Kolbe's Reaction (Kolbe-Schmitt Carboxylation)

$\text{C}_6\text{H}_5\text{O}^-\text{Na}^+ + \text{CO}_2 \xrightarrow{125°C,\ 4\text{-}7\ \text{atm}} \text{C}_6\text{H}_4(\text{OH})(\text{COONa}) \xrightarrow{\text{H}_3\text{O}^+} \text{Salicylic acid}$

Product SMILES: SMILES:OC(=O)c1ccccc1O (2-hydroxybenzoic acid) Position of entry: ortho (-COOH enters ortho to -OH)

Reimer-Tiemann Reaction (Formylation)

$\text{C}_6\text{H}_5\text{OH} + \text{CHCl}_3 \xrightarrow{\text{NaOH, reflux}} \text{C}_6\text{H}_4(\text{OH})(\text{CHO}) + \text{HCl}$

Intermediate: Dichlorocarbene $(:CCl_2)$ — generated from $CHCl_{3}$ + NaOH Product SMILES: SMILES:O=Cc1ccccc1O (salicylaldehyde, ortho-hydroxybenzaldehyde)

Williamson Ether Synthesis

$\text{R-O}^-\text{Na}^+ + \text{R'-X} \xrightarrow{\text{SN2}} \text{R-O-R'} + \text{NaX}$

Constraint: R'-X must be 1° alkyl halide (2° or 3° gives E2 elimination).

Bromination of Phenol

$\text{C}_6\text{H}_5\text{OH} + 3\text{Br}_2 \xrightarrow{\text{H}_2\text{O, no catalyst}} 2,4,6\text{-tribromophenol} + 3\text{HBr}$

Product: white precipitate (qualitative test for phenol)

Fischer Esterification

$\text{RCOOH} + \text{R'OH} \xrightarrow{\text{H}_2\text{SO}_4, \Delta} \text{RCOOR'} + \text{H}_2\text{O}$

Example: SMILES:CCOC(=O)C (ethyl acetate)