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RELATIVE

RATES

OF

ELECTROPHILIC

AROMATIC

SUBSTITUTION
J. V. DE GUZMAN
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED: MARCH 4, 2015
INSTRUCTORS NAME: ALLAN KENNETH REGUNTON

Answers to Questions:
1. Arrange the compounds used in the experiment in order of increasing
reactivity towards Br2 in CH3COOH. Explain.
Shown below are the structures of these compounds:

The reactivity of a compound with aromatic ring depends on the


substituent/s. If the substituent is an electron withdrawing group also called
deactivating group, it tends to withdraw the electron density from the ring,
making the compound less reactive toward an electrophile like bromine. On
the other hand, an electron donating group or an activating group increases
the electron density of the aromatic ring making it more reactive towards an
electrophile. Amine has an amino group while acetanilide has acylamino
group. Phenol has a hydroxyl group while chlorobenzene has a halogen
group. Nitrophenol has a nitro group and hydroxyl group whereas benzene
has hydrogens bonded only.
If arranged in order of increasing ability to donate an electron:
Nitro( -NO2)<Halogen (-X) <Hydrogen (-H) <acylamino (-NHCOR) <hydroxyl (OH) <amino (-NH2)
Therefore, it can be inferred that the compounds with the greatest ability to
donate an electron are reactive toward the electrophilic bromine. As such, we
can arrange the following compounds into:
Nitrophenol< Chlorobenzene<benzene<acetanilide<Phenol<Aniline
2. Do your experimental results agree with the theoretical data?
No. There are apparent deviations from the data obtained. Results for aniline
shows a very large time elapsed for the reaction when in fact it should be the
most reactive. Possible reasons for these deviations include personal errors in
distinguishing a positive result for a reaction. Since the test is qualitative
only, few amounts of reagents are only used making the reaction and
chemical change difficult to observe. Personal errors in obtaining the time for
each reaction can also be a reason. On the other hand, it is also difficult to
not expose the solution from sunlight since it is difficult to add the reagents in

the dark. As such, when the solution is initially exposed by sunlight, free
radical formation may have occurred therefore impeding the desired reaction
to happen.
3. Predict the order of reactivity of the following compounds towards
chlorination from the least reactive to the most reactive.
A. Toluene, nitrobenzene, anisole, methylbenzoate

Substituent (increasing ability to donate an electron)


Nitro (-NO2) < alkyl < acyloxy <alkoxy
Nitrobenzene< toluene< methylbenzoate<anisole
B. Benzene, acetophenone, bromobenzene and benzyl alcohol

Acyl<halogen<H<-CH2-OH
Acetophenone<bromobenzene<benzene<benzyl alcohol
C. Styrene, benzaldehyde, aniline and iodobenzene

Formyl<halogen<alkenyl<amine
Benzaldehyde<iodobenzene<styrene<aniline
4. Explain the effect of solvent in the reaction of acetanilide and Br 2 in part B.
Acetic acid can also become a Lewis acid. It tends to donate electrons on the
aromatic ring and thus make acetanilide more reactive towards bromination.
On the other hand, cyclohexane tends to withdraw electrons from the group
causing it to be less reactive. As predicted, it takes the reaction of bromine in
cyclohexane with acetanilide longer than with acetic acid. As such, the
solvent can increase the rate of the reaction by donating electrons to the
aromatic ring or can decrease the rate by withdrawing electrons from the ring
which is similar to what substituent groups do to the rate of reaction of an
aromatic compound.
References:
[1] Carey, F. A. (2006). Organic Chemistry 6th ed. Chapter 12: Reactions of Arenes:
Electrophilic Aromatic Substitution. McGraw-Hill: New York. pp. 496-512