Introduction
Nitration is a type of
chemical reaction which a nitro group is added to/substituted in a molecule. Basically
it can be carried out by a mixture of concentrated nitric acid and sulphuric
acid. Mixture is useful to obtain the active nitronium ion. Electrophilic aromatic
substitution is a method used when a functional group is needed to be substituted
on to an aromatic compound. In the nitration, nitronium ion acts as the
electrophile that involves the attack of the electron-rich Benzene ring. In this
experiment nitration is carried out using acetanilide.
Theory
Acetanilide displays
moderately reactivity in electrophilic aromatic substitution. Also another
advantage is, it’s not oxidized by nitric acid. Principally, acetanilide gives
Ortho and Para mono nitroacetanilides. This position of nitronium ion is
directed by the –NHCOCH3 group attached to the benzene ring. This is
due to the resonance delocalizing the benzene ring by nitrogen lone pair. Therefore
Ortho and Para positions are more resonance stabilized than the Meta. Acetanilide
undergoes ready nitration giving mainly the colourless P-nitroacetanilide,
mixed with much smaller proportion of the yellow colour O-nitroacetanilide.
Procedure
·
About 2g
of powdered acetanilide and 2mL of Glacial acetic acid were mixed well in a
100mL beaker. 4mL of con.H2SO4
was added to the mixture.
·
The beaker
was placed in crushed ice until the temperature of the mixture was dropped down
to 0-50C.
·
4mL of con.H2SO4
was added drop wisely while stirring the viscous mixture continuously
keeping the temperature below 100C.
·
Afterwards
the beaker was removed from the freezing conditions and allowed to stand 30
minutes at room temperature.
·
The mixture
was poured onto about 20g of crushed ice and stirred to obtain crystals. The beaker
was rinsed with 10mL of water containing few fragments of ice and the solution
was added to the main bulk of the product.
·
It was
allowed to stand for about 20minutes.
·
Later it
was filtered at the pump and washed thoroughly with cold water.
·
Afterwards
the crude product was recrystalized with water.
·
Finally the
melting point of the product was determined.
Observations
·
Acetanilide
powder was white in colour.
·
Glacial acitic
acid, H2SO4 and acetanilide mixture was initially in pale
yellow colour.
·
In cold
condition, white colour crystals were formed.
·
Final purified
crystals were also white.
·
The determined
melting point range was 150-1520C.
Conclusion
The initial compounds used
were known. Therefore according to those the final product should be nitroacetanilide.
As the colour of the product was white, it should be Para nitroacetanilide.
Discussion
Through the use of
electrophilic aromatic substitution, acetanilide is nitrated to nitroacetanilide.
There are several key steps involved in the nitration. The first step of the
reaction involved in the donation of an electron pair by the acetanilide to the
eletrophile, the nitronium ion. This nitronium ion was formed by the reaction
of sulfuric and nitric acids. Basically the whole mechanism undergoes as below; (Benzene is shown here instead of acetanilide )
|
Image via en.wikipedia.org |
To prevent dinitration
of the acetanilide, the nitrating mixture of concentratred nitric acid and
sulfuric acids were added in small portions to the acetanilide solution, so
that the concentration of the nitrating agent is kept at minimum.
Also the addition of
nitric acid is exothermic. Therefore the mixture would get too hot exceeding
the temperature range suitable for the nitration. To avoid this, the addition
of HNO3 acid should be done very slowly, dropwisely.
Cold temperatures were
used to slowdown the reaction rate and help to avoid over nitration.
Glacial acetic acid is
used because it is a polar solvent capable of dissolving acetanilide and the
acetate ion is a poor nucleophile, so no substitution is possible.
At the end, traces of
acid should be removed because hydrogen ions catalyze the hydrolysis of the
amide to p-nitroaniline. Acid is removed by pouring the mixture onto ice and
water and filtering.
The melting point is
determined to characterize the product. Theoretical melting point of the Para
nitroacetanilide is found to be 214-2160C. The observed value was
150-1520C and it is much lower than the theoretical values and can be
accounted for impurities in the product. Some impurities might be Ortho and Meta
directing substances. Also there can be some experimental errors occurred during
the experiment such as not controlling the exact temperatures mentioned for the
reactions.