CH2102 Organic Chemistry for Engineers

School of Chemical and Biomedical Engineering

Electrophilic aromatic substitution

Question 1

Provide correct IUPAC names for each of the following compounds.

i. Answer: m-nitrotoluene or 1-methyl-3-nitrobenzene

ii. Answer: (1-methylethyl) benzene or isopropylbenzene or cumene

iii. Answer: cis-1-methyl-3-phenylcyclohexane

Question 2

Consider the data below to answer the following questions.

The -NH2 group is listed in our textbook as the strongest o,p-directing activator in electrophilic aromatic
substitution reactions. However, when aniline is subjected to standard nitration conditions poor yields of
m-nitroaniline result.

i. Draw all the resonance forms of aniline showing the electron-donating effect of the -NH 2 substituent.

Answer:

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ii. Clearly, the reaction conditions are influencing the directing effect of the -NH 2 group. Explain why
this occurs, using both words and structures.

Answer:

When aniline is placed in strong acid the nitrogen atom is protonated. Electrophilic aromatic substitution
on the anilinium ion—whose aromatic ring is now deactivated by a positively charged substituent—occurs
primarily at the meta position since this keeps the positive charge of the intermediate carbocation away
from the positively charged nitrogen. The intermediates shown above for ortho and para substitution are
destabilized more than the intermediate for meta substitution, so m-nitroaniline is the major product.

Question 3

i. At what position, and on what ring, is bromination of phenyl benzoate expected to occur? Explain your
answer by drawing resonance structures of the intermediates.

Answer:

Attack occurs in the activated ring and yields ortho and para bromination

ii. What is the product (if any) of the following reaction? Explain your answer.

Answer: (Friedel-Crafts reactions do not proceed in the presence of a m-director).

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Question 4

Consider the data below to answer the following questions.

i. Conjugate bases QB and ZB are both resonance stabilized. Draw the indicated number of resonance
forms for QB and ZB.

Answer:

ii. Which of the compounds above, Q or Z, would you predict to be most acidic? Explain your answer.

Answer: The conjugate bases of Compounds Q and Z are both resonance stabilized. Let’s examine
all resonance structures for both conjugate bases:

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For the conjugate base QB the negative charge is delocalized into the ring. This generates a
cyclopentadienyl anion which is aromatic. For the conjugate base ZB, the negative charge is delocalized
by resonance but no aromatic ions result. Therefore, Compound Q should be the most acidic, since its
anion is the most stable.

Question 5

How do you prepare the following food preservative starting from toluene?

Answer: