After completing this section, you should be able to
- explain what is meant by the term “aromatic compound.”
- identify the aromatic portions present in naturally occurring compounds, given the necessary structures.
Make certain that you can define, and use in context, the key term below.
At this point in the course, we shall use the term aromatic to describe those compounds which contain a benzene ring. A broader definition of aromaticity will be given in Section 15.3.
The 100 Year Mystery of Benzene
It took humans over 100 years to determine and confirm the structure of benzene. Why did it take so long? Why was there such a curiosity? The 1:1 ratio of carbon to hydrogen in the empirical formula and low chemical reactivity of benzene were a paradox to chemists in the early 1800's.In 1825, Michael Faraday isolated an oily residue of gas lamps. Faraday called this liquid "bicarburet of hydrogen" and measured the boiling point to be 80°C. Additionally, Faraday determined the empirical formula to be CH. About nine years later, Eilhard Mitscherlich synthesized the same compound from benzoic acid and lime (CaO).
During the mid to late 1800's, several possible structures (shown below) were proposed for benzene.
It was not until the 1930's that Kekule's structure was confirmed by X-ray and electron diffraction. During the end of Kekule's career he revealed that the structure came to him in a vision after enjoying a glass or two of wine by the fire in his favorite chair. His inspiration for the structure of benzene was derived from an ouroboros in the flames.
Benzene, C6H6, is the simplest member of a large family of hydrocarbons, called aromatic hydrocarbons. These compounds contain ring structures and exhibit bonding that must be described using the resonance hybrid concept of valence bond theory or the delocalization concept of molecular orbital theory. (To review these concepts, refer to the earlier chapters on chemical bonding). The resonance structures for benzene, C6H6, are:
There are many derivatives of benzene. The hydrogen atoms can be replaced by many different substituents. Aromatic compounds more readily undergo substitution reactions than addition reactions; replacement of one of the hydrogen atoms with another substituent will leave the delocalized double bonds intact. The following are typical examples of substituted benzene derivatives:
Toluene and xylene are important solvents and raw materials in the chemical industry. Styrene is used to produce the polymer polystyrene.
One possible isomer created by a substitution reaction that replaces a hydrogen atom attached to the aromatic ring of toluene with a chlorine atom is shown here. Draw two other possible isomers in which the chlorine atom replaces a different hydrogen atom attached to the aromatic ring:
Since the six-carbon ring with alternating double bonds is necessary for the molecule to be classified as aromatic, appropriate isomers can be produced only by changing the positions of the chloro-substituent relative to the methyl-substituent:
Draw three isomers of a six-membered aromatic ring compound substituted with two bromines.
Most arenes that contain a single six-membered ring are volatile liquids, such as benzene and the xylenes, although some arenes with substituents on the ring are solids at room temperature. In the gas phase, the dipole moment of benzene is zero, but the presence of electronegative or electropositive substituents can result in a net dipole moment that increases intermolecular attractive forces and raises the melting and boiling points. For example, 1,4-dichlorobenzene, a compound used as an alternative to naphthalene in the production of mothballs, has a melting point of 52.7°C, which is considerably greater than the melting point of benzene (5.5°C).
Certain aromatic hydrocarbons, such as benzene and benz[a]pyrene, are potent liver toxins and carcinogens. In 1775, a British physician, Percival Pott, described the high incidence of cancer of the scrotum among small boys used as chimney sweeps and attributed it to their exposure to soot. His conclusions were correct: benz[a]pyrene, a component of chimney soot, charcoal-grilled meats, and cigarette smoke, was the first chemical carcinogen to be identified.
Although arenes are usually drawn with three C=C bonds, benzene is about 150 kJ/mol more stable than would be expected if it contained three double bonds. This increased stability is due to the delocalization of the π electron density over all the atoms of the ring. Compared with alkenes, arenes are poor nucleophiles. Consequently, they do not undergo addition reactions like alkenes; instead, they undergo a variety of electrophilic aromatic substitution reactions that involve the replacement of –H on the arene by a group –E, such as –NO2, –SO3H, a halogen, or an alkyl group, in a two-step process. The first step involves addition of the electrophile (E) to the π system of benzene, forming a carbocation. In the second step, a proton is lost from the adjacent carbon on the ring:
The carbocation formed in the first step is stabilized by resonance.
Arenes undergo substitution reactions rather than elimination because of increased stability arising from delocalization of their π electron density.
Many substituted arenes have potent biological activity. Some examples include common drugs and antibiotics such as aspirin and ibuprofen, illicit drugs such as amphetamines and peyote, the amino acid phenylalanine, and hormones such as adrenaline.
Aspirin (antifever activity), ibuprofen (antifever and anti-inflammatory activity), and amphetamine (stimulant) have pharmacological effects. Phenylalanine is an amino acid. Adrenaline is a hormone that elicits the “fight or flight” response to stress. Chiral centers are indicated with an asterisk.