Toluene

Toluene (/ˈtɒljuiːn/), also known as toluol (/ˈtɒljuɒl/), is an aromatic hydrocarbon. It is a colorless, water-insoluble liquid with the smell associated with paint thinners. It is a mono-substituted benzene derivative, consisting of a methyl group (CH₃) attached to a phenyl group. As such, its IUPAC systematic name is methylbenzene. Toluene is predominantly used as an industrial feedstock and a solvent.

Toluene
Names
Preferred IUPAC name
Toluene[1]
Systematic IUPAC name
Methylbenzene
Other names
Phenyl methane
Toluol
Anisen
Identifiers
3D model (JSmol)
Abbreviations PhMe
MePh
BnH
Tol
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard 100.003.297
KEGG
RTECS number
  • XS5250000
UNII
Properties
C7H8
Molar mass 92.141 g·mol−1
Appearance Colorless liquid[2]
Odor sweet, pungent, benzene-like[3]
Density 0.87 g/mL (20 °C)[2]
Melting point −95 °C (−139 °F; 178 K)[2]
Boiling point 111 °C (232 °F; 384 K)[2]
0.52 g/L (20 °C)[2]
log P 2.68[4]
Vapor pressure 2.8 kPa (20 °C)[3]
−66.11·10−6 cm3/mol
1.497 (20 °C)
Viscosity 0.590 cP (20 °C)
Structure
0.36 D
Hazards
Main hazards highly flammable
Safety data sheet See: data page
SIRI.org
GHS pictograms
GHS Signal word Danger
GHS hazard statements
 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 code
3
2
0
Flash point 6 °C (43 °F; 279 K)[2]
Explosive limits 1.1–7.1%[3]
50 mL/m3, 190 mg/m3
Lethal dose or concentration (LD, LC):
>26700 ppm (rat, 1 h)
400 ppm (mouse, 24 h)[5]
55,000 ppm (rabbit, 40 min)[5]
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 200 ppm C 300 ppm 500 ppm (10-minute maximum peak)[3]
REL (Recommended)
 TWA 100 ppm (375 mg/m3) ST 150 ppm (560 mg/m3)[3]
IDLH (Immediate danger)
 500 ppm[3]
Related compounds
benzene
xylene
naphthalene
Related compounds
 methylcyclohexane
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).
N verify (what is YN ?)
Infobox references

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[7] and has the potential of causing severe neurological harm.[8][9]

History

The compound was first isolated in 1837 through a distillation of pine oil by the Polish chemist Filip Walter, who named it rétinnaphte.[10] In 1841, French chemist 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.[11] In 1843, Jöns Jacob Berzelius recommended the name toluin.[12] 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.[13]

Chemical properties

Toluene reacts as a normal aromatic hydrocarbon in electrophilic aromatic substitution.[14][15][16] 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.

Importantly, the methyl side chain in toluene is susceptible to oxidation. Toluene reacts with Potassium permanganate to yield benzoic acid, and with chromyl chloride to yield benzaldehyde (Étard reaction).

The methyl group undergoes halogenation under free radical conditions. For example, N-bromosuccinimide (NBS) heated with toluene in the presence of AIBN leads 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.[17]

C6H5CH3 + Br2 → C6H5CH(Br)2 + HBr
C6H5CH2Br + Br2 → C6H5CHBr2 + HBr

The methyl group in toluene undergoes deprotonation only with very strong bases, its pKa is estimated to be approximately 41.[18] Hydrogenation of toluene gives methylcyclohexane. The methylcyclohexane then turns to ice as it dissolves.

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).

Laboratory preparation

Toluene is inexpensively produced industrially. In principle it could be prepared by a variety of methods. For example, although only of didactical interest, benzene reacts with methyl chloride in presence of a Lewis acid such as aluminium chloride to give toluene :

C6H5H + CH3Cl → C6H5CH3 + HCl

Such reactions are complicated by polymethylation because toluene is more susceptible to alkylation than is benzene.

Uses

Precursor to benzene and xylene

Toluene is mainly used as a precursor to benzene via hydrodealkylation:

C6H5CH3 + H2 → C6H6 + CH4

The second ranked application involves its disproportionation to a mixture of benzene and xylene.[19]

Nitration

Nitration of toluene give mono-, di-, and trinitrotoluene, all of which are widely used. Dinitrotoluene is the precursor to toluene diisocyanate, which used in the manufacture of polyurethane foam. Trinitrotoluene is the explosive typically abbreviated TNT.

Oxidation

Benzoic acid and benzaldehyde are produced commercially by partial oxidation of toluene with oxygen. Typical catalysts include cobalt or manganese naphthenates.[20]

toluene oxidation

Solvent

Toluene is a common solvent, e.g. for paints, paint thinners, silicone sealants,[21] many chemical reactants, rubber, printing ink, adhesives (glues), lacquers, leather tanners, and disinfectants.[19]

Fuel

Toluene can be used as an octane booster in gasoline fuels for internal combustion engines as well as jet fuel. Toluene at 86% by volume fuelled all the turbocharged engines in Formula One during the 1980s, first pioneered by the Honda team. The remaining 14% was a "filler" of n-heptane, to reduce the octane to meet Formula One fuel restrictions. Toluene at 100% can be used as a fuel for both two-stroke and four-stroke engines; however, due to the density of the fuel and other factors, the fuel does not vaporize easily unless preheated to 70 °C (158 °F). Honda solved this problem in their Formula One cars by routing the fuel lines through a heat exchanger, drawing energy from the water in the cooling system to heat the fuel.[22]

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.[23][24]

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.[25]

Toxicology and metabolism

The environmental and toxicological effects of toluene have been extensively studied.[26] In 2013, worldwide sales of toluene amounted to about 24.5 billion US-dollars.[27] Inhalation of toluene in low to moderate levels can cause tiredness, confusion, weakness, drunken-type actions, memory loss, nausea, loss of appetite, hearing loss, and colour vision loss. 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.[28][29] 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.[30]

Similar 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.[31] Additionally, toluene has been shown to display antidepressant-like effects in rodents in the forced swim test (FST) and the tail suspension test (TST),[31] 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.[31]

Toluene inhibits excitatory ion channels including the N-methyl-D-aspartate (NMDA) glutamate and nicotinic acetylcholine receptors (nAChRs) and potentiates the function of inhibitory ion channels such as the gamma-aminobutyric acid receptor type A , glycine, and serotonin receptors. In addition, toluene disrupts voltage-gated calcium channels and ATP-gated ion channels.[32]

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, 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.[33] In 2005 the European Union banned the general sale of products consisting of greater than 0.5% toluene.[34]

Bioremediation

Several types of fungi including Cladophialophora, Exophiala, Leptodontium, Pseudeurotium zonatum, and Cladosporium sphaerospermum, and certain species of bacteria can degrade toluene using it as a source of carbon and energy.[35]

gollark: As planned.
gollark: I think it would be more funner™ here if it was so slow that it was imperceptible.
gollark: Oh yes, for GEORGE.
gollark: I can make ABR rotate the image or something.
gollark: No.

References
  1. 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).
  2. Record in the GESTIS Substance Database of the Institute for Occupational Safety and Health
  3. NIOSH Pocket Guide to Chemical Hazards. "#0619". National Institute for Occupational Safety and Health (NIOSH).
  4. "toluene_msds".
  5. "Toluene". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  6. "NFPA Chemicals". New Environment, Inc.
  7. McKeown, Nathanael J. (Feb 1, 2015). Tarabar, Asim (ed.). "Toluene Toxicity, Background, Pathophysiology, Epidemiology". WebMD Health Professional Network. Cite journal requires |journal= (help)
  8. Streicher, H. Z.; Gabow, P. A.; Moss, A. H.; Kono, D.; Kaehny, W. D. (1981). "Syndromes of toluene sniffing in adults". Annals of Internal Medicine. 94 (6): 758–62. doi:10.7326/0003-4819-94-6-758. PMID 7235417.
  9. Devathasan, G.; Low, D.; Teoh, P. C.; Wan, S. H.; Wong, P. K. (1984). "Complications of chronic glue (toluene) abuse in adolescents". Aust N Z J Med. 14 (1): 39–43. doi:10.1111/j.1445-5994.1984.tb03583.x. PMID 6087782.
  10. See:
  11. See:
  12. Jacob Berzelius (1843) Jahres Berichte, 22 : 353-354..
  13. See:
  14. B. S. Furniss et al., Vogel's Textbook of Practical Organic Chemistry, 5th edition, Longman/Wiley, New York, 1989
  15. L. G. Wade, Organic Chemistry, 5th ed., p. 871, Prentice Hall, Upper Saddle RIver, New Jersey, 2003
  16. J. March, Advanced Organic Chemistry, 4th ed., p. 723, Wiley, New York, 1992
  17. Podgoršek, Ajda; Stavber, Stojan; Zupan, Marko; Iskra, Jernej (2006). "Free radical bromination by the H2O2–HBr system on water". Tetrahedron Letters. 47 (40): 7245. doi:10.1016/j.tetlet.2006.07.109.
  18. Henry Hsieh, Roderic P. Quirk. Anionic Polymerization: Principles and Practical Applications. p. 41.
  19. Fabri, Jörg; Graeser, Ulrich; Simo, Thomas A. (2005). "Toluene". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a27_147.pub2.
  20. Wade, Leroy G. (2014). Organic Chemistry (Pearson new international ed.). Harlow: Pearson Education Limited. p. 985. ISBN 978-1-292-02165-2.
  21. "Dual cure, low-solvent silicone pressure sensitive adhesives - General Electric Company".
  22. Honda Formula One Turbo-charged V-6 1.5L Engine (PDF). SAE International Congress and Exposition. February 27 – March 3, 1989.CS1 maint: date format (link)
  23. "Scam on petrol sparks spot tests". Liberty Oil. Archived from the original on 3 March 2016.
  24. "The World Today Archive - Authorities yet to acknowledge petrol scam problem".
  25. Merory, Joseph (1968). Food Flavorings: Composition, Manufacture and Use (2nd ed.). Westport, CT: AVI Publishing Company, Inc..
  26. Hogan, C. Michael (2011), "Sulfur", in Jorgensen, A.; Cleveland, C. J. (eds.), Encyclopedia of Earth, Washington DC: National Council for Science and the Environment, retrieved 26 October 2012, Sulfur is insoluble in water, but soluble in carbon disulfide, somewhat soluble in other non-polar organic solvents such as the aromatics benzene and toluene.
  27. Ceresana. "Toluene – Study: Market, Analysis, Trends - Ceresana".
  28. "Health Effects of Toluene", Canadian Centre for Occupational Health and Safety.
  29. "Toluene Toxicity Physiologic Effects" Archived 2016-10-12 at the Wayback Machine, Agency for Toxic Substances and Disease Registry.
  30. , EPA
  31. Cruz, S. L.; Soberanes-Chávez, P.; Páez-Martinez, N.; López-Rubalcava, C. (June 2009). "Toluene has antidepressant-like actions in two animal models used for the screening of antidepressant drugs". Psychopharmacology. 204 (2): 279–86. doi:10.1007/s00213-009-1462-2. PMID 19151967.
  32. "Toluene".
  33. Spigel, Saul (8 July 2009). "State Laws on Inhalant Use".
  34. "EU sets 0.1% limit on use of toluene, TCB". ICIS. Reed Business Information. 24 September 2005.
  35. Prenafeta-Boldu, Francesc X.; Kuhn, Andrea; Luykx, Dion M. A. M.; Anke, Heidrun; van Groenestijn, Johan W.; de Bont, Jan A. M. (April 2001). "Isolation and characterisation of fungi growing on volatile aromatic hydrocarbons as their sole carbon and energy source". Mycological Research. 105 (4): 477–484. doi:10.1017/S0953756201003719.
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