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Alcohols Phenols and Ethers question

2008 · Shift 2 · Q17
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Alcohols Phenols and Ethers question

2008 · Shift 2 · Q17

JEE AdvancedChemistryAlcohols Phenols and EthersMCQ+3 / −1
A tertiary alcohol H upon acid catalysed dehydration gives a product I. Ozonolysis of I leads to compounds J and K compound J upon reaction with KOHKOHKOH gives benzyl alcohol and a compound L, whereas K on reaction with KOHKOHKOH gives only M. IIT-JEE 2008 Paper 2 Offline Chemistry - Alcohols, Phenols and Ethers Question 9 English ComprehensionThe structures of compound J, K and L, respectively, are:
  1. A
    PhCOCH 3{}_33​, PhCH 2{}_22​ COCH 3{}_33​ and PHCH 2{}_22​ COO −{}^-− K +{}^++.
  2. B
    PhCHO, PhCH 2{}_22​ CHO and PhCOO −{}^-− K +{}^++
  3. C
    PhCOCH 3{}_33​, PhCH 2{}_22​ CHO and CH 3{}_33​ COO −{}^-− K +{}^++
  4. D
    PhCHO, PhCOCH 3{}_33​ and PhCOO −{}^-− K +{}^++
View written solutionFree

Correct answer: D

The problem describes a sequence of organic reactions starting from a tertiary alcohol H. We need to identify the structures of intermediate compounds J, K, and L.

Step-by-step Derivations:

  1. Analyze the reaction of Compound J:

    • The problem states that compound J reacts with KOHKOHKOH to give benzyl alcohol (PhCH2OHPhCH_2OHPhCH2​OH) and a compound L.
    • The reaction of a carbonyl compound with a strong base (KOHKOHKOH) to produce an alcohol and a carboxylate salt is characteristic of the Cannizzaro reaction.
    • The Cannizzaro reaction occurs with aldehydes that lack α-hydrogens.
    • Since one of the products is benzyl alcohol (the reduction product), the starting compound J must be benzaldehyde (PhCHOPhCHOPhCHO). Benzaldehyde has no α-hydrogens.
    • The reaction is a disproportionation where one molecule of benzaldehyde is reduced to benzyl alcohol and the other is oxidized to benzoic acid, which forms a salt with KOHKOHKOH. 2 PhCHO→KOHPhCH2OH+PhCOO−K+2 \, PhCHO \xrightarrow{KOH} PhCH_2OH + PhCOO^-K^+2PhCHOKOH​PhCH2​OH+PhCOO−K+
    • From this, we can identify:
      • J = Benzaldehyde (PhCHOPhCHOPhCHO)
      • L = Potassium benzoate (PhCOO−K+PhCOO^-K^+PhCOO−K+)
  2. Evaluate the Options based on J and L:

    • Based on our identification of J as PhCHOPhCHOPhCHO and L as PhCOO−K+PhCOO^-K^+PhCOO−K+, we can examine the given options:
      • A: J = PhCOCH3PhCOCH_3PhCOCH3​ (incorrect)
      • B: J = PhCHOPhCHOPhCHO, L = PhCOO−K+PhCOO^-K^+PhCOO−K+ (possible)
      • C: J = PhCOCH3PhCOCH_3PhCOCH3​ (incorrect)
      • D: J = PhCHOPhCHOPhCHO, L = PhCOO−K+PhCOO^-K^+PhCOO−K+ (possible)
    • We have narrowed down the correct answer to either B or D.
  3. Determine the structure of Compound K and Alkene I:

    • Compounds J and K are formed from the ozonolysis of an alkene I. Ozonolysis cleaves the double bond of the alkene and forms two carbonyl compounds.
    • The alkene I can be reconstructed by joining the carbonyl carbons of J and K with a double bond.
    • Let's consider the two possibilities for K from options B and D:
      • If K is PhCH2CHOPhCH_2CHOPhCH2​CHO (from option B): The alkene I would be formed from PhCHOPhCHOPhCHO (J) and PhCH2CHOPhCH_2CHOPhCH2​CHO (K). I=Ph−CH=CH−CH2−Ph(1,3-diphenylpropene)I = Ph-CH=CH-CH_2-Ph \quad \text{(1,3-diphenylpropene)}I=Ph−CH=CH−CH2​−Ph(1,3-diphenylpropene)
      • If K is PhCOCH3PhCOCH_3PhCOCH3​ (from option D): The alkene I would be formed from PhCHOPhCHOPhCHO (J) and PhCOCH3PhCOCH_3PhCOCH3​ (K). I=Ph−CH=C(CH3)Ph(1,2-diphenylpropene)I = Ph-CH=C(CH_3)Ph \quad \text{(1,2-diphenylpropene)}I=Ph−CH=C(CH3​)Ph(1,2-diphenylpropene)
  4. Trace back to the Tertiary Alcohol H:

    • Alkene I is formed by the acid-catalyzed dehydration of a tertiary alcohol H.
    • Let's check which of the possible structures for I could be formed from a tertiary alcohol.
      • For I = 1,3-diphenylpropene (Ph−CH=CH−CH2−PhPh-CH=CH-CH_2-PhPh−CH=CH−CH2​−Ph): The precursor alcohol would have an -OH group on a carbon atom adjacent to the double bond. Possible structures are Ph−CH2−CH(OH)−CH2−PhPh-CH_2-CH(OH)-CH_2-PhPh−CH2​−CH(OH)−CH2​−Ph or Ph−CH(OH)−CH2−CH2−PhPh-CH(OH)-CH_2-CH_2-PhPh−CH(OH)−CH2​−CH2​−Ph. Both of these are secondary alcohols. This contradicts the problem statement that H is a tertiary alcohol. So, option B is incorrect.
      • For I = 1,2-diphenylpropene (Ph−CH=C(CH3)PhPh-CH=C(CH_3)PhPh−CH=C(CH3​)Ph): The precursor alcohol H could be Ph−CH2−C(OH)(CH3)PhPh-CH_2-C(OH)(CH_3)PhPh−CH2​−C(OH)(CH3​)Ph. This alcohol (2,3-diphenyl-2-butanol) is a tertiary alcohol. Dehydration of this alcohol would proceed via a stable tertiary carbocation, Ph−CH2−C+(CH3)PhPh-CH_2-C^+(CH_3)PhPh−CH2​−C+(CH3​)Ph. Elimination of a proton from the adjacent CH2CH_2CH2​ group leads to the formation of the more substituted and conjugated alkene I, which is the major product (Saytzeff's rule). Ph−CH2−C(OH)(CH3)Ph→H+Ph−CH=C(CH3)Ph+H2OPh-CH_2-C(OH)(CH_3)Ph \xrightarrow{H^+} Ph-CH=C(CH_3)Ph + H_2OPh−CH2​−C(OH)(CH3​)PhH+​Ph−CH=C(CH3​)Ph+H2​O
      • This pathway is consistent with all the given information.
  5. Final Confirmation:

    • The sequence is as follows:
      • H: Ph−CH2−C(OH)(CH3)PhPh-CH_2-C(OH)(CH_3)PhPh−CH2​−C(OH)(CH3​)Ph (tertiary alcohol)
      • I: Ph−CH=C(CH3)PhPh-CH=C(CH_3)PhPh−CH=C(CH3​)Ph
      • Ozonolysis of I gives J and K: PhCHOPhCHOPhCHO (J) and PhCOCH3PhCOCH_3PhCOCH3​ (K).
      • J (PhCHOPhCHOPhCHO) + KOH →\rightarrow→ Benzyl alcohol + PhCOO−K+PhCOO^-K^+PhCOO−K+ (L).
      • K (PhCOCH3PhCOCH_3PhCOCH3​) + KOH →\rightarrow→ M. Acetophenone has α-hydrogens and would undergo aldol condensation, which is consistent with the reaction description.

Conclusion:

The structures are:

  • J: Benzaldehyde (PhCHOPhCHOPhCHO)
  • K: Acetophenone (PhCOCH3PhCOCH_3PhCOCH3​)
  • L: Potassium benzoate (PhCOO−K+PhCOO^-K^+PhCOO−K+)

This corresponds to option D.

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