Introduction

In this experiment, the relative activating effects of different substituents on an aromatic ring
are determined by analyzing the melting points for the bromination of aniline, acetanilide, phenol,
and anisole. The different substituents on each of the aromatic compounds are activators as well as
ortho- or para- directors. Theory 1
Electrophilic aromatic substitution is a reaction in which the aromatic ring is attacked by an
electrophile and causes the hydrogen atom to be replaced. The electrophilic attack on the benzene
ring creates an arenium ion which is a cation that is resonance stabilized. The most likely attack will
occur when the carbocation is resonance stabilized, so a full octet is highly favored. When there are
substituents on the aromatic ring, there are directing effects and three factors that determine the
location in which the electrophile attacks. The first factor is resonance. Ortho- and para- directors
are also known as activating groups because they allow for a faster reaction to occurand CF3. The
second factor in determining where the electrophile attacks is probability. The para- attack can only
occur in one position, whereas the meta- and ortho- attack can be in two different locations.
Therefore, meta- and ortho- attacks are favored and more likely. Lastly, electrophilic attacks are
determined by steric hindrance. When the electrophile is relatively small, steric hindrance is not a
factor in determining where the electrophile attacks. However, a larger electrophile will favor the
para- attack over the ortho-attack.
Based on the substituents in each compound, the substitution order is predicted to be aniline
> phenol > anisole > acetanilide. This is because the most ring activating substituent is NH2 in
aniline. The phenol also has a strong activating substituent, -OH, as well, but the oxygen is more
electronegative than the nitrogen. Both are also ortho-, para- directors. Anisole has a carbon that
holds a higher electronegativity from the hydrogen than the oxygen from the single hydrogen in

phenol. Finally, acetanilides substituent, -NHCOCH3, is the least activating and will result in only
a mono-substituted product. Therefore, the electronegativity determines the order of reactivity.
Results
Aromatic compound

Experimental

Phenol (1)
Phenol (2)
Phenol (3)
Phenol (4)
Acetanilide (1)
Acetanilide (2)
Acetanilide (3)
Aniline

melting point
68-72 C
72-79 C
84-87 C
73-92 C
164-168 C
142-145 C
197-205 C
118.5-120.5 C

Assumed product

Literature melting point of

2,4,6-tribromophenol
2,4,6-tribromophenol
2,4,6-tribromophenol
2,4,6-tribromophenol
4-bromoacetanilide
2,4,-dibromoacetanilide
2,6-dibromoacetanilide
2,4,6-tribromoaniline

assumed product
96 C
96 C
96 C
96 C
168 C
145 C
208 C
122 C

Table 1. The highlighted row shows the data and results from the experiment done in lab. The
numbers in parentheses next to the aromatic compounds are used to differentiate data from
other groups with the same compound.
Theory 2:
Based on the reaction product obtained during lab, the mechanism for the bromination of
acetanilide is shown in the appendix, and the product is shown to be 4-bromoacetanilide.
Discussion:
The substituents in aniline and phenol, -NH2 and OH respectively, are both very activating
due to conjugation. Both are also electron donating groups, which are ortho and para directing.
NH2 is less electronegative than OH, making aniline more willing to donate electrons, and thus
more reactive. This is also because aniline has a lone pair on an atom that is more basic. Anisole
and acetanilide are both bulkier than aniline and phenol, and both are also more electronegative as
well, making them less reactive than the first two compounds. Since the amide in acetanilide causes
the ortho site to be more crowded, the bromination of acetanilide favors a monosubstitution in the
para site. Anisole bromination produces a di substituted product, and is therefore more reactive than
acetanilide. Therefore, the overall reactivity order should be aniline > phenol > anisole >

acetanilide. Tri-substituted products should be the most reactive, and according to the class data,
aniline and phenol were shown to be most substituted. Anisole was not used in lab. Acetanilide had
mixed results in the evening lab section. However, results from the afternoon section were
consistent with our lab groups assumed product, which was 4-bromoacetanilide, formed after
bromination of acetanilide. This makes sense because the N-acetyl group on acetanilide favors a
product that is monosubstituted in the para site. The melting point obtained in lab was also the
same as the literature melting point, and can indicate the purity of the product as well as help
confirm its identity. Perhaps the second acetanilide groups melting point was too low because the
product was not pure enough. The crude melting point for our groups product was 141-143 C,
which is very close to the second groups melting point. However, after recrystallization, the
melting point increased to 168 C
The theoretical yield for acetanilide is 0.214 g, with calculations shown in the appendix. The
actual yield was 0.081 g. Thus, the percent yield is 38%. This low percent yield could be attributed
to the reaction not reaching completion. However, a more likely explanation is that some of the
product was lost during purificationConclusion
Bromination of different aromatic compounds results in different substituted products. Both
aniline and phenol were predicted to be ortho and para directing, and the data confirmed this.
Acetanilides bulky N-acetyl group favors a monosubstituted group, which was also confirmed in
the results. The overall reactivity is follows the electronegativity of the substituents, and should
have been aniline > phenol > anisole > acetanilide, which was also consistent with data results. Our
product was quite pure, based on the melting point, so a future experiment could be done by taking
TLC of the products as well to confirm each products identity.
Appendix
Mechanism for bromination of acetanilide:

References

Smith, J. (2014). Organic chemistry (4th ed.). New York, NY: McGraw-Hill.