EXPERIMENT 9: RELATIVE

AROMATIC SUBSTITUTION
CHEM 31.1 POST-LAB

RATES

OF

ELECTROPHILIC

J.M. EGANA1
1

NATIONAL INSTITUTE OF MOLECULAR BIOLOGY AND BIOTECHNOLOGY, COLLEGE OF SCIENCE

UNIVERSITY OF THE PHILIPPINES, QUEZON CITY 1101, PHILIPPINES
DATE PERFORMED: 24 SEPTEMBER 2014
DATE SUBMITTED: 1 OCTOBER 2014

ANSWERS TO QUESTIONS (ATQ)

1. Arrange the compounds used in the experiment in order of increasing reactivity towards Br2 in CH3COOH.
Explain.
Chlorobenzene < benzene < nitrophenol < acetanilide < phenol < aniline
The reactivity of these aromatic compounds is based mainly on the activating or deactivating effects of their
substituent groups. The table below shows the substituent groups of the aromatic compounds used.
Aromatic compound
Chlorobenzene
Benzene
Nitrophenol
Acetanilide
Phenol
Aniline

Substituent Groups
-Cl
none
-OH, -NO2
-NHCOCH3
-OH
-NH2

The common characteristic of all activating groups is that they donate electrons to the ring, thereby making the
ring more electron-rich, stabilizing the carbocation intermediate, and lowering the activation energy for its
formation. Thus, aniline, phenol, acetanilide, and Nitrophenol have activating groups making them more reactive
than the rest of the compounds used.
2. Do your experimental results agree with the theoretical data? If not, what are the possible sources of error?
No. The most probable source of error in this experiment would be human error. One example is how you observe
the reaction. In this experiment where you are to perform reaction in dark, it is difficult to judge whether the reaction
has already proceeded or not. It depends on the judgment of the experimenter when determining the reaction rates
of certain compounds. Contamination or impurities in the compounds used might also be considered as one of the
possible sources of error.
3. Predict the reactivity of the following compounds towards chlorination form the least reactive to the most
reactive:
A. Toluene, nitrobenzene, anisole, and methylbenzoate
Nitrobenzene < methylbenzoate < toluene < anisole
B. Benzene, acetophenone, bromobenzene, and benzyl alcohol
Benzyl alcohol < acetophenone < bromobenzene < benzene
C. Styrene, acetophenone, aniline, and iodobenzene
Benzaldehyde < iodobenzene < styrene < aniline
4. Explain the effect of solvent in the reaction of acetanilide and Br2 in Part B.

In this part of the experiment, the effect of solvent in the reaction of acetanilide in reaction rate is determined.
Based on the results, it can be concluded that the more polar the solvent used in this experiment, the faster the
reaction would proceed. It took minutes for the reaction to complete when the solvent used is cyclohexane, which
is a very non-polar solvent. While on the other hand, when the solvent used was acetic acid, which is a polar
solvent, it just took one second for the reaction to complete. This is because acetic acid polarizes Br2 making Brmore electrophilic. In this way, the bromide ions can attack the nucleophilic benzene ring more easily.
REFERENCES
[1] McMurry, J. (2008). Organic chemistry. Pacific Grove, CA: Brooks/Cole Pub.
[2] Retrieved from
http://www.mhhe.com/physsci/chemistry/carey/student/olc/graphics/carey04oc/ref/ch12substituenteffects.html
[3] Solomons, T. W., & Fryhle, C. B. (2011). Organic chemistry. Hoboken, NJ: Wiley.