Santos, Clarice March 6, 2019

EXPERIMENT 9: RELATIVE RATES OF ELECTROPHILIC AROMATIC SUBSTITUTION

ANSWER TO QUESTIONS

1. Arrange the compounds used in the experiment in order of increasing reactivity towards
Br2 in CH3COOH. Explain.
The reactivity of a compound with an aromatic ring depends on the nature of its
substituent/s, wheter it is an electron-donating or electron-withdrawing from the ring.
Electron-withdrawing group (EWG) makes the ring less reactive towards an electrophile
like bromine while electron-donating groups (EDG) amkes it more reactive because it
increases the electron density of the aromatic ring. For that reason, we can arrange the
substituents from fastest to slowest reactivity as follows: -CH3 > amino(-NH2) > hydroxyl
(-OH) > acylamino (-NHCOR) > hydrogen (-H) > halogen (-X) > nitro (-NO2).

Therefore, we can also arrange the following compounds into: toluene > phenol >
chlorophenol > benzaldehyde > nitrophenol.

2. Do the experimental results agree with the theoretical data? If not, what are the possible
sources of error?
There is a slight discrepancy between the theoretical data and experimental
results. Since the experiment was qualitative, errors were possibly committed during the
experiment like: contaminated chemical reagents, inappropriate proportions, environmental
factors such as temperature and light, human errors, etc.

3. Predict the order of reactivity of the following compounds towards chlorination from the
least reactive to the most reactive:
A. toluene, nitrobenzene, anisole, and methylbenzoate
nitrobenzene < methylbenzoate< anisole < toluene

B. benzene, acetophenone, bromobenzene, and benzyl alcohol

acetophene < bromobenzene < benzene < benzene

C. styrene, benzaldehyde, aniline, and iodobenzene

benzaldehyde < iodobenzene < styrene < aniline

4. Explain the effect of solvent in the reaction of toluene and Br2 in Part B.
Bromination of toluene was faster in acetic acid than in cyclohexane. Acetic acid
is a Lewis acid - it is an electron-pair acceptor. As a catalyst, the reaction of aromatic
compounds with halogen will undergo substitution since the Lewis acid will form a
complex with the halogen leaving the aromatic ring intact. On the other hand,
cyclohexane is nonpolar causing it to be less reactive that causes slower reaction.

References:
Carey, F. A. (2006). Organic Chemistry 6th ed. Chapter 12: Reactions of Arenes:
Electrophilic Aromatic Substitution. McGraw-Hill: New York. pp. 496-512.
McMurry, J. (2015). Organic Chemistry 9th ed. Chapter 16: Electrophilic Aromatic
Substitution. Brooks/Cole, Cengage Learning: Belmont, pp. 479-514.
Organic Chemistry Laboratory Manual

Name: Clarice Santos_________________

Groupmate: Alpecho, Tiampong_________ Date Performed: _03.22.2019_________
Section: _WFR____________________

EXPERIMENT 9. RELATIVE RATES OF ELECTROPHILIC AROMATIC SUBSTITUTION

A. Relative Rates of Bromination

Test Compound Structure Time of decolorization

Benzaldehyde fast

Chlorophenol slow

Phenol fast

Nitrophenol fast

Toluene immediate

B. Effect of Solvents on Reaction Rates

Solvent Time of decolorization

Cyclohexane 5 minutes
Acetic acid immediate