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Compounds Containing Nitrogen question

2018 · Shift 2 · Q7
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Compounds Containing Nitrogen question

2018 · Shift 2 · Q7

JEE AdvancedChemistryCompounds Containing NitrogenMultiple correct+4 / −1
Aniline reacts with mixed acid (conc. HNO3HN{O_3}HNO3​ and conc. H2SO4{H_2}S{O_4}H2​SO4​) at 288K288K288K to give P (51%),\left( {51\% } \right),(51%), Q (47%)\left( {47\% } \right)(47%) and R (2%).\left( {2\% } \right).(2%). The major product(s) of the following reaction sequence is (are) JEE Advanced 2018 Paper 2 Offline Chemistry - Compounds Containing Nitrogen Question 33 English
  1. A
    JEE Advanced 2018 Paper 2 Offline Chemistry - Compounds Containing Nitrogen Question 33 English Option 1
  2. B
    JEE Advanced 2018 Paper 2 Offline Chemistry - Compounds Containing Nitrogen Question 33 English Option 2
  3. C
    JEE Advanced 2018 Paper 2 Offline Chemistry - Compounds Containing Nitrogen Question 33 English Option 3
  4. D
    JEE Advanced 2018 Paper 2 Offline Chemistry - Compounds Containing Nitrogen Question 33 English Option 4
View written solutionFree

Correct answer: D

The user wants me to solve a multi-step organic chemistry reaction. Let's break down the reaction sequence step by step.

Initial Information: The question begins by describing the direct nitration of aniline with a mixture of concentrated nitric acid and sulfuric acid (mixed acid). It states that this reaction yields p-nitroaniline (P, 51%), m-nitroaniline (Q, 47%), and o-nitroaniline (R, 2%). This information serves as context to illustrate the problems with direct electrophilic substitution on aniline. In the strongly acidic medium, the amino group (−NH2-NH_2−NH2​) gets protonated to form the anilinium ion (−NH3+-NH_3^+−NH3+​), which is a deactivating and meta-directing group. This explains the unexpectedly high yield of the meta product. This problem is overcome by first protecting the amino group, which is precisely what is done in the reaction sequence we need to analyze.

The Reaction Sequence:

Step 1: Protection of the amino group Aniline is treated with acetic anhydride ((CH3CO)2O(CH_3CO)_2O(CH3​CO)2​O, or Ac2OAc_2OAc2​O) in the presence of pyridine. This is an acetylation reaction.

C6H5NH2+(CH3CO)2O→PyridineC6H5NHCOCH3+CH3COOHC_6H_5NH_2 + (CH_3CO)_2O \xrightarrow{Pyridine} C_6H_5NHCOCH_3 + CH_3COOHC6​H5​NH2​+(CH3​CO)2​OPyridine​C6​H5​NHCOCH3​+CH3​COOH

The amino group of aniline acts as a nucleophile and attacks the electrophilic carbonyl carbon of acetic anhydride. The product formed, A, is N-phenylacetamide, also known as acetanilide. This step 'protects' the amino group. The resulting acetamido group (−NHCOCH3-NHCOCH_3−NHCOCH3​) is still an activating and ortho, para-directing group, but it is less powerful than the original amino group. This moderation prevents polysubstitution in the next step.

Step 2: Electrophilic Aromatic Substitution (Bromination) Acetanilide (A) is treated with bromine (Br2Br_2Br2​) in acetic acid (CH3COOHCH_3COOHCH3​COOH). This is an electrophilic bromination reaction.

The acetamido group (−NHCOCH3-NHCOCH_3−NHCOCH3​) directs the incoming electrophile (bromine) to the ortho and para positions. However, the acetamido group is sterically bulky. This steric hindrance makes the attack at the ortho positions difficult. Consequently, substitution occurs predominantly at the sterically more accessible para position.

C6H5NHCOCH3+Br2→CH3COOHp−Br−C6H4−NHCOCH3 (Major product, B)+o−Br−C6H4−NHCOCH3 (Minor product)C_6H_5NHCOCH_3 + Br_2 \xrightarrow{CH_3COOH} p-Br-C_6H_4-NHCOCH_3 \text{ (Major product, B)} + o-Br-C_6H_4-NHCOCH_3 \text{ (Minor product)}C6​H5​NHCOCH3​+Br2​CH3​COOH​p−Br−C6​H4​−NHCOCH3​ (Major product, B)+o−Br−C6​H4​−NHCOCH3​ (Minor product)

The major product, B, is p-bromoacetanilide.

Step 3: Deprotection (Hydrolysis) The major product from the previous step, p-bromoacetanilide (B), is subjected to acid-catalyzed hydrolysis (H3O+H_3O^+H3​O+).

p−Br−C6H4−NHCOCH3+H2O→H+,Δp−Br−C6H4−NH2+CH3COOHp-Br-C_6H_4-NHCOCH_3 + H_2O \xrightarrow{H^+, \Delta} p-Br-C_6H_4-NH_2 + CH_3COOHp−Br−C6​H4​−NHCOCH3​+H2​OH+,Δ​p−Br−C6​H4​−NH2​+CH3​COOH

This step cleaves the amide bond, removing the acetyl protecting group and regenerating the amino group. The final major product of the sequence, S, is p-bromoaniline.

Evaluating the Options: Let's examine the given options based on our derived product.

  • A: This is p-bromoacetanilide. This is the major intermediate product B, but not the final product S of the sequence.
  • B: This is o-bromoaniline. This is a minor product of the reaction sequence, formed from the minor ortho-brominated intermediate.
  • C: This is m-bromoaniline. The acetamido group is ortho, para-directing, not meta-directing. This product is not formed.
  • D: This is p-bromoaniline. This is the major final product S of the reaction sequence.

Therefore, the major product of the reaction sequence is p-bromoaniline.

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