Relative Reactivities of Several Aromatic Compounds

By
Simi Kaur

Purpose: The objective of this experiment is to observe an aromatic substitution reaction of

acetanilide, aniline, and anisole with glacial acetic acid. Then, with the melting point obtained
from the experiment, we will determine the product produced from the reaction.

Reactions:
I. Anisole

II. Aniline

III. Acetanilide
Procedure:
Aniline
Running the Reaction
To a tared 5mL conical vial with its cap aniline was added(0.0744mL). Then, glacial
acetic acid was added to the same conical vial (0.50mL) along with a spin vane. An air condenser
was attached to the conical vial and the apparatus was clamped onto a ring stand and placed into
a water bath at 23-27C. The solution inside the vial was stirred until completely mixed. Then, a
drying tube was prepared with cotton that was moistened with 0.5mL of 1M sodium bisulfite. A
mixture of 1mL of bromine and hydrobromic acid was capped and set aside in a 3mL conical
vial. While stirring, the prepared bromine mixture was added to the 5mL conical vial and the
prepared drying tube trap was attached. The reaction continued to stir for 20 minutes.
Crystallization and Isolation of Product
Once the reaction was completed, the mixture was transferred to a 10mL Erlenmeyer
flask containing 5ml of water and about 0.5mL of saturated sodium bisulfite solution. This new
mixture solution was then mixed with glass stirring rod until the red color dissipated. The red
color disappeared very quickly and took on a light peachy color. Further mixing resulted in white
fluffy cloud-like precipitate swimming in clear color-less solution. After about 15 minutes of
stirring and mixing, the solution was filtered via Hirsch funnel apparatus and rinsed with three
1mL portions of cold water. The product was allowed to air dry for about 5 minutes on funnel
with the vacuum on.
Recrystallization and Melting Point
For Aniline: The solid was transferred to a 10mL flask. This flask and another flask
containing 95% ethanol were placed on a hot plate. As the solutions warmed up, the hot ethanol
was added drop by drop to the solid in order to dissolve it. Once the solid was dissolved, the
solution was decanted to separate from impurities that would not dissolve. The flask solution was
placed in an ice bath and recrystallization was allowed to occur. The crystals were then placed
over a Hirsh funnel and allowed to dry overnight. The next lab day, the crystals were weighed
(0.106g) and had melting point taken (122- 125C), which were used to calculate percent yield.
This data was then used in lieu with a melting point table in the lab notebook to determine
product identity.
 For Anisole and Acetanilide: The crude product was crystallized using a Craig tube. 95% ethanol
was used to crystallize acetanilide product and hexane to crystallize brominated anisole
compound. The pure crystal products are allowed to air dry. The weight and melting points were
then taken. The percent yields were calculated and with the melting point, the compound
identities were analyzed.
Data Analysis:

Physical Data Table

Compound MW mmol wt. Den. Vol. M.P. C B.P. Hazards

(g/mol) (g) (g/mL) (mL) C
Acetanilide 135.17 0.666 0.09 1.22 _ 114.3 304 irritant

Anisole 108.14 0.647 0.07 0.995 0.07 -37 154 flammable

irritant
Aniline 93.13 0.657 0.061 1.02 0.06 -6.3 184 corrosive toxic
irritant
2,6- dibromo 292.96 0.666 0.196 _ _ 208 NA _
acetanilide
o-bromo anisole 187.04 0.647 0.121 _ _ 3 NA _

p-bromo anisole 187.04 0.647 0.121 _ _ 13 NA irritant

2,6- dibromo 265.93 0.647 0.172 _ _ 13 NA toxic

anisole
2,4,6-tri bromo 329.80 0.655 0.216 2.35 _ 120-122 300 corrosive toxic
aniline irritant

YieldsData:

Aniline(2,4,6tribromoaniline)

Molecular Weight
mmol MeltingPoint1(C)
Weight(g/mol) (grams)

0.657
Theoretical 329.82g/mol 0.217g 122C
mmol
 0.657
Actual 329.82g/mol 0.106g 122125C
mmol

Anisole(2,6dibromoanisole)

Molecular Weight
mmol MeltingPoint1(C)
Weight(g/mol) (grams)

0.644
Theoretical 265.93g/mol 0.171g 13C
mmol

0.644
Actual 265.93g/mol 13*C
mmol

Acetanilide(pbromoacetanilide)

Molecular Weight
mmol MeltingPoint1(C)
Weight(g/mol) (grams)

0.666
Theoretical 214.06g/mol 0.143g 168C
mmol

0.666
Actual 214.06g/mol 0.0146g
mmol 208208.1C

Data Observations:
Aniline
When Aniline was combined with glacial acetic acid it formed a yellow-tinted but clear solution
formed. Upon close inspection, two layers could be seen however colorless. After mixing, they
formed one uniform yellow tinted solution. Further, when the bromine solution was added, the
color formed was of a deep red. After stirring, it quickly changed into a colorless light yellow
tinted solution. Once the water-bisulfite solution was added, the solution was a peach tinted
solution with white solid pellets swimming in it. The overall final product was of a tan-brown
color and in short straight strands, akin to that of kay strands.
 Anisole
The anisole also had two layers form when the glacial acetic acid was added. The solution
turned orange once the bromine solution was added and later disappeared. However, no solid
was acquired during this experiment with the solution remaining clear and colorless. This is due
to the very low melting point of di-substituted-bromoanisole.
Acetanilide
The Acetanilide solution became clear and colorless once added to glacial acetic acid. The
solution became very dark orange-red once the bromine solution was added. After the solution
was allowed to stir in the water bath, it was stirred again at room temperature. During this time
the color changed from dark orange-red to light yellow. This color would not fade. Once added
to the water/ sodium bisulfite, a yellow, thick yolk-like precipitate formed in the solution. The
pure precipitate that formed was white and appeared like snow.

Calculations:

Aniline Anisole Acetanilide

Actual weight 0.106 g x 0.0146g

Theoretical weight 0.217 g 0.171g 0.143 g

Percent yield (0.106g) / (0.217g) = x (0.0146g) / (0.143g)

48.85% = 10.21%

Data Analysis/Discussion:

Aniline
For this benzene derivative, a melting range of 122 125C was obtained. As shown on
page 356 of The Organic Laboratory Techniques, Fifth Edition, we are given a chart displaying
compounds as well as their melting points. The compound with the closest melting point from
the range was 2,4,6-Tribromoaniline with a literature melting point value of 122C. The range
that was received had a difference of approximately 1.5C. This is a very small difference
indicating that the product was isolated and an almost pure sample of 2,4,6-Tribromoaniline. The
difference and increase in experiment melting point is most likely due to impurities as seen in the
discolored final product appearance having a brownish-beige tint to it rather than a pristine white
outlook. This melting point range also helped determine the identity of the brominated aniline
product that was produced.
Due to the amine group being such a great activation group, three substituents (bromine)
were allowed to be added. They formed on the 2, 4, and 6 positions of the benzene. This is due to
the fact that activation groups direct ortho and para addition positions, with para being a major
product. This shows that aniline is more reactive than anisole and possibly more reactive than
acetanilide. The amine activating group attached to the benzene ring is resonance donating to the
benzene ring, allowing the ring to be more nucleophilic. Moreover, the -NH2 group is listed very
high on the order of activating ability. The percent yield of 2,4,6-tribromoaniline was calculated
to be around 48.07%. The loss of product is mostly due to improper transferring between vessels
and also filtering through the Hirsh funnel. Out of all three compounds, aniline had the highest
percent yield, further giving proof to the claim that aniline is highly reactive.
Anisole
Unfortunately, Anisole was not a good experimental solution to have been worked with in this
lab as it did not produce a viable product to test with. It did form a brominated product, but the
melting point was so below room temperature that the product was not allowed to crystallize.
However, due to the reactivity of the methoxy- substituent group on a benzene in anisole, it can
be assumed that the product was di-substituted. In addition, the literature melting point data was
utilized to find out how the identity and understanding of how the bromine groups were attached
to the benzene group. The melting point for 2,4-dibromoanisole is 60C, which suggest that a
precipitate would have occurred in this experiment setting. Hence, 2,4-dibromoanisole could not
be the identity of this solution. The melting point for 2,6-dibromoanisole is 13C, which is below
room temperature. This data suggest that the product formed from anisole was most likely 2,6-
dibromoanisole. However, due to experimental constraints and consequent lack of actual
product, there is no melting point data to confirm nor deny this supposition.
Acetanilide
The acetanilide compound isolated into the product p-bromoacetanilide. The experimental
melting point was found to be 208-208.1C, though this is not the correct melting point. This
irregularity and error is most likely due to the fact that the melting point was taken off of a still
wet product. As amide is not a strong enough activating group to add two bromines onto the
benzene ring, this is why this melting point is deemed incorrect. The Amide substituent
in this compound is not the best activation group, 1 group should be added on. It was placed on
the 4-position of the benzene, indicating a para addition. This is also due to the fact that the
activation group amide directs substituents to add on the ortho and para positions (since all
activation groups direction addition on the ortho and para positons). The major product with any
activating group should have a new substituent added to the para position, so it makes sense that
the product is para. Further, the percent yield for acetanilide was 10.21%. Hence, the percent
yield for acetanilide mostly due to incorrect transfer techniques between vessels, filtration errors
and quite possibly due to the reaction not completing all the way.
Ranking of activating groups:
Aniline > Anisole > Acetanilide
Aniline has NH2 so it will react to completion resulting in giving us a tri-substituted product.
Then, Anisole, because it has a carbon that still holds some electronegativity from hydrogen,
more than that of the oxygen from the single hydrogen. Lastly, acetanilide has the least activating
substituent (-NHCOCH3) and gave us a mono-substituted product.

Conclusion:
In this experiment, the bromination of aniline, acetanilide, and anisole was concluded to form
three products: 2,4,6-tribromoaniline (0.106g, MP:122-125, 48.8%), 2,6-dibromoacetanilide
(0.0146g, MP: 208, 10.21%), and 2,6- dibromoanisole (0.171g). In accordance to the number and
location of the bromines attached to each compound, the relative reactivities of each activating
group were determined. The most reactive was found to be aniline, followed by anisole and
finally acetanilide.

Post Lab Questions:

I. Using resonance structures, show why the amino group is activating. Consider an attack
by the electrophile E1 at the para position.
II. For the substituent in this experiment that was found to be least activating, explain why
bromination took place at the position on the ring indicated by the experimental results.
a. Acetanilide was the least reactive product even though the activating groups -O-R
(anisole) and -NH-O-R (acetanilide) both formed a disubstituted product. This is due
to the structure of the activating group -NH-O-R and the fact that it is not a donating
group because its the Oxygen electrons are used in the p orbital versus being
available for reacting or being donated to the benzene ring. Hence, because of the
lone pairs course of action there is no resonance donating occurring happening with
the benzene ring.