RELATIVE RATES OF ELECTROPHILIC AROMATIC

SUBSTITUTION
MICA FELICIANO
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE SUBMITTED: 13 FEBRUARY 2014
DATE PERFORMED: 6 FEBRUARY 2014

ANSWERS TO QUESTIONS
1. Arrange the compounds used in the experiment in order of increasing reactivity
towards Br2 in CH3COOH. Explain.
Nitrophenol < Chlorobenzene < Benzene < Acetanilide < Phenol < Aniline
The presence of a substituent in the substituted aromatic ring affects the rings reactivity
towards the electrophile, and the orientation/position of the electrophile in the aromatic ring
when it undergoes electrophilic aromatic substitution.
A substituent that is electron-donating is considered an activating group that is, it
makes the aromatic ring more reactive towards the electrophile. Moreover, most activators
attach the electrophile either in the ortho or para position of the ring (with respect to the original
substituent). On the other hand, a substituent that is electron-withdrawing makes the ring less
reactive, and is called a deactivating group. Deactivators are generally meta directors, with the
exception of halogens, which are weakly deactivating but ortho-para directing.
Of the six compounds separately reacted with Br2, nitrophenol should be least reactive
because of its strong deactivating substituent, NO2. Next to nitrophenol is chlorobenzene with a
weakly deactivating halogen substituent, which is then followed by the unsubstituted benzene.
The last three compounds, acetanilide, phenol, and aniline, contain the activating groups,
NHOR, OH, and NH2, respectively. The order of the three is determined by the relative strength
of the activating substituent.
2. Do your experimental results agree with the theoretical data? If not, what are the
possible sources of error?
Actual: Nitrophenol < Benzene < Chlorobenzene < Acetanilide < Phenol/Aniline
The general trend in the experimental result is close to the theoretical data shown in 1,
except for benzene and chlorobenzene which switched positions in the trend. This may be
attributed to an excess in the volume of chlorobenzene (or shortage in that of benzene) which
were added to Br2 that made the reaction, observed as color disappearance/change, more
evident. Also, possible contamination of the reagent bottles or droppers used could have also
affected the reactions.
3. Predict order of reactivity (from least to most) of the ff. compounds towards
chlorination.
A. Toluene, nitrobenzene, anisole, methylbenzoate

Nitrobenzene < methylbenzoate < toluene < anisole

B. Benzene, acetophenone, bromobenzene, benzyl alcohol

Acetaphone < bromobenzene < benzene < benzyl alcohol

C. Styrene, benzaldehyde, aniline, iodobenzene

Benzaldehyde < iodobenzene < styrene < aniline

4. Explain the effect of solvent in the reaction of acetanilide and Br2 in Part B.
Acetanilide readily reacts with Br2 via electrophilic aromatic substitution because of its
electron-donating substituent. Mixing Br2 with acetic acid, however, further speeds up the
reaction since acetic acid is a polar solvent that acts as a catalyst by polarizing Br 2. Meaning to
say, the electrons shared by the two Br atoms move closer to one of them, making one Br atom
electrophilic (and the other nucleophilic) such that it can react with the aromatic ring. On the
other hand, mixing Br2 with cyclohexane slows down the reaction because the solvent is nonpolar.
REFERENCES
Bruice, P. (2004). Organic Chemistry (4th ed.). Pearson Prentice Hall.
McMurry, J. (2012). Organic Chemistry (8th ed.). Cengage Learning.
Solomons, G., Fryhle, C., & Snyder, S. (2014). Organic Chemistry (11th ed.). John Wiley &
Sons.