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Question 56

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In the given reaction, the product 'A' is

Solution

When an unsymmetrical alkyne reacts with $$\text{H}_2\text{SO}_4$$ and $$\text{HgSO}_4$$, water adds across the triple bond following Markovnikov's rule. The electrophile ($$\text{H}^+$$) attacks the carbon that yields the more stable carbocation intermediate.

The triple bond is between the carbon attached to the phenyl ring ($$\text{C}_1$$) and the carbon attached to the methyl group ($$\text{C}_2$$):

$$\text{Ph}-\text{C}\equiv\text{C}-\text{CH}_3$$

Because the benzylic carbocation is significantly more stable, the nucleophile ($$-\text{OH}$$ from water) will attack $$\text{C}_1$$.

The addition of $$-\text{H}$$ and $$-\text{OH}$$ results in an unstable enol intermediate:

$$\text{Ph}-\overset{\text{OH}}{\text{C}}=\text{CH}-\text{CH}_3$$

Enols are generally unstable and rapidly undergo tautomerization to form the more thermodynamically stable carbonyl compound (keto form).

  • The hydrogen from the $$-\text{OH}$$ group shifts to the adjacent CH carbon.
  • The $$\text{C}=\text{C}$$ double bond shifts to form a $$\text{C}=\text{O}$$ double bond.
  • $$\text{Ph}-\overset{\text{OH}}{\text{C}}=\text{CH}-\text{CH}_3 \rightleftharpoons \text{Ph}-\overset{\text{O}}{\overset{\parallel}{\text{C}}}-\text{CH}_2-\text{CH}_3$$

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