TUTORIAL 14: HALOALKANES

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14.1 Introduction to haloalkanes

At the end of the topic, students should be able to:
a) Give the general formula of haloalkane.
b) Draw the structures, classify and name 1, 2, and 3 haloalkanes according to the IUPAC
nomenclature.
c) Describe haloalkanes: contain polar bond, carbon bearing the halogen is susceptible to
nucleophilic attack.

1. Classify the following compounds as primary, secondary or tertiary haloalkanes and

give their IUPAC names.
(a) CH3
CH3 CH2 CF
CH(CH3)2
(b) CH2 CH2 Br
CH3 CH2 CH2 CH CH2 CH2 CH3
(c)

(d)
CH 2Cl

2. Draw the structural formulae of the following compounds:

(a) tert-butylbromide
(b) 1-bromo-1-isopropylcyclobutane
(c) 4-bromo-3-methyl-2-pentene

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14.2 Chemical properties of haloalkanes
At the end of the topic, students should be able to:
a) Explain the nucleophilic substitution reaction of haloalkanes.
b) Explain SN1 and SN2 mechanism.
c) Compare the relative reactivities of 1, 2, and 3 haloalkanes toward hydrolysis or alcoholysis.
d) Explain the elimination reaction of haloalkanes.
e) Explain the use of haloalkanes in the synthesis of Grignard reagent, RMgX/ArMgX.
f) Describe the use of Grignard reagent in the preparation of alkanes, alcohols (1, 2, and 3) and
carboxylic acid.

3. State and write the reaction mechanism for each of the following reactions:
(a) CH3 CH3
NaOH(aq)
H3C C CH3 H3C C CH3
Br OH

(b) NaOH (aq)

CH3CH2Cl CH3CH2OH

(c) CH3 CH3 CH3

NaOH(aq)
CH3 C CH2 Br CH3 C CH2 OH + CH3 C CH2 CH3
CH3 CH3 OH
major product

4. Arrange the following compounds in order of decreasing reactivity toward SN2

reaction with aqueous solution of NaOH.
(CH3)2CHCH2Br, CH3CH2CH2CH2Br, (CH3)3CCH2Br

5. (a) Draw all four structural isomers of C4H9Br.

(b) Which of the isomers react most rapidly with aqueous NaOH through SN1
reaction?
(c) Choose two isomers which can react with KOH in ethanol to produce the same
alkene.

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6. Based on the given reaction scheme, suggest reagent X and structure P and Q.

CH=CH2 CH2CH2Br
X KCN
P

KOH (aq)

7. (a) Show how a Grignard reagent is prepared from 1-bromopropane.

(b) Draw the structure formed when the above Grignard reagent reacts with
(i) CH2O followed by hydrolysis
(ii) CH3CHO followed by hydrolysis
(iii) CH3COCH3 followed by hydrolysis
(iv) CO2 followed by hydrolysis
(v) H2O followed y hydrolysis

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8. Complete the mind map given:

NaOH(aq) H3C CH 2 OH
reflux

excess NH 3, ethanol
H3C CH 2 NH2
reflux

KCN(aq), ethanol
H3C CH 2 CN
reflux

NaOH, ethanol
H3C CH 2 Br H2O
reflux H3C CH 2 OH
reflux

CH 3OH
Mg dry ether H3C CH 2 OCH3
reflux

CH 3ONa
H3C CH 2 OCH3
reflux

CH 3COONa
reflux H3C CH 2 COOCH 3

H3C CH3 MgBr

+
H2O/H O
i) CO2
O i) H3C C H O
ii) H2O/H+
i) H C H i) H3C C CH3
ii) H2O/H+
+
ii) H2O/H ii) H2O/H+
O
H3C CH 2 C OH

OH
H3C CH 2 CH CH3

OH
H3C CH3
H3C CH 2 C H CH3
H H3C CH 2 C CH3

OH

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OBJECTIVE QUESTIONS
1. What is the IUPAC name for the following compound?
F Cl
Cl C C Cl
H Cl
A. chlorofluorocarbon.
B. trichlorofluoroethane.
C. 1-fluoro-1,2,2,2-tetrachloroethane
D. 1,1,1,2-tetrachloro-2-fluoroethane

2. Haloalkanes are more reactive than corresponding alkanes because

A. haloalkanes are ionic compounds.
B. haloalkanes are polar compounds.
C. haloalkanes are more soluble in water.
D. the size of the halogen atoms are bigger.

3. Which of the following compounds is least easily hydrolysed by aqueous sodium

hydroxide?
A. C6H4Br2
B. C6H5CH2Br
C. CH3CHClCH2CH2CH3
D. CH3CH2CH2CH2CH2Cl

4. Iodoethane reacts with hydroxide ion, OH, through SN2 mechanism.What is the
effect of doubling the concentration of OH?
A. The rate of reaction is doubled
B. The rate of reaction is quadrupled
C. The rate of reaction remains the same.
D. The rate of reaction decrease by factor of 2.

5. A bromoalkane, RBr, is hydrolysed by aqueous sodium hydroxide.The rate equation

for the reaction is
Rate = k[RBr][OH]

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R could be
A.

CH 2Br

B.

Br

C.
Br

D. (CH3)3CBr

CH 3 CH 2 Br KOHaq CH 3 CH 2 OH KBr 1
6.
CH 3 3 CBr KOH(ethanol) CH 3 2 C CH 2 KBr H 2 O 2

Which of the statements are true of these two reactions.

P Reaction 1 is an elimination reaction.
Q Reaction 1 occurs at room temperature.
R Reaction 2 occurs through the formation of carbocation.
S The rate of reaction 2 is independent of the concentration of OH- ions.

A. P and Q only.
B. P and S only
C. Q and R only
D. R and S only

7. Grignard reagents, RMgX are organometallic compounds. Which statement is true

about organometallic compounds?
A. It acts as a nucleophile.
B. It is a non-polar compound
C. It undergoes substitution reaction.
D. Its carbon atom has a positive charge.

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Summary of options
A B C D
I only I and II only II and III only I, II, and III

8. Which statement(s) is/are true about the reaction of 2-chloro-2-methylpropane with

aqueous sodium hydroxide?
I. The rate is dependent on the temperature.
II. The rate is proportional to the concentration of 2-chloro-2-methylpropane.
III. The rate is proportional to the concentration of aqueous sodium hydroxide.

9. What is the possible product, M of the following reaction?

Br
+
H
+ H2O M

I. OH

II. OH

III.
OH

10. Which of the following reagents can react with haloalkanes in a nucleophilic
substitution reaction?
I. OH
II. CN
III. NH3

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