S C O R E A S K 0 2 5 : H A L O A L K A N E S |Chapter 8 – 69

Chapter 7: Haloalkanes

PSPM 2011 / 2012

Q. 1 For the reaction of bromopropane, E below: 5m

CH3CH2CH2Br CH3OK
E H
DD
(a) Name the class of compound H.
(b) Name the type of reaction that converts E to H.
(c) Show the mechanism for the formation of H.

Answer (a) Ether

(b) SN2 or nucleophilic substitution bimolecular

(c)
CH2CH3
CH3CH2    CH2CH3
slow    fast
C Br CH3O C Br H3CO C

- H
CH3O H
H H H
H
Transition state

PSPM 2012 / 2013

Q. 2 (a) Draw the structure of the products B through F in the reaction below. 5m

Br O

Mg i) CH3CCH3
B C
dry ether ii) H3O+

KCN

H2O/H2SO4
i) LiAlH4
E D F
+
ii) H 3O
 S C O R E A S K 0 2 5 : H A L O A L K A N E S |Chapter 8 – 70

Answer (b)
B= C=

D= E=
C N

NH2

F=

Q. 2 (b) What does the symbol SN stand for? Explain using an appropriate chemical 11 m
equation, what you understand by an SN reaction of an alkyl halide.
An alkyl halide V, C5H11Br undergoes hydrolysis to form an alcohol W, C5H12O.
alcohol W becomes cloudy immediately when reacted with a Lucas reagent.
Deduce the structures of V and W. State and propose the mechanism for the
conversion of V to W.

Answer (b)(b) SN = Nucleophilic substitution

RX + Nu- RNu + X- OR give example

RX = any alkyl halide
Nu-= any nucleophile other than X
X is substituted by Nu-

W = 30 alcohol
CH3 CH3
H3C C Br H3C C OH
CH2 CH2
CH3 CH3

V W
 S C O R E A S K 0 2 5 : H A L O A L K A N E S |Chapter 8 – 71

SN 1
Mechanisme
CH3 CH3
slow -
H3C C Br H3C C+ + Br
H2O CH2 CH
CH2 3

CH3
O-H
H
CH3 CH3
CH3 fast + fast
H3C C O-H H3C C OH
H3C C+
H CH2
CH2 CH CH2
3 H-O
CH3 CH3
H

Remark:
If structure V is wrong, still can get mark max 2M as long as V is 3° alkyl halide

PSPM 2013 / 2014

Q. 3 (a) The reaction of an alkyl halide, X, with sodium methoxide, NaOCH3, produces 10 m
1-methoxybutane.

Using a suitable justification, propose the structure of X. Write the mechanism

for the formation of 1-methoxybutane. Name this mechanism.

If sodium methoxide is replaced with methanol, what is its effect on the rate of
reaction above? Explain your answer. Give another factor that influences the
rate of reaction.

Answer (a)(a)
X = CH3CH2CH2CH2Br

Primary alkyl halide @ reaction occur at C1

H H H H

H H
C Br OH3C C Br Br C

H3CH2CH2C CH 2CH 2CH 3

CH2CH2CH3

-
CH3O

Type of reaction: Bimolecular nucleophilic substitution (SN2).

The reaction rate decreases because CH3OH is a weak nucleophile.

Concentration of R-X @ Nucleophile.

 S C O R E A S K 0 2 5 : H A L O A L K A N E S |Chapter 8 – 72

Q. 3 (b) Compound C reacts with reagent D to give unsaturated compounds, E and F. 8m

CH3 reagent D

Cl
E + F

Compound C

(i) Draw the structure of E and F. Label the major product.

(ii) Explain how the major product is determined.
(iii) State reagent D.
(iv) What is the function of D? Explain your answer.

Answer (b)
CH2
(i) CH3

E (major) F *Note: Structure E and F are interchangeable

(ii) Saytzeff / Zaitsev Rule

Highly or more substituted alkene is more stable

(iii) D: C2H5ONa, C2H5OH,heat @ KOH, ethanol, ∆,

Note: OH- or any RO- can be used

(iv) Base
It removes proton from alkyl halide

PSPM 2014 / 2015

Q. 4 (a) TABLE 1 shows the relative rates of SN2 reactions for alkyl halides. 8m

Class of Alkyl Compound Relative rate

halide
Methyl bromomethane 30
1o bromoethane 1
2o A 0.03
3o 2-bromo-2-methylpentane B

TABLE 1
Explain the relationship between the class of alkyl halide with the relative rates
(i)
of reaction.
Give one example of compound A (a four carbon alkyl halide)
(ii)
Predict the value of B. Give your reason.
(iii)
Reaction of bromoethane with NaCN, NH3, and NaOCH3 gives C, D, and E
(iv)
respectively. Draw the structures for C, D, and E.
 S C O R E A S K 0 2 5 : H A L O A L K A N E S |Chapter 8 – 73

Answer (a) (i) Relative rate of SN2 reaction is higher for primary alkyl halide (or less hindered)
compared to tertiary alkyl halide (highly hindered) @ vice versa

(ii) 2-bromobutane @ 2-chlorobutane @ 2-iodobutane

(iii) Zero @ less than 0.03

(iv) Tetiary alkyl halide does not favor SN2 due to bulkiness (steric hindrance)

C: CH3CH2CN
D: CH3CH2NH2
E: CH3CH2OCH3

Q. 4 (b) Arrange the following alkyl bromides in order of decreasing reactivity towards 10 m
SN1 reaction. Explain your answer.

2-bromopropane, 1-bromopropane, 2-bromo-2-methylpropane

Write the chemical equation for the methanolysis of the most reactive alkyl
bromide in SN1 reaction above. Propose the mechanism for this reaction.

Answer ((b)
2-bromo-2-methylpropane > 2-bromopropane > 1-bromopropane

2-bromo-2-methylpropane is a tertiary alkyl halide which will form the most

stable tertiary carbocation.

(CH3)3Br + CH3OH ∆ (CH3)3COCH3 + HBr

Mechanism:
CH3OH

+ -
(CH3)3C Br (CH3)3C + Br

+ -
(CH3)3COCH3 Br (CH3)3COCH3 + HBr

H
 S C O R E A S K 0 2 5 : H A L O A L K A N E S |Chapter 8 – 74

PSPM 2015 / 2016

Q. 5 (a) Draw the structure of the product formed when 1-bromopropane reacts with 4m
the following reagents respectively:
(i) ammonia
(ii) methanol
(iii) sodium cyanide
(iv) water

Answer (i) CH3CH2CH2NH2

(ii) CH3CH2CH2 OCH3
(iii) CH3CH2CH2 CN
(iv) CH3CH2CH2 OH

Q. 5 (b) Draw and name the mechanism for the reaction between 1-bromopropane with 4m
sodium cyanide.
Answer ((b) Mechanism : SN2
(b)b)
- CH2CH3
CH3CH2CH2 Br + CN NC Br CH3CH2CH2CN
H H

Q. 5 (c) Pentanoic acid can be prepared from 1-butanol, F , as shown below: 7m

CH3CH2CH2CH2OH

F
PCl 5

Mg i. X
G H CH3CH2CH2CH2COOH
Dry ether ii. Y

(i) Draw the structures of G and H.

(ii) State reagents X and Y.
(iii) Give the reagent needed to prepare F from 1-butene.
(iv) Suggest an alternative two-step reaction to convert G to pentanoic acid.

Answer (c) (i) G : CH3CH2CH2 CH2Cl

H : CH3CH2CH2 CH2MgCl

(ii) X : CO2
Y : H3O+ @ H2O /H+ H2O,H+
(iii) (i) HBr , H2O2 , (ii) NaOH
-
CN H3O+
(iv) G CH3CH2CH2 CH2 CN CH3CH2CH2 CH2COOH
@ KCN
(ii) @ NaCN
 S C O R E A S K 0 2 5 : H A L O A L K A N E S |Chapter 8 – 75

Q. 5 (d) An alkyl bromide EE reacts with CH3CH2OH to give FF, whereas compound 10 m
CH3COOCH(CH3)CH2CH3 is formed when EE is treated with a
nucleophile.Dehydrohalogenation of EE produces GG which obeys Saytzeff`s
rule.
Deduce the structures of EE, FF, GG and nucleophile. Write reaction equation for
all reactions involved.

Answer alkyl bromide, EE + nucleophile

CH3 O
CH3CH2C O CCH3

H
CH3

EE : 2° alkyl halide : CH3CH2C Br

H
O

nucleophile O CCH3 :

FF is an ether yield from the reaction between alkyl halide and alcohol.

FF : CH3
CH3CH2C O CH2CH3

H
Saytzeff’srule : more highly substituted product.

GG : H H
C C
H3C CH3

Reaction equation :

CH3 O CH3 O
CH3CH2C Br + O CCH3 CH3CH2C O CCH3

H H

CH3 CH3
CH3CH2C Br + CH3CH2OH CH3CH2C O CH2CH3

H H

CH3 H H
KOH
CH3CH2C Br C C
ethanol H3C
H CH3
 S C O R E A S K 0 2 5 : H A L O A L K A N E S |Chapter 8 – 76

PSPM 2016 / 2017

Q. 6 (a) State and show the mechanism for the reaction of 1-bromobutane with the
hydroxide ion. 4m

Answer (a) Mechanism : SN2

H3CH2CH2C
CH2CH2CH3 CH2CH2CH3
- C Br
OH slow fast
H OH C -
H OH C Br + Br
H
H H
H

Q. 6 (b) 1-chloropropane reacts with KCN in ethanol under reflux to form HH. Reduction
of HH produce JJ while hydrolysis of HH using aqueous acid, under reflux gives 5m
KK. Grignard reagent of 1-cholropropane reacts with ethanal to form LL. Show
the formation of this Grignard reagent. Draw the strucyures of HH, JJ, KK, LL and
write the chemical equation for the formation of JJ and LL.

Answer
CH 2 CN
HH H3C CH 2

CH 2 CH 2
JJ H3C CH 2 NH2
O
CH 2 C OH
KK H3C CH 2

CH 2 CH 2 CH CH 2
LL H3C CH 2 CH3 @ H3C CH 2 CH3
OH
OMgCl

CH2 Mg CH2 MgCl

Cl H3C
H3C CH2 dry ether CH2

CH2 H2 CH2 CH2

CN H3C
H3C CH2 NH2
CH2 Pt
JJ
@ i) LiAlH 4
+
ii) H 2O/H

CH2 MgCl i) CH 3CHO CH2 CH

H3C H3C CH2 CH3
CH2 +
ii) H 3O OH
LL
 S C O R E A S K 0 2 5 : H A L O A L K A N E S |Chapter 8 – 77

PSPM 2017 / 2018

Q. 7 (a) Treatment of 2-bromo-2-methylbutane with water yields compound E. The 10 m

dehydration of E gives compounds F and G.

(i) State the reagent and reaction condition used in the dehydration of E.
(ii) Draw the structural formulae of compounds E, F and G.
(iii) Indicate the major product formed in the dehydration reaction. Explain your
answer.
(iv) Draw the mechanism for the formation of E.

Answer (a) (i) conc. H2SO4, heat/reflux/∆ @ H3PO4, heat/reflux/∆

(ii) E = CH3CH2C(CH3)(OH)CH3
F/G = CH3=CHC(CH3)2
G/F = CH2=C(CH3)CH2CH3

(iii) CH3CH=C(CH3)2
Follow Saytzeff’s rule

(iv)
CH3
CH3 CH3 CH3
CH3 CH3
H3C
H3C H3C H2O
+ +
O
Br
H H

H2O

CH3
H3O
+
+ CH3
H3C

OH
 S C O R E A S K 0 2 5 : H A L O A L K A N E S |Chapter 8 – 78

Q. 7 (b) Grignard reagent is a versatile tool in synthetic organic chemistry. Using 10 m

bromocyclopentane as a starting material, show how a Grignard reagent, X, is
synthesized.

(i) Reaction of X with water produces compound Y while treatment in carbon

(ii) dioxide followed by hydrolysis forms compound Z. 3-methyl-2-butanone reacts
(iii) with X and hydrolyses to yield compound AA. Draw the structural formulae of
compounds Y, Z and AA and write the chemical equations respectively.

Answer (b(b)
((b) Br MgBr
Mg
dry ether
X
(Grignard reagent)

COOH OH

Y Z AA

+
H2O, H @
MgBr
H2O
Y

i. CO2 COOH
MgBr
+
ii. H3O
Z

MgBr i. CH3COCH(CH3)2 OH
+
ii. H 3O
AA
 S C O R E A S K 0 2 5 : H A L O A L K A N E S |Chapter 8 – 79

PSPM 2018 / 2019

Q.8 Two organic compounds D and F with molecular formula C4H9Br react with
suitable reagents to form E and G via SN1 and SN2 reactions respectively. Both E 8m
and G have a molecular formula of C4H10O.

(a) Draw the structural formulae for D, E, F and G.

Answer (a) D: E:

CH3 CH3

Br C CH3 HO C CH3

CH3 CH3

F : CH3CH2CH2CH2Br @ ( CH3 )2CHCH2Br

G : CH3CH2CH2CH2OH @ ( CH3 )2CHCH2OH

(b) Suggest reagents for the formation of E and G.

Answer (b) E : H2O

G : NaOH @ KOH

(c) Write the mechanism for the formation of E.

Answer (c) CH3

+
CH3 CH3 H3C C OH 2

H3C C Br H3C C+ CH3

H2O
CH3 CH3 H2O

-H+

CH3

H3C C OH

CH3