions, memory loss, nausea, loss of appetite, hearing loss,[43][44][45] and colour vision loss.[46] Some of these symptoms usually disappear when exposure is stopped. Inhaling high levels of toluene in a short time may cause light-headedness, nausea, or sleepiness, unconsciousness, and even death.[47][48] Toluene is, however, much less toxic than benzene, and as a consequence, largely replaced it as an aromatic solvent in chemical preparation. The US Environmental Protection Agency (EPA) states that the carcinogenic potential of toluene cannot be evaluated due to insufficient information.[49] In 2013, worldwide sales of toluene amounted to about 24.5 billion US-dollars.[50]

Toluene occurs as an indoor air pollutant in a number of processes including electrosurgery, and can be removed from the air with an activated carbon filter.[51]

Similarly to many other solvents such as 1,1,1-trichloroethane and some alkylbenzenes, toluene has been shown to act as a non-competitive NMDA receptor antagonist and GABAA receptor positive allosteric modulator.[52] Additionally, toluene has been shown to display antidepressant-like effects in rodents in the forced swim test (FST) and the tail suspension test (TST),[52] likely due to its NMDA antagonist properties.

Toluene is sometimes used as a recreational inhalant ("glue sniffing"), likely on account of its euphoric and dissociative effects.[52]

Toluene inhibits excitatory ion channels such as the NMDA receptor, nicotinic acetylcholine receptor, and the serotonin 5-HT3 receptor. It also potentiates the function of inhibitory ion channels, such as the GABAA and glycine receptors. In addition, toluene disrupts voltage-gated calcium channels and ATP-gated ion channels.[53]

Recreational use

Toluene is used as an intoxicative inhalant in a manner unintended by manufacturers. People inhale toluene-containing products (e.g., paint thinner, contact cement, correction pens, model glue, etc.) for its intoxicating effect. The possession and use of toluene and products containing it are regulated in many jurisdictions, for the supposed reason of preventing minors from obtaining these products for recreational drug purposes. As of 2007, 24 U.S. states had laws penalizing use, possession with intent to use, and/or distribution of such inhalants.[54] In 2005 the European Union banned the general sale of products consisting of greater than 0.5% toluene.[55]

Bioremediation

Several types of fungi including Cladophialophora, Exophiala, Leptodontidium (syn. Leptodontium), Pseudeurotium zonatum, and Cladosporium sphaerospermum, and certain species of bacteria can degrade toluene using it as a source of carbon and energy.[56]

References

  1. ↑ 1.0 1.1 1.2 1.3 1.4 Haynes, p. 3.514
  2. ↑ Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 139. doi:10.1039/9781849733069-00130. ISBN 978-0-85404-182-4. "Toluene and xylene are preferred IUPAC names, but are not freely substitutable; toluene is substitutable under certain conditions, but only for general nomenclature (see P-15.1.8 for a general substitution rules for retained names)." 
  3. ↑ Record in the GESTIS Substance Database of the Institute for Occupational Safety and Health
  4. ↑ 4.0 4.1 4.2 4.3 4.4 NIOSH Pocket Guide to Chemical Hazards. "#0619". National Institute for Occupational Safety and Health (NIOSH). https://www.cdc.gov/niosh/npg/npgd0619.html. 
  5. ↑ Haynes, p. 5.164
  6. ↑ Haynes, p. 5.176
  7. ↑ Haynes, p. 3.579
  8. ↑ Haynes, p. 6.258
  9. ↑ Haynes, p. 6.246
  10. ↑ Haynes, p. 9.66
  11. ↑ Haynes, pp. 5.39, 5.67
  12. ↑ 12.0 12.1 12.2 Haynes, p. 16.30
  13. ↑ 13.0 13.1 "Toluene". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH). https://www.cdc.gov/niosh/idlh/108883.html. 
  14. ↑ "NFPA Chemicals". New Environment, Inc.. http://www.newenv.com/resources/nfpa_chemicals. 
  15. ↑ 15.0 15.1 15.2 15.3 15.4 "Ullmann's Encyclopedia of Industrial Chemistry". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. 2005. doi:10.1002/14356007.a27_147.pub2. 
  16. ↑ "Toluene Toxicity, Background, Pathophysiology, Epidemiology". WebMD Health Professional Network. Feb 1, 2015. http://emedicine.medscape.com/article/818939-overview. 
  17. ↑ "Syndromes of toluene sniffing in adults". Annals of Internal Medicine 94 (6): 758–62. June 1981. doi:10.7326/0003-4819-94-6-758. PMID 7235417. 
  18. ↑ "Complications of chronic glue (toluene) abuse in adolescents". Australian and New Zealand Journal of Medicine 14 (1): 39–43. February 1984. doi:10.1111/j.1445-5994.1984.tb03583.x. PMID 6087782. 
  19. ↑ Pelletier PJ and Walter FN (1837) "Examen des produits provenant du traitement de la résine dans la fabrication du gaz pour l'éclairage" (Examination of products arising from the treatment of resin during the production of illuminating gas), Comptes rendus, 4 : 898–899.
  20. ↑ Pelletier PJ and Walter FN (1838) "Examen des produits provenant du traitement de la résine dans la fabrication du gaz pour l'éclairage," Annales de Chimie et de Physique, 2nd series, 67 : 269–303. Toluene is named on pp. 278–279: "Nous désignerons la substance qui nous occupe par le nom de rétinnaphte, qui rappelle son origine et ses propriétés physiques (ρητίνη-νάφτα)." (We will designate the substance that occupies us by the name of rétinnaphte, which recalls its origin and its physical properties (ρητίνη-νάφτα [resin-naphtha]).
  21. ↑ Deville, H. (1841) "Recherches sur les résines. Étude du baume de Tolu" (Investigations of resins. Study of Tolu balsam), Comptes rendus, 13 : 476–478.
  22. ↑ Deville, H. (1841) "Recherches chimiques sur les résines; Premier mémoire" (Chemical investigations of resins; first memoir), Annales de Chimie et de Physique, 3rd series, 3 : 151–195. Deville names toluene on p. 170: "J'ai adopté, pour le corps qui m'occupe dans ce moment, le nom de benzoène, qui rappelle, dans les baumes dont il provient, ce caractère presque générique qui est de contenir de l'acide benzoïque." (I've adopted, for this substance that occupies me at the moment, the name benzoène, which recalls, in the balsams from which it comes, that character which is contained in benzoic acid.)
  23. ↑ "Henri Étienne Sainte-Claire Deville: A physician turned metallurgist". Journal of Materials Engineering and Performance 13 (2): 117–118. 2004. doi:10.1361/10599490418271. Bibcode: 2004JMEP...13..117W. 
  24. ↑ Berzelius, Jacob (1843) Jahres Berichte, 22 : 353–354. .
  25. ↑ "Recherches sur les huiles légères obtenues dans la distillation du bois" (in French). Comptes Rendus 30: 319–323 (320). 1850. http://gallica.bnf.fr/ark:/12148/bpt6k2987x/f319.image.langEN. Retrieved 2015-08-02. 
  26. ↑ "Auguste André Thomas Cahours". Educación Química 24 (4): 451–460. October 2013. doi:10.1016/S0187-893X(13)72500-X. 
  27. ↑ Haynes, p. 9.53
  28. ↑ Vogel's Textbook of Practical Organic Chemistry (5th ed.). New York: Longman/Wiley. 1989. ISBN 0582462363. https://faculty.ksu.edu.sa/sites/default/files/vogel_-_practical_organic_chemistry_5th_edition.pdf. 
  29. ↑ Organic Chemistry (5th ed.). Upper Saddle River, New Jersey: Prentice Hall. 2003. p. 871. ISBN 013033832X. 
  30. ↑ Advanced Organic Chemistry (4th ed.). New York: Wiley. 1992. pp. 723. ISBN 0471581488. 
  31. ↑ "Free Radical Bromination by the H2O2–HBr System on water". Tetrahedron Letters 47 (40): 7245–7247. 2006. doi:10.1016/j.tetlet.2006.07.109. 
  32. ↑ Organic Chemistry (Pearson new international ed.). Harlow: Pearson Education Limited. 2014. p. 985. ISBN 978-1-292-02165-2. 
  33. ↑ Henry Hsieh, Roderic P. Quirk. Anionic Polymerization: Principles and Practical Applications. p. 41. 
  34. ↑ "Toluene, Semiconductor Grade, 99% min, Thermo Scientific | Fisher Scientific". https://www.fishersci.com/shop/products/toluene-semiconductor-grade-99-min-thermo-scientific/AA19399AP. 
  35. ↑ 35.0 35.1 "Toluene | Medical Management Guidelines | Toxic Substance Portal | ATSDR". https://wwwn.cdc.gov/TSP/MMG/MMGDetails.aspx?mmgid=157&toxid=29. Retrieved 2023-06-02. 
  36. ↑ "Toluene". https://www.dhs.wisconsin.gov/chemical/toluene.htm. 
  37. ↑ "Dual cure, low-solvent silicone pressure sensitive adhesives – General Electric Company". http://www.freepatentsonline.com/6387487.html. 
  38. ↑ "Honda Formula One Turbo-charged V-6 1.5L Engine". SAE International Congress and Exposition. February 27 – March 3, 1989. http://www.k20a.org/upload/HondaRA168EEngine.pdf. Retrieved September 11, 2017. 
  39. ↑ "Scam on petrol sparks spot tests". http://www.libertyoil.com.au/www/230/1001164/displayarticle/1001248.html. 
  40. ↑ "The World Today Archive – Authorities yet to acknowledge petrol scam problem". http://www.abc.net.au/worldtoday/stories/s106466.htm. 
  41. ↑ Food Flavorings: Composition, Manufacture and Use (2nd ed.). Westport, CT: AVI Publishing Company, Inc... 1968. 
  42. ↑ "Sulfur", Encyclopedia of Earth, Washington DC: National Council for Science and the Environment, 2011, http://www.eoearth.org/article/Sulfur?topic=49557, retrieved 26 October 2012 
  43. ↑ "Hearing loss in workers exposed to toluene and noise". Environmental Health Perspectives 114 (8): 1283–6. August 2006. doi:10.1289/ehp.8959. PMID 16882540. 
  44. ↑ "Auditory and vestibular functions after single or combined exposure to toluene: a review". Archives of Toxicology 69 (7): 431–43. 1995. doi:10.1007/s002040050196. PMID 8526738. 
  45. ↑ (in en-us) Preventing hearing loss caused by chemical (ototoxicity) and noise exposure.. 2020-09-01. doi:10.26616/NIOSHPUB2018124. https://www.cdc.gov/niosh/docs/2018-124/default.html. 
  46. ↑ "Effects of low-level occupational exposure to styrene on color vision: dose relation with a urinary metabolite". Environmental Research 85 (1): 25–30. January 2001. doi:10.1006/enrs.2000.4227. PMID 11161648. Bibcode: 2001ER.....85...25K. 
  47. ↑ "Health Effects of Toluene" , Canadian Centre for Occupational Health and Safety.
  48. ↑ "Toluene Toxicity Physiologic Effects" , Agency for Toxic Substances and Disease Registry.
  49. ↑ [1] , EPA
  50. ↑ Ceresana. "Toluene – Study: Market, Analysis, Trends – Ceresana". http://www.ceresana.com/en/market-studies/chemicals/toluene/. 
  51. ↑ "A Peripherally Located Air Recirculation Device Containing an Activated Carbon Filter Reduces VOC Levels in a Simulated Operating Room". ACS Omega 7 (50): 46640–46645. December 2022. doi:10.1021/acsomega.2c05570. PMID 36570243. 
  52. ↑ 52.0 52.1 52.2 "Toluene has antidepressant-like actions in two animal models used for the screening of antidepressant drugs". Psychopharmacology 204 (2): 279–86. June 2009. doi:10.1007/s00213-009-1462-2. PMID 19151967. 
  53. ↑ "Toluene". http://flipper.diff.org/app/items/info/5367. 
  54. ↑ "State Laws on Inhalant Use". 8 July 2009. http://www.cga.ct.gov/2009/rpt/2009-R-0251.htm. 
  55. ↑ "EU sets 0.1% limit on use of toluene, TCB". Reed Business Information. 24 September 2005. https://www.icis.com/resources/news/2005/09/24/1008648/eu-sets-0-1-limit-on-use-of-toluene-tcb/. 
  56. ↑ "Isolation and characterisation of fungi growing on volatile aromatic hydrocarbons as their sole carbon and energy source". Mycological Research 105 (4): 477–484. April 2001. doi:10.1017/S0953756201003719. http://edepot.wur.nl/25292. Retrieved 2018-04-20. 

Cited sources

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