Nanyang Junior College

Chemistry (9729)

Lecture Notes 13
Halogen Derivatives

Lecturers: Mr Kevin Low & Mr Goh Kien Soon JC1/2024

Content
• Halogenoalkanes
(i) Nucleophilic substitution
(ii) Elimination
• Relative strength of the C-Hal bond
• Unreactivity of halogenoarenes

Learning Objectives
(a) recall the chemistry of halogenoalkanes as exemplified by
(i) the following nucleophilic substitution reactions of bromoethane: hydrolysis; formation of
nitriles; formation of primary amines by reaction with ammonia
(ii) the elimination of hydrogen bromide from 2-bromopropane
(b) describe and explain the mechanisms of nucleophilic substitutions in halogenoalkanes:
(i) SN1, in terms of stability of the carbocation intermediates
(ii) SN2, in terms of steric hindrance of the halogenoalkanes
(c) explain the stereochemical outcome in nucleophilic substitution involving optically active
substrates:
(i) inversion of configuration in SN2 mechanism
(ii) racemisation in SN1 mechanism
(d) interpret the different reactivities of halogenoalkanes and chlorobenzene with particular
reference to hydrolysis and to the relative strengths of the C-Hal bonds
(e) explain the unreactivity of chlorobenzene compared to halogenoalkanes towards
nucleophilic substitution, in terms of the delocalisation of the lone pair of electrons on the
halogen and steric hindrance
(f) suggest characteristic reactions to differentiate between:
(i) different halogenoalkanes
(ii) halogenoalkanes and halogenoarenes
e.g. hydrolysis, followed by testing of the halide ions
(g) explain the uses of fluoroalkanes and fluorohalogenoalkanes in terms of their relative
chemical inertness
(h) recognise the concern about the effect of chlorofluoroalkanes (CFCs) on the ozone layer
[the mechanistic details of how CFCs deplete the ozone layer are not required]

References

1. Chemistry for Advanced Level (2002) by Peter Cann & Peter Hughes
2. A-Level Chemistry (4th Ed) by E.N. Ramsden

1
 1 | INTRODUCTION AND NOMENCLATURE

Halogen derivatives are a class of compounds containing a halogen functional group.

When naming these compounds, the following prefixes are used: fluoro, chloro, bromo and
iodo.

These compounds can be classified into three groups:

1.1 Halogenoalkanes (Alkyl halides), R-X
1.2 Halogenoarenes (Aryl halides), Ar-X
O
1.3 Acid halides (Acyl halides), R-C-X

1.1. Halogenoalkanes (Alkyl halides)

General formula: CnH2n+1X or R-X (where R is an alkyl group)

These may be classified as primary (1o), secondary (2o) or tertiary (3o), according to the
number of carbon atoms attached directly to the carbon which carries the halogen.

Carbon
General carrying
Type Example Name
formula halogen
attached to…
Methyl halide - - CH3Cl chloromethane
H
Primary
one other CH3CH2CH2Br
alkyl halide R C H
carbon atom bromopropane
(1o)
X
R H
Secondary
two other CH3 C CH3
alkyl halide R C H 2-iodopropane
carbon atoms
(2o) I
X
R CH3
Tertiary
three other 2-bromo-2-
alkyl halide R C R CH3 CH2 C CH3
carbon atoms methylbutane
(3o)
X Br

2
1.2 Halogenoarenes (Aryl halides)
These compounds have a halogen atom attached directly to an aromatic carbon ring/aryl
group (Ar-X).
Br

Cl CH3 I
COOH

chlorobenzene 4-iodomethylbenzene 3-bromobenzoic acid

Due to the delocalisation of electrons, they are less reactive as compared to alkylhalides
(to be discussed in Section 8).

1.3 Acid halides (Acyl halides)

These compounds have a halogen atom attached to an acyl group.
O O
CH3 C Cl
Br
Ethanoyl chloride Propanoyl bromide

The reactions of these compounds will be examined in Chapter 16: Carboxylic Acids and
Derivatives.

Example 1: Complete the following table.

Structure/Formula Name Classification

(1o/2o/3o alkyl halide or aryl halide)

CH3 C CH2Br Primary alkyl halide

1-bromo-2-methylpropane
(1o RX)
CH3

Br Left: Secondary alkyl halide

(2o RX)
1,3-dibromobutane
Right: Primary alkyl halide
Br (1o RX)

Secondary alkyl halide

Iodocyclobutane
(2o RX)
I

Primary alkyl halide

(Chloromethyl)benzene
(1o RX)
CH22Cl

OH

Cl
2-chloro-3-iodophenol Aryl halide (Ar-X)

3
2 | PHYSICAL PROPERTIES

2.1 Boiling point

• Halogenoalkanes exist as simple molecular structure consisting of discrete
molecules held together by weak instantaneous-dipole induced-dipole
interactions between molecules.

The C–X bond is polar.

However, the molecule is largely non-polar due to the bulky alkyl group. Hence, the
most significant intermolecular force of attraction present is instantaneous-dipole
induced-dipole interactions.

At room temperature, CH3F, CH3Cl, CH3Br, CH3CH2F, CH3CH2Cl are gases whereas
other halogenoalkanes are liquids.

• Boiling points of R–X are relatively higher than their corresponding alkanes (with
same number of carbon atoms).

Explanation: Larger Mr of RX → increase in electron cloud size → electron cloud is

more easily polarised → more energy required to break the stronger instantaneous-
dipole induced-dipole interactions.

• For the same alkyl group, the boiling points increase in the order:
chloro < bromo < iodo

Compound CH3CH2CH2CH3 CH3CH2CH2CH2Cl CH3CH2CH2CH2Br CH3CH2CH2CH2I

Boiling
-0.5 77 102 130
point / oC

Explanation: Larger Mr → increase in electron cloud size → electron cloud is more

easily polarised → more energy required to break the stronger instantaneous-dipole
induced-dipole interactions.

• For constitutional isomers (same molecular formula i.e. same number of C atom
and containing the same halogen atom), boiling points decrease in the order:
1o > 2o > 3o

Compound CH3CH2CH2CH2I CH3CH2CHICH3 CH3C(CH3)ICH3

(1o) (2o) (3o)
Structure I
I
I
Boiling
point / oC 130 120 99

Explanation: Increase degree of branching → molecule becomes more spherical →

less surface area of contact → less energy required to break the weaker
instantaneous-dipole induced-dipole interactions.

4
2.2 Solubility
• Halogenoalkanes are not very soluble in water as energy released from the
formation of weak instantaneous-dipole induced-dipole interactions with water
molecules is insufficient to overcome the energy required to break the strong hydrogen
bonds between water molecules.
• They are good organic (non-polar) solvents e.g. CCl4 is used in the FRS reaction of
alkanes.

2.3 Density
• In general, halogenoalkanes are more dense than water due to the presence of heavy
halogen atoms.

3 | PREPARATION OF ALKYLHALIDES

(1) Free Radical Substitution of Alkanes

H H H H
+ limited X2
CH3 C C H CH3 C C H + other substituted products
u.v. light
H H H X
Note: This method is rarely used for synthesis as it gives a mixture of products.

(2) Electrophilic Addition of Hydrogen Halides to Alkenes

H H H H
+ HX(g) *Only the Markovnikov
CH3 C C H CH3 C C H
product is formed.
room temp
X H
Note: Markovnikov’s rule – The favoured product is the one that is formed via a more
stable (i.e. more substituted) carbocation.

(3) Electrophilic Addition of Halogen to Alkenes

H H H H
+ X2 in CCl4 *An alkyl dihalide
CH3 C C H CH3 C C H is obtained
room temp
X X
absence of u.v.

(4) Substitution of –OH group in alcohols [R-OH → R-X]

H H H H

CH3 C C H CH3 C C H

H OH H X

X Reagents and conditions

PCl5 or PCl3, room temp
Cl
OR SOCl2, room temp
PBr3 (or Br2 with red phosphorus), room temp
Br
OR NaBr and conc. H2SO4 (to form HBr), heat under reflux
I2 and red phosphorus (to produce PI3), heat under reflux
I
OR NaI and H3PO4 (to form HI), heat in-situ

5
 4 | REACTIONS OF HALOGENOALKANES

Halogenoalkanes undergo two types of reactions.

(1) Nucleophilic Substitution

H H H H
δ+ δ− −
C C X + Nu−

:
CH3 CH3 C C Nu + X
H H H H
The C-X bond is polar because the Nucleophile The halogen atom leaves
halogen atom is more as a halide ion.
electronegative as compared to
carbon i.e. C carries a partial The halogen atom is
positive charge δ+ while X contains being replaced by the
nucleophile
a partial negative charge δ–
⇒ substitution
⇒ C is electron deficient hence
susceptible to attack by
nucleophile

Nucleophiles
• Nucleophile means nucleus–seeking (seeking positive charge).
• Nucleophiles are electron-rich species that forms a bond by donating a lone pair of
electrons to an electron-deficient species.
• They are also Lewis base (lone pair donor).

Examples of nucleophiles:
Alkyl Halide Nucleophile Functional group formed
:OH– hydroxide R–OH (alcohol) + X–
H2O: water R–OH (alcohol) + HX
R’O: alkoxide
–
R–OR’ (ether) + X–
:CN– cyanide R–CN (nitrile) + X–
:NH3 ammonia R–NH2 (1o amine) + HX
R' R'
RX H N:
1o amine R N (2o amine) + HX
H H
R' R'
2o amine (3o amine) + HX
H N: R N
R'' R''
R' R' (quaternary ammonium salt) + X–
3o amine R +
R''' N: N
R'' R''' R''

(2) Elimination

H H CH3 H
base B
CH3 C C H C C + BH+ +X−
H H
H X

alkyl halide alkene

6
 5 | NUCLEOPHILIC SUBSTITUTION REACTION

(I) Reaction with aqueous sodium hydroxide

Type of Reaction Nucleophilic Substitution

Reagents NaOH(aq) [or KOH(aq)]
Conditions Heat under reflux
Purpose To convert to R–OH alcohol (of the same carbon length)
Equation H H H H
heat under H C C H + NaX
H C C H + NaOH
reflux
H X H OH
Note Halogenoalkanes can be hydrolysed slowly by water when heated.

H H H H

H C C H
heat under H C C H + HX
+ H2O
reflux
H X H OH

Reason:
Water is a weaker nucleophile as it is not negatively charged, hence
less attracted to the electron-deficient carbon centre.

(II) Reaction with ethanolic sodium cyanide

Type of Reaction Nucleophilic Substitution
Reagents Ethanolic NaCN
[could be presented as NaCN(alc) or KCN(alc) in some questions.
(alc) means alcohol is used as a solvent]
Conditions Heat under reflux
Purpose Step-up reaction:
To increase length of carbon chain by one C atom.
*The nitrile group can be subsequently converted into an acid or
amine.
Equation H H H H
heat under H C C C N + NaX
H C C H + NaCN (alc)
reflux
H X H H

7
 Note (1) Hydrolysis of nitrile to carboxylic acid

R&C (acidic hydrolysis): any dilute acid e.g. HCl(aq) or

H2SO4(aq), heat under reflux
H H H H

+ HCl + 2H2O heat H C CH H + NH4Cl

H C C H

H CN H COOH

nitrile acid

OR
R&C (alkaline hydrolysis): NaOH(aq) , heat under reflux
(followed by HCl(aq), room temp to convert salt back to acid)
H H H H H H
NaOH(aq) H C C H HCl(aq)
H C C H + NH3 H C C H
heat rm temp
-- ++
H CN H COO Na H COOH
COOH

nitrile carboxylate salt acid

(2) Reduction of nitrile to amine

H H H H

H C C H + 4 [H] H C C H

H CN H C
CH2NH2

nitrile 1o amine

Any of the following reducing agents can be used:

• LiAlH4 in dry ether, room temp
• H2 with Pd or Pt catalyst, room temp
• H2 with Ni, heat

Example 2: Suggest reagent and conditions for the reactions below.

n1 H3C
Reactio CH2NH2
H2C
CN
Reac
tion 2 H2C
CH2NH2

Answers:

Reaction 1: H2, Ni, heat

Reaction 2 : LiAlH4, dry ether, room temp

8
(III) Reaction with ethanolic ammonia

Type of Reaction Nucleophilic Substitution

Reagents Excess ethanolic NH3
[could be presented as NH3(alc) in questions]
Conditions Heat in a sealed tube (OR heat under pressure)
To prevent NH3 escaping because it is a gas
Purpose To convert to R–NH2 amines (of the same carbon length)
Equation H H H H
heat in a H C C H + HX
H C C H + NH3 (alc)
sealed tube
H X H NH2

RX 1o amine

Note The resulting product (1o amine) can act as a nucleophile as the
nitrogen contains a lone pair.

This can further substitute excess halogenoalkanes to form a secondary

amine (further substitution occurs).
H H H H
heat under H C C NHCH2CH3 + HX
H C C X + CH3CH2NH2
reflux
H H H H
RX
o
1 amine 2o amine

The substitution can continue until a quaternary ammonium salt is

obtained. The substitution stops because there is no more lone pair
available on an N atom in the quaternary ammonium salt.
H H
H H
heat under H C C N(CH2CH3)2 + HX
H C C X + (CH3CH2)2NH
reflux
H H H H
RX o
2 amine 3o amine

H H
H H
heat under H C C +N(CH CH ) + X−
H C C X + (CH3CH2)3N 2 3 3
reflux
H H H H
RX o
3 amine quaternary ammonium salt
(white crystalline solid with
high melting point)
Implications:
• Excess ammonia is used for mono-substitution (to obtain 1o amine)
because further substitution can take place if excess CH3CH2X is
present.
• To synthesise 2o/3o amine, the corresponding 1o/2o amine can be
used as a nucleophile (in excess).

9
6 | Nucleophilic Substitution Mechanism
In the overall reaction, the C–X bond is broken and a new C–Nu bond is formed.
H H H H
δ+ δ−
CH3 C C X + Nu− CH3 C C Nu + X−

H H bond broken bond formed

H H
Two different mechanisms are possible:

(1) Bond breaking of C–X bond followed by the formation of the new C–Nu bond:
SN1 [Substitution, Nucleophilic, unimolecular reaction (represented by “1”)]

(2) Simultaneous bond forming and bond breaking:

SN2 [Substitution, Nucleophilic, bimolecular reaction (represented by “2”)]

Note: “1” or “2” does not represent the number of steps. It represents the number of particles
that are involved in the rate determining step (e.g. the overall order of reaction).

The type of mechanism taking place depends on the type of RX molecule (1o, 2o, 3o) reacting,
among other factors.

Tip: Curve arrows in mechanism represent electron flow. Hence they start from a source of
electron (lone pair or bond pair). Charges should be balanced in each step.

6.1 SN1 mechanism

Step 1 : Formation of a carbocation (Slow)
In the first step, the polar C—X bond is broken and a carbocation ion intermediate is formed.
This is the rate-determining step.
CH3 CH3  Dipoles
slow +  Slow (r.d.s)
step 1: CH3 C X C + X−
δ+ δ− CH3  Curve arrow
CH3
CH3 starts from C–X
carbocation
intermediate bond and ends
on X.

Step 2: Nucleophilic Attack on the carbocation (Fast)

The second step is a fast attack on the carbocation intermediate by a nucleophile.
The carbocation is a strong electrophile (due to its positive charge) and hence attracts the
nucleophile strongly.
CH3 CH3  Curve arrow
+ .. fast
C + Nu − CH3 C Nu starts from lone
step 2:
CH3 CH3
CH3
pair on Nu and
carbocation ends on C+ (not +).
intermediate

The SN1 reaction follows first order kinetics.

Rate equation is rate = k [RX]
Rate is independent of [Nu], Nu does not appear in the slow step of the mechanism.

10
Energy profile diagram of a reaction by SN1 mechanism:

Ea1 Ea2

Nu
∆H < 0
+ Nu:−
Nu:−

11
Example 3: Draw step 2 of the SN1 mechanism for each of the different nucleophiles.

CH3 CH3
+ .. fast
C + Nu− CH3 C Nu
step 2:
CH3 CH3
CH3
carbocation
Consider (1) which atom bonds to carbon and (2) balance of charges/atoms carefully.
Draw your arrows precisely (think carefully about where they should start and end exactly).

Nucleophile Answer
CH3 CH3
+ ..
C + OH- CH3 C OH
OH— CH3 CH3
CH3
alcohol

CH3 CH3 H
+ .. +
C + H2O CH3 C O
CH3 CH3
CH3 H

CH3 H CH3
+
.. ..
CH3 C O + H2O CH3 C O + H3O+
CH3 H CH3 H
H2O
alcohol
• Check for two curved arrows for step 2 very carefully. They show
(1) H2O abstracting a proton (forming H3O+)
(2) O-H bond breaking (O+ gets the bond pair of electrons and as a result
becomes “neutral”).
• Understand how the charges are balanced in each step.
• This is a reversible step as it is a proton transfer between weak
acids/bases.

CH3 CH3 H
+ .. +
C + NH3 CH3 C N H
CH3 CH3 H
CH3

NH3
CH3 H CH3 H
+
.. ..
CH3 C N H + NH3 CH3 C N + NH4+
CH3 H CH3 H

amine
CH3 CH3
+ ..
C + CN− CH3 C CN
CN —
CH3 CH3
CH3
nitrile

12
6.1.1 Effect of substitution on SN1 mechanism
In the SN1 mechanism, the rate determining step is the formation of the carbocation.

The more stable The easier it is The faster the

the carbocation formed reaction

Recall alkyl groups are electron donating.

Electron-donating alkyl groups increase electron density on carbocation C centre thus
disperse the positive charge on the carbocation, hence stabilising the carbocation.

Highly substituted carbocations are more stable. Hence stability order:

R R H H

(most C
+
> C
+
> C
+
> C
+
(least
stable) R R R H R H H H stable)
o
3o 2 o
1 methyl

Thus, reactivity order for SN1 mechanism:

R H H H

(most R C X > R C X >R C X > H C X (least

reactive) R H H reactive)
R
3o 2o 1o methyl

In general, tertiary (3o) RX predominantly undergoes the SN1 mechanism.

6.1.2 Stereochemistry considerations in the SN1 mechanism

(This is relevant when product contains a chiral centre)
Recall in step 2 of the SN1 mechanism, the nucleophile attacks the carbocation:
1 1
R R
+ .. fast 2
C + Nu− R C* Nu chiral centre
step 2: 3
R
2 R
R
3 present in product
carbocation
The shape about the carbocation centre is trigonal planar (3 bond pairs and 0 lone pair).

The nucleophile can attack the trigonal planar carbocation centre from either the top or
bottom of the plane with equal probability, producing equal amounts of each enantiomer
(a racemic mixture).
Nu
- chiral centre present
.. − C 1 in product
+ Nu 2 R
2 R 3
R R
+ 1 - racemic mixture
C R mirror
3 3 obtained
R 2 R
.. R 1
− R - no observed optical
+ Nu
C
activity
Nu
The product mixture is optically inactive (i.e. does not rotate plane-polarised light) as each
enantiomer rotate plane-polarised light in the opposite direction by the same magnitude
hence the rotating powers of the enantiomers cancel out.

13
 6.2 SN2 mechanism
Bond breaking and forming occurs simultaneously in a single step.

− CH3
H3C H3 CH3
..
HO− + C X HO C X HO C + X−
δ+ δ− H
H
H H H H

pentavalent transition
state (unstable)

The C—X bond is polar. In the transition state, the C–OH is The C―OH bond then
partially formed and the C—Br is strengthens and the C―Br
OH– ion attacks the δ+ carbon partially broken (represented by bond breaks to form the
from the back (backside broken lines). products.
attack) to form an unstable The transition state only exists for
pentavalent transition state. an instant and cannot be isolated.

Reasons
o Like charges repel  Dipoles
o Large halogen impedes  Curve arrow 1 starts from lone pair on O and ends on C
approach of Nu  Curve arrow 2 starts from C–X bond and ends on X
 Check overall charge of TS based on nucleophile
 3D configuration (to show backside attack and inversion
of configuration)

The SN2 reaction is a single-step mechanism which follows overall second order kinetics.
Rate equation is rate = k [RX][OH–] or rate = k [RX][Nu]

Energy profile diagram of a reaction by SN2 mechanism:

Nu

Ea1

Nu
Nu:− ∆H < 0

14
Example 4: Draw the SN2 mechanism for reaction of 2-bromobutane with ammonia.

CH2CH3
H3C CH2CH3 CH2CH3
+
C X C X H3N C + X−
NH3 +
H H
H3C
CH3 H CH3 CH3

transition state

H CH2CH3 CH2CH3
+
NH3 + H N C H2N C + NH4+
H H
H CH3 CH3

(2) Transition state is not charged since NH3 is a neutral nucleophile

(3) Check the arrows for the second step. It’s a proton transfer between weak bases and acid
(hence reversible)

Answer:

CH2CH3
H3C CH2CH3 CH2CH3

.. C X H3N C X
+
H3N C + X−
NH3 + δ+ δ−
H H
H3C
CH3 H CH3 CH3

transition state

H CH2CH3 CH2CH3
.. +
NH3 + H N C H2N C + NH4+
H H
H CH3 CH3

15
6.2.1 Effect of substitution on SN2 mechanism
In the SN2 mechanism, the key consideration is the amount of steric hindrance around the
electron-deficient carbon centre (Cδ+) which affects its susceptibility to attack by nucleophile.

The least sterically The more susceptible The faster the

hindered the carbon it is to nucleophilic reaction
centre attack via SN2
mechanism

Bulky alkyl groups crowd the backside of the electron-deficient carbon centre, providing
greater steric hindrance to the incoming nucleophile.

H H H H3C
(least
H
C X > C X >H C C X > C X (most
hindered) H 3 H3C
hindered)
H H3C H3C H3C

methyl 1o 2o 3o

Highly substituted alkyl halides are the most hindered. Hence reactivity order for SN2
mechanism:
H H H R

(most H C X > R C X >R C X >R C X (least

reactive) H H R R reactive)
o
methyl 1 o
2 3o

In general, methyl and primary (1o) RX predominantly undergo the SN2 mechanism.

6.2.2 Stereochemistry considerations in SN2 mechanism

(This is relevant when product contains a chiral centre)
Recall in the SN2 mechanism, the nucleophile attacks from the backside.

X X−

The single step reaction involves nucleophile attacking from the direction directly
opposite the group that leaves (backside attack). This results in an inversion of
stereochemical configuration during the reaction.

Recall reasons for backside attack (as discussed on Page 14):

(i) Like charges repel (ii) Large halogen impedes approach of nucleophile

Effect on optical activity:

In the above example where a chiral alkyl halide is used, the product will be an alcohol with
an inversion in configuration.

16
Example 5: Complete the following table to compare the two nucleophilic substitution
mechanisms.

SN1 Factor SN2

rate = k[RX] Rate law rate = k [RX][Nu]

2 No. of steps 1

Mechanism
Carbocation intermediate Pentavalent transition state
proceeds via…
Factor: Stability of carbocation Factor: Steric hindrance
around Cδ+
Effect of
Relative rates for different substitution Relative rates for different
types of RX: 3o > 2o > 1o types of RX: 1o > 2o > 3o

Type of RX: 3o Predominated by… Type of RX: 1o

Stereochemistry
Racemic mixture obtained of product Inversion
(relevant when it
contains a chiral centre)
Optical Activity
Optically active. Rotates plane-
Optically inactive of product polarised light in opposite
(relevant when it direction compared to RX rxt.
contains a chiral centre)

Energy profile
See Page 11 diagram See Page 14

6.3 Additional notes about Nucleophilic Substitution Mechanism

• Overall, we expect 1o alkyl halides to react predominantly by the SN2 mechanism,

3o alkyl halides to react predominantly by the SN1 mechanism.
• However, there may be some exceptions. We will discuss them in Tutorial Question 11.

• In reality, the reaction of an alkyl halide may be a combination of both mechanisms,

especially secondary halides, illustrating a continuum from 100% SN1 to 100% SN2.

• For 2o alkyl halide, the rate law/order with respect to Nu and the optical activity of the
products will provide information on the type of mechanism.

17
7 | ELIMINATION REACTION

Type of Reaction Elimination

Reagents Ethanolic NaOH
[could be presented as NaOH(alc) or KOH(alc) in questions]
Conditions Heat under reflux
Purpose To eliminate H and X atoms to form a double bond (alkene)
Equation H H H H
heat under
H C C H + NaOH (alc) H C C H + NaBr + H2O
reflux
H Br
alpha carbon
alkyl halide alkene

Under alcoholic conditions, NaOH acts as a base rather than a

nucleophile and abstracts an alpha proton readily.
This is an elimination reaction NOT nucleophilic substitution reaction.

Note Saytzeff’s Rule:

In an elimination reaction, the predominant product is the one which
contains the more highly substituted double bond i.e. the major
product is the alkene that has the greater number of alkyl groups
attached to C=C.

(if Ha is eliminated)
H H
H H H H
NaOH, ethanol
H C C C C H H C C CH2CH3
heat under
Ha Cl Hb H reflux
but-1-ene
2-chloro butane (minor)
+
(if Hb is eliminated)
H H H CH3
C C C C
H3C CH3 H3C H
cis-but-2-ene trans-but-2-ene
(major) (major)
There are 3 possible isomeric butenes that are formed in this reaction.

Note: The more highly substituted the C=C, the more stable the alkene.

R R R R R H R H

> > >

R R R H R H H H

most stable least stable

(4 alkyl groups) (1 alkyl groups)

18
Nucleophilic Substitution v.s. Elimination of RX
When a halogenoalkane is subjected to a strong base like OH—, BOTH elimination and
nucleophilic substitution take place simultaneously and compete with each other.

The predominant reaction that occurs is controlled by the solvents:

aqueous NaOH
• RX ROH (Nucleophilic substitution to form alcohol)
Heat under reflux

ethanolic NaOH
• RX C=C (Elimination to form alkene)
Heat under reflux

Example 6: Suggest the products for following reactions.

1
+ NaOH (aq)
heat under
I reflux OH

2 Ethanolic NaOH is heated under reflux with 3-bromo-3-methylpentane

H H H
H C H H C H H C
H H ethanolic NaOH H H H H
CH3 C C C CH3 heat under CH3 C C C CH3 CH3 C C C CH3
H Br H
reflux H
H H
major minor
*The major product exhibits cis-trans isomerism hence there are three isomeric
products in all. You only need to draw the cis and trans isomers if the question context
requires so.

 Self check: Tutorial Q1-5

19
 8 | ARYLHALIDES

Chemical Properties
Arylhalides contain two functional groups: benzene and aryl halide.

 They undergo electrophilic substitution reactions associated with benzene.

 They do not undergo nucleophilic substitution (unless under vigorous conditions)
because:

Cl Cl

(i) The p–orbital of Cl in chlorobenzene overlaps with the π electron cloud of the
benzene ring, resulting in the delocalisation of lone pair of electrons on the Cl
atom into the benzene ring. This introduces a partial double bond between C and
Cl and strengthening the C–Cl bond.
(therefore the bond is stronger than that in an alkyl halide)

(ii) The rear side of the C–X bond is sterically hindered by the bulky benzene ring.

(iii) The high electron density of the aromatic ring repels the approaching nucleophile.

Preparation

Electrophilic Substitution of benzene

X
Cl

+ X2 + HX

X Reagents and Conditions

Cl2(g), anhydrous AlCl3, room temp
Cl or Cl2(g), anhydrous FeCl3, room temp
or Cl2 with finely divided Fe, room temp
Br2(l), anhydrous FeBr3, room temp
Br or Br2(l), anhydrous AlBr3, room temp
or Br2 with finely divided Fe, room temp

20
Comparison of halogen derivatives

R–Cl Cl 2Cl
CH Cl
Cl
Compound
(chloromethyl)benzene Chlorobenzene

Functional
Alkyl halide Benzene + alkyl halide Aryl halide
group

Delocalisation Within benzene ring Between benzene

No
of electrons only ring and chlorine

Nucleophilic No (under vigorous

Readily
substitution conditions only)

Elimination Forms alkene No elimination

Electrophilic
No Yes, in the benzene ring
substitution

Other
— Oxidation of side chain —
reactions

21
 9 | DISTINGUISHING TESTS FOR HALOGEN DERIVATIVES

The halogen derivatives can be identified from their halide ions by two methods.

Method 1
(1) Addition of NaOH(aq) and heat
Nucleophilic substitution to release halogen as halide X—.
R–X + NaOH(aq) → R–OH + NaX

(2) Addition of dilute HNO3(aq)

To remove excess NaOH(aq), otherwise Ag2O will be precipitated in step 3 when
AgNO3 is added.
HNO3 + NaOH → NaNO3 + H2O

(3) Addition of AgNO3(aq)

Precipitation of AgX. RX can be identified based on colour of ppt.
X— + Ag+ → AgX(s)

Observations:

R–I R–Br R–Cl Cl

Cl

Immediate Immediate Immediate

yellow ppt, cream ppt, white ppt, No white ppt.
AgI AgBr AgCl
Note: Ppt formed immediately as OH— is a strong nucleophile and substitution is complete
(and X− formed) in step 1 before Ag+ is added in step 3.

(4) Addition of aqueous/concentrated ammonia (if required)

It may be difficult to distinguish between the colours when there is not much precipitate.
An additional solubility test in aqueous/ concentrated NH3 can be carried out to confirm
the identity of the AgX precipitate.
Ag+(aq) + 2NH3(aq) ⇌ [Ag(NH3)2]+(aq)
Ag+(aq) + X− (aq) ⇌ AgX(s)
*Refer to Chapter 19 on Group 17 Halogens for explanation.

Observations:

AgI AgBr AgCl

Yellow ppt Cream ppt White ppt
insoluble in excess insoluble in excess dissolves in excess
aqueous and concentrated aqueous NH3. aqueous (& concentrated)
NH3. NH3 to form a colourless
Cream ppt solution.
dissolves in excess
concentrated NH3 to form a
colourless solution.

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Method 2
R&C: ethanolic AgNO3, warm
Equal amounts of ethanolic silver nitrate or ethanolic silver ethanoate are added to the alkyl
halides respectively and the mixture warmed in a water bath.

Note:
Ethanolic solvent (water + ethanol) increases the solubility of organic RX.
Ethanol and water acts as a weak nucleophile so relative rates of substitution can be observed.

R–X + CH3CH2OH + Ag+ → R–OCH2CH3 + AgX(s) + H+

R–X + H2O + Ag+ → R–OH + AgX(s) + H+

Observations:

CH3CH2I CH3CH2Br CH3CH2Cl

Cl
Iodoethane Bromoethane Chloroethane

Yellow ppt, Cream ppt, White ppt, No ppt formed

AgI formed AgBr formed AgCl formed due to strengthening
immediately. after a while. after a long time. of the C–X bond
(see Page 20).

Explanation:
Rate of hydrolysis depends on the strength of the C—X bond.
Down the group, atomic radius of halogens increases.
Hence bond length increases: (shortest) C–Cl < C–Br < C–I (longest). Note: We cannot
explain in terms of
Orbital overlap becomes less effective down the group and bond polarity as it
bond strength decreases: (strongest) C–Cl > C–Br > C–I (weakest). would not explain the
observed trend.
Down the group, the weaker C-X bond is broken more easily.
Hence rate of hydrolysis: (slowest) RCl < RBr < RI (fastest)

OR Use Bond Energies (MUST quote if qn says “Using the data booklet”)
Bond BE / kJ mol-1
C–Cl 340
C–Br 280
C–I 240
Down the group, bond energy of the C—X decreases.
Degree of orbital overlap becomes less effective,
hence less energy is needed to break the weaker bonds.

Rate of hydrolysis: (slowest) RCl < RBr < RI (fastest)

Note: A similar test may be carried out to compare the reactivities of 1o, 2o and 3o alkyl halides.
See appendix 11.2 for the expected results and explanation.

 Self check: Tutorial Q6,7

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 10 | FLUOROHALOGENOALKANES

Fluorohalogenoalkanes are commonly known as chlorofluorocarbons (CFCs) or industrially

as Freons. As the name suggests, these are organic compounds containing only chlorine and
fluorine e.g. CF2Cl2, C2Cl2F4. Bromine may be present sometimes, but not hydrogen.

Properties and Uses

These compound have some useful properties:
• Inert and stable (C–F bond is very strong)
• Non-flammable (no C–H bonds)
• Non-toxic
• Odourless
• Good organic solvents

They are used as refrigerants, cleaning agents, aerosol propellants, fire retardants, foaming
agents used to manufacture styrofoam cups.

Their inertness and stability made them very ideal chemicals but created a lot of environmental
issues for us.

Environmental concern
• In the atmosphere, the CFCs are inert and non-biodegradable and have life spans
up to 100 years.

• They can diffuse into the stratosphere (20km above the Earth’s surface) where they
absorb ultraviolet light which causes the C–Cl bonds to break homolytically and
release Cl free radicals.

• These Cl radicals deplete the ozone layer by attacking the ozone molecules in
the ozone layer, converting them to oxygen molecules.

• Ozone depletion endangers us from u.v. radiation which can cause skin cancer in
human and widespread failure in crops cultivation.

Mechanism for depletion of ozone by CFCs (FYI only)

(i) Formation of Cl free radicals
CF3Cl 
CF3 + Cl
The C–Cl bond is weak enough to be broken homolytically by ultraviolet light.

(ii) Destruction of ozone

Cl + O3 ClO +O2

(iii) Ozone on its own, also absorb UV to form

O3 O2 + O (natural ozone depletion)

(iv) Regeneration of Cl free radicals

ClO + O Cl +O2

24
 11 | APPENDIX

11.1 Elimination Mechanism (E2)

Extracted from http://www.chemguide.co.uk/mechanisms/elim/elim.html#top

In elimination reactions, the hydroxide ion acts as a base - removing a hydrogen as a hydrogen
ion from the carbon atom adjacent to the one holding the bromine.

The resulting re-arrangement of the electrons expels the bromine as a bromide ion and
produces propene.
−
HO:
H CH3 H CH3
−
H C C H C C +H2O + Br
H Br H H

That’s why for the elimination reaction (pg 18 lecture notes), the products are NaBr and H2O,
not HBr.

11.2 Comparison of reactivities of 1o, 2o and 3o bromoalkane

Test:
Equal amounts of ethanolic silver nitrate or ethanolic silver ethanoate are added to the
alkyl halides respectively and the mixture warmed in a water bath.

Observations:
H H CH3

H C CH2CH2CH3 CH3 C CH2CH3 CH3 C CH3

Br Br Br
1-bromobutane 2-bromobutane 2-bromo-2-methylpropane
(1o) (2o) (3o)
Cream ppt, AgBr formed Slight cream ppt, AgBr formed Cream ppt, AgBr formed
after a long time. after a while, thickens with immediately.
time.
Note: Bromoalkanes are used as they have moderate reaction rates.

Explanation:
The rate of reaction depends on the mechanism undergone.
3o alkyl halides react quickly via the SN1 mechanism to release the halide.
1o alkyl halides react more slowly via the SN2 mechanism.
2o alkyl halides undergo a bit of both mechanisms.

25
11.3 Grignard Reagents
Extracted from http://www.chemguide.co.uk/organicprops/haloalkanes/grignard.html and
Chemistry for Advanced Level (2002) by Peter Cann & Peter Hughes

What is a Grignard reagent?

A Grignard reagent has a formula RMgX where X is a halogen, and R is an alkyl or aryl (based
on a benzene ring) group. For the purposes of this page, we shall take R to be an alkyl group.
A typical Grignard reagent might be CH3CH2MgBr.

The preparation of a Grignard reagent

Grignard reagents are made by adding the halogenoalkane to small
bits of magnesium in a flask containing ether solvent. The flask is fitted
with a reflux condenser, and the mixture is warmed over a water bath
for 20 - 30 minutes.

Everything must be perfectly dry because Grignard reagents react with

water (see below).

An example of a reflux setup

Reactions of Grignard Reagents

Because magnesium is more electropositive than carbon, the C–Mg bond is polarised
Cδ––Mgδ+. This causes Grignard reagents to act as nucleophiles in their reactions, acting rather
like carbanions:

CH3CH2 MgBr ⇌ CH3CH2– + MgBr+

Grignard reagents react with water to give alkanes:

2 CH3CH2 MgBr + 2H2O 2CH3CH3 + MgBr2 + Mg(OH)2

They can also react with carbonyl compounds as a nucleophile to form the respective alcohols
in a nucleophilic addition reaction.

O OH
+ CH3CH2MgX R C R
C
R R
CH2CH3
ketone 3o alcohol
O OH
+ CH3CH2MgX
C H C R
H R
CH2CH3
aldehyde o
2 alcohol

You can try drawing the mechanism for the reaction after we have covered carbonyls.

26