Aromatic hydrocarbon

"Arene" redirects here. For other uses, see Arene (disambiguation).

An aromatic hydrocarbon or arene^[1] (or sometimes aryl hydrocarbon)^[2] is a hydrocarbon with alternating double and single bonds between carbon atoms. The term 'aromatic' was assigned before the physical mechanism determining aromaticity was discovered, and was derived from the fact that many of the compounds have a sweet scent. The configuration of six carbon atoms in aromatic compounds is known as a benzene ring, after the simplest possible such hydrocarbon, benzene. Aromatic hydrocarbons can be monocyclic (MAH) or polycyclic (PAH).

Some non-benzene-based compounds called heteroarenes, which follow Hückel's rule, are also aromatic compounds. In these compounds, at least one carbon atom is replaced by one of the heteroatoms oxygen, nitrogen, or sulfur. Examples of non-benzene compounds with aromatic properties are furan, a heterocyclic compound with a five-membered ring that includes an oxygen atom, and pyridine, a heterocyclic compound with a six-membered ring containing one nitrogen atom.^[3]

Benzene ring model

Benzene

Main article: aromaticity

Benzene, C₆H₆, is the simplest aromatic hydrocarbon and was recognized as the first aromatic hydrocarbon, with the nature of its bonding first being recognized by Friedrich August Kekulé von Stradonitz in the 19th century. Each carbon atom in the hexagonal cycle has four electrons to share. One goes to the hydrogen atom, and one each to the two neighboring carbons. This leaves one to share with one of its two neighboring carbon atoms, which is why the benzene molecule is drawn with alternating single and double bonds around the hexagon.

The structure is also illustrated as a circle around the inside of the ring to show six electrons floating around in delocalized molecular orbitals the size of the ring itself. This also represents the equivalent nature of the six carbon-carbon bonds all of bond order ~1.5. This equivalency is well explained by resonance forms. The electrons are visualized as floating above and below the ring with the electromagnetic fields they generate acting to keep the ring flat.

General properties:

1. Display aromaticity.
2. The carbon-hydrogen ratio is high.
3. They burn with a sooty yellow flame because of the high carbon-hydrogen ratio.
4. They undergo electrophilic substitution reactions and nucleophilic aromatic substitutions.

The circle symbol for aromaticity was introduced by Sir Robert Robinson in 1925 and popularized starting in 1959 by the Morrison & Boyd textbook on organic chemistry. The proper use of the symbol is debated, it is used to describe any cyclic pi system in some publications, or only those pi systems that obey Hückel's rule on others. Jensen ^[4] argues that in line with Robinson's original proposal, the use of the circle symbol should be limited to monocyclic 6 pi-electron systems. In this way the circle symbol for a 6c–6e bond can be compared to the Y symbol for a 3c–2e bond.

Arene synthesis

A reaction that forms an arene compound from an unsaturated or partially unsaturated cyclic precursor is simply called an aromatization. Many laboratory methods exist for the organic synthesis of arenes from non-arene precursors. Many methods rely on cycloaddition reactions. Alkyne trimerization describes the [2+2+2] cyclization of three alkynes, in the Dötz reaction an alkyne, carbon monoxide and a chromium carbene complex are the reactants.Diels-Alder reactions of alkynes with pyrone or cyclopentadienone with expulsion of carbon dioxide or carbon monoxide also form arene compounds. In Bergman cyclization the reactants are an enyne plus a hydrogen donor.

Another set of methods is the aromatization of cyclohexanes and other aliphatic rings: reagents are catalysts used in hydrogenation such as platinum, palladium and nickel (reverse hydrogenation), quinones and the elements sulfur and selenium.^[5]

Arene reactions

Arenes are reactants in many organic reactions.

Aromatic substitution

In aromatic substitution one substituent on the arene ring, usually hydrogen, is replaced by another substituent. The two main types are electrophilic aromatic substitution when the active reagent is an electrophile and nucleophilic aromatic substitution when the reagent is a nucleophile. In radical-nucleophilic aromatic substitution the active reagent is a radical. An example is the nitration of salicylic acid ^[6]:

Coupling reactions

In coupling reactions a metal catalyses a coupling between two formal radical fragments. Common coupling reactions with arenes result in the formation of new carbon-carbon bonds e.g., alkylarenes, vinyl arenes, biraryls, new carbon-nitrogen bonds (anilines) or new carbon-oxygen bonds (aryloxy compounds). An example is the direct arylation of perfluorobenzenes ^[7]

Hydrogenation

Hydrogenation of arenes create saturated rings. The compound 1-naphthol is completely reduced to a mixture of decalin-ol isomers.^[8]

The compound resorcinol, hydrogenated with Raney nickel in presence of aqueous sodium hydroxide forms an enolate which is alkylated with methyl iodide to 2-methyl-1,3-cyclohexandione:^[9]

Cycloadditions

Cycloaddition reaction are not common. Unusual thermal Diels-Alder reactivity of arenes can be found in the Wagner-Jauregg reaction. Other photochemical cycloaddition reactions with alkenes occur through excimers.

Benzene and derivatives of benzene

Benzene derivatives have from one to six substituents attached to the central benzene core. Examples of benzene compounds with just one substituent are phenol, which carries a hydroxyl group and toluene with a methyl group. When there is more than one substituent present on the ring, their spatial relationship becomes important for which the arene substitution patterns ortho, meta, and para are devised. For example, three isomers exist for cresol because the methyl group and the hydroxyl group can be placed next to each other (ortho), one position removed from each other (meta), or two positions removed from each other (para). Xylenol has two methyl groups in addition to the hydroxyl group, and, for this structure, 6 isomers exist.

• Representative arene compounds
• 

  Toluene

• 

  Ethylbenzene

• 

  p-Xylene

• 

  m-Xylene

• 

  Mesitylene

• 

  Durene

• 

  2-Phenylhexane

• 

  Biphenyl

• 

  Phenol

• 

  Aniline

• 

  Nitrobenzene

• 

  Benzoic acid

• 

  Aspirin

• 

  Paracetamol

• 

  Picric acid

The arene ring has an ability to stabilize charges. This is seen in, for example, phenol (C₆H₅-OH), which is acidic at the hydroxyl (OH), since a charge on this oxygen (alkoxide -O^–) is partially delocalized into the benzene ring.

Polyaromatic hydrocarbons

An illustration of typical polycyclic aromatic hydrocarbons. Clockwise from top left: benz(e)acephenanthrylene, pyrene and dibenz(ah)anthracene.

Crystal structure of a hexa-tert-butyl derivatized hexa-peri-hexabenzo(bc,ef,hi,kl,no,qr)coronene, reported by Klaus Müllen and co-workers.^[10] The tert-butyl groups make this compound soluble in common solvents such as hexane, in which the unsubstituted PAH is insoluble.

Poly-aromatic hydrocarbons (PAHs), also known as polycyclic aromatic hydrocarbons or polynuclear aromatic hydrocarbons, are potent atmospheric pollutants that consist of fused aromatic rings and do not contain heteroatoms or carry substituents.^[11] Naphthalene is the simplest example of a PAH. PAHs occur in oil, coal, and tar deposits, and are produced as byproducts of fuel burning (whether fossil fuel or biomass). As a pollutant, they are of concern because some compounds have been identified as carcinogenic, mutagenic, and teratogenic. PAHs are also found in cooked foods. Studies have shown that high levels of PAHs are found, for example, in meat cooked at high temperatures such as grilling or barbecuing, and in smoked fish.^[12][13][14]

They are also found in the interstellar medium, in comets, and in meteorites and are a candidate molecule to act as a basis for the earliest forms of life. In graphene the PAH motif is extended to large 2D sheets.

Occurrence and pollution

Polycyclic aromatic hydrocarbons are lipophilic, meaning they mix more easily with oil than water. The larger compounds are less water-soluble and less volatile (i.e., less prone to evaporate). Because of these properties, PAHs in the environment are found primarily in soil, sediment and oily substances, as opposed to in water or air. However, they are also a component of concern in particulate matter suspended in air.

Natural crude oil and coal deposits contain significant amounts of PAHs, arising from chemical conversion of natural product molecules, such as steroids, to aromatic hydrocarbons. They are also found in processed fossil fuels, tar and various edible oils.^[15]

PAHs are one of the most widespread organic pollutants. In addition to their presence in fossil fuels they are also formed by incomplete combustion of carbon-containing fuels such as wood, coal, diesel, fat, tobacco, and incense.^[16] Different types of combustion yield different distributions of PAHs in both relative amounts of individual PAHs and in which isomers are produced. Thus, coal burning produces a different mixture than motor-fuel combustion or a forest fire, making the compounds potentially useful as indicators of the burning history. Hydrocarbon emissions from fossil fuel-burning engines are regulated in developed countries.^[17]

List of PAHs

Although the health effects of individual PAHs are not exactly alike, the following 17 PAHs are considered as a group in this profile issued by the Agency for Toxic Substances and Disease Registry (ATSDR):^[18]

• acenaphthene
• acenaphthylene
• anthracene
• benz[a]anthracene
• benzo[a]pyrene
• benzo[e]pyrene
• benzo[b]fluoranthene
• benzo[ghi]perylene
• benzo[j]fluoranthene
• benzo[k]fluoranthene
• chrysene
• dibenz(a,h)anthracene
• fluoranthene
• fluorene
• indeno(1,2,3-cd)pyrene
• phenanthrene
• pyrene

Human health

PAHs toxicity is very structurally dependent, with isomers (PAHs with the same formula and number of rings) varying from being nontoxic to being extremely toxic. Thus, highly carcinogenic PAHs may be small or large. One PAH compound, benzo[a]pyrene, is notable for being the first chemical carcinogen to be discovered (and is one of many carcinogens found in cigarette smoke). The EPA has classified seven PAH compounds as probable human carcinogens: benz[a]anthracene, benzo[a]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, chrysene, dibenz(a,h)anthracene, and indeno(1,2,3-cd)pyrene.

PAHs known for their carcinogenic, mutagenic and teratogenic properties are benz[a]anthracene and chrysene, benzo[b]fluoranthene, benzo[j]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene, coronene, dibenz(a,h)anthracene (C₂₀H₁₄), indeno(1,2,3-cd)pyrene (C₂₂H₁₂) and ovalene.^[19]

High prenatal exposure to PAH is associated with lower IQ and childhood asthma.^[20] The Center for Children's Environmental Health reports studies that demonstrate that exposure to PAH pollution during pregnancy is related to adverse birth outcomes including low birth weight, premature delivery, and heart malformations. Cord blood of exposed babies shows DNA damage that has been linked to cancer. Follow-up studies show a higher level of developmental delays at age three, lower scores on IQ tests and increased behaviorial problems at ages six and eight.^[21]

Chemistry

The simplest PAHs, as defined by the International Union of Pure and Applied Chemistry (IUPAC) (G.P Moss, IUPAC nomenclature for fused-ring systems), are phenanthrene and anthracene, which both contain three fused aromatic rings. Smaller molecules, such as benzene, are not PAHs.

PAHs may contain four-, five-, six- or seven-member rings, but those with five or six are most common. PAHs composed only of six-membered rings are called alternant PAHs. Certain alternant PAHs are called benzenoid PAHs. The name comes from benzene, an aromatic hydrocarbon with a single, six-membered ring. These can be benzene rings interconnected with each other by single carbon-carbon bonds and with no rings remaining that do not contain a complete benzene ring.

The set of alternant PAHs is closely related to a set of mathematical entities called polyhexes, which are planar figures composed by conjoining regular hexagons of identical size.

PAHs containing up to six fused aromatic rings are often known as "small" PAHs, and those containing more than six aromatic rings are called "large" PAHs. Due to the availability of samples of the various small PAHs, the bulk of research on PAHs has been of those of up to six rings. The biological activity and occurrence of the large PAHs does appear to be a continuation of the small PAHs. They are found as combustion products, but at lower levels than the small PAHs due to the kinetic limitation of their production through addition of successive rings. In addition, with many more isomers possible for larger PAHs, the occurrence of specific structures is much smaller.

PAHs possess very characteristic UV absorbance spectra. These often possess many absorbance bands and are unique for each ring structure. Thus, for a set of isomers, each isomer has a different UV absorbance spectrum than the others. This is particularly useful in the identification of PAHs. Most PAHs are also fluorescent, emitting characteristic wavelengths of light when they are excited (when the molecules absorb light). The extended pi-electron electronic structures of PAHs lead to these spectra, as well as to certain large PAHs also exhibiting semi-conducting and other behaviors.

Naphthalene (C₁₀H₈ constituent of mothballs), consisting of two coplanar six-membered rings sharing an edge, is another aromatic hydrocarbon. By formal convention, it is not a true PAH, though is referred to as a bicyclic aromatic hydrocarbon.

Aqueous solubility decreases approximately one order of magnitude for each additional ring.

PAH compounds

Chemical compound		Chemical compound
Anthracene		Benzo[a]pyrene
Chrysene		Coronene
Corannulene		Tetracene
Naphthalene		Pentacene
Phenanthrene		Pyrene
Triphenylene		Ovalene

The United States Environmental Protection Agency (EPA) has designated 32 PAH compounds as priority pollutants. The original 16 are listed. They are naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]flouranthene, benzo[a]pyrene, dibenz(ah)anthracene, benzo[ghi]perylene, and indeno(1,2,3-cd)pyrene. This list of the 16 EPA priority PAHs is often targeted for measurement in environmental samples.

Aromaticity

Although PAHs clearly are aromatic compounds, the degree of aromaticity can be different for each ring segment. According to Clar's rule (formulated by Erich Clar in 1964)^[22] for PAHs the resonance structure with the most disjoint aromatic п-sextets—i.e., benzene-like moieties—is the most important for the characterization of the properties.^[23]

Phenanthrene (1)		Anthracene (2)		Chrysene (3)		Clar rule

For example, in phenanthrene (1) one Clar structure has two sextets at the extremities, while the other resonance structure has just one central sextet. Therefore in this molecule the outer rings are firmly aromatic while its central ring is less aromatic and therefore more reactive. In contrast, in anthracene (2) the number of sextets is just one and aromaticity spreads out. This difference in number of sextets is reflected in the UV absorbance spectra of these two isomers. Phenanthrene has a highest wavelength absorbance around 290 nm, while anthracene has highest wavelength bands around 380 nm. Three Clar structures with two sextets are present in chrysene (3) and by superposition the aromaticity in the outer ring is larger than in the inner rings. Another relevant Clar hydrocarbon is zethrene.

Two extremely bright stars illuminate a mist of PAHs in this Spitzer image.

Origins of life

Main article: PAH world hypothesis

In January 2004 (at the 203rd Meeting of the American Astronomical Society), it was reported^[24] that a team led by A. Witt of the University of Toledo, Ohio studied ultraviolet light emitted by the Red Rectangle nebula and found the spectral signatures of anthracene and pyrene (no other such complex molecules had ever before been found in space). This discovery was considered as a controversial^[25] confirmation of a hypothesis that as nebulae of the same type as the Red Rectangle approach the ends of their lives, convection currents cause carbon and hydrogen in the nebulae's core to get caught in stellar winds, and radiate outward. As they cool, the atoms supposedly bond to each other in various ways and eventually form particles of a million or more atoms. Witt and his team inferred^[24] that since they discovered PAHs—which may have been vital in the formation of early life on Earth—in a nebula, by necessity they must originate in nebulae.^[25] More recently, fullerenes (or "buckyballs"), have been detected in other nebulae.^[26] Fullerenes are also implicated in the origin of life; according to astronomer Letizia Stanghellini, "It’s possible that buckyballs from outer space provided seeds for life on Earth.”^[27]

Detection

Detection of PAHs in materials is often done using gas chromatography-mass spectrometry or liquid chromatography with ultraviolet-visible or fluorescence spectroscopic methods or by using rapid test PAH indicator strips.

Tables

See also

• Asphaltene
• Hydrodealkylation
• Simple aromatic rings
• Aromatic substituents: Aryl, Aryloxy and Arenediyl

References

1. ^ Definition IUPAC Gold Book Link
2. ^ Mechanisms of Activation of the Aryl Hydrocarbon Receptor by Maria Backlund, Institute of Environmental Medicine, Karolinska Institutet
3. ^ HighBeam Encyclopedia: aromatic compound
4. ^ The Origin of the Circle Symbol for Aromaticity by William B. Jensen 424 Journal of Chemical Education Vol. 86 No. 4 April 2009
5. ^ Jerry March Advanced Organic Chemistry 3Ed., ISBN 0-471-85472-7
6. ^ Webb, K. (1995). "A mild oxidation of aromatic amines". Tetrahedron Letters 36 (14): 2377–2378. doi:10.1016/0040-4039(95)00281-G.  edit
7. ^ Lafrance, M.; Rowley, C.; Woo, T.; Fagnou, K. (2006). "Catalytic intermolecular direct arylation of perfluorobenzenes.". Journal of the American Chemical Society 128 (27): 8754–8756. doi:10.1021/ja062509l. PMID 16819868.  edit
8. ^ Organic Syntheses, Coll. Vol. 6, p.371 (1988); Vol. 51, p.103 (1971). http://orgsynth.org/orgsyn/pdfs/CV6P0371.pdf
9. ^ Organic Syntheses, Coll. Vol. 5, p.743 (1973); Vol. 41, p.56 (1961). http://orgsynth.org/orgsyn/pdfs/CV5P0567.pdf
10. ^ Herwig, Peter T.; Enkelmann, Volker; Schmelz, Oliver; Müllen, Klaus (2000). "Synthesis and Structural Characterization of Hexa-tert-butyl- hexa-peri-hexabenzocoronene, Its Radical Cation Salt and Its Tricarbonylchromium Complex". Chemistry: A European Journal (Chem.-Euro.J.) 18 (10): 1834–1839. doi:10.1002/(SICI)1521-3765(20000515)6:10<1834::AID-CHEM1834>3.0.CO;2-L. 
11. ^ Fetzer, J. C. (2000). "The Chemistry and Analysis of the Large Polycyclic Aromatic Hydrocarbons". Polycyclic Aromatic Compounds (New York: Wiley) 27 (2): 143. doi:10.1080/10406630701268255. ISBN 0471363545. 
12. ^ "Polycyclic Aromatic Hydrocarbons – Occurrence in foods, dietary exposure and health effects". European Commission, Scientific Committee on Food. December 4, 2002. http://ec.europa.eu/food/fs/sc/scf/out154_en.pdf. 
13. ^ Larsson, B. K.; Sahlberg, GP; Eriksson, AT; Busk, LA (1983). "Polycyclic aromatic hydrocarbons in grilled food". J Agric Food Chem. 31 (4): 867–873. doi:10.1021/jf00118a049. PMID 6352775. 
14. ^ "Polycyclic Aromatic Hydrocarbons (PAHs)". Agency for Toxic Substances and Disease Registry. 1996. http://www.atsdr.cdc.gov/toxfaqs/tf.asp?id=121&tid=25. 
15. ^ Glenn Michael Roy (1995). Activated carbon applications in the food and pharmaceutical industries. CRC Press. p. 125. ISBN 1566761980. http://books.google.com/?id=nmmpK0oDE20C&pg=PA125. 
16. ^ "Incense link to cancer". BBC News. 2001-08-02. http://news.bbc.co.uk/2/hi/health/1467409.stm. 
17. ^ For example, EPA regulations for small engines are at 40 CFR §90.103; see emission standard for more information.
18. ^ ATSDR
19. ^ Luch, A. (2005). The Carcinogenic Effects of Polycyclic Aromatic Hydrocarbons. London: Imperial College Press. ISBN 1-86094-417-5. 
20. ^ Exposure to Common Pollutant in Womb Might Lower IQ
21. ^ http://www.ccceh.org/pdf-press/Time10-4-10.pdf
22. ^ Clar, E. (Erich) (1964). Polycyclic Hydrocarbons. New York: Academic Press. LCCN 63012392. 
23. ^ Portella, Guillem; Poater, Jordi; Solà, Miquel (2005). "Assessment of Clar's aromatic π-sextet rule by means of PDI, NICS and HOMA indicators of local aromaticity". Journal of Physical Organic Chemistry 18 (8): 785. doi:10.1002/poc.938. 
24. ^ ^{a b} Battersby, S. (2004). "Space molecules point to organic origins". New Scientist. http://www.newscientist.com/article/dn4552-space-molecules-point-to-organic-origins.html. Retrieved 2009-12-11. 
25. ^ ^{a b} Mulas, G.; Malloci, G.; Joblin, C.; Toublanc, D. (2006). "Estimated IR and phosphorescence emission fluxes for specific polycyclic aromatic hydrocarbons in the Red Rectangle". Astronomy and Astrophysics 446 (2): 537. arXiv:astro-ph/0509586. Bibcode 2006A&A...446..537M. doi:10.1051/0004-6361:20053738. 
26. ^ García-Hernández, D. A.; Manchado, A.; García-Lario, P.; Stanghellini, L.; Villaver, E.; Shaw, R. A.; Szczerba, R.; Perea-Calderón, J. V. (2010-10-28). "Formation Of Fullerenes In H-Containing Planatary Nebulae". The Astrophysical Journal Letters 724 (1): L39–L43. Bibcode 2010ApJ...724L..39G. doi:10.1088/2041-8205/724/1/L39. 
27. ^ Atkinson, Nancy (2010-10-27). "Buckyballs Could Be Plentiful in the Universe". Universe Today. http://www.universetoday.com/76732/buckyballs-could-be-plentiful-in-the-universe. Retrieved 2010-10-28. 

External links

• ATSDR - Toxicity of Polycyclic Aromatic Hydrocarbons (PAHs) U.S. Department of Health and Human Services
• Fused Ring and Bridged Fused Ring Nomenclature
• Database of PAH structures
• National Pollutant Inventory: Polycyclic Aromatic Hydrocarbon Fact Sheet
• Understanding Polycyclic Aromatic Hydrocarbons NASA Spitzer Space Telescope
• Astrobiology magazine Aromatic World An interview with Professor Pascale Ehrenfreund on PAH origin of life. Accessed June 2006
• Oregon State University Superfund Research Center focused on new technologies and emerging health risks of Polycyclic Aromatic Hydrocarbons (PAHs)
• Carcinogenic FAC list in Portable Document Format.
• Toxicological profiles of PAH.
• LIST of PAH.
• Abiogenic Gas Debate 11:2002 (EXPLORER)