Benzene

Benzene is an organic chemical compound with the molecular formula C₆H₆. The benzene molecule is composed of six carbon atoms joined in a planar hexagonal ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms, benzene is classed as a hydrocarbon.
Benzene is a natural constituent of petroleum and is one of the elementary petrochemicals. Because of the cyclic continuous pi bonds between the carbon atoms and satisfying Hückel's rule, benzene is classed as an aromatic hydrocarbon. Benzene is a colorless and highly flammable liquid with a sweet smell, and is partially responsible for the aroma of gasoline. It is used primarily as a precursor to the manufacture of chemicals with more complex structures, such as ethylbenzene and cumene, of which billions of kilograms are produced annually. Although benzene is a major industrial chemical, it finds limited use in consumer items because of its toxicity. Benzene is a volatile organic compound.
Benzene is classified as a carcinogen. Its particular effects on human health, such as the long-term results of accidental exposure, have been reported on by news organizations such as The New York Times. For instance, a 2022 article stated that benzene contamination in the Boston metropolitan area caused hazardous conditions in multiple places, with the publication noting that the compound may eventually cause leukemia in some individuals.

History

Discovery

The word "benzene" derives from "gum benzoin", 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 acidic material was derived from benzoin by sublimation, and named "flowers of benzoin", or benzoic acid. The hydrocarbon derived from benzoic acid thus acquired the names benzin, benzol, and benzene. Michael Faraday 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 benzoic acid and lime. He gave the compound the name benzin. In 1836, the French chemist Auguste Laurent named the substance "phène"; this word has become the root of the English word "phenol", which is hydroxylated benzene, and "phenyl", the radical formed by abstraction of a hydrogen atom from benzene.
In 1845, Charles Blachford Mansfield, working under August Wilhelm von Hofmann, isolated benzene from coal tar. 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" 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 for benzene was long known, but its highly polyunsaturated structure, with just one hydrogen atom for each carbon atom, was challenging to determine. Archibald Scott Couper in 1858 and Johann Josef Loschmidt 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 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. Kekulé used evidence that had accumulated in the intervening years—namely, that there always appeared to be only one isomer 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.
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 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. 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, 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 using X-ray diffraction methods. Using large crystals of hexamethylbenzene, 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. In 1870, the German chemist Viktor Meyer first applied Gräbe's nomenclature to benzene.

Early applications

In 1903, Ludwig Roselius popularized the use of benzene to decaffeinate coffee. This discovery led to the production of Sanka. This process was later discontinued. Benzene was historically used as a significant component in many consumer products such as liquid wrench, several paint strippers, rubber cements, 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, much of benzene was obtained as a by-product of coke production for the steel industry. However, in the 1950s, increased demand for benzene, especially from the growing polymers industry, necessitated the production of benzene from petroleum. Today, most benzene comes from the petrochemical industry, with only a small fraction being produced from coal. Benzene has been detected on Mars.

Structure

shows that all six carbon-carbon bonds in benzene are of the same length, at 140 picometres. The C–C bond lengths are greater than a double bond but shorter than a single bond. This intermediate distance is caused by electron delocalization: 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, hexane, which has 14. Benzene and cyclohexane 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. It is likely that this stability contributes to the peculiar molecular and chemical properties known as aromaticity. 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 Consortium has allocated a symbol in the Miscellaneous Technical 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. Examples of simple benzene derivatives are phenol, toluene, and aniline, abbreviated PhOH, PhMe, and PhNH₂, respectively. Linking benzene rings gives biphenyl, C₆H₅–C₆H₅. Further loss of hydrogen gives "fused" aromatic hydrocarbons, such as naphthalene, anthracene, phenanthrene, and pyrene. The limit of the fusion process is the hydrogen-free allotrope of carbon, graphite.
In heterocycles, carbon atoms in the benzene ring are replaced with other elements. The most important variations contain nitrogen. Replacing one CH with N gives the compound pyridine, 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, pyrimidine, or pyrazine.