Arenes

Arenes are aromatic hydrocarbons. The term “aromatic” originally referred to their pleasant smells (e.g., from cinnamon bark, wintergreen leaves, vanilla beans and anise seeds), but now implies a particular sort of delocalized bonding. Aromatic hydrocarbons (or sometimes called arenes or aryl hydrocarbon) are hydrocarbons with sigma bonds and delocalized π electrons between carbon atoms forming rings.

Course Contents

  • Arenes (exemplified by benzene and methylbenzene)
  • (i) influence of delocalised π electrons on structure and properties
  • (ii) electrophilic substitution reactions
  • (iii) oxidation of side-chain

Learning Outcomes

Candidates should be able to:

  • (a) explain, in terms of delocalisation of π electrons, the difference between benzene and alkene:
  • (b) reactivity towards electrophiles
  • (ii) preference of benzene to undergo substitution rather than addition reaction
  • (i) describe the chemistry of the benzene ring as exemplified by the following reactions of benzene and methylbenzene:
  • (c) electrophilic substitution reactions with chlorine and with bromine (recognise the use of Lewis acid as catalysts; see also Section 4)
  • (ii) nitration with concentrated nitric acid (recognise concentrated sulfuric acid as a Brønsted-Lowry acid catalyst; see also Section 4)
  • (iii) Friedel-Crafts alkylation with halogenoalkanes (recognise the use of Lewis acid as catalysts; see also Section 4)
  • (d)
  • (i) describe the mechanism of electrophilic substitution in arenes, using the mono-bromination of benzene as an example
  • (ii) describe the effect of the delocalisation of electrons in arenes in such reactions
  • (e) describe the chemistry of the alkyl side-chain of benzene ring as exemplified by the following reactions of methylbenzene:
  • (i) free-radical substitution by chlorine and by bromine
  • (ii) complete oxidation to give benzoic acid
  • (f) predict whether halogenation will occur in the side-chain or aromatic nucleus in arenes depending on reaction conditions
  • (g) apply the knowledge of positions of substitution in the electrophilic substitution reactions of monosubstituted arenes