I. Modified True or False.

Write TRUE if the statement is correct; otherwise, change the

underlined word to make the statement correct.

1. The radical chain mechanism is characterized by three steps: cleaving, electron transfer and
termination.
2. When an H-X bond such as H-Cl or H-Br gets close to the alkene, the pi bonds will reach out to
grab the partially positive hydrogen atom.
3. Alkyl halides are insoluble in organic solvents because the intermolecular attractions between the
separate halogenoalkane and alkane have similar strength.
4. Epoxides are three-membered ring structures in which one of the vertices is an oxygen and the
other two are carbons.
5. Stability of the benzene ring is attributed to its resonance.
6. Cleavage of the C-O bond by strong acids occurs in tertiary alkyl groups by either an SN1 or an
E1 mechanism while it occurs in primary alkyl groups by E2 mechanism.
7. Delocalized electrons within benzene make it very reactive.
8. Aromatic compounds undergo addition reactions.

II. Multiple Choice. Choose the letter of the correct answer.

1. The chlorination of methane proceeds through what type of mechanism?

a. Free radical substitution
b. Electrophilic addition
c. Electrophilic substitution
d. Acid-Base substitution
2. Arrange the following steps in the hydrohalogenation of alkenes?

V: Haloalkane is produced
W: Negative halide in solution attacks the carbocation forming a bond
X: Nucleophilic pi bond reaches for electrophilic H in H-X, pi bond breaks in the process
Y: More substituted carbon is now deficient getting a formal charge of +1
Z: Hydrogen adds to the less substituted carbon atom following Markovnikov’s rule

a. Z, Y, Z, W, V
b. W, X, Y, Z, V
c. X, Z, Y, W, V
d. Y, Z, W, X, V
3. Arrange the carbon-halide bonds based on increasing bond strength.
 a. C-F < C-Cl < C-Br < C-I
b. C-I < C-Br < C-Cl < C-F
c. C-Cl < C-Br < C-I < C-F
d. C-Br < C-F < C-Cl < C-I
4. Which of the following is a tertiary alkyl halide?

a.

b.

c.

d.
5. What would be the product if the following alkyl halide reacts with a strong base via E2
mechanism?

a.

b.

c.

d.
6. What is the product when S-2-chloropentane is attacked by a strong base?
 a. S-2-pentanol
b. S-3-pentanol
c. R-2-pentanol
d. R-3-pentanol
7. The reaction below goes through a ________.

a. Pentavalent transition state

b. Free radical intermediate
c. Carbocation intermediate
d. Carbanion intermediate
8. What would be the configuration of the product of the following substitution reaction?

a. R
b. S
c. 50% R, 50% S
d. Cannot be determined
9. Which of the following is not needed to make a Grignard reagent?
a. Aldehyde
b. Alkyl Halide
c. Magnesium Metal
d. Diethyl Ether
10. What is the main organic product derived from the reaction of an ester with a Grignard reagent?
a. 1° alcohol
b. 2° alcohol
c. 3° alcohol
d. Ketone
11. What is/are the product/s formed in the reaction below?

a.

b.
c. Both A and B
d. Neither A nor B
12. Name the following ether.
 a. Ethoxy-2-methyl-propane
b. Cis-1-ethoxy-2-methoxycyclopentane
c. Oxirane
d. 1-ethoxy-1-methylcyclohexane
13. Which of the following reactions will not lead to the synthesis of an epoxide?
a. Treatment of halohydrin with base
b. Intramolecular Williamson ether mechanism
c. Friedel-Crafts mechanism
d. Catalytic oxidation of ethylene by air
14. Which of the following describes a Williamson ether synthesis?
a. Reaction between an alkoxide ion with a primary alkyl halide via an SN2 reaction.
b. Reaction between an alkoxide ion with a primary alkyl halide via an SN1 reaction.
c. Reaction between an alkoxide ion with a secondary alkyl halide via an SN1 reaction.
d. Reaction between an alkoxide ion with a secondary alkyl halide via an SN2 reaction.
15. In a reaction where ether cleavage proceeds with a potential carbocation which can not be
stabilized, what mechanism will the cleavage follow?
a. E1
b. E2
c. SN1
d. SN2
16. What is the name of this molecule?

a. 2-methoxy-5-bromophenol
b. 2-bromo-5-methoxyphenol
c. 1-hydroxy-3-methoxy-6-bromobenzene
d. 1-hydroxy-3-bromo-6-methoxybenzene
17. Which group is both ortho-para directing and ring deactivating?
a. -Cl
b. -CH3
c. -CHO
d. -OCH3
18. Which reagent/s should be used in the second step to produce the desired product below?

a. Hot KMnO4
b. CH3CH2CH2Cl, AlCl3
c. (CH3)2CHCl, AlCl3
 d. Cl2, AlCl3
19. Which sequence of reagents will yield the following product, using toluene as the starting
material?

a. Cl2 and AlCl3, hot KMnO4, HNO3 and H2SO4

b. HNO3 and H2SO4, hot KMnO4, Cl2 and AlCl3
c. Cl2 and AlCl3, HNO3 and H2SO4, hot KMnO4
d. HNO3 and H2SO4¸ Cl2 and AlCl3, hot KMnO4
20. The following are criteria of aromaticity EXCEPT:
a. Cyclic structure
b. Neutral charge
c. 4n+2 pi electrons
d. Conjugation is present
21. Which is the weakest acid?
a. p-nitrophenol
b. Phenol
c. m-chlorophenol
d. 3,4-dimethylphenol
22. Which of the following compounds is aromatic?

a.

b.

c.
d. None of the above
23. Phenols are stronger acids than alcohols because of the _____:
a. resonance stabilization of alkoxide ions.
b. hydrogen bonding in phenols.
c. resonance stabilization of phenoxide ions.
d. resonance stabilization of phenols.
III. Problem Solving

1. Propose a mechanism for the following reactions. Pay special attention to stereochemistry if
indicated. Look at the conditions given to determine if it is unimolecular or bimolecular. Explain.

2. Write out a mechanism for the reaction below, including formal charges. Identify if the reaction is
SN1 or SN2.

3. Provide the missing compounds/reagents in the reactions below. Show correct stereochemistry if
necessary.
4. Starting from benzene, use the necessary reagents to synthesize 4-chloro-2-nitroaniline.
ANSWER KEY
Modified True or False
1. Initiation, propagation, then termination
2. TRUE
3. Soluble
4. TRUE
5. TRUE
6. SN2
7. Unreactive
8. Substitution reactions

Multiple Choice
1. A
2. C
3. B
4. B
5. D
6. C
7. A
8. B
9. A
10. C
11. C
12. D
13. C
14. A
15. D
16. B
17. A
18. D
19. A
20. B
21. D
22. B
23. C

Problem Solving
1. The elimination mechanism is bimolecular (E2) because there is a strong base present.
Remember: a strong base favors E2.
2. Ethers react with 2 equivalents of H-X to form water and two equivalents of alkyl halide. In this
case, the ether was cyclic, so the ring had to open up. The reaction can go through either an SN1
or SN2 mechanism. Since this was a primary ether, it will go through an SN2 mechanism (the
carbocation is too unstable for the reaction to go SN1).

3. Answers:

1)

2)

3)

4)
 5)
***4 and 5 are interchangeable
6) CH3COCl, FeCl3
7) HNO3, H2SO4

8)
9) Cl2, FeCl3
10) No reaction
4. Benzene is transformed into nitrobenzene by substitution reaction with concentrated nitric acid
and concentrated sulfuric acid. Then, nitrobenzene is reduced using H2, Pd/C or SnCl2 to obtain
aniline. Following this, aniline is subjected to halogenation with Cl2 using FeCl3 as a catalyst
resulting in p-chloroaniline. The final step is another nitration step using concentrated nitric acid
and concentrated sulfuric acid.

What is important in the synthesis of aromatic hydrocarbons is that you know which are ortho,
para, & meta directors and which deactivates or activates the ring. In this case, we first subjected
benzene to nitration because it is a direct step that can give us something to work with. NO2 may
be a meta-director (for Cl in the desired compound) however, NO2 deactivates the ring making it
less reactive to electrophilic attack. Then, it’s best to leave substitution of NO 2 for the last step.
Hence, we transform NO2 group first to an NH2 an ortho,para director which activates the ring. The
next logical step would be to add the group para to NH2 which is Cl. Finally, NO2 is substituted to
the ring.