16.0: Introduction
- Page ID
- 67324
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After completing this section, you should be able to
1. identify electrophilic substitution as the single most important reaction of aromatic compounds.
2. explain why aromatic compounds, such as benzene, are susceptible to attack by electrophiles.
Make certain that you can define, and use in context, the key terms below.
- acylation
- alkylation
- electrophilic substitution
- halogenation
- hydroxylation
- nitration
- sulfonation
In this chapter, you will study all of the reactions shown in the Reaction Type table. In addition to these five reaction types, we also add a sixth common electrophilic substitution known as hydroxylation.
It is important that you recognize the similarities between these reactions to minimize the amount you must memorize.
The six pi electrons obey Huckel's rule so benzene is especially stable. This means that the aromatic ring want to be retained during reactions. Because of this benzene does not undergo addition like other unsaturated hydrocarbons.
Benzene can undergo electrophilic aromatic substitution because aromaticity is maintained.
Other Examples of Electophilic Aromatic Substitution
Many other substitution reactions of benzene have been observed, the five most useful are listed below (chlorination and bromination are the most common halogenation reactions). Since the reagents and conditions employed in these reactions are electrophilic, these reactions are commonly referred to as Electrophilic Aromatic Substitution. The catalysts and co-reagents serve to generate the strong electrophilic species needed to effect the initial step of the substitution. The specific electrophile believed to function in each type of reaction is listed in the right hand column.
| Reaction Type | Typical Equation | Electrophile E(+) | |||
|---|---|---|---|---|---|
| Halogenation: | C6H6 | + Cl2 & heat FeCl3 catalyst |
——> | C6H5Cl + HCl Chlorobenzene |
Cl(+) or Br(+) |
| Nitration: | C6H6 | + HNO3 & heat H2SO4 catalyst |
——> | C6H5NO2 + H2O Nitrobenzene |
NO2(+) |
| Sulfonation: | C6H6 | + H2SO4 + SO3 & heat |
——> | C6H5SO3H + H2O Benzenesulfonic acid |
SO3H(+) |
| Alkylation: Friedel-Crafts |
C6H6 | + R-Cl & heat AlCl3 catalyst |
——> | C6H5-R + HCl An Arene |
R(+) |
| Acylation: Friedel-Crafts |
C6H6 | + RCOCl & heat AlCl3 catalyst |
——> | C6H5COR + HCl An Aryl Ketone |
RCO(+) |
Contributors and Attributions
Dr. Dietmar Kennepohl FCIC (Professor of Chemistry, Athabasca University)
Prof. Steven Farmer (Sonoma State University)
- William Reusch, Professor Emeritus (Michigan State U.), Virtual Textbook of Organic Chemistry