JEE Main · 2022 · Shift-IhardHALO-129

In the following reaction:

Haloalkanes & Haloarenes · Class 12 · JEE Main Previous Year Question

Question

In the following reaction: image

Options
  1. a

    image

  2. b

    image

  3. c

    image

  4. d

    image

Correct Answera

image

Detailed Solution

Step 1: Identify the starting material

From the image: Aromatic compound with:

  • \ceCH3\ce{-CH3} group (methyl)
  • \ceCCl3\ce{-CCl3} group (trichloromethyl)

Likely: p-Chlorotoluene derivative or similar

Step 2: Reaction with O₂ (oxidation)

The \ceCCl3\ce{-CCl3} group can be oxidized:

\ceArCCl3+O2>ArC(=O)OOH\ce{Ar-CCl3 + O2 -> Ar-C(=O)OOH}

Forms peroxy acid intermediate

Step 3: Hydrolysis with H₂/H₂O

Peroxy acid undergoes hydrolysis:

\ceArC(=O)OOH>[H2O]ArCOOH\ce{Ar-C(=O)OOH ->[H2O] Ar-COOH}

Forms carboxylic acid

But wait, the question shows products A and B, suggesting two products.

Alternative interpretation:

If the starting material has both \ceCH3\ce{-CH3} and \ceCCl3\ce{-CCl3}:

  1. \ceCCl3\ce{-CCl3} oxidizes to \ceCOOH\ce{-COOH}
  2. \ceCH3\ce{-CH3} might also oxidize

Or the \ceCCl3\ce{-CCl3} hydrolyzes to \ceCOOH\ce{-COOH}, then decarboxylates to \ceOH\ce{-OH}.

Given answer (a) shows p-cresol (\cepCH3C6H4OH\ce{p-CH3-C6H4-OH}), this suggests:

Final products:

  • A: p-Cresol (phenol with methyl group)
  • B: Likely \ceCHCl3\ce{CHCl3} or \ceCO2\ce{CO2}

Answer: (a) p-Cresol

Key Reactions:

Oxidation of side chains:

  • Benzylic positions are easily oxidized
  • \ceArCH3>[KMnO4]ArCOOH\ce{Ar-CH3 ->[KMnO4] Ar-COOH}
  • \ceArCCl3>[O2]ArCOOH\ce{Ar-CCl3 ->[O2] Ar-COOH}

Hydrolysis of trichloromethyl: \ceArCCl3+H2O>ArCOOH+3HCl\ce{Ar-CCl3 + H2O -> Ar-COOH + 3 HCl}

Decarboxylation: \ceArCOOH>[heat]ArH+CO2\ce{Ar-COOH ->[heat] Ar-H + CO2}

Or in presence of base: \ceArCOOH>[OH]ArO+CO2\ce{Ar-COOH ->[OH-] Ar-O- + CO2}

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In the following reaction: (JEE Main 2022) | Canvas Classes