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Haloalkanes and Haloarenes question

2009 · Shift 0 · Q12
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Haloalkanes and Haloarenes question

2009 · Shift 0 · Q12

JEE MainChemistryHaloalkanes and HaloarenesMCQ+4 / −1
Which of the following on heating with aqueous KOH, produces acetaldehyde ?
  1. A
    CH3COClCH_3COClCH3​COCl
  2. B
    CH3CH2ClCH_3CH_2ClCH3​CH2​Cl
  3. C
    CH2ClCH2ClCH_2ClCH_2ClCH2​ClCH2​Cl
  4. D
    CH3CHCl2CH_3CHCl_2CH3​CHCl2​
View written solutionFree

Correct answer: D

  1. We need to identify which compound gives acetaldehyde (CH3CHOCH_3CHOCH3​CHO) on heating with aqueous KOH.

  2. Let us check each option.

Option A: CH3COClCH_3COClCH3​COCl

Acetyl chloride undergoes hydrolysis with aqueous KOH: CH3COCl+KOH→CH3COOH+KClCH_3COCl + KOH \rightarrow CH_3COOH + KClCH3​COCl+KOH→CH3​COOH+KCl In alkaline medium, the acid further gives acetate salt. So this does not produce acetaldehyde.

Option B: CH3CH2ClCH_3CH_2ClCH3​CH2​Cl

Ethyl chloride with aqueous KOH gives nucleophilic substitution: CH3CH2Cl+KOH→CH3CH2OH+KClCH_3CH_2Cl + KOH \rightarrow CH_3CH_2OH + KClCH3​CH2​Cl+KOH→CH3​CH2​OH+KCl Product is ethanol, not acetaldehyde.

Option C: CH2ClCH2ClCH_2ClCH_2ClCH2​ClCH2​Cl

1,2-Dichloroethane with aqueous KOH mainly gives ethylene glycol by substitution: ClCH2CH2Cl+2KOH→HOCH2CH2OH+2KClClCH_2CH_2Cl + 2KOH \rightarrow HOCH_2CH_2OH + 2KClClCH2​CH2​Cl+2KOH→HOCH2​CH2​OH+2KCl This is not acetaldehyde.

Option D: CH3CHCl2CH_3CHCl_2CH3​CHCl2​

This is a gem-dihalide. Gem-dihalides on hydrolysis with aqueous KOH form unstable gem-diols, which lose water to give carbonyl compounds.

First hydrolysis gives: CH3CHCl2→aq.KOHCH3CH(OH)2CH_3CHCl_2 \xrightarrow{aq.KOH} CH_3CH(OH)_2CH3​CHCl2​aq.KOH​CH3​CH(OH)2​ The gem-diol is unstable and converts to acetaldehyde: CH3CH(OH)2→CH3CHO+H2OCH_3CH(OH)_2 \rightarrow CH_3CHO + H_2OCH3​CH(OH)2​→CH3​CHO+H2​O Hence, this produces acetaldehyde.

  1. Therefore, the correct option is: D\boxed{D}D​
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