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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
1,2-dichloroethene
1,2-dichlorocyclopropane
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
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.
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
Name of reaction
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
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 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
346
290
228
So, when C X bond is longer, lesser energy is required to break the bonding,
thus the rate increase
CX
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
Rate equation :
rate = k [C(CH3)3Br]
SN2 mechanism
Meaning
:
Occur at
:
Process
:
is the
intermediate
formed in
reaction
Rate equation :
rate = k [CH3CH2CH2CH2Br][OH-]
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
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
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
4.
Propylmagnesium bromide
butoxide ion
Step 2 : Hydrolysis in acid. Alkoxide (strong base) react with acid to form
alcohol + water.
butoxide ion
propylmagnesium bromide
ethanal
1-methylbutoxide ion
1-methylbutoxide
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
white
cream
yellow
soluble
soluble
insoluble insoluble
soluble
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
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
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
Initiation
F2ClCCl F2ClC + Cl
Propagation
O3 + Cl O2 + OCl
O3 + OCl 2 O2 + Cl
Termination
Cl + Cl Cl2
CH3CH=CHCH3
Elimination reaction
Reflux
Ethanolic sodium hydroxide
G : C6H5CH2OH
C6H5Cl does not react with hot ethanolic KOH, while C6H5CH2CH2Cl react with
hot ethanolic KOH.
Equation : C6H5CH2CH2Cl
C6H5CH=CH2
SN2 mechanism
Rate of reaction increase with the bond length. Since C-Br has longer bond
length than C-Cl, so it has high