Haloalkanes and Haloarenes: Chapter - 00

Brilliant STUDY CENTRE REPEATERS CHEMISTRY -2021 (ONLINE CLASS NOTESA)
CHAPTER - 00
HALOALKANES AND HALOARENES
Replacement of H atoms in hydrocarbons by halogen atoms give halogen compounds.

Classification
Halogen compounds
Aliphatic halogen compounds Aromatic halogen compounds
Haloalkenes Haloalkynes Nuclear halogen Side chain halogen

Haloalkanes
derivative derivative
ALIPHATIC HALOGEN COMPOUNDS

1. HALOALKANES OR ALKYL HALIDE
Monohalogen derivatives of alkanes are called haloalkanes, general formula C n H 2n 1X or RX

[X  F,Cl, Br or I]
Eg : CH 3  Cl, CH 3CH 2  Br
Haloalkanes are classified as : Primary, secondary and tertiary haloalkanes based on the nature of the
carbon atom to which the halogen is bonded.
1
R
R
1° 2° 3°
CH X R C X
Eg : R CH2 X
R
1° haloalkane 2° haloalkane R
Eg : CH3 CH2 Cl CH3 3° haloalkanes
CH Cl CH3
CH3
CH3 C Cl
CH3
2. Dihaloalkanes
a. Gem or geminal dihalides or alkylidene halides
The two halogen atoms are on the same carbon.
X Cl
R CH Eg : CH3 CH
X Cl
b. Vic or vicinal dihalides or alkylene dihalides

The two halogen atoms on adjacent carbon atoms.
Cl
X X
Eg : CH3 CH CH2 Cl
R CH CH2
3. Haloalkenes
General formula - C n H 2n 1X
Eg : CH2 = CH – Cl
4. Haloalkynes
General formula - C n H 2n 3X
Eg : H  C  C  Cl , CH 3  C  C  Br
2
II. AROMATIC HALOGEN COMPOUNDS
1. Nuclear halogen derivatives or haloarenes
Halogen atom is directly bonded to the aromatic ring
General formula - Ar - X
CH3
Cl
Eg : ,
Chlorobenzene Br
Para bromo toluene
2. Side chain halogen derivatives or aralkyl halides

Halogen atom is bonded to alkyl side chain on aromatic ring.
CH2 Cl
Eg :
(Benzyl chloride)
III. CLASSIFICATION OF HALOCOMPOUNDS ON THE BASIS OF HYBRIDISATION OF C ATOM

TO WTHICH HALOGEN IS BONDED
Reactivity of halocompounds depends on the hybridisation of C atom bonded to the halogen atom.
1. Halogen on sp3C
sp3 sp3
a. Haloalkanes : Eg : CH3 Cl, CH3 CH2 Br
b. Allylic halides : Allylic C is the sp3 hybridised C atom next to C = C bond.
Br
sp3
Eg : CH2 CH CH2 Cl,
(Allyl chloride)
(3,-Bromocyclohexene)
3
c. Aralkyl halides
sp3 CH3
CH2 Cl
CH Br
Eg : , sp3
Benzyl chloride
2. Halogen on sp2C
a. Vinylic halides : X on sp2C atom of C = C bond.
Br
CH2 CH Cl
Eg : ,
(Vinyl chloride)
(1-Bromocyclohexene)
b. Haloarenes : X on sp2 hybridised carbon atom of aromatic ring.
Cl Br
Eg : ,
H3C
I. PREPARATION METHODS OF HALOALKANES

1. From alcohols
Alcohols react with concentrated halogen acids to form haloalkanes
 R  OH  H 2O  HX  HCl, HBr or HI 
R  OH  HX 
Order of reactivity of HX - HI > HBr > HCl

Order of reactivity of alcohols - 3° > 2° > 1°
Mechanism
  Protonation Slow fast

R OH + H X R OH2 R + X RX
X RDS
Carbocation
H2O
This intermediate carbocation may undergo rearrangement.
4
CH3 CH3
C CH2 OH + HCl CH3 C CH2 CH3

Eg : CH3
CH3 Cl
Neopentyl alcohol 2-chloro-2-methyl butane (major)
CH3 CH3
+ -
  Slow
CH3 C CH2 OH + H Cl CH3 C CH2 OH2
-Cl RDS
CH3 CH3
CH3 CH 3 CH 3
CH 3 C CH 2
CH 3 shift
CH 3 C CH 2 CH 3 + Cl fast CH3 C CH 2 CH 3
for more stability
CH 3 Cl
3° carbocation
(more stable)
1° carbocation
(less stable)
PREPARATION OF CHLOROALKANE FROM ALCOHOL IN GOOD YIELD

a. Groove’s process
Alcohol is treated with HCl in the presence of anhydrous ZnCl2 (Lewis acid)
R  OH  H  Cl 
anhy.ZnCl2
 R  Cl  H 2 O
b. Darsen’s process
Alcohol is treated with thionyl chloride, SOCl2 (Darsen reagent). By products being gases pure sample
of chloroalkane is obtained.
R  OH  SOCl 2 
Pyridine
R  Cl  HCl  SO 2 
c. Treating w ith PCl 3 and PCl5
3 R  OH  PCl3 
 3 R  Cl  H 3 PO3
R  OH  PCl5 
 R  Cl  HCl  POCl3
5
Bromo and iodoalkane

(Re d P  X 2 )
a. 3 R  OH  PX 3 
(X  Br or I)
3 RX  H 3PO3

b. R  OH  KBr  H 2SO 4   R  Br  KHSO 4  H 2 O

c. R  OH  KI  H 3 PO 4   R  I  KH 2 PO 4  H 2 O
2. From Alkanes
Free radial halogenation of alkanes in the presence of UV light or heat give halo-alkanes.
Eg :
(a) Chlorination of CH4 in the presence of UV light.
CH 4  Cl2 hv
 HCl
 CH3Cl  Cl2 hv
 HCl
 CH 2 Cl2  Cl2 hv
 HCl
 CCl3  Cl2 hv
 HCl
 CCl4
A mixture of halo derivatives are formed.
Cl
2° 1° hv
CH2 CH3 + Cl2 CH3 CH2 CH2Cl + CH3 CH CH3
(b) CH3
(1equiv) 298 K 1-chloropropane 2-chloropropane
(minor) (major)
The ease of substitution of various H atoms in the alkanes follow the sequenes - 3° > 2° > 1°
Bromination proceeds same as chlorinatino. But free radical iodination of alkanes is reversible.
 CH 3  I  HI
Eg : CH 4  I2 
For better yield of alkyl iodide, strong oxidising agents like HNO3 or HIO3 are used, which oxidise HI to
I2.
HIO3  5HI 
 3I 2  3H 2 O
3. From alkenes
Alkenes add HX to form haloalkanes.
C C + H – X 
 C C
H X
6
R  CH  CH 2  HX 
Markownikov
R CH CH3 + R CH2 CH2 X
addition
(Major) (Minor)
Cl
Eg : CH 3  CH  CH 2  HCl 
 CH3 CH CH3 + CH3 CH2 CH2 Cl
(Major) (Minor)
+ HBr Br
(Major)
The reaction is an electrophilic addition reaction and it follows Markownikov’s rule.

Mechanism
 H + X
H  X 
X
I Fast R CH CH3
I R CH CH3 + X
2° (Major)
Slow
R CH CH2 + H 2° > 1°
RDS
Fast X
R CH2 CH2 + X R CH2 CH2
II II
1° carbocation (Minor)
The intermediate carbocation can rearrange to have more stability.
CH3 CH3
Eg: CH3 CH CH CH2 + HBr CH3 C CH2 CH3
Br
(Major)
7
Mechanism
CH3 CH3
RDS H shift
CH3 C CH CH2 + H CH3 C CH CH3
H H
2° carbocation
(less stable)
CH3 CH3
CH3 C CH2 CH3 + Br fast CH3 C CH2 CH3
3° carbocation Br
(more stable)
PEROXIDE EFFECT OR KHARASCH EFFECT
O O
In the presence of organic peroxides (Ex : Benzoyl peroxide, C6H5 C O O C C6H5)

HBr adds to unsymmetrical alkenes opposite to Markownikov’s rule and is called Kharasch effect.
C H CO  O
R  CH  CH 2  HBr  6 5 2 2
Anti  Markownikov addition
 R  CH 2  CH 2 Br
(Major)
The reaction has free radical mechanism.

Mechanism
O O O
C 6H 5 C O O homolysis
C C 6H 5 2C 6H 5 C O
(Benzyl peroxide) Benzoyloxy radical
O O
C6H5 C O+H Br Br + C6H5 C OH

(Bromine radical)
8
R CH CH2Br + H Br R CH2 CH2Br + Br

(20) (Major)
R CH CH2 + Br 2° > 1° Br
R CH CH2 + H Br R CH CH3 + Br
(Minor)
(1°)
Br
HCl and HI even in the presence of organic peroxides give Markovnikov addition product.
HCl
(C6H5CO)2O Cl
HI
I
(C6H5CO)2O2
C6H5 C O+H Cl No chlorine free radical is formed
O O
C6H5 C O+H I C6H5 C OH + I
Dimerisation
I+I I2
4. Allylic halogenation [Preparation of allyl halide]

Test for unsaturation
Unsaturated hydrocarbon treated with red solution of bromine in CCl4 undergoes decolourisation due
to the addition of dissolved Bromine to substrate
Br Br
CCl4
Eg : R CH CH2 + Br2 R CH CH2
(Vic dibromide)
In allylic halogenation allylic H atoms are replaced by halogens.
9
X
X2 CH CH2
CH2 CH CH3 CH2
HX (Allylic halide)
The reaction has free radical mechanism

Conditions for allylic halogenation
1. X at high temperature [400 – 500°C]
2. NBS - allylic bromination [hv or  ]
3. SO2Cl2 - allylic chlorination [hv or  ]
a. High temperature halogenation

Allylic hydrocarbon is heated wtih Cl2 or Br2 at very high temperature.
X
400  500 C
CH 2  CH  CH 3  X 2 
 X  Cl2 or Br2   CH2 CH CH2 + HX
The reaction has free radical mechanism

X X 
hom olysis
 2X (Halogen free radical)
CH CH2 CH2 CH CH2

CH2 CH CH2 H+X CH2
HX Allyl free radical - resonance stabilised
CH2 CH CH2 + X CH2 CH CH2 X

(allylic halide)
b. Allylic bromination
CH2 C
N Br
N-Bromosuccinimide or NBS CH2 is a specific reagent for allylic
C
bromination.
10
O O
Br
CH CH3 + N Br 
hv or 
 CH2 CH CH2 + NH
CH2
(Allyl bromide)
O O
Br

NBS
hv or 

CH3
CH2 Br

NBS
hv
Toluene
c. Allylic chlorination
Alkene with allylic H is treated with sulphuryl chloride [SO2Cl2] at high temperature in the presence of
UV light.
Cl
hv / 
CH 2  CH  CH 3  SO 2 Cl 2   CH2 CH CH2 + HCl + SO2
5. Preparation of Fluroalkanes - Swarts reaction

Chloro or bromoalkane is heated with metallic fluorides like AgF, Hg2F2, CoF2 or SbF3. Swarts reaction
is a halogen exchange reaction

R  X  AgF 
 X  Cl or Br   R  F  AgX
6. Preparation of Iodoalkanes - Finkelstein reaction

Chloro or bromo alkane is heated wtih NaI in acetone. It is a halogen exchange reaction.
 ,Acetone
R  X  NaI 
(X  Cl or Br )
 R  I  NaX 
The reaction is reversible. NaCl or NaBr being less soluble in acetone gets precipitated and the forward
reaction is promoted.
11
7. Preparation of Bromoalkane - Borodine Hundsdiecker reaction
Silver salt of carboxylic acid is refluxed with bromine in CCl4 solvent.

R  COOAg  Br2 
CCl4
 R  Br  AgBr  CO 2
The reaction has free radical mechanism. Silver salt of carboxylic acid refluxed with chlorine in CCl4
gives very poor yield of chloroalkane.
BIRNBAUM - SIMONINI REACTION
Silver salts of carboxylic acids refluxed with I2 in CCl4 gives ester.

2R  COOAg  I 2 
CCl4
 R  COOR  CO2  2AgI
Ester

Eg : 2CH 3  COOAg  I2 
CCl
 CH 3  COOCH3  CO 2  2AgI
4
(methyl ethanoate)
II. PREPARATION OF HALOARENES

1. By nuclear halogenation
Direct chlorination or bromination of arenes is carried out in the absence of sunlight and in the presence
of anhydrous Ferric or aluminium halide catalyst. It is an electrophilic substitutions reactions.
Ar  H  X 2 
FeX3
 Ar  X  HX
 Arene   haloarene 
Cl
Cl2 + FeCl3
+ HCl
Br
Br2 + FeBr3 + HBr
Eg :
I
I2 + HIO3 + HI (reversible reaction)
Or HNO3
Direct iodination is carried out in the presence of oxidising agents such as HNO3 or HIO3. Oxidising
agents oxidise HI to I2 and the forward reaction is only promoted.
12
CH3 CH3 CH3

Cl
FeCl3
+ Cl2 +
Eg :
(dark)
(Toluene)
Cl
Alkyl group on benzene ring is ortho para orienting towards electrophilic substitution.
2. By Sandmeyer Reaction
Cl
CuCl + HCl + N2
Chloro benzene
NH2 N NCl Br
NaNO2  HCl
  CuBr + HBr + N2
0 C
(Aniline) Benzene diazonium I

chloride
KI(aq) + N2 + KCl
F
N N BF4
H BF4  +
BF3 + N2
Tetra fluro boric acid
(Benzene diazonium
tetra fluroburate)
Thermal decomposition of benzene diazonium tetra fluroborate to give fluro benzene is called BALZ-
SCHIEMAN REACTION.
3. By Gattermann Reaction
It is a modificcation of Sandmeyer reaction. Copper powder is used in the presence of halogen acids.
13
Cl
Cu/HCl
N NCl
Br
Cu/HBr
III. Preparation of Aralkyl Halides

Direct halogenation of alkyl arenes in the presence of UV light and heat give side chain halogen arenes.
It is a free radical substitution reaction and a mixture of halo compounds are formed.
CH2 Cl CHCl2
CH3 CCl3
hv,  hv, 
hv,  + Cl2    
Eg : + Cl2 
HCl
  HCl + Cl2  HCl
Benzyl chloride Benzal chloride Benzo trichloride
Br
CH CH3
(Major)
CH2 CH3
hv, 
+ Br2 HBr
CH2 CH2Br
(Minor)
The major product involves a more stable free radical intermediate.

PROPERTIES
1. Solubility in water
Haloalkanes and haloarenes are very sparingly soluble in water due to the inability to form H bonds
with water molecules, but soluble in organic solvents.
2. Boiling points
14
Due to greater polarity and higher molecular mass haloalkanes and haloarenes have higher boiling
points than comparable hydrocarbons.
Order of B.P. - RI > RBr > RCl > RF
Order of B.P - Ar–I > Ar – Br > Ar – Cl > Ar – F
In isomeric haloalkanes boiling points decrease with branching of carbon chain
Ex : Butyl bromide -M.F. - C4H9Br
Br CH3
CH2 CH CH3 > CH3 C Br

CH3 CH2 CH2 CH2 Br > CH3
CH3
1-bromo butane (375 K) 2-bromobutane (364 K)
(346 K)
3. Melting points
Order of melting points in isomeric dichlorobenzenes
Cl Cl Cl
Cl
> >
Cl
(256 K) (249 K)
Cl
(323 K)
Para dichloro benzene being more symmetrical is closely packed in the solid and more energy is
needed to release the molecules from the crystal lattice. Boiling points of isomeric dichlorobenzenes
are almost the same as the Vander Waal’s attraction is comparable.
4. Dipole moment
The C–X bond in haloalkane has partial polar character and can exhibit dipole moment. Order of
dipole moment in CH3–X is –CH3–Cl > CH3 – F > CH3 – Br > CH3 – I.
Fluorides have lower dipole moment than chlorides due to its small size.
X F Cl Br I
Order of dipole moment in -
(Halobenzene)
15
Cl Cl
Cl
Cl
Order of dipole moment in isomeric dichloro benzenes - Cl

=2.54 D =1.72 D Cl
=0
5. Bond strength
Order of bond strength of C–X bond is C–F > C – Cl > C – Br > C–I
Alkyl iodides are the most reactive among haloalkanes due to less bond strength. The order of reactivity
of haloalkanes is –R–I > R – Br > R–Cl > R – F
6. Density
Order of density of alkyl halides is : R–I > R – Br > R – Cl > R – F
Alkyl fluorides and chlorides are lighter than water whereas alkyl bromides and iodides are denser
than water.
I. REACTIONS OF HALOALKANES
Haloalkanes give mainly 3 types of reactions
1) Nucleophilic substitutions reactions
2) Elimination reactions
3) Reaction with metals
I. Nucleophilic substitution reactions
 
The characteristic reaction of haloalkanes is nucleophilic substitution reactions. The C X bond in
haloalkanes has partial polar character and the +vely charged carbon is easily attacked by nucleophiles.
+ -
Nu + R X R Nu + X
(Nucleophile)
Examples:
16
H2O
R OH
neutral nucleophile (alcohol)
OH R OH
NaOH(aq)
KOH(aq) or
moist Ag2O
CN
R C N
KCN-alcohol alkyl cyanide
(ionic)
C N R NC
Ag C N alkyl isocyanide
(covalent)
R  O
R  O  R
R   ONa (ether)
R X 
Ag  O  N  O
R NO2
AgNO2
nitroalkane
(covalent)

O N  O
R O N O
KNO2 (aq) alkyl nitrile
(ionic)
R   COO
R   COOR
R   COOAg (ester)
H
R H
LiAlH 4 (alkane)
NH3
R NH2
NH3 (1° amine)
17
Mechanism of nucleophilic substitution reactions
Two types of mechanism are suggested for nucleophilic substitution reactoins
1. Substitution nucleophilic bimolecular – SN2
2. Substitution nucleophilic unimolecular - SN1
SN2
Primary haloalkanes easily undergo SN2 type reactions. The reaction is bimolecular as the concentration
of both haloalkane and nucleophilie determine the rate of the reaction.
1. Rate of the reaction   RX   Nu 
2. Example : CH3  Cl KOH(aq) 

 CH 3  OH  KCl(aq)
1
3. The reaction is a one step process: The attack of nucleophile from the back side and the removal of
X take place in one step [concerted reaction]
4. Stereospecific and stereoselective
5. The rate determining step in the formation of the transition state.
6. Mechanism
H H
H 
    fast


slow
HO C Cl HO C H
HO + H C Cl RDS Cl
H H H
(Nucleophile) H 100% inversion in
Transition state
configuration
(Unstable)
SN2 reaction is followed by inversion in configuration called Walden Inversion.

7. Order of reactivity
SN2 reaction happens in the case of haloalkanes where the bond making by nucleophile is least
sterically hindered.
Order of reactivity of RX towards SN2 is
CH 3  X  1  2  3
Among CH 3  X , the order of reactivity is
CH 3  I  CH 3  Br  CH3  Cl  CH3  F
18
8. Polar aprotic solvents favour SN2 reactions
Example
O
O O
CH3 S
C N CH3 CH3
CH3 CH3, CH 3  CN , H C ,
acetonitrile CH3 DMSO
(acetone) DMF (Dimethyl sulphoxide)
(Dimethyl formamide)
Polar protic solvents retard the bond making ability of nucleophile
SN1
Tertiary haloalkanes easily given SN1 reactions. The reaction is UNIMOLECULAR, as the reaction rate
depends on the concentration of haloalkane only.
1. Rate Rate   RX 
CH3 CH3
+ C OH + KBr(aq)
2. Example : CH3 C Br KOH (aq) CH3
(3°) CH3 CH3
3. Non-stereospecific and non-stereoselective

4. The reaction is a two step process
6. Mechanism
Step-1 : Formation of carbocation
The rate determining step is the formation of carbocation.
CH3
H3C
Slow C + Br
H3C C Br
RDS
H3C CH3
H3C
Carbocation
sp2-planar
19
Step-2 : Attack of carbocation by nucleophile
Carbocation being planar is attacked by nucleophile from both sides with equal probability.
OH
CH3 H3C
CH 3

fast
HO C CH3 + H3C C Br
C
H 3C CH 3 CH3 H3C
(50% inversion) (50% retention)
6. Order of reactivity
Greater the stability of carbocation, greater will be the ease of formation of product.
Order of reactivity towards SN1 - 3° > 2° > 1° > CH3 – X
7. Polar protic solvents favour SN1 reactions
Eg: H2O, C2H5OH, CH3 – COOH
Polar protic solvents solvate the negatively charged X atoms of RX by the H+ end of the polar protic
solvents and facilitates the formation of carbocation. Secondary haloalkanes undergo both SN1 and
SN2 reactions based on the solvent used.
Polar protic
Solvents SN1
2° haloalkane
Polar aprotic SN2
Solvents
Allylic and benzylic halides, though primary, undergo nucleophilic substitution reactions mainly by SN1
mechanism. The allylic and benzylic carbocations have considerable stability due to resonance.
SN1 CH2 CH CH2

CH2 CH CH2 Cl CH2 CH CH2
Cl (resonance stabilised allyl carbocation)
(allyl chloride)
CH2 Cl
CH2
SN1
Cl
(Benzyl chloride)
20
CH2
CH2 CH2
(Resonance stabilised benzyl carbocation)
OPTICAL ISOMERISM
Optical isomers are stereoisomers which differ only in optical activity. Ability to rotate plane
polarised light is called optical activity. Optical rotation is measured using a POLARIMETER.
Chiral molecules exhibit optical activity. A molecule which is not super-imposable on its mirror
image is called a chiral molecule. Achiral molecules are super imposable on its mirror images and are
optically inactive.
In the case of organic compounds presence of an asymmetric C atom or stereocentre makes
the molecule CHIRAL if it is dissymmetric. Molecules which have no elements of symmetry are called
dissymmetric molecules.
Examples:
Br Br
CH3 CH CH2 CH3 CH3 CH CH3
(asymmetric C atom) (symmetric - no asymmetric C atom)

optically active optically inactive
1. Optical isomerism in molecules with one asymmetric C atom (One chiral C atom)
Molecules with one asymmetric C atom lack all elements of symmetry and can exist only in optically
active forms.
Example
Cl
2 - chloro butane CH3 CH CH2 CH3
No. of optical isomers = 2n = 21 = 2

(n = no.of asymmetric C atom)
The molecule exists in two optically active forms.
21
1. Dextro, d or (+) - 2-chloro butane
2. Laevo, l or (–) - 2-chloro butane
The d and l isomers rotate plane polarised light to right and left respectively to equal extent.
Fischer projection formula is used to represent three dimensional molecules in a two dimensional
manner. Parent C chain is denoted by vertical lines and stereocentre by horizontal lines.
Cl
1 2 3 4
CH3 CH CH2 CH3
*
mirror CH3
CH3
H * Cl d * H
CH2CH3 CH2CH3
d or (+)-2-chloro butane l or (-)-2-chloro butane
I Enantiomers II
Enantiomers
Optically active stereosimers which are non-superimposable mirror images of each other are
called enantiomers.
2. Optical isomerism in molecules with two similar asymmetric C atoms
Molecules with even number of similar asymmetric C atoms have symmetry and can exist in optically
active and optically inactive MESO FORMS.
MESO FORMS
Stereoisomers which do not show optical activity eventhough asymmetric carbon atoms are present.
Example:
Cl Cl
2, 3- dichloro butane CH CH CH CH3

* *
(2 similar asymmetric C atoms)
No. of optical isomers = 2n–1 = 22–1 = 2
22
n
No. of meso forms = 2 2 1  2  1
The molecule exists in three stereoisomeric forms.

– (+), (–) and meso-2,3-dichloro butane.
CH3 Mirror CH3 CH3
H * Cl Cl * H H * Cl
Plane of symmetry
Cl * H H * Cl H * Cl
CH3 CH3 CH3

(-)
(+) III
II
I Meso-2,3-dichlorobutane
(optically inactive)
Enantiomers
Meso form is symmetric due to the presence of plane of symmetry and is optically inactive due to
internal compensation.
Diastereomers
Stereoisomers which are not mirror images of each other are called diastereomers.
Eg: I & III; II & III
Racemic mixture d or   
Mixture containing enantiomers in equal amounts. Optically inactive due to external compensation
Racemisation
Conversion of enantiomers into racemic mixture is called racemisation
( )    
     
Resolution
Separation of enantiomers in a racemic mixture is called resolution.
23
Stereochemistry of SN1 and SN2 reactions
SN1
In SN1 reaction if the substrate is optically active, the product will be optically inactive due to the
formation of racemic mixture. Racemisation happens in SN1 reactions.
Nu
R1 R1 R1
R1 *
* Step I Step II * C
C X C Nu C R2 + R2 Nu
R2 Slow Fast
R2 R3 R3 (-)
R3 X R3
(+)
Optically active Carbocation 50% inversion 50% retention
racemic mixture
In many cases a little more of inversion than retention is observed in SN1 reactions.
SN2
If the alkyl halide is optically active, the product will also be optically active due to the formation of
only one enantiomer as the product.
R R R
* SN2   fast
Nu *C
Nu + H C X Nu C X H
RDS X
D H D
D
Optically active Transition state Optically active (+) or (-)
Inversion of configuration may not always lead to inversion in optical activity. If the substrate in SN2
reaction is dextro rotatory the product will be dextro or laevo forms.
SNi reactions (substitution nucleophilic intramolecular)
The reaction of alcohols with SOCl2 to form chloroalkane has SNi mechanism.
R  OH  SOCl 2 
SNi
R  Cl  HCl  SO 2
Mechanism
The reaction has a 4 membered cyclic transition state as intermediate
H Cl H
R O + S O R O S O
Cl H
Cl Cl24
O
R S O 
fast
 R–Cl
 SO 2
Cl
4 membered cyclic T.S.
Stereochemistry
If the alcohol is optically active, the reaction is followed by Retention of configuration.
OH COOH
O  
RDS
Eg : CH3 CH COOH H * OH + Cl S  HCl
Lactic acid Cl
(optically active) CH3
COOH
COOH
O
H S O H Cl
SO2
Cl
CH3 CH3
4 membered T.S. retention of stereocentre
II. Elimination Reactions

Haloalkanes when heated with ethanolic KOH undergoes dehydrohalogenation to form alkene.
 
C C  
 C C
C2 H5 OH/KOH + HX
alkene
H X
(haloalkane)
HX is eliminated from ,  carbon atoms of the haloalkane and the reaction is called  -elimination
The reagent ethanolic KOH generates ethoxide anion C2H5O , which is a strong base
25
C2H5OH + KOH C2H5O K + H2O
C2H5O K C2H5O + K
ethoxide anion
(base)
  
Eg: CH
3 CH2 CH2 Br + KOH 
C2 H5 OH
 CH3 – CH = CH2 + KBr + H2O
The order of dehydrohalogenation of haloalkanes is 3° > 2° > 1°

ZAITSEV RULE
If elimination reactions give more than one alkene, the more alkyl substituted alkene will be the
major product.
CH3 CH2 CH CH CH3

H Br H Pent-2-ene [major]
 Zaytsev product
Eg : CH3 CH2 CH CH CH2
   KOH C2H5OH
CH3 CH2 CH2 CH CH2

2-bromo pentane HBr
Pent-1-ene [minor]
Hofmann product
Elimination and substitution reactions compete with each other.

Two types of elimination reactions
1. Elimination Bimolecular - E2
2. Elimination Unimolecular - E1
1. E2
The specifics of E2 reaction are
1. Rate   RX   Base
2. One step process with a single transition state
  
3. Example : CH
3 CH2 Br + KOH 
C2 H5 OH
 CH 2  CH 2  KBr  H 2C
4. Stereospecific and stereoselective

The eliminating groups must have Anti-periplanar spatial arrangement on substrate. Trans alkene
will be the major product.
26
5. Mechanism


H Br H Br H H
  slow C C
H C C H H C C H 
fast
+ C2H5OH + Br
RDS  H
 H
H H C2H5O H H
C2H5O
T.S.
(Base)
H3 C H H3 C

 H alc.KOH
 HCl
H  H H
Cl
3-methyl pentene (major)
SN2 and E2 reactions have the same conditions. (Bases are also nucleophiles). With increase in
the steric hindrance of the substrate (E2 is less affected by steric hindrance) E2 reaction is
favoured over SN2.
6. Order of reactivity - 3° > 2° > 1°
7. Polar aprotic solvents favour E2 reaction
Hofmann elimination
In E2 reaction if the base is bulky
CH3
CH3 C O
Eg : tertiary butoxide, , less sterically hindered  –H atom is abstracted by base to
CH3
form Hofmann product.
27
 H3C H
C2H5OH KOH
C C
C2H5O
CH3
(Base) H
Cl Trans but-2-ene (major)
Zaytzev product
CH3 CH2 CH CH3
  
CH3
CH3 C OH/KOH
CH3 CH2 CH CH2

CH3
CH3
But-1-ene (major)
CH3 C O Hofmann product
CH3
(Bulky base)
2. E1
The characteristics of E1 reaction are
1. Rate of reaction   RX 
2. Two step process - ionisation and deprotonation

3. Not stereospecific but stereoselective, trans alkene will be the major product
4. Tertiary haloalkanes given E1 reactions easily
CH3 CH3
 
Example : CH3 C Br+ KOH 
C2 H5OH
 CH3 C + KBr + H2O
CH3 CH2
28
5. Mechanism
Step-I : Formation of carbocation
CH3 CH3
slow C
CH3 C Br CH3
RDS
Br
CH3 CH3
Step-II : Abstraction of H+ from  carbon of carbocation by base (C2H5O–)
CH3 CH3
C + OC2H5 fast C + C2H5OH

CH3 CH3
CH2 H CH2
6. Order of reactivity - 3° > 2° > 1°

E1 and SN1 reactions occur together. Substitution is favoured by good nucleophiles [donates electrons
to form covalent bond]. Strong base Ex : R O, NH2 proton acceptors and high temperature
favour elimination reactions.

7. Polar protic solvents favour E1 reactions
E1CB reactions [Elimination Unimolecular Conjugate base]
In the presence of strong base [NaNH2], fluroalkanes undergo eliminatino reaction by E1CB mechanism.
   
Ex : CH3 CH CH3 + Na NH2 CH3 CH CH2 + NaF + NH3
Mechanism - 2 step reaction
slow
  RDS CH2
fast CH3 CH CH2
CH3 CH CH2 H + NH2 CH3 CH
NH3 F
(base)
F
F
Carbanion (conjugate base)
stabilised by electron
withdrawing F
29
In E1CB reactions, Hofmann product will be the major product
CH CH2 CH3 CH2 CH CH2 CH3

CH2 F Major
F Hofmann product
   NH2 1° (more stable)
H CH2 CH CH CH3
NH3
1° > 2°
F H
CH CH CH3 CH3 CH CH CH3

CH3 F
Minor
F Zaytsev product
2° (less stable)
III. Reaction with metals

Haloalkanes react with metals to form organometallic compounds.
1. With Mg
Haloalkanes react with Mg in dry ether medium to form alkyl magnesium halide or Grignard reagent.
R  X  Mg 
dry
ether
 R  Mgx
Grignard reagent
Ex : CH 3  CH 2  Br  Mg 
dry
ether
 CH3  CH 2  MgBr
Ethyl magnesium bromide
The C–Mg covalent bond is highly polar due to electronegativity difference and Grignard reagent may
 
be represented as R  Mg X
Grignard reagent reacts with compounds containing acidic H like H2O, R–OH, H2S, RSH, NH3 and
terminal alkynes to form hydrocarbons.

O   
H N H + R MgX R X + Mg(OH)X
alkane
30
2. With Na – Wurtz reaction
Haloalkanes react with metallic Na in dry ether to form alkanes with even no.of C atoms
R    R R
dry ether
R X + 2Na + X 2NaX
dialkyl
Eg : CH3 Br + 2Na + Br CH3  

dry ether
2NaBr
 CH 3  CH 3
Ethane
3. With Zn
a. Vicinal dihalides or 1, 2-dihaloalkanes react with Zn to form alkene.
X X

R CH CH2 + Zn R CH CH2 + ZnBr2
(Vicinal di halide) alkene
Br Br
 CH2 + ZnBr2
Ex : CH3 CH CH2 + Zn CH3 CH
b. 1, 3 dihaloalkanes react with Zn to form cyclopropane derivatives.
CH2 Br CH2

Ex : CH2 + Zn CH2
ZnBr2
CH2
CH2 Br
Cyclopropane
REACTIONS OF HALOARENES
Haloarenes are less reactive than haloalkanes due to the following reasons.
1. X on sp2c and less polar character to C–X bond
2. C–X bond has partial = bond character due to resonance.
Eg : Resonating structures of chloro benzene
Cl Cl Cl Cl   Cl
 

Resonance hybrid
31
I. Nucleophiic substitution reactions[SNAr]

Aromatic ring of haloarene is a centre of high electron density and the nucleophiles experience repulsion
x
repulsion
when it attacks the substrate
+ Nu
SN1 type reactions are ruled out due to the instability of phenyl carbocation.
X
X
Unstable phenyl
carbocation
Haloarenes undergo nucleophilic substitution reactions only under drastic conditions (high temperature
and pressure)
Ex : (1) Dow’sprocess
Chlorobenzene heated with aqueous NaOH or KOH at 623 K and 300 atmospheres gives sodium
phenoxide which one acidification gives phenol.
ONa+ OH
Cl
+ 2NaOH 
623, 300atm
 H2O
 
dil.HCl
 NaCl

 NaCl
Sodium phenoxide Phenol
2. Ability of haloarene to undergo nucleophilic substitution reactions is enhanced considerably when

electron withdrawing groups are present on aromatic ring at ortho and para positions. Electron
withdrawing groups increase the stabilit of intermediate carbanion.
OH
Cl
Ex : 
(1) NaOH,443K
(2)dil.HCl

NO2
NO2
32
Cl
OH
NO2
NO2

(1) NaOH,368K
(2)dil.HCl

NO2
NO2
Cl OH
O2N NO2
O2N NO2
2,4,6-trinitro phenol or picric acid

(1)H 2 O,323 K

NO2 NO2
Mechanism
X X Nu X Nu
X Nu
+ Nu  
slow
RDS
Carbanion- resonance
Nu
X Nu
fast
X
Resonance hybrid
G Electron withdrawing groups incrase the stability of carbanion
Presence of –NO2 group at meta position does not stabilize the carbanion and the effect on reactivity
will be very less.
33
Order of reactivity towards nucleophilic substitution
Cl Cl Cl
O2N NO2 NO2 NO2
Ex :
I
NO2 NO2 R
Cl Cl Cl
NO2
NO2 I
I (less)
R
II. Electrophilic substitution reaction (SEAr)

Rate of electrophiic substitution reactions on the aromatic ring is decreased when x is substituted.
Halogen atom on the aromatic ring exerts two opposing electronic effects. Electron withdrawing –I
effect and electron donating +R effect.
+R effect X
I effect
I>+R
X atom on the aromatic ring deactivates the arene towards electrophilic substitution reactions due to
the dominance of –I effect over +R effect. The intermediate carbocation is less stable.
Cl
Cl
H Cl
RDS E
+E E
Eg : Electrophile 
fast
 H

Carbocation less
stable due to -I effect
34
But X atom on the aromatic ring is ortho para directing towards further electrophilic substitution reactions.
(Normally deactivating groups are meta directing)
Eg : Chloro benzene on nitration gives a mixture of ortho and para nitro chlorobenzene.
Cl Cl Cl
NO2


HNO3  H 2SO 4 +
NO2
The ortho para directing nature of halogen atom is due to +R effect. Reactivity is thus controlled by the
strong -I effect of X atom and orientation is controlled by weak +R effect.
III. Reaction with metals
1. With Mg : Haloarenes react with Mg in dry ether medium to form aryl magnesium halide or Grignard
reagent.
 
Ar  X  Mg 
 Ar  Mg X
dry
ether
MgX
Eg : X + Mg 
dry ether
(X  Br or I)

Phenyl magnesium halide
2. With Na
(a) Fittig reaction :
Haloarenes react with sodium in dry ther medium to form diaryls.
Ar  X  2Na  X  Ar    Ar  Ar
dry ether
2 NaX diaryl
Ex : Cl + 2Na + Cl
-2 NaCl
Biphenyl
(b) Wurtz-Fittig Reaction

Haloarenes react with haloalkane in the presence of metallic Na to form alkylarene
Ar  X  2Na  X  R  
dry ether
2NaX
 Ar  R
alkyl arene
35
Cl + 2Na + Cl CH3 CH3

Eg :
-2NaCl
Toluene
3. With Cu
Iodobenzene on heating with Cu powder gives Biphenyl in good yield and the reaction is called -
Ullmann biaryl synthesis.
I + 2Cu + I 

2CuI
Biphenyl
POLYHALOGEN COMPOUNDS
Many of these compounds are useful in industry and agriculture.
1. CH2Cl2 - Dihloromethane (methylene chloride)
Industrial solvent
a. Reaction with aqueous alkali [KOH (aq) or NaOH (aq)
Dichloro methane treated with aqueous alkali gives formaldehyde
OH
Cl CH2
CH2 + 2KOH   OH   CH 2 O
2KCl  H2O
Cl Formaldehyde
Unstable
2. CHCl3 - Trichloromethane (Chloroform)

–Solvent
– was used as an anaesthetic
a. Oxidation
Chloroform is kept in dark coloured bottles filled to the brim because it is oxidised by air in the presence
of light to a poisonous gas called carbonyl chloride or phosgene.
1
CHCl3  O 2 
hv
 COCl 2  HCl
2
b. Reaction with Ag powder
On heating with Ag powder CHCl3 forms ethyne or acetylene.
36

CH Cl3 + 6Ag + Cl3 CH 
6AgCl
CH  CH
c. Hydrolysis with aqueous alkali

CHCl3 on hydrolyis of KOH (Aq) gives potassium formate.
Cl OH
C Cl + 3 KOH   H COOH + KOH H COOH + H2O
H 3KCl
 H C OH  H 2O
Formic acid Potassium formate
Cl OH
Unstable
d. Nitration
On heating with conc. HNO3, chloroform forms nitrochloroform or chloropicrin, which is used as an
insecticide.

CHCl3  HONO 2   CCl3  NO 2  H 2 O
chloropicrin
e. With acetone
CHCl3 reacts with acetone to form CHLORETONE, a hypnotic drug.
H atom in CHCl3 is acidic, CCl3 can act as a nucleophile and give nucleophilic addition product with
acetone.
CH3 H3C
  OH
C O+H CCl3 C
CH3 H3C CCl3
(Chloretone)
f. Riemer - Tiemann Reaction

Chloroform reacts with phenol in alkaline medium to form SALICYLALDEHYDE. The reaction has
dichlorocarbne :CCl2  as the reactive intermediate.
OH OH
OH CHO
+
CHCl3  NaOH

 
(Salicylaldehyde) CHO
37
3. CHI3 - IODOFORM
–Iodoform is used as an Antiseptic
Iodoform reaction
Compounds which contain CH3 C group and compounds which are easily oxidised to
O OH OH
CH3 C group (alcohols which contain CH3 CH , Eg : CH3 CH CH3, CH3–CH2–

OH] on heating with iodine and alkali give yellow ppt. of iodoform.
I2 + NaOH Na OI + HI
(Iodate anion)
Iodate anion OI is the attacking species in the reaction.
O O O
OI R Na+ OH R
R C CH3 + 3I2 C CI3 + OH C CI3
-3HI
O H
O
H + transfer
R C O H + CI3 CHI3 + RCOO Na
Na +
OH O
I 2  NaOH
CH3   R  COONa  CHI3 

R CH CH3 + [O] 
O I
 H2O
R C 
OH
Esters which are hydrolysed by alkali to alcohols with CH3 CH group can give iodoform reaction.
O OH
CH3  [O]

R C O CH2 NaOH(aq)
 CH3 CH H CH3 – CH = O
 RCOONa
(Ethyl ester) (Ethanol) OI
38

I2  NaOH
  CHI3   HCOO Na
4. CCl4 (Tetrachloro methane or carbon tetrachloride)

–non polar solvent
–CCl4 is used as a fire extinguisher under the name Pyrene
a. Oxidation
CCl4 is oxidised by water vapour at high temperature to form carbonyl chloride or phosgene.

CCl4  H 2 O   COCl 2  2HCl
b. Preparation of Freons (CFC or chlorofluro carbons)

Chlorofluro carbon compounds of methane and ethane are called Freons, which were used as
refrigerants.
CCl4 subjected to SWARTZ REACTION give freons.

3CCl4  2SbF3   3CCl2 F2  2SbCl3
 freon 12 
Cl
5 DDT CCl3 CH 2, 2-Bis[4-chlorophenyl]-1,1,1-trichloro ethane
Cl
–Insecticide
Preparation
By heating chlorobenzene with chloral [Trichloro acetaldehyde] in the presence of conc. H2SO4.
 Cl
H Cl
CCl3 CH O+ conc. H 2SO4
CCl3 CH
H H 2O
Cl Cl
(DDT)
39
6. Benzene hexachloride [BHC] - C6H6Cl6
–pesticide
Cl
Cl Cl
1, 2, 3, 4, 5, 6 hexachloro cyclohexane
Cl Cl
Cl
Preparation
Cl
Cl Cl
+ 3Cl2 
uv
 [BHC]
Cl Cl
Cl
The  -isomer of BHC called GAMMEXANE is used as the pesticide
7. Industrial solvents
Example:
1) WESTRON - CHCl2 – CHCl2 : 1, 1, 2, 2, tetra chloro methane
2) WESTROSOL - CHCl = CCl2 : 1, 1, 2-trichloro ethene
40

Haloalkanes and Haloarenes: Chapter - 00

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Haloalkanes and Haloarenes: Chapter - 00

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Brilliant STUDY CENTRE REPEATERS CHEMISTRY -2021 (ONLINE CLASS NOTESA)

Replacement of H atoms in hydrocarbons by halogen atoms give halogen compounds.

Aliphatic halogen compounds Aromatic halogen compounds

Haloalkenes Haloalkynes Nuclear halogen Side chain halogen

ALIPHATIC HALOGEN COMPOUNDS

Monohalogen derivatives of alkanes are called haloalkanes, general formula C n H 2n 1X or RX

b. Vic or vicinal dihalides or alkylene dihalides

General formula - C n H 2n 1X

General formula - C n H 2n 3X

2. Side chain halogen derivatives or aralkyl halides

III. CLASSIFICATION OF HALOCOMPOUNDS ON THE BASIS OF HYBRIDISATION OF C ATOM

b. Allylic halides : Allylic C is the sp3 hybridised C atom next to C = C bond.

b. Haloarenes : X on sp2 hybridised carbon atom of aromatic ring.

I. PREPARATION METHODS OF HALOALKANES

Order of reactivity of HX - HI > HBr > HCl

  Protonation Slow fast

This intermediate carbocation may undergo rearrangement.

C CH2 OH + HCl CH3 C CH2 CH3

PREPARATION OF CHLOROALKANE FROM ALCOHOL IN GOOD YIELD

c. Treating w ith PCl 3 and PCl5

A mixture of halo derivatives are formed.

The reaction is an electrophilic addition reaction and it follows Markownikov’s rule.

The intermediate carbocation can rearrange to have more stability.

Eg: CH3 CH CH CH2 + HBr CH3 C CH2 CH3

CH3 C CH2 CH3 + Br fast CH3 C CH2 CH3

PEROXIDE EFFECT OR KHARASCH EFFECT

In the presence of organic peroxides (Ex : Benzoyl peroxide, C6H5 C O O C C6H5)

The reaction has free radical mechanism.

C6H5 C O+H Br Br + C6H5 C OH

R CH CH2Br + H Br R CH2 CH2Br + Br

C6H5 C O+H Cl No chlorine free radical is formed

C6H5 C O+H I C6H5 C OH + I

4. Allylic halogenation [Preparation of allyl halide]

In allylic halogenation allylic H atoms are replaced by halogens.

The reaction has free radical mechanism

2. NBS - allylic bromination [hv or  ]

3. SO2Cl2 - allylic chlorination [hv or  ]

a. High temperature halogenation

The reaction has free radical mechanism

CH CH2 CH2 CH CH2

CH2 CH CH2 + X CH2 CH CH2 X

5. Preparation of Fluroalkanes - Swarts reaction

6. Preparation of Iodoalkanes - Finkelstein reaction

II. PREPARATION OF HALOARENES

CH3 CH3 CH3

(Aniline) Benzene diazonium I

III. Preparation of Aralkyl Halides

Benzyl chloride Benzal chloride Benzo trichloride

The major product involves a more stable free radical intermediate.

CH2 CH CH3 > CH3 C Br

Order of dipole moment in -

Order of dipole moment in isomeric dichloro benzenes - Cl

1. Rate of the reaction   RX   Nu 

2. Example : CH3  Cl KOH(aq) 

SN2 reaction is followed by inversion in configuration called Walden Inversion.

Among CH 3  X , the order of reactivity is

(3°) CH3 CH3

3. Non-stereospecific and non-stereoselective

SN1 CH2 CH CH2

(Resonance stabilised benzyl carbocation)

CH3 CH CH2 CH3 CH3 CH CH3

(asymmetric C atom) (symmetric - no asymmetric C atom)