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Aldehydes Ketones and Carboxylic Acids question

2016 · 10 Apr · Shift 1 · Q4
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Aldehydes Ketones and Carboxylic Acids question

2016 · 10 Apr · Shift 1 · Q4

JEE MainChemistryAldehydes Ketones and Carboxylic AcidsMCQ+4 / −1
The correct statement about the synthesis of erythritol (C(CH2OH)4C(CH_2OH)_4C(CH2​OH)4​) used in the preparation of PETN is :
  1. A
    The synthesis requires four aldol condensations between methanol and ethanol.
  2. B
    The synthesis requires two aldol condensations and two Cannizzaro reactions.
  3. C
    The synthesis requires three aldol condensations and one Cannizzaro reaction.
  4. D
    Alpha hydrogens of ethanol and methanol are involved in this reaction.
View written solutionFree

Correct answer: C

  1. Identify the target compound

    Erythritol has structure: HOCH2−CH(OH)−CH(OH)−CH2OHHOCH_2-CH(OH)-CH(OH)-CH_2OHHOCH2​−CH(OH)−CH(OH)−CH2​OH and is often written as C(CH2OH)4C(CH_2OH)_4C(CH2​OH)4​ in condensed form sense of a four-carbon polyol framework.

  2. Relevant industrial/laboratory synthesis idea

    Erythritol is obtained from formaldehyde (from methanol) and acetaldehyde (from ethanol) under basic conditions.

    • Formaldehyde: HCHOHCHOHCHO
    • Acetaldehyde: CH3CHOCH_3CHOCH3​CHO

    Here:

    • acetaldehyde has α\alphaα-hydrogen, so it can form an enolate and undergo aldol addition,
    • formaldehyde has no α\alphaα-hydrogen, so it cannot form enolate; after carbon-chain construction, aldehyde groups without α\alphaα-H can undergo Cannizzaro reduction.
  3. How the carbon chain is built

    Start with acetaldehyde as the enolizable aldehyde and add formaldehyde stepwise.

    Each aldol addition with formaldehyde introduces one −CH2OH-CH_2OH−CH2​OH unit after protonation.

    The sequence is:

    First aldol: CH3CHO+HCHO→HOCH2CH2CHOCH_3CHO + HCHO \rightarrow HOCH_2CH_2CHOCH3​CHO+HCHO→HOCH2​CH2​CHO (3-hydroxypropanal)

    Second aldol: HOCH2CH2CHO+HCHO→(HOCH2)2CHCHOHOCH_2CH_2CHO + HCHO \rightarrow (HOCH_2)_2CHCHOHOCH2​CH2​CHO+HCHO→(HOCH2​)2​CHCHO

    Third aldol: (HOCH2)2CHCHO+HCHO→(HOCH2)3CCHO (HOCH_2)_2CHCHO + HCHO \rightarrow (HOCH_2)_3CCHO(HOCH2​)2​CHCHO+HCHO→(HOCH2​)3​CCHO This product is pentaerythrose-like intermediate containing one aldehyde group.

    Thus, 3 aldol condensations/additions are needed to attach three CH2OHCH_2OHCH2​OH groups to the carbon adjacent to the original aldehyde carbon.

  4. Final conversion to erythritol-type polyol framework

    The remaining aldehyde group is converted to alcohol through Cannizzaro reaction (self oxidation-reduction under strong base, since this aldehyde has no α\alphaα-hydrogen at that stage).

    Hence, 1 Cannizzaro reaction is involved.

  5. Check the options

    A. Four aldol condensations between methanol and ethanol.
    ❌ Incorrect. Methanol and ethanol themselves do not directly undergo aldol condensation; their oxidation products formaldehyde and acetaldehyde are involved. Also the count is not four.

    B. Two aldol condensations and two Cannizzaro reactions.
    ❌ Incorrect. Chain extension requires three aldol steps, not two.

    C. Three aldol condensations and one Cannizzaro reaction.
    ✅ Correct.

    D. Alpha hydrogens of ethanol and methanol are involved in this reaction.
    ❌ Incorrect. Formaldehyde (from methanol) has no α\alphaα-hydrogen. Only acetaldehyde-derived species provides the enolizable hydrogen in aldol steps.

  6. Final answer

    The correct statement is: C: Three aldol condensations and one Cannizzaro reaction\boxed{\text{C: Three aldol condensations and one Cannizzaro reaction}}C: Three aldol condensations and one Cannizzaro reaction​

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