Engineering Chemistry Laboratory

Course Code: BCHY101P

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

NO2 NH2
Reduction

OH OH
 Importance of p-aminophenol
O
NO2 NH2 NH
Reduction N-Acetylation

OH OH OH

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

NO2 NH2
TiCl4, LiAlH4

Dry THF, 30 min

OH OH

• 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
Step-I

LiAlH4 + TiCl4 LiCl + AlCl3 + 2H2 + Ti (0)

Step-II
Ti(O), H2
NO2 NH2

Step-III -(Quenching reaction)

LiAlH4 + 4H2O LiOH + Al(OH)3 + 4H2

TiCl4 + 2H2O TiO2 + 4HCl

NH4OH + HCl NH4Cl + H2O

 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

NO2

OH

NH2

OH

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

NH2

OH

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
1. Based on the given reactants, the students need to calculate the number of moles and the theoretical yield of the
final product.

S. Reactant Wt MW Moles = Product MW Expected P Isolated Yield

No. Wt compound (g)

g R Wt/MW P W

1 p-Nitrophenol 1.39 139 0.01 p-Aminophenol 109 1.09 1.0 1.0  

2 p-Nitrophenol 2     p-Aminophenol          

3 p-Nitrophenol 3     p-Aminophenol          

2. Students can apply the reduction methodology to other similar examples in the identification of the structure(s)
of the product(s).

3. To test the understanding of the students’ knowledge in organic chemistry, students will be asked to design and
draw appropriate new derivatives from p-aminophenol.