Question:medium

Nitration of aniline in strong acidic medium gives significant amount of m-nitroaniline because

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Always consider the effect of the reaction medium on the functional groups present. The directing influence of a group like -NH\(_2\) can be completely altered by pH. In acidic solution, it becomes -NH\(_3\)\(^+\) and its directing effect changes from o,p-directing to m-directing.
Updated On: Apr 28, 2026
  • In electrophilic substitution reaction, amino group is meta directing
  • In strong acidic medium, aniline is present as anilinium ion
  • -NH\(_2\) group always directs to meta position
  • m-nitroaniline has higher molar mass than o\&p nitroanilines
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The Correct Option is B

Solution and Explanation

Step 1: Understanding the Concept:
The free $-NH_{2}$ group in aniline is strongly activating and ortho/para directing. However, the nitration reaction conditions vastly alter its directing nature.
Step 2: Key Formula or Approach:
Analyze the effect of a strongly acidic nitrating mixture (conc. $HNO_3$ and conc. $H_2SO_4$) on the basic amino group during electrophilic aromatic substitution.
Step 3: Detailed Explanation:
In the presence of the strong acid used for nitration, the highly basic amino group of aniline gets protonated to form the anilinium ion ($C_{6}H_{5}NH_{3}^{+}$).
The $-NH_{3}^{+}$ group is a strongly deactivating group. Because it has a full positive charge directly attached to the benzene ring, it withdraws electron density strongly via the inductive effect ($-I$ effect) and does not possess lone pairs for resonance donation. As a result, it acts as a meta-directing group.
Therefore, a significant amount (about $47%$) of the meta isomer is formed alongside the expected para ($51%$) and ortho ($2%$) products.
Step 4: Final Answer:
The formation of the meta product is due to the presence of the meta-directing anilinium ion in the acidic medium.
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