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Question 55

The major product of the following reaction is:

1. Generation of the Carbocation

The primary alkyl chloride reacts with the Lewis acid, anhydrous aluminium chloride (AlCl3), to form a complex. Because it is a primary carbon, it can undergo a synchronized hydride shift as the leaving group departs to form a more stable carbocation directly:

  • A hydride (H-) shifts from the adjacent secondary carbon to the terminal carbon.
  • This expels the [AlCl4]- leaving group and creates a more stable secondary carbocation.

2. Further Carbocation Rearrangement (Hydride Shift)

The newly formed secondary carbocation is separated from the electron-rich aromatic ring by a chain of CH2 groups. To achieve the most stable intermediate before ring closure, another 1,2-hydride shift occurs along the alkyl chain.

  • This moves the positive charge closer to the benzene ring, generating an even more stable secondary carbocation position that sets up a highly favorable 6-membered ring closure.

3. Intramolecular Electrophilic Aromatic Substitution (Ring Closure)

The methoxy group (-OCH3) attached to the benzene ring is a strong ortho/para-directing group due to resonance activation.

  • The position para to the methoxy group is stericly less hindered and highly nucleophilic.
  • The benzene ring attacks the rearranged carbocation intermediate intramolecularly.
  • This ring-closure forms a fused 6-membered ring (a tetralin derivative).

4. Aromatization and Hydrolysis

Loss of a proton (H+) restores the aromaticity of the benzene ring. The subsequent addition of water (H2O) during the workup step breaks down the aluminum complexes.

Final Major Product Structure

The final product is a 6-membered saturated ring fused to the methoxybenzene ring system, specifically forming at the position para to the methoxy group.

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