MILLENNIA INSTITUTE

H2 CHEMISTRY (2018)

Organic Chemistry Tutorial : Halogen Derivatives

Name: _________________ Class: ______ Date: ________

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Section A: Bread and Butter
Structured Questions
1 Describe the mechanism of reaction between chloromethane and hot aqueous KOH.

Nucleophilic Substitution

2 Describe the mechanism of the reaction of bromoethane with hot excess ethanolic
ammonia.

Nucleophilic substitution

3 Describe the mechanism of reaction between (CH3)3CCl and hot ethanolic KCN.

Nucleophilic substitution (SN1)

4 Draw the structure of the organic product formed when 2-bromopropane reacts with the
following:
a) hot ethanolic NaOH
CH2=CHCH3
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b) hot aqueous NaOH

CH3CH(OH)CH3
c) hot ethanolic NaCN, followed by dilute H2SO4

d) excess hot ethanolic ammonia

Section B: Charging Forward!

MCQ
1) Which compound reacts with ammonia?
A bromoethane
B chlorobenzene
C ethanol
D phenol

2) Which of the following would react with aqueous silver nitrate to produce a precipitate that is
insoluble in dilute aqueous ammonia?
1 (CH3)4N+I-
2 C6H5Br
3 CaCl2

A 1 only
B 1 and 2 only
C 2 and 3 only
D 2 only

3) The following reaction scheme outlines the production of one of the monomers of nylon-6,6,
hexane-1,6-diamine, from 1,4-dibromobutane.

Step I Step II
BrCH2CH2CH2CH2Br NCCH2CH2CH2CH2CN H2N(CH2)6NH2
1,4-dibromobutane hexane-1,6-diamine

Which one of the following shows the reagents and conditions for each step?

Step I Step II

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A alcoholic NH3, heat aqueous KOH, room temperature

B alcoholic KCN, heat aqueous NaOH, heat

HCN, with trace amount of KCN,

C LiAlH4 in dry ether
10-20 °C

D alcoholic KCN, heat LiAlH4 in dry ether

4) Which one of the following statements is true about SN1 and SN2 mechanisms?

A SN1 is a one-step reaction.

B SN1 will cause an inversion in the configuration.

C SN2 results in the formation of a carbocation intermediate.

D SN2 is more likely to occur for CH3CH2CH2CH2Cl as compared to CH3C(Cl)(CH3)2.

5) When (chloromethyl)benzene, C6H5CH2Cl, is treated in succession with two reagents O and P, it

gives phenylethanoic acid, C6H5CH2CO2H. Which of the following is a possible combination for
reagents O and P?
O P
A NaOH (aq) K2Cr2O7 (aq)
B Cl2 (aq) NaOH (aq)
C NaCN (in aqueous ethanol) dilute H2SO4
D HCN (in presence of alkaline) dilute HCl

6) Anethole and estragole are organic compounds used in flavouring to provide the odour and taste
of anise and liquorice. Anethole and estragole are isomers of each other.

anethole estragole

Which of the following reagents and conditions can be used to synthesise estragole from
anethole in two steps? Assume that the CH3O– group is inert.

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Step 1
A Br2(l)
B HBr(g)
C H2O(g), acid catalyst,
high temperature and
pressure
D HCl(g)
Step 2
heat with KOH(aq)
heat with concentrated H2SO4
LiAlH4 in dry ether
heat with ethanolic NaOH

Structured Questions
1) The halogenoethanes C2H5Cl, C2H5Br and C2H5I differ in their physical properties and reactivities.
a. Suggest and explain how the boiling points of these three compounds differ.
B.p. increases from C2H5Cl to C2H5Br to C2H5I. As the electron cloud size increases
from C2H5Cl to C2H5Br to C2H5I. The larger the electron cloud size, the greater the ease
of distortion of the electron cloud, the stronger the instantaneous dipole-induced dipole
attractions, more energy is required to overcome these forces of attraction, the b.p.
increases.

b. Suggest and explain how the C–X bond polarities in these three compounds differ.
Electronegativity of Cl > Br > I as the size of atom increases down the group and
effective nuclear charge decreases. Thus bond polarity of C–Cl > C–Br > C–I;

c. Describe and explain how the reactivities of the three compounds differ towards
nucleophilic reagents.
Reactivity for nucleophilic reagents increases from C2H5Cl to C2H5Br to C2H5I. C2H5I is
most reactive as the C–X bond strength decreases down the group, the C–I bond is the
weakest and easiest to break.
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[5]
(N2008/3/1d)

2) Some reactions of 2-bromopropane are shown in reaction scheme below.

reaction C
CH3CH(OH)CH3 CH3CH=CH2

reaction A reaction B

reaction D reaction E
CH3CHBrCH3 X CH3CH(COOH)CH3

Ethanolic
reaction F concentrated reaction G
ammonia in excess,
heat in sealed tube

Y CH3CH(CH2NH2)CH3

Fill in the table below for each reaction shown above.

Reaction Reagents and Conditions Type of Reaction

Nucleophilic
A NaOH(aq), heat with reflux
substitution

B Ethanolic NaOH, heat with reflux Elimination

Electrophilic
C H2O(g), H3PO4 catalyst, high temp and pressure
addition
Nucleophilic
D Ethanolic KCN, heat with reflux
substitution

E HCl(aq), heat with reflux Acidic Hydrolysis

Ethanolic concentrated ammonia in excess, Nucleophilic

F
heat in sealed tube substitution
LiAlH4 in dry ether OR
G Reduction
Heat with H2 over Ni catalyst

3) Describe a simple chemical test to distinguish between the following pairs of compounds. State
your observations.
a. CH3CH2Cl and CH3CH2I

b. and

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a.
Reagent/condition: To a test tube containing the unknown, add NaOH(aq) and AgNO3(aq)
and warm. Then, slowly add NH3 until excess.
Observations: For CH3CH2Cl, a white precipitate forms which dissolves in excess
NH3.
For CH3CH2I, a yellow precipitate forms which is insoluble in excess
NH3.
b.
Reagent/condition: To a test tube containing the unknown, add NaOH(aq) and AgNO3(aq)
and warm. Then, slowly add NH3 until excess.
Observations:

For , a cream precipitate forms which dissolves only in

concentrated NH3.

For , no visible reaction is seen and no precipitate forms.

4) Draw the structures of the organic compounds formed for the following reactions and state the
type of reaction:
a. (CH3)2CHCH2Br with hot KOH in ethanol
(CH3)2C=CH2, elimination

b. (CH3)2CHBr heated with ethanolic KCN

(CH3)2CHCN, nucleophilic substitution

c. BrCH2CH2Br heated with excess CH3CH2NH2 in ethanol

CH3CH2NHCH2CH2NHCH2CH3, nucleophilic substitution (SN2)

d. heated under reflux with NaOH(aq)

, nucleophilic substitution (SN2)

[8]
5) Halogenoalkanes are readily hydrolysed by OH– ions to form alcohols.
Primary halogenoalkanes and tertiary halogenoalkanes are hydrolysed by different mechanisms.
a) Describe the mechanism of the hydrolysis of CH3CH2Br. In your answer show any relevant
charges, dipoles or lone pairs of electrons you consider to be important in this mechanism.
[3]
Mechanism is SN2 nucleophilic substitution reaction.

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‡–

b) The bromine atom in CH2=CHCH2Br is very reactive.

The bromine atom in CH2=CHBr is unreactive.
Suggest an explanation for the unreactivity of the bromine atom in CH2=CHBr. [2]
The carbon bonded to bromine in CH2=CHCH2Br has a partial positive charge and can
attract nucleophiles for reaction.
The carbon bonded to bromine in CH2=CHBr forms a double bond with the neighbouring
carbon. The C-Br bond is strengthened as a lone pair of electrons on Br can delocalise due
to the overlapping of the p-orbital of Br with the  orbitals of the alkene, making it unreactive.

6) (i) When chiral 2-chloroheptane, C7H15Cl reacts with ethanolic sodium cyanide, the optical
isomerism of the product is reversed.
Explain, with the aid of structural formula, why the optical isomerism is reversed.
(ii) Another compound A with the same molecular formula C7H15Cl also reacts with ethanolic
sodium cyanide. A, which is optically active, eventually loses its optical activity after reaction
with ethanolic sodium cyanide.
Give the structural formula of A and describe the mechanism of its reaction with ethanolic
sodium cyanide.
[6]

(i) This is because the SN2 reaction proceeds with an inversion of configuration.
H3C CH3
+  -
-
NC C Cl NC C + Cl
H
H
(CH 2)4CH 3 (CH 2)4CH 3

To illustrate the inversion in structural formula (3D wedge diagram)

(ii)
CH 2CH 3

H3C C Cl

CH 2CH 2CH 3
Isomer A:

Type of reaction: Nucleophilic Substitution (SN1)

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7) A student found a bottle of a liquid substance labelled Compound Z, which has a molecular
formula C6H9Br. He suggested that Compound Z has the following structure.
CH3

Br
(i) Plan two chemical reactions to confirm the presence of the functional groups in the
suggested structure. Include your observations and deductions for each test.
[4]
Test 1:
To a test tube containing the unknown, add NaOH(aq) and AgNO3(aq) and warm. Then,
slowly add NH3 until excess.
Observation: Cream precipitate of AgBr formed. Precipitate dissolves in concentrated NH3.
Deduction: It contains bromoalkane.

Test 2:
Add Br2(aq).
Observation: Orange Br2(aq) decolourises.
Deduction: It contains C=C double bond.

(ii) The reaction of compound Z with ethanolic KCN yields the following products in a 80:20
ratio:

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80% 20%

Deduce and describe the specific nucleophilic substitution mechanism of the reaction. [5]
Mechanism: Nucleophilic Substitution (SN1)

(iii) Explain clearly, in terms of stability of carbocation and/or steric hindrance, why
a. the specific nucleophilic substitution mechanism identified in (ii) is favoured
b. the two products in (ii) are not in 50:50 ratio. [4]
Modified from [PJC2011/P3/4]
a. Although carbocation formed is 2°, reaction mechanism is SN1 instead of SN2 because
the carbocation is resonance-stabilised due to the overlapping p orbitals of the adjacent
alkene carbons.
b. The 80% product is the major product as the corresponding carbocation is more stable.
It is a 3° carbocation with 3 electron donating alkyl groups compared to the 2°
carbocation with only 2 electron donating alkyl groups.

8) The molecules of compound P, C7H15Br, are chiral. On treatment with NaOH(aq), P produces
alcohol Q, C7H15OH, which does not react with hot, acidified Na2Cr2O7(aq). The elimination of
HBr from compound P produces a mixture of four different isomeric alkenes with the formula
C7H14, only two of which are cis-trans isomers of each other.

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Suggest the structural formulae of compound P and the four alkenes.

[4]
Modified from (N2008/3/1e)

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Section C: Hot and Spicy

1) Although phosphorus is present in numerous harmful chemicals, it is a useful feature in organophosphorus

compounds. Ylides are a class of organophosphorus compounds that are well-known for their role in the
Wittig reaction. The synthesis of methylpropene via the Wittig reaction is shown below.

CH3Br C4H9Li
P P CH3 P CH2 III
I II

(i) Name the type of reaction that occurs in step I and outline the mechanism for the reaction.

Nucleophilic Substitution (SN2).

H
–
P CH3 Br P C Br P CH3 + Br–
+ H H

(ii) Suggest why 2-bromo-2-methylpropane is not preferred in step I.

SN2 reactions are favoured by the lower steric hindrance in the 1° CH3Br compared to the 3°
(CH3)3CBr.
This is amplified by the fact that the PPh3 nucleophile is bulky due to its three phenyl groups on the
P atom (high steric hindrance).

(iii) State the role of butyl lithium, C4H9Li, in step II.

C4H9Li acts as a base.

Two resonance structures exist to stabilise the ylide used in step III above.

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P CH2 P CH2

In this step, tetrahydrofuran, THF, is used as an aprotic solvent – one that lacks an acidic hydrogen.

(iv) Explain why, unlike phosphorus, nitrogen cannot form organic compounds similar to ylides.
Nitrogen is a period 2 element and does not have energetically accessible vacant d orbitals in its
valence shell to accommodate electrons.
Hence, it cannot expand beyond the octet structure.

END

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