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Alcohols Phenols and Ethers question

2014 · Shift 1 · Q12
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Alcohols Phenols and Ethers question

2014 · Shift 1 · Q12

JEE AdvancedChemistryAlcohols Phenols and EthersMultiple correct+3 / −1
The reactivity of compound Z with different halogens under appropriate conditions is given below JEE Advanced 2014 Paper 1 Offline Chemistry - Alcohols, Phenols and Ethers Question 22 English The observed pattern of electrophilic substitution can be explained by
  1. A
    the steric effect on the halogen
  2. B
    the steric effect of the tert-butyl group
  3. C
    the electronic effect of the phenolic group
  4. D
    the electronic effect of the tert-butyl group
View written solutionFree

Correct answer: A, B, C

  1. Identify compound ZZZ and the directing effects

    From the statement, ZZZ is a phenolic aromatic compound containing a tert-butyl group. For such a ring:

    • The phenolic group (−OH)(-OH)(−OH) is a strong activating, ortho/para-directing group due to its +M+M+M (resonance donating) effect.
    • The tert-butyl group is an alkyl group, also ortho/para-directing by hyperconjugation/+I+I+I effect, but its most important contribution here is often steric hindrance because it is bulky.
  2. Nature of halogenation of phenols

    In electrophilic substitution of phenols with halogens:

    • The ring is strongly activated by −OH-OH−OH.
    • Hence substitution occurs readily at positions activated by the phenolic group.
    • However, the actual position and extent of substitution depend on both:
      • electronic activation/directing effects, and
      • steric accessibility of positions.
  3. Examine the given explanations one by one

    Option C: electronic effect of the phenolic group

    This is definitely important.

    The −OH-OH−OH group donates electron density to the ring by resonance: \ce−OH−>ring\ce{-OH -> ring}\ce−OH−>ring making the ortho and para positions highly reactive toward electrophiles such as \ceCl+\ce{Cl+}\ceCl+, \ceBr+\ce{Br+}\ceBr+, etc.

    So, Option C is correct.

    Option B: steric effect of the tert-butyl group

    The tert-butyl group is very bulky. Even if a position is electronically favored, approach of the electrophile to nearby positions can be hindered.

    Therefore, differences in substitution pattern can certainly be explained by steric hindrance from the tert-butyl group.

    So, Option B is correct.

    Option A: steric effect on the halogen

    Different halogens have different sizes: \ceF<Cl<Br<I\ce{F < Cl < Br < I}\ceF<Cl<Br<I Larger halogens face greater steric difficulty in approaching crowded positions on the aromatic ring.

    Thus, the pattern of substitution changing with different halogens can be explained partly by the steric size of the halogen electrophile.

    So, Option A is correct.

    Option D: electronic effect of the tert-butyl group

    Although tert-butyl is weakly electron donating by +I+I+I/hyperconjugation, this effect is much weaker than the phenolic +M+M+M effect and generally does not explain the observed special pattern of halogen substitution in such questions. The key role of tert-butyl here is steric, not electronic.

    Hence, Option D is not taken as a correct explanation.

  4. Final selection

    The observed electrophilic substitution pattern is explained by:

    • steric effect on the halogen,
    • steric effect of the tert-butyl group,
    • electronic effect of the phenolic group.

    Therefore, the correct options are: A, B, C\boxed{A,\ B,\ C}A, B, C​

  5. Comparison with stored answer

    Stored correct answer: A,B,CA, B, CA,B,C

    Derived answer: A,B,CA, B, CA,B,C

    These match exactly.

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