Haloalkanes

Haloalkanes are halogen derivatives of alkanes in which one or more H from

alkane are replaced by halogen (-F, -Cl, -Br and –I). It is represented as R-X, where R
is an alkyl group and X is a halogen atom. General formula is CnH2n+1X. Where n = 1,
2, 3, 4 etc. Thus,
-H
R-H R-X
+X

Classification of haloalkanes:- Depending upon the number of halogen atoms

present in the compound it may be classified as:
1. Monohaloalkanes:- Haloalkanes containing only one halogen atom per
molecule. It is of three types. CnH2n+1X.
a) Primary haloalkanes:- In such haloalkanes carbon bearing –X must
have two H-atoms. eg.
CH3-Cl, CH3-CH2-I, CH3-CH2-CH2-Cl.
b) Secondary haloalkanes:- In such haloalkanes carbon bearing –X
must have one H-atom. eg.

CH3-CH-CH3
|
Cl
2-Chloropropane
c) Tertiary haloalkanes:- In such haloalkanes carbon bearing –X have
no H-atom. eg.
CH3
|
CH3-C-Cl
|
CH3
2-Chloro-2-methylpropane
2. Dihaloalkanes:- They contain two halogen atoms per molecule. It is of two
types. CnH2nX2.
a) Geminal dihalide:- Two halogen atoms are on same carbon. eg.
Cl
|
CH3-C-H
|
Cl

b) Viccinal (vic) dihalide:- Two halogens are present on adjacent

carbon. eg.
Cl-CH2-CH2-Cl
1,2-dichloroethane

3. Trihaloakanes:- These haloalkanes contain three halogen atoms per

molecule. CnH2n-1X3. eg.
CH-Cl3
Chloroform

1
 CH2-Cl
|
CH-Cl
|
CH2-Cl
1,2,3-Trichloropropane
4. Tetrahaloalkanes:- These haloalkanes contain four halogen atoms per
molecule. eg.
Cl
|
Cl-C-Cl
|
Cl
Carbon tetrachloride
Nomenclature
Aliphatic halogen compounds are named according to both of the following two
ways.
1. Common system:- In common or trivial system, the monohalogen
derivatives of alkane are named as alkyl halide. eg.

2. IUPAC system:-In IUPAC system, the monohalogen derivatives are named

by prefixing the word halo before the name of the parent alkane. Placing a
numeral before the prefix indicates the position of halogen atom and carbon
atom having the halogen on it gets the lowest number. eg.

2
 Isomerism in haloalkanes
Haloalkanes exhibit two types of structural isomerism.
1. Chain isomerism:- Haloalkanes containing four or more carbon atoms show
chain isomerism in which the isomers are differ in the chain of carbon atoms.
eg. C4H9Cl has two chain isomers.
i) CH3-CH2-CH2-CH2-Cl
1-Chlorobutane
ii) CH2-CH-CH3-Cl
|
CH3
1-Chloro-2-methylpropane

C5H11Cl has four chain isomers.

i) CH3-CH2-CH2-CH2-CH2-Cl
1-Chloropentane

ii) CH3-CH-CH2-CH2-Cl
|
CH3
1-Chloro-3-methylbutane

3
 CH3
|
iii) CH3-C-CH2-Cl

CH3
1-Chloro-2,2-dimethylpropane
CH3
|
iv) CH3-CH2-CH-CH2-Cl
1-Chloro-2-methylbutane
2. Positional isomerism:- Haloalkanes containing three or more carbon atoms
show positional isomerism in which the isomers differ in the position of the
halogen atom. eg. C3H7I has two positional isomers.
i) CH3-CH2-CH2-I
1-Iodopropane
ii) CH3-CH-CH3
|
I
2-Iodopropane
General methods of preparation of monohaloalkanes
Haoalkanes are generally prepared from either hydrocarbons or alcohols.
1. From alkanes:- Alkanes react with halogens in suitable condition such as
light, heat or suitable catalyst to form haloalkanes and reaction is called
halogenation. This reaction is free radical substitution reaction.
h or heat
R-H + X2 ( Cl or Br) R-X + HX
Sunlight
CH4 + Cl2 CH3-Cl + HCl
(limited) Chloromethane
Heat
CH4 + Br2 CH3-Br + HBr
(limited) Bromomethane
If an excess of halogen is used, a mixture of mono-, di-, tri- and
poly-substituted haloalkane is formed.

CH4 + Cl2sunlightCH3Cl Cl
2 CH2Cl2 Cl2 CHCl3 Cl2 CCl4
-HCl -HCl -HCl -HCl

Iodination of alkane is reversible because HI is a strong reducing

agent and I2 least reactive hence reduces iodoalkane back to alkane. For this, it
is carried out in presence of a strong oxidizing agent such as conc. HNO3,
HIO3 etc. to stop the reversibility.

CH4 + I2 CH3I + HI

5HI + HIO3 3I2 + 3H2O

When alkanes larger than ethane are halogenated, isomeric products are
formed then major product is considered on the basis of reactivity of different
hydrogen towards halogenation. The reactivity of alkane is 3o> 2o> 1o towards

4
 halogen. Thus the product obtained by replacing 3oH is major than that of the
2oH and so on.
Cl
CH3- CH2-CH3 2 CH3-CH-CH3 + CH3-CH2-CH2-Cl
| 1-Chloropropane
Cl
2-Chloropropane
(major)
CH3 CH3 
 
CH3-C-H + Cl2h CH3-C-Cl + CH3-C-CH2-Cl + HCl
heat
CH3 CH3 CH3
2-Methyl propane2-chloro-2-methylpropane1-chloro-2,2-dimethylpropane
(major) (minor)
2. From Alkene:-Alkenes add with hydra acid of halogen ( HCl, HBr, HI) to
form alkyl halides as electrophilic addition product.

CH2=CH2 + HX CH3-CH2-X
Alkene Haloalkane
The addition of halogen acid to unsymmetrical alkene, Markownikoff’s rule is
followed and secondary and tertiary haloalkanes are obtained.

R-CH=CH2 + HX R-CH-CH3

X

CH3-CH=CH2 + HBr CH3-CH-CH3

Propene 
Br
2-bromopropane
But in the presence of organic peroxide the addition takes place via free
radical formation according to antimarkownikoff’s rule.
Peroxide
CH3-CH=CH2 + HBr CH3-CH2-CH2-Br
Propene 1-Bromopropane

Note:-Antimarkownikoff’s rule applies to the addition of HBr only and not in

case of HCl and HI because H-Cl bond is stronger, which cleavage to give .Cl
is unfavorable while in case of H-I bond .I radical formed immediately
combine with each other to form I2 rather than forming C-I bond.

3. From alcohol:- Haloalkanes can be prepared from alcohol in the following

different ways.
a) Using halogen acids:- Alcohol reacts with halogen acids in presence
of dehydrating agent like anhydrous ZnCl2 or conc. H2SO4 to give

5
 haloalkanes.
anhyd.ZnCl or conc.H SO
R-OH + HX 2 2 4 R-X + H2O
Heat
alcohol haloalkane
Eg.
C2H5-OH + HCl(g)anhyd.ZnCl2 C2H5-Cl + H2O
Heat
ethanol chloroehtane

C2H5-OH + HBr(g)conc.H2SO4 C2H5-Br + H2O

Heat
ethanol bromoehtane
HI is more reactive than HCl and HBr, reacts in absence of dehydrating agent.
C2H5-OH + HI(g)Heat C2H5-I + H2O
ethanol iodoehtane
Similarly, tertiary alcohol is more reactive than 1o and 2o, reacts in absence of
dehydrating agent.
CH3 CH3

CH3-C-OH + conc. HCl CH3-C-Cl + H2O

CH3 CH3
2-methyl-2-propanol 2-chloro-2-methyl-propane
Note:- ZnCl2 is Lewis acid, coordinates withthe oxygen atom of alcohol. As a
result, cleavage of C-O bond easily occurs.
# Secondary and tertiary bromides and iodides cannot be prepared from the
respective alcohols because these alcohols in heating with conc. H 2SO4
undergo dehydration to alkene.
b) Using phosphorus halides:- When alcohol is refluxed with
phosphorus halide (PX3 or PX5), haloalkane is obtained.

3R-OH + PX3heat 3R-X + H3PO3

alcohol alkyl halide

R-OH + PX5heat R-X + POX3 + HX

Alcohol alkyl halide

C2H5-OH + PCl3heat 3C2H5-Cl + H3PO3

ethanol chloroethane

CH3-CH-CH3 + PCl5heat CH3-CH-CH3 + POCl3 + HCl

 
OH Cl
Propane-2-ol 2-chloropropane
Bromo and iodoalkane are prepared by heating alcohol with red P4 and
bromine or iodine instead of PBr3 and PI3 respectively they are unstable in
nature.
P4 + 6Br2 heat 4PBr3

3C2H5-OH + PBr3heat 3C2H5-Br + H3PO3

ethanol bromoethane
heat
P4 + 6I2 4PI3

6
 3C2H5-OH + PI3heat 3C2H5-I + H3PO3
ethanol iodoethane
c) Using thionyl chloride (SOCl2):- Suitable alcohol is refluxed with
thionyl chloride in the presence of pyridine, chloroalkane is obtained.

R-OH + SOCl2reflux R-Cl + SO2 + HCl

alcohol thionyl chloride alkyl chloride

C2H5-OH + SOCl2reflux C2H5-Cl + SO2 + HCl

ethanol chloroethane
Note:- Bromo and iodoalkanes cannot be prepared by this method
because SOBr2 and SOI2 are unstable in nature.
Properties
Physical properties
1. Physical state and odour:- Lower members i.e. chloromethane,
bromomethane and chloroethane are gases. Iodomethane and other alkyl
halides up toC18 are sweet smelling liquids, but still higher members beyond
C18 are colourless solid.
2. Solubility:- Alkyl halides are insoluble in water because they cannot form H-
bond with water but soluble in organic solvent.
3. Boling point:- Haloalkanes have higher boiling and melting points than that
of respective alkanes. This is due to the presence of polar C-X bond, which
increases intermolecular force of attraction.
Boiling point of haloakanes increases with increase of number of
carbon atom due to increase of molecular mass, which increases Vander Waal
force. eg.
CH3-Cl < CH3-CH2-Cl < CH3-CH2-CH2-Cl
Boiling point also increases from chloroalkane to iodoakane keeping
same number of carbon atom due to increase in size and mass of halogen atom
increases Vander Waal force. eg.
CH3-Cl < CH3-Br < CH3-I
In case of isomeric haloalkanes, boiling point decreases from
primary to tertiary haloalkane with increase of branching of alkyl group. With
increase in branching, the molecule attains spherical shape with less surface
area. As result intermolecular force decreases, which in turn decrease the
boiling point.

CH3
|
CH3-CH2-CH2-CH2-Cl > CH3-CH-CH2-Cl > CH3-C-Cl
||
CH3CH3
4. Density:- Density increases with increase of size of halogen atom, so
chloroalkanes are lighter than water while bromo and iodoalkanes are heavier
than water. With increase of size of alkyl group, the densities go on
decreasing.
Chemical properties
Reactivity

7
Due to the difference in electronegativity of carbon and halogen, carbon gets partial +
ve charge and the halogen atom get partial –ve charge. As a result polarity of C-X
bond, which makes the haloalkane more reactive.
Reactivity of haloalkane increases from chloro- to iodoalkane with increase
of size of halogen atom due to decrease of C-X bond energy.

CH3-Cl < CH3-Br < CH3-I

Similarly, reactivity of haloalkane increases from primary to tertiary

haloalkane with increase of number and size of alkyl groups. Because alkyl groups
show +I, effect. As a result, the C-X bond becomes more and more polar and hence
the halogen atom can be substituted easily.
Tertiary haloalkane > Secondary haloakane > Primary haloakane
Chemical reaction
Haloakanes undergo the following types of reactions.
A. Nucleophilic substitution reaction:-The presence of partial +ve charge on carbon
atom makes it susceptible to attack by electron rich groups (nucleophiles) in which a
nucleophile stronger than the halide ion approaches the positively charged carbon
atom of an alkyl halide, the halogen atom along with its bonding pair gets displaced
and a new bond with the carbon and the nucleophile is formed. Such reactions are
called nucleophilic substitution reactions.

a)Rxn with aq. KOH:- Haloalkane when heated with aqueous KOH or moist Ag2O,
undergoes hydrolysis to give alcohol.

R-X + K+OH-(aq) Heat

R-OH + KX
Haloakane alcohol
Heat
CH3-CH2-I + KOH CH3-CH2-OH + KI
Iodoethane ethanol
Heat
CH3-CH2-Br + Ag2OH CH3-CH2-OH + AgBr
Bromoethane ethanol
b)Rxn with sodium or potassium alkoxide:- When haloakane is heated with
sodium or potassium alkoxide, ether is formed. This rxn is called Williamson’s
synthesis.

R-X + K+OR- Heat

R-O-R + KX
Haloakane ether

Heat
CH3-CH2-I + CH3-CH2-OK CH3-CH2-O-CH2-CH3 + KI
Iodoethane pot.ethoxide eythoxyethane
Haloalkanes can also be converted into ethers by heating with dry silver oxide.

8
 Heat
2CH3-CH2-Br + Ag2O CH3-CH2-O-CH2-CH3 + 2AgBr
Bromoethane eythoxyethane
c) Rxn. with pot.cyanide:- When haloalkane is heated with alcoholic KCN,
alkanenitrile is obtained, which is important synthetic reagent.

R-X + alc.K+ CN- Heat

R-CN + KX
Haloakane alkanenitrile
Heat
CH3-CH2-Br + KCN CH3-CH2-CN + KBr
Bromoethane propane nitrile
Alkane nitrile can further be converted into acid amides, carboxylic acids,
primary amines under different conditions.
# Partial hydrolysis in presence of conc. HCl or alkaline H2O2 gives amide.

O

conc.HCl
CH3-CH2-CN + H2O CH3-CH2-C-NH2
or H O /OH-
Propane nitrile 2 2 propanamide
# Complete hydrolysis with dilute acid or alkali gives carboxylic acid.
dil. HCl
CH3-CH2-CN + H2O CH3-CH2-COOH + NH3
or dil. NaOH
Propane nitrile propanoic acid
# Reduction in presence of H2/Ni or LiAlH4 or Na/C2H5OH gives primary amines.
LiAlH
CH3-CH2-CN + 4[H] 4 CH3-CH2-CH2-NH2
or Na/C H OH
Propane nitrile 2 5 1-aminopropane
d)Rxn with AgCN:-Haloalkanes react with alcoholic AgCN to give alkyl isocyanide
or alkyl carbylamines.

R-X + alc.AgCN R-NC + AgX

Haloakane alkyl isocyanide

CH3-CH2-Br + alc.AgCN CH3-CH2-NC + AgBr

Bromoethane ethyl isocyanide

4[H] Na/C2H5OH

CH3-CH2-N-CH3

H
Ethyl methylamine
e)Rxn with nitrite group:- When haloalkane is treated with NaNO2 or KNO2, alkyl
nitrite is formed.

Haloalkane sodium nitrite alkyl nitrite

9
 CH3-CH2-I + NaNO2 CH3-CH2-O-N=O + NaI
Ethyl iodide ethyl nitrite
If alcoholic AgNO2 is used, it gives nitroalkane. This is due to the covalent nature of
AgNO2.

silver nitrite nitroalkane

CH3-CH2-I + alc.AgNO2 CH3-CH2-NO2 + AgI

Ethyl iodide nitroethane
f) Rxn with ammonia:- When haloalkane is heated with alcoholic ammonia in
sealed tube at 100oC, primary amine is formed.

R-X + NH3Heat R-NH2 + HX

Haloakane aminoalkane

CH3-CH2-Cl + NH3Heat CH3-CH2-NH2 + HCl

Chloroehtane aminoethane
If alkyl halide is in excess then reaction will go further up to the formation of
3o amine and finally quaternary ammonium salt, called Hoffmann’s ammonolysis
process.

2) Elimination reaction (dehydrohalogenation):-When haloalkane with -hydrogen

atom is boiled with alcoholic KOH, undergoes elimination of hydrogen halide
resulting in the formation of alkene called -elimination reaction because the -
hydrogen atom of haloalkane is removed and also called dehydrohalogenation due to
removal of hydrogen halide.

Boil
CH3-CH2-Cl + alc.KOH CH2=CH2 + KCl + H2O

10
 Chloroehtane ethene
Br

Boil
CH3-CH-CH2 + alc.KOH CH3-CH=CH2 + KBr + H2O
2-Bromopropanepropene

Haloalkane containing two -carbon atoms then the elimination takes place from the
-carbon atom with less number of H-atoms and this is called Saytzeff’s rule.
Cl

CH3-CH2-CH-CH3 + alc.KOHBoilCH3-CH=CH-CH3+ CH3-CH2-CH=CH2 + HCl
2-Chlorobutane 2-butene (major) 1-butene (minor)

3) Formation of Grignard reagent:- When haloakane is treated with metallic

magnesium in presence of dry ether, alky magnesium halide called Grignard reagent
is obtained.
Dry ether
R-X + Mg R-Mg-X
Grignard reagent
Dry ether
CH3-CH2-I + Mg CH3-CH2-MgI + HCl
Ethyl iodide ethyl magnesium iodide
4) Wurtz reaction:-Alkyl halides when treated with sodium metal in presence of
ether form alkanes with twice the number of carbon as in alkyl halides.
Dry ether/Heat
R -X + 2Na + X-R R-R + 2NaX
alkane
Dry ether/Heat
2CH3-CH2-Cl + 2Na CH3-CH2-CH2-CH3 + 2NaCl
Chloroethane butane
Alkanes with even number of carbon can be prepared by this method.
Unsymmetrical alkane cannot be prepared because mixture of alkane is obtained,
which can not be isolated.
Dry ether/Heat
CH3-I + 6Na + CH3CH2-I CH3-CH3 + CH3CH2-CH2CH3 + CH3CH2CH3
Iodomethan iodoethane ethane butane propane

5) Reduction:- Haloakane undergoes reduction to give alkane having same number

of carbon with reducing agent such as Zn/HCl, Sn/HCl, Na/C2H5OH, LiAlH4.

R -X + 2[H]LiAlH4 R-H + HX
alkane
LiAlH
CH3-CH2-Cl + 2[H] 4 CH3-CH3 + HCl
Chloroethane ethane

Polyhaloalkanes
Organic compounds having more than one halogen atoms in its molecule are
called polyhalogen compounds. eg.

CH2-Cl2 Br-CH2-CH2-Br CH3-CHBr2

Dichloromethane 1,2-Dibromoethane 1,1-Dibromoethane

11
(Methylene chloride) (Ethylene bromide) (Ethyledene bromide)

CHCl3 CHBr3 CHI3

Trichloromethane Tribromomethane Triiodomethane
(Chloroform) (Bromoform) (Iodoform)

CCl4
Tetrachloromethane
(Carbontetrachloride)

Trichloromethane (Chloroform)
It is the simplest trihalogen compound in which three hydrogen atoms of
methane are substituted by three chlorine atoms.
Principle:-Chloroform is prepared in lab by heating ethyl alcohol or acetone with
aqueous suspension of bleaching powder where bleaching powder acts as an
oxidizing, chlorinating and hydrolyzing agent.

CaOCl2 + H2O Ca(OH)2 + Cl2

A.From ethanol. O

CH3-CH2-OH + Cl2Oxidation CH3-C-H + 2HCl
Ethanol ethanal
O O
 
Chlorination
CH3-C-H + 3Cl2 CCl3-C -H + 3HCl
Ethanal Trichloroacetaldehyde
(chloral)

B. From propanone.

O O
 
CH3-C-CH3 + 3Cl2Chlorination CCl3-C –CH3 + 3HCl
Propanone Trichloroacetone
(1,1,1-trichloropropanone)

12
Procedure:- The paste formed by mixing bleaching powder and water is taken in a
R.B. flask and rest of apparatus is fitted as shown in below.

Fig: Lab preparation of chloroform.

Then ethanol or acetone is added to it. The content of flask is heated gently on a water
bath until a mixture of chloroform and water distils over. The mixture from receiver is
transferred into a separating funnel and lower dark layer of chloroform is separated.
Impure chloroform is washed with NaOH solution and then with water in the
separating funnel. Finally it is dried over anhydrous CaCl2 and redistilled at 61oC.
This is pure CHCl3.
Physical properties:-
1) Colorless liquid with boiling point 61oC and freezing point -63oC.
2) Sweet sticky smell.
3) Sparingly soluble in water but soluble in alcohol, ether etc.
4) Heavier than water.
5) It has anesthetics effect.
Chemical properties
1)Oxidation:- Chloroform itself is not poisonous but when exposed to light and air it
form carbonyl chloride (phosgene), which is highly poisonous.

2CHCl3 + O2Sunlight2COCl2 + 2HCl

Phosgene
To prevent formation of COCl2 it is filled in dark brown bottle up to the
stopper in order to keep out air. A small amount of ethanol (0.6-1%) is also added at
the time of packing to convert phosgene to a non-poisonous diethyl carbonate.

2) Reduction:- Chloroform can be reduced with nascent hydrogen in presence of

ethanol in acidic medium to methylene chloride while in neutral medium it gives
methane.

13
 Zn/HCl
CHCl3 + 2[H] CH2Cl2 + HCl
ethanol
methylene chloride
Zn/H O
CHCl3 + 6[H] 2 CH4 + 3HCl

3) Rxn with silver powder (Dehalogenation):-Chloform when heated with silver

powder, acetylene is obtained.

4) Rxn with conc HNO3:- Chloroform reacts with conc. nitric acid in presence of
heat to give nitrochloroform which is used as an insecticide and tear gas.

Cl Cl

Cl-C-H + HO-NO2Heat Cl-C-NO2 + H2O

Cl Conc.Cl
Nitrochloroform
(Chloropicrin)
5)Rxn with propanone:- Chloroform condenses with propanone in presence of base
such as KOH to give chloretone which acts as a hypnotic (sleep inducing) drug.

(1,1,1-trichloro-2-methyl propan-2-ol)
6)Rxn with aq. Alkali:- Chloroform gets hydrolysis by aq. KOH to form potassium
formate which on acidification gives formic acid.

14
7) Rxn with primary amine or carbylamines reaction:- Chloroform when heated
with primary aliphatic or aromatic amine in presence of alcoholic KOH, an offensive
smell of carbylamines is obtained and reaction is referred to as carbylamines reaction.
Heat
CH3-CH2-NH2 + CHCl3+ alc.KOH CH3-CH2-N = C + 3KCl + 3H2O
Ethylamine ethyl isocyanide
(ethyl carbylamine)

This reaction is used as a test reaction of primary amine because secondary

and tertiary amines do not give this reaction.
8) Reimer-Tiemann reaction:- Chloroform when heated with phenol at 60-70oC in
presence of sodium or potassium hydroxide followed by hydrolysis, ortho-
hydroxybenzaldehyde (salicyaldehyde) is formed.

9) Iodoform reaction:- Any compound which contains a methyl keto group ( CH3-
C-) or the compound which can form methyl keto group on oxidation, i.e. those contai
OH
O 
-ning CH3-CH- group. Thus, ethanol, acetaldehyde, propanone and isopropyl alcohol
give iodoform test. For example.

15
 I2 + 2NaOH NaI + NaOI + H2O
O

Oxidation
CH3-CH2-OH + NaOI CH3-C-H + NaI + H2O

O O

Iodination
CH3-C-H + 3NaOI CI3-C-H + 3NaOH
Sodium hypoiodite iodal

O

NaO H + CI3-C-H Hydrolysis
CHI3 + HCOONa
Iodoform
(Yellow crystal)
Iodoform is a yellow colored crystalline solid having characteristic hospital
smell and insoluble in water and use as an antiseptic.
Uses:- It is used;
1. As an important organic solvent for fats, oils, waxes, rubber, resin etc.
2. As an anaesthetic.
3. As a preservative for biological specimen.
4. For testing primary amines (Carbide amide reaction).
5. For the preparation of chloretone, chloropicrin etc.

16