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Basics of Organic Chemistry question

2011 · Shift 1 · Q5
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Basics of Organic Chemistry question

2011 · Shift 1 · Q5

JEE AdvancedChemistryBasics of Organic ChemistryMCQ+1 / −0.25
Among the following compounds, the most acidic is
  1. A
    p-nitrophenol
  2. B
    p-hydroxybenzoic acid
  3. C
    o-hydroxybenzoic acid
  4. D
    p-toluic acid
View written solutionFree

Correct answer: C

  1. Identify the acidic functional groups

    We compare the acidity of the given compounds:

    • A: ppp-nitrophenol
    • B: ppp-hydroxybenzoic acid
    • C: ooo-hydroxybenzoic acid
    • D: ppp-toluic acid

    Phenols are generally less acidic than carboxylic acids.
    Therefore, options B, C, D (carboxylic acids) are expected to be more acidic than A.

  2. Eliminate the weaker acid

    • ppp-nitrophenol has acidity enhanced by the electron-withdrawing −NO2-NO_2−NO2​ group.
    • But even substituted phenols usually have pKa≈7pK_a \approx 7pKa​≈7 to 888.
    • Carboxylic acids typically have pKa≈4pK_a \approx 4pKa​≈4 to 555.

    Hence, A is not the most acidic.

  3. Compare the carboxylic acids: B, C, D

    • D: ppp-toluic acid has a −CH3-CH_3−CH3​ group at para position.

      • −CH3-CH_3−CH3​ is electron-donating by +I+I+I effect.
      • It destabilizes the carboxylate ion slightly.
      • So acidity decreases.
    • B: ppp-hydroxybenzoic acid has an −OH-OH−OH group at para position.

      • The −OH-OH−OH group has a weak −I-I−I effect but a strong +R+R+R effect.
      • At para position, resonance donation dominates.
      • This donates electron density to the ring and reduces acidity of the carboxylic acid compared to a strongly withdrawing substituent.
    • C: ooo-hydroxybenzoic acid is salicylic acid.

      • It is known to be more acidic than benzoic acid and its para-hydroxy isomer.
      • The key reason is the ortho effect.
      • Also, the conjugate base is stabilized due to special interactions in the ortho position.
      • In salicylic acid, intramolecular hydrogen bonding and ortho substitution favor greater acidity.
  4. Use known acidity order

    A standard order is: o-hydroxybenzoic acid>benzoic acid>p-hydroxybenzoic acido\text{-hydroxybenzoic acid} > benzoic\ acid > p\text{-hydroxybenzoic acid}o-hydroxybenzoic acid>benzoic acid>p-hydroxybenzoic acid and also o-hydroxybenzoic acid>p-toluic acido\text{-hydroxybenzoic acid} > p\text{-toluic acid}o-hydroxybenzoic acid>p-toluic acid

    Thus, among all given compounds, the most acidic is: o-hydroxybenzoic acid\boxed{o\text{-hydroxybenzoic acid}}o-hydroxybenzoic acid​

  5. Option check

    • A: No
    • B: No
    • C: Yes
    • D: No

Therefore, the correct option is C.

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