Tutorial Chapter 4 Benzene

For each molecule below, predict whether the molecule would be expected to show aromatic character or not.
Explain your answer in each case.
O

12.
N
H
OH
+

13.

15.

N
O

Consider the data below to answer the following questions.

base

CH3

QB

_ CH

and
H2C

H2C
CH3

base

Test Items for McMurrys Organic Chemistry, Seventh Edition

CH2

ZB

145

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

_ CH

QB

H2C
_

CH2

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

Consider the Friedel-Crafts alkylation reaction below to answer the following questions:
CH2CH3

CH3CH2Cl

AlCl3

HCl

6.

Draw the structure of the electrophilic intermediate in this reaction.

7.

What is the role of the AlCl3 in the reaction?

8.

Write the complete stepwise mechanism for this reaction. Show all electron flow with arrows and include
all intermediate structures.

Consider the reaction below to answer the following questions.

Br

Br

Br
Cl

Cl2
FeCl3

Cl
12. Write the complete stepwise mechanism for the formation of the ortho product. Show all intermediate
structures and show all electron flow with arrows.
13. Draw resonance structures for the intermediate carbocation that explain the directing effect of the -Br.

146

Chapter 16: Chemistry of Benzene: Electrophilic Aromatic Substitution

16. At what position, and on what ring, is bromination of phenyl benzoate expected to occur? Explain your
answer.
O
C

phenyl benzoate

To answer the following questions, refer to the data below:

Isobutylbenzene is the starting material for the industrial synthesis of the NSAID, ibuprofen.
six steps

isobutylbenzene

CO2H

ibuprofen

17. Attempts to prepare isobutylbenzene by direct Friedel-Crafts alkylation of benzene result in tertbutylbenzene as the major product. Write the complete stepwise mechanism for this reaction, showing all
electron flow with arrows and showing all intermediate structures.

Cl

AlCl3

19. Would you expect (nitromethyl)benzene to be more reactive or less reactive than toluene toward
electrophilic substitution? Explain.
CH2NO2

Give the major organic product(s) of each of the following reactions. If none is predicted, write N.R.
28.
H3 C

31.

Cl

1)NaOH
2)H3O+

C(CH3)3
KMnO4
H3O+
CH3

Test Items for McMurrys Organic Chemistry, Seventh Edition

147

OCH3
32.

Br2
FeBr3
NO2

CH3
SO3
H2SO4

34.

37.

CH2CH3

NBS
(PhCO2)2, CCl4

38.

CH3

H2, Pt, ethanol

2000 psi, rt

CH3

39.

NO2
CH3Cl
AlCl3

CH3
42.

KMnO4
+

H3O

148

Br2
FeBr3

Chapter 16: Chemistry of Benzene: Electrophilic Aromatic Substitution