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CHEMISTRY FORM 6

ORGANIC CHEMISTRY
CHAPTER 4
HALOALKANE

4.0
Haloalkane
 ~ derivatives of alkanes where one or more H is substitute with
halogen, X.
 ~ Homologous series of haloalkane is CnH2n+1X (where X may
represent Cl, Br and I)
 ~ compare to alkane, most haloalkanes are toxic and highly
carcinogenic
4.1
Nomenclature (Naming haloalkane)
 The way of naming haloalkane is similar to the way of alkane.
 Find the longest possible carbon chain that contain halogen in the
chain
 Find the branched alkyl and halogen attached. if there are more
than 1 branched substance, arrange them according to
alphabetical order.
 Give the numbering of branched alkyl or halogen accordingly.

2-chloropentane

2,3-dichloropent-2-ene
2-bromo-3-ethylpentane

2-chloro-4-methylhexane

1,3-dichlorocyclopentane

2-bromo-1-chlorobenzene
2-iodo-1-phenylpropane
1,1,1-trichloroethane

2,3-dibromo-3-methylbut-1-ene

4.1.1

Classification of Halogen

Primary haloalkane

Secondary haloalkane

Tertiary haloalkane

Example

Example

Example

20
10

20
20

30

4.2
Isomerism in haloalkane
 Haloalkane exhibit various types of structural and geometrical
isomerism
 In structural isomerism, haloalkane may exhibit a chain isomerism
and positional isomerism
 Example chlorobutane, C4H9Cl, exhibit chain and positional isomerism
Chain isomerism OR Positional isomerism

Not only it may exhibit structural isomerism, haloalkane sometimes


exhibit stereoisomerism
Geometrical isomerism may be exhibit when it involve haloalkene or
halocycloalkane

1,2-dichloroethene

1,2-dichlorocyclopropane

Some haloalkane easily shows an optical isomerism, as such in


the example above, chlorobutane.

4.3
Physical properties of haloalkane
1. Boiling point of haloalkane
 The trend of the boiling points of haloalkane bay be caused by many factors
a) Factors of the number of carbon atom

Boiling point increase


Explanation : When going down to homologous series, the boiling point increase. This
is due to the increase in relative molecular mass, which increase the weak Van Der
Waals forces causing boiling point increase.

b) Factors of the branched structure

Boiling point increase


Explanation : Straight chain molecule has a larger total surface area compare to a
branched chain molecule. Hence, greater the total surface area exposed, greater the
Van Der Waals forces, higher the boiling point.

c) Factors of different halogen used

Boiling point increase

Explanation : When going down to halogen group, the molecular mass increase,
causing a greater weak Van Der Waals forces which eventually resulting higher
boiling point.

2. Solubilities of haloalkane in water Even though CX is polar, haloalkane are


insoluble in water because they are not able to form hydrogen bond with
water. Though, it is soluble in organic solvent.
3. Density of haloalkane.
CCl4
Solubility trend :

Solubility decrease
Explanation :
When theres more substituent group of Cl, molecule become less polar.
As a result, polarity decrease and cause the solubility decrease.

4.4
4.4.1

Chemical Properties of Haloalkane


Preparation of Haoalkane

Name of reaction

Reagent used and


condition

Displacement of
alcohol

Hydrogen halide
(H X) catalysed
by zinc chloride,
propan-1-ol
ZnCl2 under reflux

Addition of
hydrogen halide
to alkene (see
Chapter 2)

Equation

hydrogen
chloride

1-chloropropane

Hydrogen halide
(HX)
(X = Cl ; Br ; I)

Other than the 2 above, some of the reaction like halogenation of alkene
(under UV) [refer Chapter 2] and halogenation of alkene may produce a
dihaloalkane compound

4.4.2

Reaction of Haloalkane

Name of reaction

Reagent used and


condition

Hydrolysis of
haloalkane

NaOH (aq)
under reflux

Formation of nitrile

KCN / ethanol
under reflux

Formation of amine
(alkylation)

concentrated NH3 /
ethanol

1-bromopropane

Formation of
alkene

NaOH /
conc. ethanol
under reflux

1-chloropropane

Formation of
organometallic
compound
(Grignard reagent)

Mg / ether

Equation

1-chloropropane

sodium
hydroxide

1-bromopropane potassium
cyanide

conc.
Ammonia

butanenitrile

propylamine

propene

CH3CH2CH2Br + Mg
1-bromopropane

propan-1-ol

magnesium

ether

CH3CH2CH2MgBr
propylmagnesium
bromide

1)


Hydrolysis of haloalkane
Haloalkane react moderately with sodium hydroxide, NaOH, under reflux
condition. OH- act as nucleophile and attack the C that is bond to the halogen
General equation for hydrolysis of haloalkane is

The rate of hydrolysis depend on the following factors


 The bonding of CX
 The class of haloalkane


The bonding of C X
 For a given alkyl group, the rate of hydrolysis of haloalkane increase from R
Cl to RI.
 This is because, CX become longer going down to halogen
Bond

C Cl

C Br

CI

Bond energy (kJ / mol)

346

290

228

So, when C X bond is longer, lesser energy is required to break the bonding,
thus the rate increase




The class of haloalkane


 For haloalkane with the same halogen atom, the rate of hydrolysis
increase in the order
30 haloalkane < 20 haloalkane < 10 haloalkane
 The extension of the reactivity of the class of haloalkane shall be discussed
in the mechanism.
The mechanism of the hydrolysis can be describe below
The reactivity of haloalkane is due to the polarity of the C X bond as
+

CX


The partially positively charges carbon atom is susceptible to attack by


nucleophile. In this substitution reaction, there are 2 types of mechanism to
discuss. SN1 mechanism and SN2 mechanism

SN1 mechanism
 Meaning
:
substitution of nucleophile in 1st order
 Occur at
:
Some 20 but mostly 30 haloalkane
 Process
:
Occur in 2 steps
Step 1 : Formation of carbocation

Step 2 : Nucleophilic attack

Rate equation :
rate = k [C(CH3)3Br]

SN2 mechanism
 Meaning
:
 Occur at
:
 Process
:

substitution of nucleophile in 2nd order


Some 20 but mostly 10 haloalkane
Occur in 1 steps

is the
intermediate
formed in
reaction


Rate equation :
rate = k [CH3CH2CH2CH2Br][OH-]

2. Formation of nitrile method of increasing the number of carbon.


 Haloalkane when react with alcoholic potassium cyanide causes halogen to be
substituted by cyanide ion to produce nitrile.

Haloalkane
Alkylnitrile
Example, when 2-chlorobutane reacts with ethanolic potassium cyanide under
reflux

2-chlorobutane
2-methylbutylnitrile
The nitril formed will further react to form either an amine or carboxylic
acid.

Name of reaction

Reagent used and


condition

Reduction of
nitrile

Lithium aluminium
tetrahydride
LiAlH4

Hydrolysis of
nitrile

Equation

2-methylbutylnitrile

2-methylbutylamine

2-methylbutylnitrile

2-methylbutanoic acid

Diluted sulphuric
acid H2SO4
under reflux

3. Formation of amine : alkylation reaction


 When haloalkane is dissolve using ethanolic concentrated ammonia (NH3)
solution, amine is formed.

Haloalkane
Alkylamine
 Unlike the reaction in the reduction of nitril, alkylation of haloalkane to
concentrated ammonia does not increase in number of carbon.
Example : Write out the chemical reaction when
 1-chlorobutane react with ethanolic concentrated ammonia

2-bromopentane react with ethanolic concentrated ammonia

If excess haloalkane is used, the reaction may further continue


until it forms a quaternary salt.

4.


Formation of alkene : An elimination reaction


When reacted with concentrated ethanolic sodium hydroxide,
elimination of HX occur and alkene is formed.

Unlike the formation of alcohol in (1), here, the hydroxide OH serve as


the base and remove H+ from haloalkane and at the same time, break
the CX bond and form alkene
Similar to the elimination learned earlier, according to Saytzeff rule, it
formed 2 products.
Example in the reaction below

5. Formation of Organometallic Compounds : Grignard reagent


 Grignard reagents are class of organometallic compound of magnesium
with the general formula of RMgX, where R is the alkyl group and X is
halogen
 Grignard reagent is prepared by dissolving haloalkane to magnesium
metal in dry ether

Grignard reagent is useful in producing different class of alcohol, by


reacting with aldehyde and ketone. In CMg, since C is more
electronegative, so C carries a partial negative charge (). Thus, it act
as a strong nucleophile which attack the C which carries partial
positive charge (+)

Formation of primary (1o) alcohol using Grignard reagent


 When reacting Grignard reagent with methanal, it form a primary alcohol.
Reaction occur in 2 steps where
 Step 1 : Addition of Grignard reagent. Grignard attack C atom of methanal to
form alkoxide ion

Propylmagnesium bromide


butoxide ion

Step 2 : Hydrolysis in acid. Alkoxide (strong base) react with acid to form
alcohol + water.
butoxide ion

butan-1-ol (1o alcohol)

Formation of secondary (20) alcohol using Grignard reagent


 Reacting Grignard reagent with aldehyde (except methanal), it
form a secondary (20) alcohol. Similar to the reaction in the formation of
primary alcohol, it occurs in 2 steps.
 Step 1 : Addition of Grignard reagent. Grignard attack C atom of
propanal to form alkoxide ion

propylmagnesium bromide


ethanal

1-methylbutoxide ion

Step 2 : Hydrolysis in acid. Alkoxide (strong base) react with acid to


form alcohol + water.

1-methylbutoxide

pentan-2-ol (2o alcohol)

Formation of tertiary (30) alcohol using Grignard reagent


 Reacting Grignard reagent with ketone will yield a tertiary (30)
alcohol.
 Step 1 : Addition of Grignard reagent. Grignard attack C atom of
butanone to form alkoxide ion

Step 2 : Hydrolysis in acid. Alkoxide (strong base) react with acid to


form alcohol + water.

Formation of carboxylic acid using carbon dioxide


 Reacting Grignard reagent with carbon dioxide will produce a carboxylic
acid. The steps of the formation of carboxylic acid from the reaction of
Grignard reagent with carbon dioxide are similar to those of the
formation of alcohol.
 Step 1 : Addition of Grignard reagent. Grignard attack C atom of
butanone and form a complex of magnesium salt.

Step 2 : Hydrolysis in acid. Alkoxide (strong base) react with acid to


form alcohol + water.

4.4.3 Other organometallic compound


 Organolithium can be prepared using the same way but required lower
temperature. Example, when 1-bromobutane react with lithium under
the presence of dry ether :

Tetraethyllead (IV) can be prepared by heating mixture of chloroethane


with alloy of sodiumlead (NaPb) according to the equation
4 CH3CH2Cl + 4 Na + Pb  (CH3CH2)4Pb + 4 NaCl

Tetraethyllead (IV) is used as an anti-block additive to increase the


octane number of petrol.

4.5
Chemical Test for haloalkane
4.5.1 Reaction of haloalkane with solution of silver nitrate
 The halogen which bond directly with C in haloalkane is readily to
dissociate with other substance. If an ethanolic silver nitrate is treated
to different halogen of haloalkane, different colour of precipitate will
formed. The results are described below.

Silver halide

AgCl

AgBr

AgI

Colour of silver halide

white

cream

yellow

Solubility in diluted ammonia solution

soluble

Solubility in concentrated ammonia solution

soluble

insoluble insoluble
soluble

From the colour of precipitate formed, solubility in dilute and


concentrated ammonia, Halogen in RX can be determined

insoluble

4.5.2
Alkaline hydrolysis of haloalkanes
 When haloalkane is hydrolysed (discussed in 4.4.2 (1) Alcohol can be formed
under such way.
R X + NaOH  ROH + NaCl
From the angle of alcohol, the class of haloalkane can be determined by using
different alcohol test.
4.6
Nucleophilic substitution of aryl halide
 Aryl halide ~ halogen attached to benzene ring directly.
 Compare to alkyl halide, aryl halide react less readily in nucleophilic
substitution reaction. Neither does it go through SN mechanism as explained
earlier. Under high temperature and pressure


The passiveness of the reaction of halo aryl is because


 The inductive effect of C X bonding when unhybridise p-orbital in
chlorine interact with the p-orbital in benzene ring, will cause a drift of
electron toward C atom in benzene ring, to which it actually decrease the
polarity between CX. thus the bond become shorter and harder to remove.
 The high charge density in alcohol ring repels the approaching negative
OH-. As a result, chlorobenzene react with NaOH (aq) with moderate speed

4.7
Application of Haloalkane in our Daily Life
 Chlorofluorocarbon (CFC) is alkane which all the hydrogen atoms are
substituted by other halogen atom. The commercial name of CFC is
called as Freon





Formula

Systematic name

Commercial name

CF2Cl2

Dichlorodifluoromethane

Freon 12

CFCl3

Trichlorofluoromethane

Freon 11

CFCl2CF2Cl (C2F3Cl3)

Trichlorotrifluoroethane

Freon 113

CFC has the following characteristics. They are volatile and odourless ;
non-toxic and non-corrosive ; inert to chemical reaction and they are
non-flammable. Because of these properties, CFC is used as solvents
for cleaning and as inert substance use as
i)
propellants in aerosol cans ii)
refrigerant
iii) blowing agents in the plastic industries
iv) fire extinguishers

Aerosol Propellant Freon12 (CF2Cl2) is suitable for use as an aerosol


propellant. Under high pressure in an aerosol can the propellant is
liquid but when valve is open, some of the liquid become vapour and
carries with the active component, for example insecticide, paint or
hair lacquer.
Refrigerants also used Freon-12 as it has a low boiling point (30oC).
It is widely apply as refrigerant in refrigerator and air-conditioner.
Freon-12 is liquefied by pressure in refrigerant. It is then vapourised
by sudden expansion and this give the cooling effect. Freon-12 is very
suitable for this purpose because it is unreactive and does not corrode
the machinery. Furthermore, Freon-12 is non-toxic and it is not
dangerous if theres a leakage.
Insecticides well known by DDT (dichlorodiphenyldichloroethane).
The structure of DDT is shown as the diagram below. It is best known
of a number of highly chlorinated aromatic compound. Used widely as
insecticide in the early 40-50s to control mosquitoes from spreading
malaria.

Since DDT is highly chlorinated, it is highly toxic. It also caused various kinds
of pollutions. DDT is very stable and does not decompose easily. This gives
an advantage as DDT stayed there and killed insects for weeks. Despite of
this property, it will stay permanently and accumulate in the soil.
Furthermore, DDT is fat-soluble and not water-soluble, when DDT is ingested
as a contaminant in food / water, it will concentrate in the fatty tissue of
living things and caused a toxic effect on the living things body, which will
results death. That is why, since 1972, many countries banned DDT.
Fire Extinguishers organic compound obtained by replacing halogen with
hydrogen are called halons. Example : (CBrClF2) well known as BCF ;
(CBr2ClF) or (CBrF3). Halon is used extensively as fire extinguishers as they
are chemically inert and denser than air. When sprayed at fired object, halon
effectively covered with dense vapour. Furthermore, combustion will produce
radical reaction where bromine radical (Br) is produced. These radicals then
combined with the object burned and eventually stopped the combustion

Solvent Freon-113 are used in industrially as solvent to


dissolve non-polar solutes. They are used to dissolve grease in
engineering equipment and electronic circuit. They are also used
in laundry for dry cleaning especially for textile materials
made of wool.
 Anaesthetics diethyl ether as first general anaesthetic used in
surgical practices, but due to its highly flammable and has side
effect of nausea, a modern fluorine base anaesthetics are used,
such as halothane, isoflurane and sevofkurane. They have
common features, which is contain a trifluoromethyl (CF3-)
group.
 Plastic the most well-known fluorine based polymer is known
as Teflon, where the monomer is CF2=CF2. This polymer is
chemically inert toward most of reagent and it is an excellent
insulator. It has a slippery feel and is best known for its used
as a coating for non-stick pans


E Effects of the haloalkane to the Environment.


 CFC and ozone depletion CFC are unreactive, and this inert
nature allow then to persist in atmosphere. CFC diffuse into the
stratosphere where they react with UV to form free radicals.
These highly reactive radicals react with ozone layer, therefore
deplete the ozone layer through these mechanisms

Initiation

F2ClCCl  F2ClC + Cl

Propagation

O3 + Cl  O2 + OCl
O3 + OCl  2 O2 + Cl

Termination

Cl + Cl  Cl2

From the reaction above, the ozone molecule eventually


converted to become oxygen according to the general equation :
2 O3 (g)
3 O2 (g)
 In order to reduce the depletion, an alternative source of HFC
(hydrofluoroalkane) such as CH2FCF3 is used to replace Freon12.


CH3CH=CHCH3
Elimination reaction
Reflux
Ethanolic sodium hydroxide

CH3CH2OH + OH-  CH3CH2O- + H2O

G : C6H5CH2OH

Type of reaction : nucleophilic substitution reaction

H, an ether, is formed when ethoxide ion react with G as CH3CH2O- is a strong


base, that react with G

C6H5Cl does not react with hot ethanolic KOH, while C6H5CH2CH2Cl react with
hot ethanolic KOH.
Equation : C6H5CH2CH2Cl

C6H5CH=CH2

I : sodium hydroxide under reflux


II : ethanolic sodium hydroxide under reflux

All 3 isomers react with Br2 via electrophilic additional reaction




Easiness of haloalkane to dissociate increase from CH3CHFCH2CH3 <


CH3CHClCH2CH3 < CH3CHBrCH2CH3 < CH3CHICH2CH3
This is due to bond length increase from C-F < C-Cl < C-Br < C-I
As for C6H5Cl, no precipitate is formed since benzene is an electron withdrawing
group
This will shortened C-Cl bond and caused no precipitate formed when AgNO3

SN2 mechanism

Rate of reaction increase with the bond length. Since C-Br has longer bond
length than C-Cl, so it has high

Reagent : sodium hydroxide


Condition : ethanolic under reflux

CO2 + 2 NaOH  Na2CO3 + H2O

RBr + NaOH  ROH + NaBr


Nucleophilic substitution reaction

a cream precipitate is formed


Ag+ + Br -  AgBr

Pale yellow solution turned brown


2 Br- + Cl2  2 Cl + Br2