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10.7: Aromatic Hydrocarbons

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    174986
  • https://chem.libretexts.org/Textbook...c_Hydrocarbons

    https://chem.libretexts.org/Core/Org...ties_of_Arenes

    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:

    This structural formula shows a six carbon hydrocarbon ring. On the left side there are six C atoms. The C atom on top and to the left forms a single bond to the C atom on the top and to the right. The C atom has a double bond to another C atom which has a single bond to a C atom. That C atom has a double bond to another C atom which has a single bond to a C atom. That C atom forms a double bond with another C atom. Each C atom has a single bond to an H atom. There is a double sided arrow and the structure on the right is almost identical to the structure on the left. The structure on the right shows double bonds where the structure on the left showed single bonds. The structure on the right shows single bonds where the stucture on the left showed double bonds.

    Valence bond theory describes the benzene molecule and other planar aromatic hydrocarbon molecules as hexagonal rings of sp2-hybridized carbon atoms with the unhybridized p orbital of each carbon atom perpendicular to the plane of the ring. Three valence electrons in the sp2 hybrid orbitals of each carbon atom and the valence electron of each hydrogen atom form the framework of σ bonds in the benzene molecule. The fourth valence electron of each carbon atom is shared with an adjacent carbon atom in their unhybridized p orbitals to yield the π bonds. Benzene does not, however, exhibit the characteristics typical of an alkene. Each of the six bonds between its carbon atoms is equivalent and exhibits properties that are intermediate between those of a C–C single bond and a \(\mathrm{C=C}\) double bond. To represent this unique bonding, structural formulas for benzene and its derivatives are typically drawn with single bonds between the carbon atoms and a circle within the ring as shown in Figure \(\PageIndex{10}\).

    A six carbon hydrocarbon ring structural formula is shown. Each C atom is bonded to only one H atom. A circle is at the center of the ring.
    Figure \(\PageIndex{10}\): This condensed formula shows the unique bonding structure of benzene.

    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:

    Three structural formulas are shown. The first is labeled toluene. This molecule has a six carbon hydrocarbon ring in which five of the C atoms are each bonded to only one H atom. At the upper right of the ring, the C atom that does not have a bonded H atom has a red C H subscript 3 group attached. A circle is at the center of the ring. The second is labeled xylene. This molecule has a six carbon hydrocarbon ring in which four of the C atoms are each bonded to only one H atom. At the upper right and right of the ring, the two C atoms that do not have bonded H atoms have C H subscript 3 groups attached. These C H subscript 3 groups appear in red. A circle is at the center of the ring. The third is labeled styrene. This molecule has a six carbon hydrocarbon ring in which five of the carbon atoms are each bonded to only one H atom. At the upper right of the ring, the carbon that does not have a bonded H atom has a red C H double bond C H subscript 2 group attached. A circle is at the center of the ring.

    Toluene and xylene are important solvents and raw materials in the chemical industry. Styrene is used to produce the polymer polystyrene.

    Example \(\PageIndex{7}\): Structure of Aromatic Hydrocarbons

    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:

    Two structural formulas are shown. The first has a six carbon hydrocarbon ring in which four of the carbon atoms are each bonded to only one H atom. At the upper right of the ring, the carbon that does not have a bonded H atom has a C H subscript 3 group attached. The C to the lower right has a C l atom attached. A circle is at the center of the ring. The second molecule has a hexagon with a circle inside. From a vertex of the hexagon at the upper right a C H subscript 3 group is attached. From the vertex at the lower right, a C l atom is attached.

    Solution

    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:

    Two pairs of structural formulas are shown. The first has a six carbon hydrocarbon ring in which four of the C atoms are each bonded to only one H atom. At the upper right of the ring, the C atom that does not have a bonded H atom has a C H subscript 3 group attached. The C atom to the right has a C l atom attached. A circle is at the center of the ring. The second molecule in the first pair has a hexagon with a circle inside. From a vertex of the hexagon at the upper right a C H subscript 3 group is attached. From the vertex at the right, a C l atom is attached. The second pair first shows a six carbon hydrocarbon ring in which four of the C atoms are each bonded to only one H atom. A C l atom is attached to the left-most C atom and a C H subscript 3 group is attached to the right-most C atom. A circle is at the center of the ring. The second molecule in the pair has a hexagon with a circle inside. A C H subscript 3 group is attached to a vertex on the right side of the hexagon and to a vertex on the left side, a C l atom is bonded.

    Exercise \(\PageIndex{7}\)

    Draw three isomers of a six-membered aromatic ring compound substituted with two bromines.

    Answer:

    Three pairs of structural formulas are shown. The first has a six carbon hydrocarbon ring in which four of the C atoms are each bonded to only one H atom. At the upper right and right of the ring, the two C atoms that do not have bonded H atoms have one B r atom bonded each. A circle is at the center of the ring. Beneath this structure, a similar structure is shown which has a hexagon with a circle inside. From vertices of the hexagon at the upper right and right single B r atoms are attached. The second has a six carbon hydrocarbon ring in which four of the C atoms are each bonded to only one H atom. At the upper right and lower right of the ring, the two C atoms that do not have bonded H atoms have a single B r atom bonded each. A circle is at the center of the ring. Beneath this structure, a similar structure is shown which has a hexagon with a circle inside. From vertices of the hexagon at the upper right and lower right single B r atoms are attached. The third has a six carbon hydrocarbon ring in which four of the C atoms are each bonded to only one H atom. At the upper right and lower left of the ring, the two C atoms that do not have bonded H atoms have B r atoms bonded. A circle is at the center of the ring. Beneath this structure, a similar structure is shown which has a hexagon with a circle inside. From vertices of the hexagon at the upper right and lower left, single B r atoms are attached.

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