JEE Challenger
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Identify Structure of Product Y from Reflux of Glyoxal with KOH

An organic compound "x" where molar ratio of C, O and H are equal, on treatment with 50%50\% KOH\text{KOH} under reflux followed by acidification produced "y". The most likely structure of "y" is : [Molar mass of 'x' is 58 g mol158\text{ g mol}^{-1}]

Options

A

CH2=CHCOOH\text{CH}_2=\text{CH}-\overset{\underset{\parallel}{\text{O}}}{\text{C}}-\text{OH}

B

CH3CH=CHCH=O\text{CH}_3-\text{CH}=\text{CH}-\text{CH}=\text{O}

C

O=COHCH2OH\begin{array}{c} \text{O}=\text{C}-\text{OH} \\ | \\ \text{CH}_2-\text{OH} \end{array}

Correct
D

OCH3COH\begin{array}{c} \text{O} \\ \parallel \\ \text{CH}_3-\text{C}-\text{OH} \end{array}

Step-by-Step Solution

To determine the structure of product "yy", we analyze the steps as follows:

  1. Determination of Molecular Formula of Compound "xx": It is given that the molar ratio of C\text{C}, H\text{H}, and O\text{O} in compound "xx" is equal (1:1:11:1:1).

    • Empirical formula of x=CHOx = \text{CHO}
    • Empirical formula mass =12+1+16=29 g mol1= 12 + 1 + 16 = 29 \text{ g mol}^{-1}

    The given molar mass of compound "xx" is 58 g mol158 \text{ g mol}^{-1}. n=Molar massEmpirical formula mass=5829=2n = \frac{\text{Molar mass}}{\text{Empirical formula mass}} = \frac{58}{29} = 2

    Therefore, the molecular formula of compound "xx" is (CHO)2=C2H2O2(\text{CHO})_2 = \text{C}_2\text{H}_2\text{O}_2. The only compound with the molecular formula C2H2O2\text{C}_2\text{H}_2\text{O}_2 containing carbonyl functionality is glyoxal (OHCCHO\text{OHC}-\text{CHO}).

  2. Reaction with 50%50\% KOH\text{KOH} followed by Acidification: Glyoxal (OHCCHO\text{OHC}-\text{CHO}) lacks α\alpha-hydrogen atoms. When treated with a concentrated base (50%50\% KOH\text{KOH}) under reflux, it undergoes an intramolecular Cannizzaro reaction:

    • Hydroxide ion (OH\text{OH}^-) attacks one of the aldehyde carbonyl carbons.
    • Hydride ion (H\text{H}^-) shifts internally to the adjacent aldehyde carbon.
    • One aldehyde group is oxidized to a carboxylate group (-COOK+\text{-COO}^-\text{K}^+) while the other aldehyde group is reduced to a primary alcohol group (-CH2OH\text{-CH}_2\text{OH}), forming potassium glycolate (HOCH2COOK\text{HO}-\text{CH}_2-\text{COOK}).

    Upon subsequent acidification, potassium glycolate is converted into glycolic acid (2-hydroxyethanoic acid): OHCCHOn(i) 50% KOH, refluxHOCH2COOK(ii) H+HOCH2COOH\text{OHC}-\text{CHO} \xrightarrow[n]{\text{(i) } 50\% \text{ KOH, reflux}} \text{HO}-\text{CH}_2-\text{COOK} \xrightarrow{\text{(ii) } \text{H}^+} \text{HO}-\text{CH}_2-\text{COOH}

  3. Structure of Compound "yy": The structure of glycolic acid is: O=COHCH2OH\begin{array}{c} \text{O}=\text{C}-\text{OH} \\ | \\ \text{CH}_2-\text{OH} \end{array}

Thus, the correct option representing the structure of compound "yy" is C.

Identify Structure of Product Y from Reflux of Glyoxal with KOH | Chemistry PYQ Solution - JEE Challenger