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Benzene is an organic
chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element ...
with the
molecular formula A chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, such as paren ...
C6H6. The benzene
molecule A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...
is composed of six
carbon Carbon () is a chemical element; it has chemical symbol, symbol C and atomic number 6. It is nonmetallic and tetravalence, tetravalent—meaning that its atoms are able to form up to four covalent bonds due to its valence shell exhibiting 4 ...
atoms joined in a planar hexagonal
ring (The) Ring(s) may refer to: * Ring (jewellery), a round band, usually made of metal, worn as ornamental jewelry * To make a sound with a bell, and the sound made by a bell Arts, entertainment, and media Film and TV * ''The Ring'' (franchise), a ...
with one
hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
atom attached to each. Because it contains only
carbon Carbon () is a chemical element; it has chemical symbol, symbol C and atomic number 6. It is nonmetallic and tetravalence, tetravalent—meaning that its atoms are able to form up to four covalent bonds due to its valence shell exhibiting 4 ...
and hydrogen atoms, benzene is classed as a
hydrocarbon In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and Hydrophobe, hydrophobic; their odor is usually fain ...
. Benzene is a natural constituent of
petroleum Petroleum, also known as crude oil or simply oil, is a naturally occurring, yellowish-black liquid chemical mixture found in geological formations, consisting mainly of hydrocarbons. The term ''petroleum'' refers both to naturally occurring un ...
and is one of the elementary
petrochemical Petrochemicals (sometimes abbreviated as petchems) are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewable s ...
s. Due to the cyclic continuous
pi bond In chemistry, pi bonds (π bonds) are covalent chemical bonds, in each of which two lobes of an orbital on one atom overlap with two lobes of an orbital on another atom, and in which this overlap occurs laterally. Each of these atomic orbital ...
s between the carbon atoms, benzene is classed as an
aromatic hydrocarbon Aromatic compounds or arenes are organic compounds "with a chemistry typified by benzene" and "cyclically conjugated." The word "aromatic" originates from the past grouping of molecules based on odor, before their general chemical properties were ...
. Benzene is a colorless and highly
flammable A combustible material is a material that can burn (i.e., sustain a flame) in air under certain conditions. A material is flammable if it ignites easily at ambient temperatures. In other words, a combustible material ignites with some effort ...
liquid with a sweet smell, and is partially responsible for the aroma of
gasoline Gasoline ( North American English) or petrol ( Commonwealth English) is a petrochemical product characterized as a transparent, yellowish, and flammable liquid normally used as a fuel for spark-ignited internal combustion engines. When for ...
. It is used primarily as a precursor to the manufacture of chemicals with more complex structures, such as
ethylbenzene Ethylbenzene is an organic compound with the formula . It is a highly flammable, colorless liquid with an odor similar to that of gasoline. This monocyclic aromatic hydrocarbon is important in the petrochemical industry as a reaction intermediat ...
and
cumene Cumene (isopropylbenzene) is an organic compound that contains a benzene ring with an isopropyl substituent. It is a constituent of crude oil and refined fuels. It is a flammable colorless liquid that has a boiling point of 152 °C. Near ...
, of which billions of kilograms are produced annually. Although benzene is a major
industrial chemical The chemical industry comprises the companies and other organizations that develop and produce industrial, specialty and other chemicals. Central to the modern world economy, the chemical industry converts raw materials (oil, natural gas, air, wa ...
, it finds limited use in consumer items because of its toxicity. Benzene is a
volatile organic compound Volatile organic compounds (VOCs) are organic compounds that have a high vapor pressure at room temperature. They are common and exist in a variety of settings and products, not limited to Indoor mold, house mold, Upholstery, upholstered furnitur ...
. Benzene is classified as a
carcinogen A carcinogen () is any agent that promotes the development of cancer. Carcinogens can include synthetic chemicals, naturally occurring substances, physical agents such as ionizing and non-ionizing radiation, and biologic agents such as viruse ...
. Its particular effects on
human health Health has a variety of definitions, which have been used for different purposes over time. In general, it refers to physical and emotional well-being, especially that associated with normal functioning of the human body, absent of disease, pain ...
, such as the long-term results of accidental exposure, have been reported on by news organizations such as ''
The New York Times ''The New York Times'' (''NYT'') is an American daily newspaper based in New York City. ''The New York Times'' covers domestic, national, and international news, and publishes opinion pieces, investigative reports, and reviews. As one of ...
''. For instance, a 2022 article stated that benzene contamination in the
Boston metropolitan area Greater Boston is the metropolitan region of New England encompassing the municipality of Boston, the capital of the U.S. state of Massachusetts and the most populous city in New England, and its surrounding areas, home to 4,941,632. The most s ...
caused hazardous conditions in multiple places, with the publication noting that the compound may eventually cause
leukemia Leukemia ( also spelled leukaemia; pronounced ) is a group of blood cancers that usually begin in the bone marrow and produce high numbers of abnormal blood cells. These blood cells are not fully developed and are called ''blasts'' or '' ...
in some individuals.


History


Discovery

The word "''benzene''" derives from "''gum benzoin''" (
benzoin resin Benzoin or benjamin (corrupted pronunciation) is a balsamic resin obtained from the bark of several species of trees in the genus '' Styrax''. It is used in perfumes and some kinds of incense and as a flavoring and medicine (see tincture of ...
), an aromatic resin known since ancient times in Southeast Asia, and later to European pharmacists and perfumers in the 16th century via trade routes. An
acid An acid is a molecule or ion capable of either donating a proton (i.e. Hydron, hydrogen cation, H+), known as a Brønsted–Lowry acid–base theory, Brønsted–Lowry acid, or forming a covalent bond with an electron pair, known as a Lewis ...
ic material was derived from benzoin by sublimation, and named "flowers of benzoin", or benzoic acid. The hydrocarbon derived from benzoic acid thus acquired the name benzin, benzol, or benzene.
Michael Faraday Michael Faraday (; 22 September 1791 – 25 August 1867) was an English chemist and physicist who contributed to the study of electrochemistry and electromagnetism. His main discoveries include the principles underlying electromagnetic inducti ...
first isolated and identified benzene in 1825 from the oily residue derived from the production of illuminating gas, giving it the name ''bicarburet of hydrogen''. In 1833, Eilhard Mitscherlich produced it by
distilling Distillation, also classical distillation, is the process of separating the component substances of a liquid mixture of two or more chemically discrete substances; the separation process is realized by way of the selective boiling of the mixt ...
benzoic acid Benzoic acid () is a white (or colorless) solid organic compound with the formula , whose structure consists of a benzene ring () with a carboxyl () substituent. The benzoyl group is often abbreviated "Bz" (not to be confused with "Bn," which ...
(from gum benzoin) and lime. He gave the compound the name ''benzin''. In 1836, the French chemist
Auguste Laurent Auguste Laurent (14 November 1807 – 15 April 1853) was a French chemist who helped in the founding of organic chemistry with his discoveries of trichloroethylene, anthracene, phthalic acid, and carbolic acid. He devised a systematic nomenc ...
named the substance "phène"; this word has become the root of the English word "
phenol Phenol (also known as carbolic acid, phenolic acid, or benzenol) is an aromatic organic compound with the molecular formula . It is a white crystalline solid that is volatile and can catch fire. The molecule consists of a phenyl group () ...
", which is
hydroxylated In chemistry, hydroxylation refers to the installation of a hydroxyl group () into an organic compound. Hydroxylations generate alcohols and phenols, which are very common functional groups. Hydroxylation confers some degree of water-solubility ...
benzene, and "
phenyl In organic chemistry, the phenyl group, or phenyl ring, is a cyclic group of atoms with the formula , and is often represented by the symbol Ph (archaically φ) or Ø. The phenyl group is closely related to benzene and can be viewed as a benzene ...
", the radical formed by abstraction of a hydrogen atom from benzene. In 1845, Charles Blachford Mansfield, working under
August Wilhelm von Hofmann August Wilhelm von Hofmann (8 April 18185 May 1892) was a German chemist who made considerable contributions to organic chemistry. His research on aniline helped lay the basis of the aniline-dye industry, and his research on coal tar laid the g ...
, isolated benzene from
coal tar Coal tar is a thick dark liquid which is a by-product of the production of coke and coal gas from coal. It is a type of creosote. It has both medical and industrial uses. Medicinally it is a topical medication applied to skin to treat psoria ...
. Four years later, Mansfield began the first industrial-scale production of benzene, based on the coal-tar method. Gradually, the sense developed among chemists that a number of substances were chemically related to benzene, comprising a diverse chemical family. In 1855, Hofmann was the first to apply the word "
aromatic In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated system, conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected from conjugati ...
" to designate this family relationship, after a characteristic property of many of its members. In 1997, benzene was detected in deep space.


Ring formula

The
empirical formula In chemistry, the empirical formula of a chemical compound is the simplest whole number ratio of atoms present in a compound. A simple example of this concept is that the empirical formula of sulfur monoxide, or SO, is simply SO, as is the empir ...
for benzene was long known, but its highly polyunsaturated structure, with just one
hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
atom for each
carbon Carbon () is a chemical element; it has chemical symbol, symbol C and atomic number 6. It is nonmetallic and tetravalence, tetravalent—meaning that its atoms are able to form up to four covalent bonds due to its valence shell exhibiting 4 ...
atom, was challenging to determine.
Archibald Scott Couper Archibald Scott Couper (; 31 March 1831 – 11 March 1892) was a Scottish chemist who proposed an early theory of chemical structure and bonding. He developed the concepts of tetravalent carbon atoms linking together to form large molecules ...
in 1858 and
Johann Josef Loschmidt Johann Josef Loschmidt (15 March 1821 – 8 July 1895), better known as Josef Loschmidt, was an Austrian scientist who performed ground-breaking work in chemistry, physics (thermodynamics, optics, electrodynamics), and crystal forms. Born in Karl ...
in 1861 suggested possible structures that contained multiple double bonds or multiple rings, but in these years very little was known about aromatic chemistry, and so chemists were unable to adduce appropriate evidence to favor any particular formula. But many chemists had begun to work on aromatic substances, especially in Germany, and relevant data was coming fast. In 1865, the German chemist Friedrich August Kekulé published a paper in French (for he was then teaching in Francophone Belgium) suggesting that the structure contained a ring of six carbon atoms with alternating single and double bonds. The next year he published a much longer paper in German on the same subject. On p. 100, Kekulé suggests that the carbon atoms of benzene could form a "chaîne fermée" (closed chain). Kekulé used evidence that had accumulated in the intervening years—namely, that there always appeared to be only one
isomer In chemistry, isomers are molecules or polyatomic ions with identical molecular formula – that is, the same number of atoms of each element (chemistry), element – but distinct arrangements of atoms in space. ''Isomerism'' refers to the exi ...
of any monoderivative of benzene, and that there always appeared to be exactly three isomers of every disubstituted derivative—now understood to correspond to the ortho, meta, and para patterns of arene substitution—to argue in support of his proposed structure. Kekulé's symmetrical ring could explain these curious facts, as well as benzene's 1:1 carbon-hydrogen ratio. Historic Benzene Formulae Kekulé (original).png, Kekulé's 1872 modification of his 1865 theory, illustrating rapid alternation of double bondsCritics pointed out a problem with Kekulé's original (1865) structure for benzene: Whenever benzene underwent substitution at the ortho position, two distinguishable isomers should have resulted, depending on whether a double bond or a single bond existed between the carbon atoms to which the substituents were attached; however, no such isomers were observed. In 1872, Kekulé suggested that benzene had two complementary structures and that these forms rapidly interconverted, so that if there were a double bond between any pair of carbon atoms at one instant, that double bond would become a single bond at the next instant (and vice versa). To provide a mechanism for the conversion process, Kekulé proposed that the valency of an atom is determined by the frequency with which it collided with its neighbors in a molecule. As the carbon atoms in the benzene ring collided with each other, each carbon atom would collide twice with one neighbor during a given interval and then twice with its other neighbor during the next interval. Thus, a double bond would exist with one neighbor during the first interval and with the other neighbor during the next interval. Therefore, between the carbon atoms of benzene there were no fixed (i.e., constant) and distinct single or double bonds; instead, the bonds between the carbon atoms were identical. Se
pages 86–89
of Auguste Kekulé (1872) "Ueber einige Condensationsprodukte des Aldehyds" (On some condensation products of aldehydes), ''Liebig's Annalen der Chemie und Pharmacie'', 162(1): 77–124, 309–320. From p. 89: ''"Das einfachste Mittel aller Stöße eines Kohlenstoffatoms ergiebt sich aus der Summe der Stöße der beiden ersten Zeiteinheiten, die sich dann periodisch wiederholen. ... man sieht daher, daß jedes Kohlenstoffatom mit den beiden anderen, ... daß diese Verschiedenheit nur eine scheinbare, aber keine wirkliche ist."'' (The simplest average of all the collisions of a carbon atom n benzenecomes from the sum of the collisions during the first two units of time, which then periodically repeat. ... thus one sees that each carbon atom collides equally often with the two others against which it bumps, ndthus stands in exactly the same relation with its two neighbors. The usual structural formula for benzene expresses, of course, only the collisions that occur during ''one'' unit of time, thus during one phase, and so one is led to the view
hat A hat is a Headgear, head covering which is worn for various reasons, including protection against weather conditions, ceremonial reasons such as university graduation, religious reasons, safety, or as a fashion accessory. Hats which incorpor ...
doubly substituted derivatives f benzenemust be different at positions 1,2 and 1,6 f the benzene ring If the idea hat wasjust presented—or a similar one—can be regarded as correct, then tfollows therefrom that this difference etween the bonds at positions 1,2 and 1,6is only an apparent ne not a real ne)
The new understanding of benzene, and hence of all aromatic compounds, proved to be so important for both pure and applied chemistry that in 1890 the
German Chemical Society The German Chemical Society () is a learned society and professional association founded in 1949 to represent the interests of German chemists in local, national and international contexts. GDCh "brings together people working in chemistry and th ...
organized an elaborate appreciation in Kekulé's honor, celebrating the twenty-fifth anniversary of his first benzene paper. Here Kekulé spoke of the creation of the theory. He said that he had discovered the ring shape of the benzene molecule after having a reverie or day-dream of a snake biting its own tail (a symbol in ancient cultures known as the
ouroboros The ouroboros or uroboros (; ) is an ancient symbol depicting a serpent symbolism, snake or European dragon, dragon Autocannibalism, eating its own tail. The ouroboros entered Western tradition via Egyptian mythology, ancient Egyptian iconogra ...
). This vision, he said, came to him after years of studying the nature of carbon-carbon bonds. This was seven years after he had solved the problem of how carbon atoms could bond to up to four other atoms at the same time. Curiously, a similar, humorous depiction of benzene had appeared in 1886 in a pamphlet entitled ''Berichte der Durstigen Chemischen Gesellschaft'' (Journal of the Thirsty Chemical Society), a parody of the ''Berichte der Deutschen Chemischen Gesellschaft'', only the parody had monkeys seizing each other in a circle, rather than snakes as in Kekulé's anecdote. Some historians have suggested that the parody was a lampoon of the snake anecdote, possibly already well known through oral transmission even if it had not yet appeared in print. Kekulé's 1890 speech in which this anecdote appeared has been translated into English. If the anecdote is the memory of a real event, circumstances mentioned in the story suggest that it must have happened early in 1862. In 1929, the cyclic nature of benzene was finally confirmed by the crystallographer
Kathleen Lonsdale Dame Kathleen Lonsdale ( Yardley; 28 January 1903 – 1 April 1971) was an Irish crystallographer, pacifist, and prison reform activist. She proved, in 1929, that the benzene ring is flat by using X-ray diffraction methods to elucidate the str ...
using
X-ray diffraction X-ray diffraction is a generic term for phenomena associated with changes in the direction of X-ray beams due to interactions with the electrons around atoms. It occurs due to elastic scattering, when there is no change in the energy of the waves. ...
methods. Using large crystals of
hexamethylbenzene Hexamethylbenzene, also known as mellitene, is a hydrocarbon with the molecular formula C12H18 and the condensed structural formula C6(CH3)6. It is an aromatic compound and a derivative of benzene, where benzene's six hydrogen atoms have each ...
, a benzene derivative with the same core of six carbon atoms, Lonsdale obtained diffraction patterns. Through calculating more than thirty parameters, Lonsdale demonstrated that the benzene ring could not be anything but a flat hexagon, and provided accurate distances for all carbon-carbon bonds in the molecule.


Nomenclature

The German chemist Wilhelm Körner suggested the prefixes ortho-, meta-, para- to distinguish di-substituted benzene derivatives in 1867; however, he did not use the prefixes to distinguish the relative positions of the substituents on a benzene ring. It was the German chemist Carl Gräbe who, in 1869, first used the prefixes ortho-, meta-, para- to denote specific relative locations of the substituents on a di-substituted aromatic ring (viz, naphthalene). In 1870, the German chemist
Viktor Meyer Viktor Meyer (8 September 18488 August 1897) was a German chemist and significant contributor to both organic and inorganic chemistry. He is best known for inventing an apparatus for determining vapour densities, the Viktor Meyer apparatus, and ...
first applied Gräbe's nomenclature to benzene.


Early applications

In 1903,
Ludwig Roselius Ludwig Roselius (2 June 1874 – 15 May 1943) was a German coffee merchant and founder of the company Kaffee HAG. He was born in Bremen and is credited with the development of commercial decaffeination of coffee. As a patron, he supported ar ...
popularized the use of benzene to decaffeinate
coffee Coffee is a beverage brewed from roasted, ground coffee beans. Darkly colored, bitter, and slightly acidic, coffee has a stimulating effect on humans, primarily due to its caffeine content, but decaffeinated coffee is also commercially a ...
. This discovery led to the production of
Sanka Sanka is a brand of instant decaffeinated coffee, sold around the world, and was one of the earliest decaffeinated varieties. Sanka is distributed in the United States by Kraft Heinz. History Decaffeinated coffee was developed in 1903 (see Dec ...
. This process was later discontinued. Benzene was historically used as a significant component in many consumer products such as liquid wrench, several
paint stripper Paint stripper or paint remover is a chemical product designed to remove paint, finishes, and coatings, while also cleaning the underlying surface. Chemical paint removers are advantageous because they act on any kind of geometry and they are ch ...
s,
rubber cement Rubber cement (cow gum in British English) is an adhesive made from elastic polymers (typically natural rubber, latex) mixed in a solvent such as acetone, hexane, heptane or toluene to keep it fluid enough to be used. This makes it part of the cla ...
s, spot removers, and other products. Manufacture of some of these benzene-containing formulations ceased in about 1950, although Liquid Wrench continued to contain significant amounts of benzene until the late 1970s.


Occurrence

Trace amounts of benzene are found in petroleum and coal. It is a byproduct of the incomplete combustion of many materials. For commercial use, until
World War II World War II or the Second World War (1 September 1939 – 2 September 1945) was a World war, global conflict between two coalitions: the Allies of World War II, Allies and the Axis powers. World War II by country, Nearly all of the wo ...
, much of benzene was obtained as a by-product of coke production (or "coke-oven light oil") for the
steel Steel is an alloy of iron and carbon that demonstrates improved mechanical properties compared to the pure form of iron. Due to steel's high Young's modulus, elastic modulus, Yield (engineering), yield strength, Fracture, fracture strength a ...
industry. However, in the 1950s, increased demand for benzene, especially from the growing
polymer A polymer () is a chemical substance, substance or material that consists of very large molecules, or macromolecules, that are constituted by many repeat unit, repeating subunits derived from one or more species of monomers. Due to their br ...
s industry, necessitated the production of benzene from petroleum. Today, most benzene comes from the
petrochemical industry file:Jampilen Petrochemical Co. 02.jpg, 300px, Jampilen Petrochemical co., Asaluyeh, Iran The petrochemical industry is concerned with the production and trade of petrochemicals. A major part is constituted by the plastics industry, plastics (poly ...
, with only a small fraction being produced from coal. Benzene has been detected on
Mars Mars is the fourth planet from the Sun. It is also known as the "Red Planet", because of its orange-red appearance. Mars is a desert-like rocky planet with a tenuous carbon dioxide () atmosphere. At the average surface level the atmosph ...
.


Structure

X-ray diffraction X-ray diffraction is a generic term for phenomena associated with changes in the direction of X-ray beams due to interactions with the electrons around atoms. It occurs due to elastic scattering, when there is no change in the energy of the waves. ...
shows that all six carbon-carbon bonds in benzene are of the same length, at 140
picometre The picometre (international spelling as used by the International Bureau of Weights and Measures; SI symbol: pm) or picometer (American spelling) is a unit of length in the International System of Units (SI), equal to , or one trillionth of ...
s (pm). The C–C
bond length In molecular geometry, bond length or bond distance is defined as the average distance between Atomic nucleus, nuclei of two chemical bond, bonded atoms in a molecule. It is a Transferability (chemistry), transferable property of a bond between at ...
s are greater than a double bond (135 pm) but shorter than a single bond (147 pm). This intermediate distance is caused by electron
delocalization In chemistry, delocalized electrons are electrons in a molecule, ion or solid metal that are not associated with a single atom or a covalent bond.IUPAC Gold Boo''delocalization''/ref> The term delocalization is general and can have slightly diff ...
: the electrons for C=C bonding are distributed equally between each of the six carbon atoms. Benzene has 6 hydrogen atoms, fewer than the corresponding parent
alkane In organic chemistry, an alkane, or paraffin (a historical trivial name that also has other meanings), is an acyclic saturated hydrocarbon. In other words, an alkane consists of hydrogen and carbon atoms arranged in a tree structure in whi ...
,
hexane Hexane () or ''n''-hexane is an organic compound, a straight-chain alkane with six carbon atoms and the molecular formula C6H14. Hexane is a colorless liquid, odorless when pure, and with a boiling point of approximately . It is widely used as ...
, which has 14. Benzene and
cyclohexane Cyclohexane is a cycloalkane with the molecular formula . Cyclohexane is non-polar. Cyclohexane is a colourless, flammable liquid with a distinctive detergent-like odor, reminiscent of cleaning products (in which it is sometimes used). Cyclohexan ...
have a similar structure; only the ring of delocalized electrons and the loss of one hydrogen per carbon distinguishes it from cyclohexane. The molecule is planar. The molecular orbital description involves the formation of three delocalized π orbitals spanning all six carbon atoms, while the valence bond description involves a superposition of
resonance structures In chemistry, resonance, also called mesomerism, is a way of describing bonding in certain molecules or polyatomic ions by the combination of several contributing structures (or ''forms'', also variously known as ''resonance structures'' or '' ...
. It is likely that this stability contributes to the peculiar molecular and chemical properties known as
aromaticity In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected from conjugation alone. The e ...
. To reflect the delocalized nature of the bonding, benzene is often depicted with a circle inside a hexagonal arrangement of carbon atoms. Derivatives of benzene occur sufficiently often as a component of organic molecules, so much so that the
Unicode Unicode or ''The Unicode Standard'' or TUS is a character encoding standard maintained by the Unicode Consortium designed to support the use of text in all of the world's writing systems that can be digitized. Version 16.0 defines 154,998 Char ...
Consortium has allocated a symbol in the
Miscellaneous Technical Miscellaneous Technical is a Unicode block ranging from U+2300 to U+23FF. It contains various common symbols which are related to and used in the various technical, programming language, and academic professions. For example: * Symbol ⌂ (HTML ...
block with the code U+232C (⌬) to represent it with three double bonds, and U+23E3 (⏣) for a delocalized version.


Benzene derivatives

Many important chemical compounds are derived from benzene by replacing one or more of its hydrogen atoms with another
functional group In organic chemistry, a functional group is any substituent or moiety (chemistry), moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions r ...
. Examples of simple benzene derivatives are
phenol Phenol (also known as carbolic acid, phenolic acid, or benzenol) is an aromatic organic compound with the molecular formula . It is a white crystalline solid that is volatile and can catch fire. The molecule consists of a phenyl group () ...
,
toluene Toluene (), also known as toluol (), is a substituted aromatic hydrocarbon with the chemical formula , often abbreviated as , where Ph stands for the phenyl group. It is a colorless, water Water is an inorganic compound with the c ...
, and
aniline Aniline (From , meaning ' indigo shrub', and ''-ine'' indicating a derived substance) is an organic compound with the formula . Consisting of a phenyl group () attached to an amino group (), aniline is the simplest aromatic amine. It is an in ...
, abbreviated PhOH, PhMe, and PhNH2, respectively. Linking benzene rings gives
biphenyl Biphenyl (also known as diphenyl, phenylbenzene, 1,1′-biphenyl, lemonene or BP) is an organic compound that forms colorless crystals. Particularly in older literature, compounds containing the functional group consisting of biphenyl less one ...
, C6H5–C6H5. Further loss of hydrogen gives "fused" aromatic hydrocarbons, such as
naphthalene Naphthalene is an organic compound with formula . It is the simplest polycyclic aromatic hydrocarbon, and is a white Crystal, crystalline solid with a characteristic odor that is detectable at concentrations as low as 0.08 Parts-per notation ...
,
anthracene Anthracene is a solid polycyclic aromatic hydrocarbon (PAH) of formula C14H10, consisting of three fused benzene rings. It is a component of coal tar. Anthracene is used in the production of the red dye alizarin and other dyes, as a scintil ...
,
phenanthrene Phenanthrene is a polycyclic aromatic hydrocarbon (PAH) with formula C14H10, consisting of three fused benzene rings. It is a colorless, crystal-like solid, but can also appear yellow. Phenanthrene is used to make dyes, plastics, pesticides, expl ...
, and
pyrene Pyrene is a polycyclic aromatic hydrocarbon (PAH) consisting of four fused benzene rings, resulting in a flat aromatic system. The chemical formula is . This yellow-green solid is the smallest peri-fused PAH (one where the rings are fused thro ...
. The limit of the fusion process is the hydrogen-free allotrope of carbon,
graphite Graphite () is a Crystallinity, crystalline allotrope (form) of the element carbon. It consists of many stacked Layered materials, layers of graphene, typically in excess of hundreds of layers. Graphite occurs naturally and is the most stable ...
. In heterocycles, carbon atoms in the benzene ring are replaced with other elements. The most important variations contain
nitrogen Nitrogen is a chemical element; it has Symbol (chemistry), symbol N and atomic number 7. Nitrogen is a Nonmetal (chemistry), nonmetal and the lightest member of pnictogen, group 15 of the periodic table, often called the Pnictogen, pnictogens. ...
. Replacing one CH with N gives the compound
pyridine Pyridine is a basic (chemistry), basic heterocyclic compound, heterocyclic organic compound with the chemical formula . It is structurally related to benzene, with one methine group replaced by a nitrogen atom . It is a highly flammable, weak ...
, C5H5N. Although benzene and pyridine are ''structurally'' related, benzene cannot be converted into pyridine. Replacement of a second CH bond with N gives, depending on the location of the second N,
pyridazine Pyridazine is an aromatic, heterocyclic, organic compound with the molecular formula . It contains a six-membered ring with two adjacent nitrogen atoms. It is a colorless liquid with a boiling point of 208 °C. It is isomeric with two other ...
,
pyrimidine Pyrimidine (; ) is an aromatic, heterocyclic, organic compound similar to pyridine (). One of the three diazines (six-membered heterocyclics with two nitrogen atoms in the ring), it has nitrogen atoms at positions 1 and 3 in the ring. The oth ...
, or pyrazine.


Production

Four chemical processes contribute to industrial benzene production: catalytic reforming,
toluene Toluene (), also known as toluol (), is a substituted aromatic hydrocarbon with the chemical formula , often abbreviated as , where Ph stands for the phenyl group. It is a colorless, water Water is an inorganic compound with the c ...
hydrodealkylation, toluene disproportionation, and steam cracking etc. According to the ATSDR Toxicological Profile for benzene, between 1978 and 1981, catalytic reformates accounted for approximately 44–50% of the total U.S. benzene production.


Catalytic reforming

In catalytic reforming, a mixture of
hydrocarbon In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and Hydrophobe, hydrophobic; their odor is usually fain ...
s with boiling points between 60 and 200 °C is blended with
hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
gas and then exposed to a bifunctional platinum(II) chloride, platinum chloride or rhenium chloride catalyst at 500–525 °C and pressures ranging from 8–50 atm. Under these conditions, aliphatic hydrocarbons form rings and lose hydrogen to become aromatic hydrocarbons. The aromatic products of the reaction are then separated from the reaction mixture (or reformate) by Liquid-liquid extraction, extraction with any one of a number of solvents, including diethylene glycol or sulfolane, and benzene is then separated from the other aromatics by distillation. The extraction step of aromatics from the reformate is designed to produce aromatics with lowest non-aromatic components. Recovery of the aromatics, commonly referred to as BTX (chemistry), BTX (benzene, toluene and xylene isomers), involves such extraction and distillation steps. In similar fashion to this catalytic reforming, UOP LLC, UOP and BP commercialized a method from LPG (mainly propane and butane) to aromatics.


Toluene hydrodealkylation

Toluene hydrodealkylation converts
toluene Toluene (), also known as toluol (), is a substituted aromatic hydrocarbon with the chemical formula , often abbreviated as , where Ph stands for the phenyl group. It is a colorless, water Water is an inorganic compound with the c ...
to benzene. In this hydrogen-intensive process, toluene is mixed with hydrogen, then passed over a chromium, molybdenum, or platinum oxide catalyst at 500–650 °C and 20–60 atm pressure. Sometimes, higher temperatures are used instead of a catalyst (at the similar reaction condition). Under these conditions, toluene undergoes dealkylation to benzene and methane: : This irreversible reaction is accompanied by an equilibrium side reaction that produces
biphenyl Biphenyl (also known as diphenyl, phenylbenzene, 1,1′-biphenyl, lemonene or BP) is an organic compound that forms colorless crystals. Particularly in older literature, compounds containing the functional group consisting of biphenyl less one ...
(diphenyl) at higher temperature: :2 + If the raw material stream contains much non-aromatic components (paraffins or naphthenes), those are likely decomposed to lower hydrocarbons such as methane, which increases the consumption of hydrogen. A typical reaction yield exceeds 95%. Sometimes, xylenes and heavier aromatics are used in place of toluene, with similar efficiency. This is often called "on-purpose" methodology to produce benzene, compared to conventional BTX (benzene-toluene-xylene) extraction processes.


Toluene disproportionation

Toluene disproportionation (TDP) is the conversion of toluene to benzene and xylene. Given that demand for ''para''-xylene (P-Xylene, ''p''-xylene) substantially exceeds demand for other xylene isomers, a refinement of the TDP process called Selective TDP (STDP) may be used. In this process, the xylene stream exiting the TDP unit is approximately 90% ''p''-xylene. In some systems, even the benzene-to-xylenes ratio is modified to favor xylenes.


Steam cracking

Steam cracking is the process for producing ethylene and other alkenes from Aliphatic compound, aliphatic hydrocarbons. Depending on the feedstock used to produce the olefins, steam cracking can produce a benzene-rich liquid by-product called ''pyrolysis gasoline''. Pyrolysis gasoline can be blended with other hydrocarbons as a gasoline additive, or routed through an extraction process to recover BTX (chemistry), BTX aromatics (benzene, toluene and xylenes).


Other methods

Although of no commercial significance, many other routes to benzene exist. Phenol and halobenzenes can be reduced with metals. Benzoic acid and its salts undergo decarboxylation to benzene. The reaction of the diazonium compound derived from
aniline Aniline (From , meaning ' indigo shrub', and ''-ine'' indicating a derived substance) is an organic compound with the formula . Consisting of a phenyl group () attached to an amino group (), aniline is the simplest aromatic amine. It is an in ...
with hypophosphorus acid gives benzene. Alkyne trimerisation of acetylene gives benzene. Complete decarboxylation of mellitic acid gives benzene.


Uses

Benzene is used mainly as an intermediate to make other chemicals, above all
ethylbenzene Ethylbenzene is an organic compound with the formula . It is a highly flammable, colorless liquid with an odor similar to that of gasoline. This monocyclic aromatic hydrocarbon is important in the petrochemical industry as a reaction intermediat ...
(and other alkylbenzenes),
cumene Cumene (isopropylbenzene) is an organic compound that contains a benzene ring with an isopropyl substituent. It is a constituent of crude oil and refined fuels. It is a flammable colorless liquid that has a boiling point of 152 °C. Near ...
,
cyclohexane Cyclohexane is a cycloalkane with the molecular formula . Cyclohexane is non-polar. Cyclohexane is a colourless, flammable liquid with a distinctive detergent-like odor, reminiscent of cleaning products (in which it is sometimes used). Cyclohexan ...
, and nitrobenzene. In 1988 it was reported that two-thirds of all chemicals on the American Chemical Society's lists contained at least one benzene ring. More than half of the entire benzene production is processed into ethylbenzene, a precursor to styrene, which is used to make polymers and plastics like polystyrene. Some 20% of the benzene production is used to manufacture cumene, which is needed to produce
phenol Phenol (also known as carbolic acid, phenolic acid, or benzenol) is an aromatic organic compound with the molecular formula . It is a white crystalline solid that is volatile and can catch fire. The molecule consists of a phenyl group () ...
and acetone for resins and adhesives. Cyclohexane consumes around 10% of the world's benzene production; it is primarily used in the manufacture of nylon fibers, which are processed into textiles and engineering plastics. Smaller amounts of benzene are used to make some types of rubbers, lubricants, dyes, detergents, drugs, explosives, and pesticides. In 2013, the biggest consumer country of benzene was China, followed by the USA. Benzene production is currently expanding in the Middle East and in Africa, whereas production capacities in Western Europe and North America are stagnating. Toluene is now often used as a substitute for benzene, for instance as a fuel additive. The solvent-properties of the two are similar, but toluene is less toxic and has a wider liquid range. Toluene is also processed into benzene. File:Benzene_uses.png, center, Major commodity chemicals and polymers derived from benzene. Clicking on the image loads the appropriate article, 600px, thumb rect 39 660 435 807 #Uses, Benzene rect 665 60 1062 207 Ethylbenzene rect 665 426 1062 579 Cumene rect 665 795 1062 942 Cyclohexane rect 665 1161 1062 1317 Aniline rect 665 1533 1062 1686 Chlorobenzene rect 1215 345 1614 495 Acetone rect 1215 636 1614 783 Phenol rect 1764 57 2163 210 Styrene rect 1764 432 2163 585 Bisphenol A rect 1764 1083 2163 1233 Adipic acid rect 1764 1332 2163 1482 Caprolactam rect 2313 57 2712 207 Polystyrene rect 2313 315 2712 462 Polycarbonate rect 2313 570 2712 717 Epoxy resin rect 2313 822 2712 975 Phenolic resin rect 2313 1083 2712 1233 Nylon 6-6 rect 2313 1335 2712 1485 Nylon 6 desc bottom-left


Component of gasoline

As a
gasoline Gasoline ( North American English) or petrol ( Commonwealth English) is a petrochemical product characterized as a transparent, yellowish, and flammable liquid normally used as a fuel for spark-ignited internal combustion engines. When for ...
(petrol) additive, benzene increases the octane rating and reduces Engine knocking, knocking. As a consequence, gasoline often contained several percent benzene before the 1950s, when tetraethyl lead replaced it as the most widely used antiknock additive. With the global phaseout of leaded gasoline, benzene has made a comeback as a gasoline additive in some nations. In the United States, concern over its negative health effects and the possibility of benzene entering the groundwater has led to stringent regulation of gasoline's benzene content, with limits typically around 1%. European petrol specifications now contain the same 1% limit on benzene content. The United States Environmental Protection Agency introduced new regulations in 2011 that lowered the benzene content in gasoline to 0.62%. In some European languages, the word for petroleum or gasoline is an exact cognate of "benzene". For instance all North Germanic languages, Scandinavian languages refer to gasoline as 'bensin'. In Catalan language, Catalan the word 'benzina' can be used for gasoline, though now it is relatively rare.


Reactions

The most common reactions of benzene involve substitution of a proton by other groups. Electrophilic aromatic substitution is a general method of derivatizing benzene. Benzene is sufficiently nucleophile, nucleophilic that it undergoes substitution by acylium ions and alkyl carbocations to give substituted derivatives. : The most widely practiced example of this reaction is the ethylation of benzene. :: Approximately 24,700,000 tons were produced in 1999. Highly instructive but of far less industrial significance is the Friedel-Crafts alkylation of benzene (and many other aromatic rings) using an alkyl halide in the presence of a strong Lewis acid catalyst. Similarly, the Friedel-Crafts acylation is a related example of electrophilic aromatic substitution. The reaction involves the acylation of benzene (or many other aromatic rings) with an acyl chloride using a strong Lewis acid catalyst such as aluminium chloride or Iron(III) chloride.


Sulfonation, chlorination, nitration

Using electrophilic aromatic substitution, many functional groups are introduced onto the benzene framework. Aromatic sulfonation, Sulfonation of benzene involves the use of oleum, a mixture of sulfuric acid with sulfur trioxide. Sulfonated benzene derivatives are useful detergents. In nitration, benzene reacts with nitronium ions (NO2+), which is a strong electrophile produced by combining sulfuric and nitric acids. Nitrobenzene is the precursor to
aniline Aniline (From , meaning ' indigo shrub', and ''-ine'' indicating a derived substance) is an organic compound with the formula . Consisting of a phenyl group () attached to an amino group (), aniline is the simplest aromatic amine. It is an in ...
. Chlorination is achieved with chlorine to give chlorobenzene in the presence of a Lewis acid catalyst such as aluminium tri-chloride.


Hydrogenation

Via hydrogenation, benzene and its derivatives convert to
cyclohexane Cyclohexane is a cycloalkane with the molecular formula . Cyclohexane is non-polar. Cyclohexane is a colourless, flammable liquid with a distinctive detergent-like odor, reminiscent of cleaning products (in which it is sometimes used). Cyclohexan ...
and derivatives. This reaction is achieved by the use of high pressures of
hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
in the presence of heterogeneous catalysts, such as finely divided nickel. Whereas alkenes can be hydrogenated near room temperatures, benzene and related compounds are more reluctant substrates, requiring temperatures >100 °C. This reaction is practiced on a large scale industrially. In the absence of the catalyst, benzene is impervious to hydrogen. Hydrogenation cannot be stopped to give cyclohexene or cyclohexadienes as these are superior substrates. Birch reduction, a non catalytic process, however selectively hydrogenates benzene to the diene.


Metal complexes

Benzene is an excellent ligand in the complex (chemistry), organometallic chemistry of low-valent metals. Important examples include the sandwich and half-sandwich complexes, respectively, Bis(benzene)chromium, Cr(C6H6)2 and (Benzene)ruthenium dichloride dimer, [RuCl2(C6H6)]2.


Health effects

Benzene is classified as a
carcinogen A carcinogen () is any agent that promotes the development of cancer. Carcinogens can include synthetic chemicals, naturally occurring substances, physical agents such as ionizing and non-ionizing radiation, and biologic agents such as viruse ...
, which increases the risk of cancer and other illnesses, and is also a notorious cause of bone marrow failure. Substantial quantities of epidemiologic, clinical, and laboratory data link benzene to aplastic anemia, acute
leukemia Leukemia ( also spelled leukaemia; pronounced ) is a group of blood cancers that usually begin in the bone marrow and produce high numbers of abnormal blood cells. These blood cells are not fully developed and are called ''blasts'' or '' ...
, bone marrow abnormalities and cardiovascular disease. The specific hematologic malignancies that benzene is associated with include: acute myeloid leukemia (AML), aplastic anemia, myelodysplastic syndrome (MDS), acute lymphoblastic leukemia (ALL), and chronic myeloid leukemia (CML). Carcinogenic activity of benzene was discovered by Swedish pharmacologist in 1897 on female workers of a tire-making factory. The American Petroleum Institute (API) stated in 1948 that "it is generally considered that the only absolutely safe concentration for benzene is zero". There is no safe exposure level; even tiny amounts can cause harm. The US Department of Health and Human Services (DHHS) classifies benzene as a human carcinogen. Long-term exposure to excessive levels of benzene in the air causes leukemia, a potentially fatal cancer of the blood-forming organs. In particular, acute myeloid leukemia or acute nonlymphocytic leukemia (AML & ANLL) is caused by benzene. IARC rated benzene as "known to be carcinogenic to humans" (IARC group 1 Carcinogens, Group 1). As benzene is ubiquitous in gasoline and hydrocarbon fuels that are in use everywhere, human exposure to benzene is a global health problem. Benzene targets the liver, kidney, lung, heart and brain and can cause DNA strand breaks and chromosomal damage, hence is Teratology#Teratogenesis, teratogenic and mutagenic. Benzene causes cancer in animals including humans. Benzene has been shown to cause cancer in both sexes of multiple species of laboratory animals exposed via various routes.


Exposure to benzene

According to the Agency for Toxic Substances and Disease Registry (ATSDR) (2007), benzene is both a synthetically made and naturally occurring chemical from processes that include: volcanic eruptions, wild fires, synthesis of chemicals such as
phenol Phenol (also known as carbolic acid, phenolic acid, or benzenol) is an aromatic organic compound with the molecular formula . It is a white crystalline solid that is volatile and can catch fire. The molecule consists of a phenyl group () ...
, production of synthetic fibers, and fabrication of rubbers, lubricants, pesticides, medications, and dyes. The major sources of benzene exposure are tobacco smoke, automobile service stations, exhaust from motor vehicles, and industrial emissions; however, ingestion and dermal absorption of benzene can also occur through contact with contaminated water. Benzene is hepatically metabolized and excreted in the urine. Measurement of air and water levels of benzene is accomplished through collection via activated charcoal tubes, which are then analyzed with a gas chromatograph. The measurement of benzene in humans can be accomplished via Urine test, urine, Blood test, blood, and breath tests; however, all of these have their limitations because benzene is rapidly metabolized in the human body. Exposure to benzene may lead progressively to aplastic anemia, leukaemia, and multiple myeloma. Occupational Safety and Health Administration, OSHA regulates levels of benzene in the workplace. The maximum allowable amount of benzene in workroom air during an 8-hour workday, 40-hour workweek is 1 ppm. As benzene can cause cancer, National Institute for Occupational Safety and Health, NIOSH recommends that all workers wear special Self-contained breathing apparatus, breathing equipment when they are likely to be exposed to benzene at levels exceeding the recommended (8-hour) exposure limit of 0.1 ppm.


Benzene exposure limits

The United States Environmental Protection Agency has set a maximum contaminant level for benzene in drinking water at 0.005 mg/L (5 ppb), as promulgated via the U.S. National Primary Drinking Water Regulations. This regulation is based on preventing benzene leukemogenesis. The maximum contaminant level goal (MCLG), a nonenforceable health goal that would allow an adequate margin of safety for the prevention of adverse effects, is zero benzene concentration in drinking water. The EPA requires that spills or accidental releases into the environment of 10 pounds (4.5 kg) or more of benzene be reported. The U.S. Occupational Safety and Health Administration (OSHA) has set a permissible exposure limit of 1 part of benzene per million parts of air (1 ppm) in the workplace during an 8-hour workday, 40-hour workweek. The short term exposure limit for airborne benzene is 5 ppm for 15 minutes. These legal limits were based on studies demonstrating compelling evidence of health risk to workers exposed to benzene. The risk from exposure to 1 ppm for a working lifetime has been estimated as 5 excess leukemia deaths per 1,000 employees exposed. (This estimate assumes no threshold for benzene's carcinogenic effects.) OSHA has also established an action level of 0.5 ppm to encourage even lower exposures in the workplace. The U.S. National Institute for Occupational Safety and Health (NIOSH) revised the Immediately Dangerous to Life and Health (IDLH) concentration for benzene to 500 ppm. The current NIOSH definition for an IDLH condition, as given in the NIOSH Respirator Selection Logic, is one that poses a threat of exposure to airborne contaminants when that exposure is likely to cause death or immediate or delayed permanent adverse health effects or prevent escape from such an environment. The purpose of establishing an IDLH value is (1) to ensure that the worker can escape from a given contaminated environment in the event of failure of the respiratory protection equipment and (2) is considered a maximum level above which only a highly reliable Self-contained breathing apparatus, breathing apparatus providing maximum worker protection is permitted. publication No. 2005-100. In September 1995, NIOSH issued a new policy for developing recommended exposure limits (RELs) for substances, including carcinogens. As benzene can cause cancer, NIOSH recommends that all workers wear special breathing equipment when they are likely to be exposed to benzene at levels exceeding the REL (10-hour) of 0.1 ppm. The NIOSH short-term exposure limit (STEL – 15 min) is 1 ppm. American Conference of Governmental Industrial Hygienists (ACGIH) adopted Threshold Limit Values (TLVs) for benzene at 0.5 ppm TWA and 2.5 ppm STEL.


Toxicology


Biomarkers of exposure

Several tests can determine exposure to benzene. Benzene itself can be measured in breath, blood or urine, but such testing is usually limited to the first 24 hours post-exposure due to the relatively rapid removal of the chemical by exhalation or biotransformation. Most people in developed countries have measureable baseline levels of benzene and other aromatic petroleum hydrocarbons in their blood. In the body, benzene is enzymatically converted to a series of oxidation products including muconic acid, phenylmercapturic acid,
phenol Phenol (also known as carbolic acid, phenolic acid, or benzenol) is an aromatic organic compound with the molecular formula . It is a white crystalline solid that is volatile and can catch fire. The molecule consists of a phenyl group () ...
, catechol, hydroquinone and Hydroxyquinol, 1,2,4-trihydroxybenzene. Most of these metabolites have some value as biomarkers of human exposure, since they accumulate in the urine in proportion to the extent and duration of exposure, and they may still be present for some days after exposure has ceased. The current ACGIH biological exposure limits for occupational exposure are 500 μg/g creatinine for muconic acid and 25 μg/g creatinine for phenylmercapturic acid in an end-of-shift urine specimen.


Biotransformations

Even if it is not a common substrate for metabolism, benzene can be oxidized by both bacteria and eukaryotes. In bacteria, dioxygenase enzyme can add an oxygen to the ring, and the unstable product is immediately reduced (by NADH) to a cyclic diol with two double bonds, breaking the aromaticity. Next, the diol is newly reduced by NADH to catechol. The catechol is then metabolized to acetyl CoA and succinyl CoA, used by organisms mainly in the citric acid cycle for energy production. The pathway for the metabolism of benzene is complex and begins in the liver. Several enzymes are involved. These include cytochrome P450 2E1 (CYP2E1), quinine oxidoreductase (NQ01 or DT-diaphorase or NAD(P)H dehydrogenase (quinone 1)), GSH, and myeloperoxidase (MPO). CYP2E1 is involved at multiple steps: converting benzene to oxepin (benzene oxide),
phenol Phenol (also known as carbolic acid, phenolic acid, or benzenol) is an aromatic organic compound with the molecular formula . It is a white crystalline solid that is volatile and can catch fire. The molecule consists of a phenyl group () ...
to hydroquinone, and hydroquinone to both benzenetriol and catechol. Hydroquinone, benzenetriol and catechol are converted to polyphenols. In the bone marrow, MPO converts these polyphenols to benzoquinones. These intermediates and metabolites induce genotoxicity by multiple mechanisms including inhibition of Type II topoisomerase, topoisomerase II (which maintains chromosome structure), disruption of microtubules (which maintains cellular structure and organization), generation of oxygen free radicals (unstable species) that may lead to point mutations, increasing oxidative stress, inducing DNA strand breaks, and altering DNA methylation (which can affect gene expression). NQ01 and GSH shift metabolism away from toxicity. NQ01 metabolizes benzoquinone toward polyphenols (counteracting the effect of MPO). GSH is involved with the formation of phenylmercapturic acid. Genetic polymorphisms in these enzymes may induce loss of function or gain of function. For example, mutations in CYP2E1 increase activity and result in increased generation of toxic metabolites. NQ01 mutations result in loss of function and may result in decreased detoxification. Myeloperoxidase mutations result in loss of function and may result in decreased generation of toxic metabolites. GSH mutations or deletions result in loss of function and result in decreased detoxification. These genes may be targets for genetic screening for susceptibility to benzene toxicity.


Molecular toxicology

The paradigm of toxicological assessment of benzene is shifting towards the domain of molecular toxicology as it allows understanding of fundamental biological mechanisms in a better way. Glutathione seems to play an important role by protecting against benzene-induced DNA breaks and it is being identified as a new biomarker for exposure and effect. Benzene causes chromosomal aberrations in the peripheral blood leukocytes and bone marrow explaining the higher incidence of leukemia and multiple myeloma caused by chronic exposure. These aberrations can be monitored using fluorescent in situ hybridization (FISH) with DNA probes to assess the effects of benzene along with the hematological tests as markers of hematotoxicity. Benzene metabolism involves enzymes coded for by polymorphic genes. Studies have shown that genotype at these loci may influence susceptibility to the toxic effects of benzene exposure. Individuals carrying variant of NAD(P)H:quinone oxidoreductase 1 (NQO1), microsomal epoxide hydrolase (EPHX) and deletion of the glutathione S-transferase T1 (GSTT1) showed a greater frequency of DNA single-stranded breaks.


Biological oxidation and carcinogenic activity

One way of understanding the carcinogenic effects of benzene is by examining the products of biological oxidation. Pure benzene, for example, oxidizes in the body to produce an epoxide, benzene oxide, which is not excreted readily and can interact with DNA to produce harmful mutations.


Routes of exposure


Inhalation

Outdoor air may contain low levels of benzene from automobile service stations, wood smoke, tobacco smoke, the transfer of gasoline, exhaust from motor vehicles, and industrial emissions. About 50% of the entire nationwide (United States) exposure to benzene results from smoking tobacco or from exposure to tobacco smoke. After smoking 32 cigarettes per day, the smoker would take in about 1.8 milligrams (mg) of benzene. This amount is about 10 times the average daily intake of benzene by nonsmokers. Inhaled benzene is primarily expelled unchanged through exhalation. In a human study 16.4 to 41.6% of retained benzene was eliminated through the lungs within five to seven hours after a two- to three-hour exposure to 47 to 110 ppm and only 0.07 to 0.2% of the remaining benzene was excreted unchanged in the urine. After exposure to 63 to 405 mg/m3 of benzene for 1 to 5 hours, 51 to 87% was excreted in the urine as phenol over a period of 23 to 50 hours. In another human study, 30% of absorbed dermally applied benzene, which is primarily metabolized in the liver, was excreted as phenol in the urine.


Exposure from soft drinks

Under specific conditions and in the presence of other chemicals
benzoic acid Benzoic acid () is a white (or colorless) solid organic compound with the formula , whose structure consists of a benzene ring () with a carboxyl () substituent. The benzoyl group is often abbreviated "Bz" (not to be confused with "Bn," which ...
(a preservative) and ascorbic acid (Vitamin C) may interact to produce benzene. In March 2006, the official Food Standards Agency in United Kingdom conducted a survey of 150 brands of soft drinks. It found that four contained benzene levels above World Health Organization limits. The affected batches were removed from sale. Similar problems were reported by the FDA in the United States.


Contamination of water supply

In 2005, the water supply to the city of Harbin in China with a population of almost nine million people, was cut off because of a major benzene exposure. Benzene leaked into the Songhua River, which supplies drinking water to the city, after Jilin chemical plant explosions 2005, an explosion at a China National Petroleum Corporation (CNPC) factory in the city of Jilin on 13 November 2005. When plastic water pipes are subject to high heat, the water may be contaminated with benzene.


Genocide

Nazi Germany used benzene administered via Injection (medicine), injection as one of their many methods for killing.


See also

* BTEX * 1,2,3-Cyclohexatriene * ''Industrial Union Department v. American Petroleum Institute'' * Six-membered aromatic rings with one carbon replaced by another element: borabenzene, silabenzene, germabenzene, stannabenzene,
pyridine Pyridine is a basic (chemistry), basic heterocyclic compound, heterocyclic organic compound with the chemical formula . It is structurally related to benzene, with one methine group replaced by a nitrogen atom . It is a highly flammable, weak ...
, phosphorine, arsabenzene, bismabenzene, pyrylium salt, pyrylium, thiopyrylium, selenopyrylium, telluropyrylium


Explanatory notes


References


External links


Benzene
at ''The Periodic Table of Videos'' (University of Nottingham)
International Chemical Safety Card 0015




*
Dept. of Health and Human Services: TR-289: Toxicology and Carcinogenesis Studies of Benzene

Video Recording
of Sir John Cadogan giving a lecture on Benzene at the Royal Institution, 22nd September 1991
Substance profile

NLM Hazardous Substances Databank – Benzene
{{Authority control Benzene, Annulenes Aromatic hydrocarbons Aromatic solvents Carcinogens Commodity chemicals GABAA receptor positive allosteric modulators Hydrocarbon solvents IARC Group 1 carcinogens Immunotoxins Mutagens Chemical hazards Petrochemicals Simple aromatic rings Six-membered rings Soil contamination Sweet-smelling chemicals Teratogens