Engineering Chemistry Laboratory

Course Code: BCHY101P

Experiment # 4
Reduction of p-Nitrophenol to p-Aminophenol
 Importance of p-aminophenol

Paracetamol

• The aromatic amines are very important in the preparation of dyes,

antioxidants, pharmaceuticals, and agrochemicals.

• P-Aminophenol is the key intermediate for preparation of paracetamol.

• It is commonly used as a developer for black and white film.

 Most commonly used reagents

Reagents
LiAlH4
NaBH4 in presence of a catalyst
Metal nanoparticles + H2
Sn/HCl
Pd/C + H2
Graphene +H2
 Limitations

1. Excess reaction time 2. Side products

3. Costly reagents 4. Anhydrous solvents

 Reaction

• Reaction requires relatively less time.

• No side products will be formed.

Reference: J. Prakt. Cliem. 1988, 330 , 811-813

 Reagents required

Lithium aluminium hydride Titanium tetrachloride Anhydrous Tetrahydrofuran

(LiAlH4 ) (TiCl4) (THF)
 Reaction Procedure
• Lithium aluminium hydride (0.5 g , 0.014 mol) is added portions wise to a stirred suspension
obtained by slow addition of titanium tetrachloride (2.2 ml, 0.02 mol) to dry tetrahydrofuran (60 ml)
at 0°C and the black slurry is stirred at room temperature for 15 min.

• p-Nitrophenol (0.01 mol) is added portions wise at 0°C to the stirred slurry of active titanium
reagent.

• The reaction mixture is stirred for 15 min. at room temperature and then decomposed with water (50
ml) and 25% ammonia solution (50 mL). The mixture is extracted with ether (5 x 50 mL) or
continuously with chloroform, the organic layer is dried with magnesium sulfate and evaporated.

• The residue will be recrystallized to give the pure product, p-Aminophenol.

Possible Reaction
 Observation

After addition of water and

Titanium(0) reagent formation After addition of LiAlH4
ammonia - Yellow
-Green colour - Black colour

• Final product (p-aminophenol)- Dark brown to black colour solid

Thin Layer Chromatography (TLC)

Picture -1 Picture -2 (Solvent )

Picture -3 Picture -4
Thin Layer Chromatography (TLC) Observation

Under UV light Ninhydrin stain

Mobile phase: 10 % Ethyl acetate/Hexane
Reaction With primary amine

Ninhydrin stain
COLUMN CHROMATOGRAPHY

Picture -1 Picture -2
High resolution mass spectrometry

Observed mass for [M]+ = m/z 109.0503

Observed mass for [M+H]+ = m/z 110.0600
High resolution mass spectrometry-VIT Vellore
 IR

N-H bend (Primary

amines)

N-H stretchings
(Primary amines)
 % Yield of the Product

% Yield =

For example:

Weight of the product calculated (Theoretical yield): 10.9 g

Weight of the product obtained by the experiment (practical yield) = 9.1 g

Yield (%) = 9.1 X 100 = 83.48 %
10.9