The correct statement for the following transformation is

F2 Madhuri Teaching 27.03.2023 D29

Condition A: aq. KOH EtOH 0°C

Condition B: H2SO4, AcOH reflux

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CSIR-UGC (NET) Chemical Science: Held on (26 Nov 2020)
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  1. P is preferentially formed via condition A, under thermodynamic control.
  2. Q is preferentially formed via condition B, under thermodynamic control.
  3. P is preferentially formed via condition B, under kinetic control.
  4. Q is preferentially formed via condition A, under kinetic control.

Answer (Detailed Solution Below)

Option 2 : Q is preferentially formed via condition B, under thermodynamic control.
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Detailed Solution

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Concept:-

  • The reaction that occurs at lower temperatures and at a lower time are kinetically controlled reactions
  • The kinetically controlled reaction leads to the formation of a kinetically controlled product (KCP). The kinetically controlled products (KCP) are less stable.
  • Kinetically controlled means that although the mixture could convert to a more stable set of products (TCP),
    it doesn’t do so because of an energy barrier.
  • The 1,2 addition reaction is an example of KCP.
  • The reaction that occurs at higher temperatures and at a slow rate are thermodynamically controlled reactions. Thermodynamically controlled products (TCP) are more stable than kinetically controlled products (KCP) because they are more substituted.
  • The 1,4 addition reaction is an example of TCP.

Explanation:-

  • The reaction pathway is shown below:

Condition A: aq. KOH EtOH 0°C

qImage646f3baaed6f6334c8887750

  • From the above reaction, we see that the kinetically controlled enolate ion (condition A) reacts with the carbonyl compound and undergoes an aldol reaction.
  • Finally, the aldol product undergoes a cyclodehydration reaction to give the kinetically controlled products (KCP).

Condition B: H2SO4, AcOH reflux

qImage646f3baaed6f6334c8887755

  • H2SO4 and AcOH (condition B) will lead to the formation of a thermodynamically controlled more substituted enolate.  
  • Thermodynamically controlled enolate reacts with the carbonyl compound and undergoes an aldol reaction.
  • Finally, the aldol product undergoes a cyclodehydration reaction to give the kinetically controlled product (KCP) Q.   

Conclusion:-

Hence, the correct statement for the following transformation is that Q is preferentially formed via condition B, under thermodynamic control.

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