Question
Explain. Aryl halides are less reactive than alkyl halides towards nucleophilic substitution reactions.

Answer

  1. The low reactivity of aryl halides is due to the resonance effect and $sp ^2$ hybrid state of carbon to which halogen atom is attached.
  2. In aryl halides, one of the lone pairs of electrons on the halogen atom is in conjugation with $\pi$-electrons of the ring. Due to resonance, the $C - X$ bond acquires partial double bond character. Thus, the $C - X$ bond in aryl halides is stronger and shorter than alkyl halides. Hence, it is difficult to break $C - X$ bond in aryl halides.
  3. Further, the phenyl cation produced due to the self-ionization of aryl halide will not be stabilised by resonance. This rules out the possibility of $S_N 1$ mechanism. Also, the backside attack of nucleophiles is blocked by the aromatic ring. This rules out the possibility of $S_N 2$ mechanism. As a result, nucleophilic substitution reaction involving cleavage of $C - X$ bond in haloarenes proceeds with difficulty.
  4. Therefore, aryl halides are less reactive than alkyl halides towards nucl71eophilic substitution reactions.

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