Part of OC-05 — Alcohols, Phenols & Ethers

Named Reactions: Kolbe, Reimer-Tiemann, and Phenol Bromination

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Named reactions of phenol constitute a consistent NEET topic. All three major reactions exploit the activated nature of the phenol ring.

1. Kolbe Reaction (Kolbe-Schmitt Carboxylation):

C6H5ONa++CO2125°C, 4-7 atm[sodium salicylate]H3O+Salicylic acid\text{C}_6\text{H}_5\text{O}^-\text{Na}^+ + \text{CO}_2 \xrightarrow{125°C,\ 4\text{-}7\ \text{atm}} [\text{sodium salicylate}] \xrightarrow{\text{H}_3\text{O}^+} \text{Salicylic acid}

  • Substrate: sodium phenoxide (NOT phenol directly)
  • Reagent: CO2CO_{2} under pressure
  • Conditions: 125°C, 4-7 atm
  • Product: salicylic acid (SMILES:OC(=O)c1ccccc1O) — -COOH at ortho position
  • Significance: salicylic acid → acetylation → aspirin (acetylsalicylic acid)

2. Reimer-Tiemann Reaction (Formylation):

C6H5OH+CHCl3NaOH, refluxC6H4(OH)(CHO)+3NaCl+H2O\text{C}_6\text{H}_5\text{OH} + \text{CHCl}_3 \xrightarrow{\text{NaOH, reflux}} \text{C}_6\text{H}_4(\text{OH})(\text{CHO}) + 3\text{NaCl} + \text{H}_2\text{O}

  • Substrate: phenol
  • Reagent: CHCl3CHCl_{3} + NaOH
  • Intermediate: dichlorocarbene (:CCl2CCl_{2}) — electrophilic, attacks phenoxide at ortho position
  • Product: salicylaldehyde (SMILES:O=Cc1ccccc1O) — ortho-hydroxybenzaldehyde

3. Bromination of Phenol:

C6H5OH+3Br2/H2O2,4,6-tribromophenol+3HBr\text{C}_6\text{H}_5\text{OH} + 3\text{Br}_2/\text{H}_2\text{O} \rightarrow 2,4,6\text{-tribromophenol} + 3\text{HBr}

  • No Lewis acid catalyst (FeBr3FeBr_{3}) required — unlike benzene
  • Product: white crystalline precipitate
  • Also serves as qualitative test for phenol

Summary Comparison:

ReactionReagentProductPosition
KolbeCO2CO_{2}, pressureSalicylic acid (-COOH)Ortho
Reimer-TiemannCHCl3CHCl_{3}/NaOH, :CCl2CCl_{2}Salicylaldehyde (-CHO)Ortho
BrominationBr2Br_{2}/H2OH_{2}O, no catalyst2,4,6-tribromophenolO, O, P

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