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Haloalkanes and Haloarenes question

2025 · 8 Apr · Shift 2 · Q17
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Haloalkanes and Haloarenes question

2025 · 8 Apr · Shift 2 · Q17

JEE MainChemistryHaloalkanes and HaloarenesMCQ+4 / −1
Choose the correct set of reagents for the following conversion. JEE Main 2025 (Online) 8th April Evening Shift Chemistry - Haloalkanes and Haloarenes Question 6 English
  1. A
    Cl2/\mathrm{Cl}_2 /Cl2​/ anhy ⋅AlCl3;Br2/Fe;\cdot \mathrm{AlCl}_3 ; \mathrm{Br}_2 / \mathrm{Fe} ;⋅AlCl3​;Br2​/Fe; alc. KOH
  2. B
    Cl2/Fe;Br2/\mathrm{Cl}_2 / \mathrm{Fe} ; \mathrm{Br}_2 /Cl2​/Fe;Br2​/ anhy. AlCl3\mathrm{AlCl}_3AlCl3​; aq. KOH
  3. C
    Br2/Fe;Cl2,Δ\mathrm{Br}_2 / \mathrm{Fe} ; \mathrm{Cl}_2, \DeltaBr2​/Fe;Cl2​,Δ; alc. KOH
  4. D
    Br2/\mathrm{Br}_2 /Br2​/ anhy. AlCl3;Cl2,Δ\mathrm{AlCl}_3 ; \mathrm{Cl}_2, \DeltaAlCl3​;Cl2​,Δ; aq. KOH
View written solutionFree

Correct answer: C

  1. Interpret the reagent sequences

We need to identify which sequence can bring about the required aromatic side-chain transformation.

The key reagent patterns are:

  • Br2/Fe\mathrm{Br}_2/\mathrm{Fe}Br2​/Fe or Cl2/anhy. AlCl3\mathrm{Cl}_2/\text{anhy. }\mathrm{AlCl}_3Cl2​/anhy. AlCl3​ →\rightarrow→ electrophilic aromatic substitution on benzene ring.
  • Cl2,Δ\mathrm{Cl}_2, \DeltaCl2​,Δ →\rightarrow→ free-radical side-chain chlorination at benzylic position.
  • alc. KOH →\rightarrow→ generally elimination.
  • aq. KOH →\rightarrow→ generally nucleophilic substitution / hydrolysis.

So, if the conversion involves:

  • first introducing a halogen on the ring,
  • then chlorinating the side chain,
  • then eliminating HCl to form an alkene,

we need the sequence:

ring bromination  →  side-chain chlorination  →  elimination by alcoholic KOH\text{ring bromination} \; \to \; \text{side-chain chlorination} \; \to \; \text{elimination by alcoholic KOH}ring bromination→side-chain chlorination→elimination by alcoholic KOH
  1. Check each option

Option A

Cl2/anhy. AlCl3;  Br2/Fe;  alc. KOH\mathrm{Cl}_2/\text{anhy. }\mathrm{AlCl}_3 ;\; \mathrm{Br}_2/\mathrm{Fe} ;\; \text{alc. KOH}Cl2​/anhy. AlCl3​;Br2​/Fe;alc. KOH
  • First two steps are both aromatic halogenations.
  • No side-chain chlorination step like Cl2,Δ\mathrm{Cl}_2,\DeltaCl2​,Δ is present.
  • Hence this sequence cannot generate a benzylic halide needed for elimination.

So, A is incorrect.


Option B

Cl2/Fe;  Br2/anhy. AlCl3;  aq. KOH\mathrm{Cl}_2/\mathrm{Fe} ;\; \mathrm{Br}_2/\text{anhy. }\mathrm{AlCl}_3 ;\; \text{aq. KOH}Cl2​/Fe;Br2​/anhy. AlCl3​;aq. KOH
  • Again, first two are ring halogenation steps.
  • No benzylic radical chlorination.
  • Final reagent is aq. KOH, which favors substitution, not elimination.

So, B is incorrect.


Option C

Br2/Fe;  Cl2,Δ;  alc. KOH\mathrm{Br}_2/\mathrm{Fe} ;\; \mathrm{Cl}_2,\Delta ;\; \text{alc. KOH}Br2​/Fe;Cl2​,Δ;alc. KOH
  • Br2/Fe\mathrm{Br}_2/\mathrm{Fe}Br2​/Fe: bromination of benzene ring.
  • Cl2,Δ\mathrm{Cl}_2,\DeltaCl2​,Δ: benzylic chlorination of side chain.
  • alc. KOH: elimination of HCl from side-chain chloride to form the corresponding alkene.

This is the chemically consistent sequence.

So, C is correct.


Option D

Br2/anhy. AlCl3;  Cl2,Δ;  aq. KOH\mathrm{Br}_2/\text{anhy. }\mathrm{AlCl}_3 ;\; \mathrm{Cl}_2,\Delta ;\; \text{aq. KOH}Br2​/anhy. AlCl3​;Cl2​,Δ;aq. KOH
  • First step (ring bromination) is acceptable.
  • Second step (side-chain chlorination) is also acceptable.
  • But final step uses aq. KOH, which would tend to give substitution/hydrolysis rather than the required elimination.

So, D is incorrect.

  1. Conclusion

The only suitable reagent set is:

C: Br2/Fe;  Cl2,Δ;  alc. KOH\boxed{\text{C: } \mathrm{Br}_2/\mathrm{Fe} ;\; \mathrm{Cl}_2,\Delta ;\; \text{alc. KOH}}C: Br2​/Fe;Cl2​,Δ;alc. KOH​
  1. Comparison with stored answer

Stored correct answer: C

My derived answer: C

Hence, they agree.

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