JEE-ADV CHEM-VOL-V HALOGEN COMPOUNDS

HALOGEN COMPOUNDS
2) Vicinal dihalides: In these, the halogen atoms
SYNOPSIS
are attached to adjacent carbon atoms. These are
ALKYL HALIDES: Compounds derived called as alkylene halides.
from hydrocarbons by the replacement of one or eg: CH2Cl–CH2Cl CH3–CHCl–CH2Cl
more hydrogen atoms by the corresponding number Ethylene chloride Propylene chloride
of halogen atoms are known as Alkyl Halides.
3) Terminal dihalides:In these, both the halogen
HALOGEN DERIVATIVES OF ALKANES atoms are attached to terminal carbon atoms. These
(OR) HALOALKANES:- are also called    halides or polymethylene
 These are derived from the alkanes by the halides.
replacement of one or more hydrogen atoms by
halogen atoms. eg : CH2BrCH2CH2Br Trimethylene bromide
ClCH2CH2CH2CH2Cl Tetramethylene chloride
R H
H
R X  Terminal halides are also called as Poly methylene
X
ALKYL
ALKANE
HALIDE
halides.
 Trihalogen derivatives are also called as Haloforms.
 Depending on number of halogen atoms present in
the halogen derivative, they are classified as mono, Eg:- CHCl3 (Chloroform)
di, tri and tetra halogen derivatives  The general formula of trihalogen derivatives is
Eg:-
Cn H 2 n 1 X 3 .
CH H H H H
4 CH 3 X CH 2 X 2 CHX 3 CX 4
X X  X X
MONO DI TRI TETRA Halogen derivatives of unsaturated
CLASSIFICATION OF ALKYL HALIDES: hydrocarbons: Replacement of some hydrogen
Monohalogen derivatives : Monohalogen atoms in alkenes or alkynes by some halogen atoms
derivatives of alkanes are called alkyl halides. yields these compounds.
 They have the general formula RX, where R is Vinyl chloride CH2=CH–Cl
an alkyl group and X is a halogen atom. Allyl chloride CH2=CH–CH2Cl
eg : CH3Cl, C2H5Br, C3H7I, etc.  In vinyl halides halogen atom is bonded to vinylic
 Alkyl halides are classified as primary, carbon i.e. one of the carbon atoms of C=C
secondary and tertiary depending on whether
Eg:- H 2C  CH  Cl
the halogen atom is attached to a primary,
Br
secondary and tertiary carbon atom respectively
Dihalogen derivatives:Dihalogen derivatives
of alkanes are derived by the replacement of two
hydrogen atoms by two halogen atoms.
 The dihalogen derivatives are mainly of three 1-Bromo cyclo hex-1-ene
types.  In vinyl halides halogen atom is bonded to sp2
1) Geminal dihalides: In these, both the halogen carbon.
atoms are attached to the same carbon atom.  In halo alkynes halogen atom is attached to one of
These are called alkylidene halides. the carbon atoms of C  C .
Cl
CH3 CH
CH3 C CH3 Eg;- HC  C  Br Bromo ethyne
Br Br
eg : Cl H 3C  C  C  Cl 1 - Chloro prop-1-yne
Ethylidene Isopropylidene  In Allylic halides halogen atom is bonded to allylic
chloride bromide carbon i.e. sp3 carbon attached to sp2 carbon.
NARAYANAGROUP 1
HALOGEN COMPOUNDS JEE-ADV CHEM-VOL-V
 In Allylic halides also halogen atom is bonded to  Allylic halides may be 10, 20 or 30.
sp3 carbon. H2C = CH – CH2 – Cl H2C = CH C CH3

H2C = CH CH2 Cl Eg. 1) 2)

0
2

Eg:-
3) H C = CH
2 C CH3
3
allylic carbon (sp carbon)
3°
IUPAC name: 3 chloro prop -1 - ene NOMENCLATURE:
In common system alkyl part is named first followed
Common name: Allyl chloride
by the name of halogen. Eg:- CH 3  Cl
Methyl chloride
CH 3  CH 2  Br Ethyl bromide

COMMON AND IUPAC NAMES OF SOME HALOGEN DERIVATIVES

S.No. Structure Common name IUPAC name

1 CH3CH2CH2CH2Cl n-Butyl chloride 1-Chlorobutane
2 (CH3)2CHCH2Cl Iso-Butyl chloride 1-Chloro-2-methylpropane
3 CH3CH(Cl)CH2CH3 sec-Butyl chloride 2-Chlorobutane
4 (CH3)3CBr tert-Butyl bromide 2-Bromo-2-methylpropane
5 (CH3)3CCH2Br neo-Pentyl bromide 1-Bromo-2,2-dimethylpropane
6 CH2=CHCH2Cl Allyl chloride 3-Chloroproene
7 CH2Cl CH2Cl Ethylene chloride 1,2-Dichloroethane
8 CH3 CHCl2 Ethylidene chloride 1,1-Dichloroethane
9 CHCl3 chloroform Trichloromethane
10 CCl4 Carbontetrachloride Tetrachloromethane
11 CF3CHClBr Halothane 2-Bromo-2-chloro-1,1,1-trifluoroethane
Cl
12 ortho-Chorotoluene 1-Chloro-2-methylbenzene
CH3

CH2Cl
13 Benzyl chloride Chlorophyenylmethane

CHCl2
14 Benzal chloride Dichlorophenylmethane

Br
15 sym-Tribromobezene 1,3.5-Tribromo benzene
Br Br
2 NARAYANAGROUP
 JEE-ADV CHEM-VOL-V HALOGEN COMPOUNDS

Preparation methodS of alkyl halides:  Groove’s reaction is nucleophilic substitution

From alcohols: Alkyl halides are prepared from reaction in which the nucleophile i.e halide ion
alcohols by replacing -OH group of alcohols by attacks the protonated alcohol with the expulsion
halogen atom. of H 2 O  a good leaving group by the formation
Cn H 2 n 1OH  HX  Cn H 2 n 1 X  HOH of a protonated alcohol.
Alkylhalide R OH + H + R OH2+
Eg : R  OH  HX  R  X  H 2 O
Protonated alcohol
 Alkyl halides can be prepared by treating alcohols
either by
1) Hydrogen Halides (HX) R OH2+ + X - R X + H2O
2) Phosphorous Halides  PCl3 , PCl5 
nucleophile
3) Thionyl Chloride  SOCl2 

Preparation of alkyl halides by Hydrogen  The purpose of anhydrous ZnCl2 in Groove’ss

Halides: (GROOVE’S PROCESS) process is to help the cleavage of C-O bond
 The order of reactivity of halogen acids is because anhydrous ZnCl2 is a Lewis acid
HI  HBr  HCl (Parallel to their acidity
H
order of nucleophilicity I   Br   Cl  )
ZnCl2
 Order of reactivity of alcohols CH 3  CH 2  OH   CH 3  CH 2  O 

R ZnCl2

Cl
R CH2 OH < R CH OH < R C OH
CH 3  CH 2  Cl
R R
 There can be 1,2 hydride or 1,2 methyl shift to attain
1° 2° 3° a greater stability of carbocation
 The reaction of conc. HCl and anhydrous ZnCl2 is Eg.
known as Groove’s process.
anhyd . ZnCl2 CH3 CH3
R  OH  HCl  R  Cl  H 2O H
CH3 CH CH CH3 CH3 CH CH CH3
 Conc. HCl and anhydrous ZnCl2 is known as
..

Lucas reagent ..OH ..OH 2

 The reaction rates with Lucas reagent for CH3

-H2O
different types of alcohols follows the order -
1,2 H Shift 
CH3 C CH2 CH3 CH3 CH CH CH3
o o o 
3  2 1
[3° carbo cation more stable than 2°] CH3
1o alcohol   No turbidity appears
Lucas Re agent
[2° carbo cation ]

2o alcohol   turbidity appears with Cl -

Lucas Re agent

in 5 min
CH3
3o alcohol 
Lucas Re agent
 turbidity appears
immediately CH3 C CH2 CH3

 Conc. HCl does not react with 1o alcohols in Cl

[2- Chloro 2 methyl butane]
presence anhyd. ZnCl2
NARAYANAGROUP 3
HALOGEN COMPOUNDS JEE-ADV CHEM-VOL-V

W.E-1: Find the products in the following  Bromo alkanes are prepared from HBr and Conc.
CH3 H 2 SO4
Conc. H 2 SO4
R  OH  HBr   R  Br  H 2O
CH3 C CH CH3+HCl ? Eg:-
H2SO4
CH3 OH CH3 CH OH+HBr CH3 CH Br+H2O
Sol:
CH3 CH3
2-Propanaol 2-Bromo Propane
CH3 CH3  HBr is genarated by the action of conc.
H
CH3 CH CH CH3 CH3 CH CH CH3 H 2 SO4 on KBr

.. 2
CH3 OH KBr  H 2 SO4  HBr  KHSO4
..

OH
CH3 ..
Conc . H 2 SO4
-H2O CH 3  CH 2  OH  HBr  CH 3  CH 2  Br  H 2O

Preparation of alkyl halides from

CH3 CH3
1,2 CH3
phosphorous halides: Chloro alkanes are
CH3 C CH2 CH3 C CH CH3 prepared by the action of
 
either PCl3 or PCl5 on alcohols.
3° carboation CH3 CH3
o
3 carbocation 3R  OH  PCl3  3R  Cl  H 3 PO3
Cl
- [Basicity = 2]
R  OH  PCl5  R  Cl  POCl3  HCl
Eg:-
CH3
3CH3 CH CH3+ PCl3 3CH3 CH CH3+H3PO3
CH3 C CH CH3
OH Cl
Cl CH3
 Similary bromo alkanes are prepared by the action
Major Product
of PBr3 on alcohol
 Normally free radicals do not undergo P4  6 Br2  4 PBr3
rearrangement 3R  OH  PBr3  3R  Br  H 3 PO3
 Hence neo pentyl chloride from neo pentane is
Preparation of alkyl chloride from
obtained by photo chemical free radical chlorination
hv
Cl2   2Cl .
alcohols using thionyl chloride  SOCl2  :
Pyridine
R  OH  SOCl2  R  Cl  SO2   HCl
CH3 CH3  This method is known as Darzen’s method.
CH3 C CH + Cl
3
 CH3 C

CH + H - Cl
2
 This is the best method to get good yield of alkyl
chlorides because the by products are gases
CH3 CH3  Alkyl bromides and iodides cannot be obtained by
Bond formed
this method because SOBr2 is unstable while
SOI 2 do not exist.
CH3 CH3 Halogen exchange method: Iodo alkanes
CH3 C

CH + Cl CH3 C CH2Cl + Cl
 can easily be obtained from corresponding
2 2
bromoalkanes or chloro alkanes by heating with
CH3 CH3 NaI in acetone.
Neo Pentyl chloride Acetone
CH 3  CH 2  Br  NaI  CH 3  CH 2  I  NaBr

4 NARAYANAGROUP
 JEE-ADV CHEM-VOL-V HALOGEN COMPOUNDS
 This reaction is called Finkelstein reaction.  This reaction is known as Swart’s reaction
 It is based on the fact that NaBr being less soluble  Allylic and Benzylic compounds are both more
than NaI in acetone gets deposited as a result reactive than saturated compounds in radical
equilibrium shifts towards the forward catalysed halogenation.
direction.  N-Bromo succinimide (NBS) is used for
Halogenation of alkanes: bromination generally at allylic and Benzylic
X2 position.
Cn H 2n  2 
 HX
 Cn H 2 n1 X
Alkane Alkylhalide O
X2
R  H  R  X  HX

W.E-2: Which one of the following is the best

condition for the better yield of CH 3Cl during N – Br
the chlorination of methane in presence of
sunlight
h
CH 4  Cl2  
hv
a) b) CH 4  Cl2   O
Excess

h
CH 4  Cl2   CH3 + NBS CH2Br
c) dart
d) CH 4  Cl2  Eg:
Excess
Sol. ' c ' because chlorine free radicals formed will
Borodine-Hunsdiecker Reaction:
colloide with excess of CH 4 molecules again
 This reaction is used to descend series
and again to give CH 3Cl as a main product. CCl4
RCOOAg  Br2   R  Br  CO2  AgBr
Iodination: Iodination of alkanes is a slow  The yield of alkyl halides follows the order
and reversible process because of formation of
strong reducing agent HI, as a by product which 10  20  30
reduces iodo alkane back to alkane.  Yield of alkyl chloride is less than alky bromide
  It follows free radical mechanism.
CH 4  I 2  CH 3 I  HI
 Hence Iodination is carried out in presence of RCOOAg  Br2  RCOOBr  AgBr
strong oxidising agent like HIO3 (Iodic acid) or RCOOBr  Br  RCOO. .
HIO4 (per iodic acid) or HNO3 , or HgO which RCOO.  R.  CO2
converts HI to I 2 or destroy HI. R.  Br2  RBr  Br.
5 HI  HIO3  3 I 2  3H 2O  Iodine forms esters instead of alkyl halide
2 HI  2 HNO3  I 2  2 H 2O  2 NO2  This reaction is known as Birnbaum simmonini
2HI  HgO  HgI 2  H 2O reaction.
Fluorination: Fluoro alkanes can be obtained 2 RCOOAg  I 2  RCOOR  CO2  2 AgI
either by carrying out the reaction by dilluting Physical properties of alkyl halides:
fluorine with an inert gas like nitrogen or 1. For the same alkyl group the order of B.P
argon or more conveniently by halogen
is R  I  R  Br  R  Cl  R  F
exchange method using inorganic fluorides
such as 2. For the same halogens B.P decrease as the size
of the alkyl part decreases
SbF3 , AgF , Hg 2 F2 , CoF2 etc.
CH 3  CH 2  CH 2  X  CH 3  CH 2  X  CH 3  X
2C2 H 5 Br  Hg 2 F2  2C2 H 5 F  HgBr2

NARAYANAGROUP 5
HALOGEN COMPOUNDS JEE-ADV CHEM-VOL-V
3. The decreasing order of B.P among the isomeric Chemical properties: Alkyl halides generally
alkyl halides is 1o  2o  3o gives two types of reactions. They are
CH 3 * Nucleophilic substitution reactions
|
CH 3  CH 2  CH 2  CH 2  Cl  CH 3  CH 2  CH  CH 3  CH 3  C  Cl * Elimination reactions
Eg. | |
Cl CH 3 S N2 mechanism: The type of concerted
substitution reaction in which bond breaking and
4. Decreasing order of density among the alkyl halides
will be bond making occur at same time is known as SN2
reaction.
RI  RBr  RCl  RF
5. For alkyl iodides decreasing order of density is  The reaction of CH 3 Br with CH 3COO  is an
CH 3  I  CH 3  CH 2  I  CH 3  CH 2  CH 2  I example of SN2 reaction.
6. Bond strength of C-X bond follows the order O O
CH 3  F  CH 3  Cl  CH 3  Br  CH 3  I –
CH3 Br+O C CH3 CH3 O C CH3+Br–
7. Order of dipole moment is
Substrate Nucleophile product leaving
CH 3  Cl  CH 3  F  CH 3  Br  CH 3  I
group
8. Stability of C-X bond decreases as the strength of
the C-X bond decreases. Thus stability order of Kinetics: Rate  K [CH 3 Br ][CH 3COO  ]
R-X is R  F  R  Cl  R  Br  R  I
9. It is alkyl iodide only decomposes in the presence  An SN2 reaction exhibits second order kinetics.
of sunlight which on standing becomes violet or That the reaction is bimolecular and both alkyl
hv
halide and nucleophile appear in the rate equation.
brown. 2 RI   R  R  I2
Aliphatic nucleophilic substitution Mechansim: The C-Br bond breaks as the C-
reactions: Replacement of an atom or group O bond forms
by another atom or group is known as substitution
O O
reaction
 If the reaction is carried out by a nucleophilie, then CH3 C O- + CH3 Br CH3 C O CH3 + Br -
it is known as nucleophilic substitution reaction.
 Generally a nucleophilic substitution reaction is new C Obond
represented as R  L  Nu   R  Nu  L Stereo chemistry of SN2 reaction:
Where L is a leaving group Nu  is a incoming H CH3
CH3 H
nucleophilie
Nu-  C Br Nu C  Br-
 Nucleophiles may be neutral or negatively charged,
where as substrate undergoing nucleophilic D D
substitution may be neutral or positively charged
 
Nu  replaces Br  from the opposite side
Eg: CH 3  Cl  CN  CH 3  CN  Cl
 All SN2reactions proceed with back side attack of


CH 3  O H 2  I  CH 3  I  H 2 O nucleophilie, resulting in inversion of
configuration at a stereogenic centre.
CH 3  OTS  NH 3  CH 3  NH 2  TsOH
 Inversion of configuration in an SN2 reaction is
OTS = Tosylate called as Walden inversion
It is the best leaving group.
6 NARAYANAGROUP
 JEE-ADV CHEM-VOL-V HALOGEN COMPOUNDS

W.E-3:Write the product in the following SN2 4. Polar aprotic solvents are especially good for SN2
reaction reactions.
Ex. DMS, DMSO, DMF, HMPA
CH3 Br 5. Presence of hetero atom on   carbon in
halides also increases reactivity of substrate for
–
+CN SN2 reaction, lone pair of electrons present on
hetero atom stabilize the stability of transition state
H H by resonance.
Eg:
Sol: Br  is the leaving group and CN  is the nucleophile

 

 
CH3 O CH2 Br + KSH CH3 O CH2 SH + KBr
6. Presence of carbonyl group at   carbon is one
CH3 Br CH3 H of the most suitable substrate for SN2 reaction.
–
+CN +Br
- Electron with drawing groups always
H H H CN increases the rate of SN2 reaction.
Eg:
O O O O
Inversion of configuration occurs at C-Br bond
CH3 C CH2 Cl + CH3 C O CH3 C CH2 O C CH3

7. Vinyl and aryl halides do not undergo SN2 reaction.

 Back side attack converts the starting material which W.E-4:Which SN2 reaction is faster in each pair.
has two group, cis to each other, to a product with
two groups trans to each other because the 
Br + OH

I+ OCH
CH OH 3

(i) (A) 3
(ii)
nucleophile CN  attacks from below the plane of 
(A)

Cl + OH DMSO
(B) I + OCH
the ring. 3

(B)

 Cl + NaOH
Br + OH
Factors affecting rate of SN2 reactions: (iii)
(A)
(iv)
(A) O

Br + OH Cl + CH3 C ONa
1. As the no. of ‘R’ groups on carbon with leaving (B) (B)
group increases, the rate of SN2 decreases
Sol. (i) A  B (ii) B  A (iii) A  B (iv) A  B
R
CH3 X > R CH2 X > R CH X > R CH X > R C X Characteristics of SN2 mechanism:
R R
0
1 2
0
3
0 CHARACTERISTIC RESULT

Second Order kinetics

2. A better leaving group increases the rate of SN2 Kinetics
Rate = K[R - X] [Nu–]
reactions.
Mechanism One step
Eg: CH 3  F  CH 3  Cl  CH 3  Br  CH 3  I Backside attack of nucleophile.
Stereo chemistry
Inversion of configuration at a
3. Since S N 2 involves the substrate and the stereogenic centre
nucleophile the rate of reaction depends largely
on the concentration of nucleophile so strong Unhindered halides react fastest
nucleophiles present in high concentration favour Identity of R
Rate :
SN2 reaction. CH3X > RCH2X > R2CHX > R3CX

NARAYANAGROUP 7
HALOGEN COMPOUNDS JEE-ADV CHEM-VOL-V

SN1 reaction: The reaction of  CH 3 3 CBr with  Because there is no preference for nucleophilic
attack from either direction, an equal amount of two

CH 3COO is an example of SN1 mechansim. enantiomers are formed i.e. a Racemic Mixture
is formed.
O O  SN1 reactions proceed with racemization at a
single stereogenic center.

 3 3
CH CBr  O  C  CH 3   3 2
CH C  O  C  CH 3  Br
W.E-5: Find the major product in the following.
Kinetics: The SN1 reaction exhibits first order
kinetics. Rate  k  CH 3 3 CBr 
Cl H2S
Mechanism: SN1 mechanism invloves two steps.
 In this mechanism bond breaking occurs before
bond making. Sol.


-Cl H H-Shift H2S
Step-1 : Cl SH2 SH
-H

CH3 CH3 Factors affecting rate of SN1 reactions :

CH3 C Br C  + Br– 1. As the number of R groups on the carbon with
the leaving group increaes, the rate of SN1 reaction
CH3 CH3 CH3 increases.
carbocation R R

Ex: CH3 X < R CH2 X < R CH X < R C X Rate of SN1

Step-2:
Methyl 10 20 30 R

CH3 O O 2. A better leaving group increases rate of SN1

fast reactions.
 

+ +
C C (CH3)3C O C
Ex:-
 

CH3 CH3 -O CH3 CH3

CH3 CH3 CH3 CH3
new bond
H3C F > H3C Cl < H3C Br < H3C I Rate of SN1

Stereo chemistry of S 1
reaction : CH3 CH3 CH3 CH3
N
3. Since, SN1 reaction is unimolecular, involving only
CH2D
(from the left) CH3 alkyl halide, so the identity and concentration of
-
Nu C B the nucleophile have no effect on the reaction rate.
 Nu
CH2D CH2D CH3CH2
CH3
CH3
[1]
4. Polar protic sovents like H 2O , R  OH ,
[2]
C Br C+
CH3CH2 CH3CH2 CH2D HCOOH , CH 3COOH are especially good for
CH3
A Nu– can attack  Nu-
C Nu
SN1 reaction, because polar protic solvent solvate
from either side
(from the right) CH3CH2 carbocation by ion dipole interaction and leaving
C
group is solvated by hydrogen bonding.
 Loss of the leaving group in Step-1 generates a 5. SN1 reactions are highly favoured if there is a
planar carbocation that is now achiral. e– pair donor atom is present at the   carbon,
 Attack of the nucleophile in Step-2 can ocur from because it highly stabilise the carbocation.
either side to afford two products B and C. These H2O
 

two products are different compounds containing

Br
one stereogenic centre. Ex: -H


H2O
 B and C are stereo isomers i.e. enantiomers.
 

8 NARAYANAGROUP
 JEE-ADV CHEM-VOL-V HALOGEN COMPOUNDS
6. Vinyl and aryl halides do not undego SN1 reactions W.E-6:Determine the mechanism of nucleophilic
beause they form highly destabilised
substitution for each reaction and draw the
carbocation.
products.
Ex:
HO2
(a) CH 3  CH 2  CH 2  Br  : C  CH 
H2C = CH Cl S No Reaction
N1
Sol. (a) The alkyl halide is 10 so it must react by an
SN2 mechanism
HO
2
 Cl No reaction
SN1
- –
CH3CH2CH2 Br + :CCH CH3CH2CH2 CCH + Br
7. Because of its rigid structure, bridge head C-atoms SN2
cannot assume planarity, hence heterolysis leading 0
1 alkyl halide
strong
nucleophile
to formation of carbocation is also prevented. The
bridge head C-atoms are resistant towards SN1 Elimination Reactions: Reactions in which
and SN2 two atoms or groups are removed from a compound
Ex: are known as elimination reactions.
Cl  The E2 and E1 mechanisms differ in the timing of
Cl bond cleavage and bond formation.
H2O
or No reaction E2 Mechanism: The type of elimination reaction
which proceed through strong base (alc.KOH,

8. Substrate containing carbonyl group on   carbon C2 H 5O  , NaNH 2 ,  CH 3 3 C  O etc is known
does not give SN1 reaction because as elimination reaction.
carbonyl has strong-I power which destabilise the  Such reactions occur in one step.
carbocation intermediate.  In E2 reaction as the stability of transition state
Ex : increases, rate of reaction increases.
O  The most common mechanism for dehydro
halogenation is the E2 mechanism.
H2O .
CH3 C CH2 Cl No reaction Ex:
CH3 -
CH3
OH
E2 reaction CH3 C CH3 C=CH2 + H2O + Br-
1
CHARACTERISTICS OF SN MECHANISM: Br CH3
Kinetics: An E2 reaction exhibits second order
CHARACTERISTIC RESULT kinetics. Hence the reaction is bimolecular and both
the alkyl halide and the base appear in the rate
Kinetics First Order. Rate = K[R - X]
equation.
Mechanism Two steps
Rate  K [(CH 3 )3 C  Br ] OH  
Trigonal planar carbocation Mechanism:In E2 mechanism all bonds are
intermediate
Stereo chemistry broken and formed in single step.
Racemization at a single 
stereogenic ceentre CH3 H CH3
 

 OH-


C= CH2 + H2O + Br
-
CH3 C CH3
More substituted halides
Br CH3
react fastest
Identity of R  new  bond
Rate :
R3CX > R2CHX > RCH2X > CH3X

NARAYANAGROUP 9
HALOGEN COMPOUNDS JEE-ADV CHEM-VOL-V

Characteristics of E2 Mechanism Ex:

Characteristic Result H CH3 CH3CH2 CH3
1. Kinetics Second Order C=C C=C
CH3CH2 H H
2. Mechanism One step H
(E)2-Pentene (Z)2-Pentene
(i)More substituted
react fastest 41% 14%
3. Identity of R
halides (ii) Rate: The E1 mechanism: Type of elimination
R3CX > R2CHX >RCH2X reaction,which proceed in two steps,in which first
4. Base Favoured by strong bases step is slow ionisation to form carbocation, while
the second step is fast attack of base to produce
5. Leaving group Better leaving group faster more substi tuted alkene (Saytzeef alkene).
reaction
 The dehydrohalogenation of  CH 3 3 CI with
6. Solvent
H 2O to form  CH 3  2 C  CH 2 can be used to
W.E-7: Predict the major products in the following explain E1 Mechanism.
CH3 CH3
CH2CH3 H2O

OCH2CH3 CH3 C CH3 C=CH2 + H3O + I -
reaction E2 I CH3
Cl
Kinetics: An E1 reaction exhibits first order
1
kinetics. Rate  k  CH 3 3 CI 
CH2CH3
Mechanism: E1 mechanism is a two step
mechanism.

Step-1 :
Cl
Sol. CH3 CH3
2 
CH 3 C I C  CH3 + I
slow
two different  carbons CH3
CH3
1 carbocation
CH2CH3
CH2CH3
Step-2 :
H trisubstituted alkene CH3 H CH3


major product H2O



 Cl [-HCl] A C CH2 C= CH2 + H3O

CH3 CH3
 E2 reaction is regeoselective which means that
more of one constitutional isomer is formed than  The E1 and E2 both mechanisms involve the same
the other. number of bonds broken and formed. The o n l y
Ex: difference is the timing.
Br  In an E1 reaction the leaving group comes off
C2H5O
CH3CH2CH2CHCH3 CH3CH2CH = CHCH3 + CH3CH2CH = CH2 before the   proton is removed and the reaction
C2H5OH
(Major) (Major)
(2-Pentene) (1-Pentene) occurs in two steps.
 E2 reaction is also stereo selective which means  In an E2 reaction, the leaving group comes off as
that More of one stereo isomer is formed than the the   proton is removed and the reaction occurs
other. in one step.
10 NARAYANAGROUP
 JEE-ADV CHEM-VOL-V HALOGEN COMPOUNDS

Characteristics of E1 Mechanism  10Alkyl halide + Strong nucleophiles or bases

Characteristic Result  SN2 product
1. Kinetics First Order
SN 2
CH 3  CH 2  Br  OH    CH 3  CH 2  OH
2. Mechanism Two step Strong nucleophile
(i)More substituted  0
1 Alkyl halide + Strong Sterically hindered
3. Identity of R react fastest
halides (ii) Rate:
bases  E2 product
R3CX > R2CHX >RCH2X E2
CH 3  CH 2  Br  K  O  (CH 3 )3 C   CH 2  CH 2
Favoured by weaker bases  20Alkyl halide + Strong bases & nucleophiles
4. Base like H2O and ROH
 E2 product + SN2 product
5. Leaving group Better leaving group faster
reaction Br OH
+ OH  +
6. Solvent

SN2 E2
W.E-8:Which elimination reaction in each pair is product product
faster. Strong base
& nucleophile
Cl
(iii) (CH ) C Cl OH
OH (ii) H2O 3 3
H2O  20Alkyl halide + Strong sterically hindered
(i) Cl H2O
(P) (P) bases  E2 product
(P)
Br
H3C Cl
Cl OH
OH
H2O (CH3)3C Cl
H2O DMSO
(Q) (Q) (Q)
Sol. (i) P (ii) Q (iii) P E2 product
Strong sterically
Determining whether Alkyl Halide hindered base
reacts by an S N 1 , S N 2 E1 or E2
 20Alkyl halide + Weak nucleophiles or bases
Mechanisms:
 SN1 product + E1 Product
 30 Alkyl halide + Strong Base  E2 Product
Br OH
Ex:
+
Br
CH 3
CH3  C  CH3  E1 SN1
OH CH 3  C  CH 2
+ Weak nucleophile product product
E2
CH3 and base
Stro n g ba se E2 P rod u ct
 0
3 Alkyl halide + weak nucleophiles or bases W.E-9:Write the products of the following reaction.
 SN1 product + E1 product -
Br + CH3O ?
Br CH3 OH CH3OH
| | |
CH 3  C  CH 3  H 2O  CH 3  C  CH 2  CH 3  C  CH 3
| | Sol. In this case alkyl halide is 20 and  CH 3O   is a
CH3 CH3
strong base and nucleophile, so products of both
Weak nucleophile
and base
E1 Product SN1 Product
SN1 S N 2 and E2 mechanisms are formed.

NARAYANAGROUP 11
HALOGEN COMPOUNDS JEE-ADV CHEM-VOL-V

W.E-10:Write the products formed in the following SN2 Product E2 Product

reaction and include the mechanism showing
how each product is formed. 
CH3
 Br 

 

 
Br + CH3O- OCH3
CH3CH2 C CH3 + CH3OH  
nucleophile SN2product H

 
CH3O- E2 product
Br
Sol. In this case alkyl halide is 30 and the reagent
 CH3OH  is a weak base and nucleophile, so
Chemical properties: The reactions of
products of both S N 1 and E1 mechanisms are
haloalkanes may be divided into the
formed. following categories
a) Nucleophilic substitution
 Both mechanisms begin with the same first step i.e. b) Elimination reactions
loss of the leaving group to form a carbocation.
c) Reaction with metals
CH3 CH3  Action of aqueous KOH:Haloalkanes on
CH3CH2 C CH3 CH3CH2 C  + Br -
treating with boiling aqueous alkali solution give
alcohols.
Br CH3
aq . KOH / NaOH
carbocation C2 H 5Cl  CH 3Ethyl  CH 2OH
1 alcohol
For SN :
CH3 CH3 CH3  Action of moist silver oxide: Haloalkanes are
CH3CH2 C+ CH3CH2 C CH3 CH3CH2 C CH3 + CH3OH2 hydrolysed to corresponding alcohols by moist
:

nucleophilic proton
CH3 attack :O+ CH3 transfer :O CH3 silver oxide.
:

H
SN1 product Ag2O + H2O   2AgOH
:

CH3OH CH3OH
:

For E1 C2H5Cl + AgOH 

 C2H5OH + AgCl
Proton removal  Action of alcoholic KCN: Haloalkanes on
from the 1 C treatment with alcoholic potassium cyanide solution
1 give alkane nitriles as the major product with a small
CH3 CH3 CH3 amount of isocyanide. KCN is predominantly ionic
CH3CH C+ C=C + CH3OH2 KCN
 alcoholic   CH 3  CH 2CN  ethyl cyanide 
C2 H 5Cl 
:

H CH3 H CH3
 Action of AgCN: Alkyl halides react with
aqueous ethanolic silver cyanide to form alkyl
:

CH3OH E1 product
:

isocyanide as major product with a small amount

Proton removal of alkyl cyanide. Silver cyanide is mainly covalent.
from the 1 C AgCN
C2 H 5Cl  CHethyl
3  CH 2 NC
iso cyanide
CH3 CH3 H
 Action of KNO2: Alkyl halides react with
CH3CH C+ C=C + CH3OH2
potassium or sodium nitrite to give ethyl nitrite as
:

CH3 CH3CH2 CH3

the major product. Dimethyl formamide (DMF) is
H used as solvent. About 30% ethyl nitrate is formed.
:

CH3OH E1 product
2
:

potassium Nitrite / DMF

C2 H 5Cl  
KNO2  aqueous ethanolic 

 In this reaction, these products are formed:
one from an S N 1 reaction and two from E1 CH 3  CH 2  O  N  O  CH 3  CH 2  NO2
reactions. (Major) (Minor)

12 NARAYANAGROUP
 JEE-ADV CHEM-VOL-V HALOGEN COMPOUNDS
 Action of AgNO2: On treating ethanolic solution  Action of Benzene:[Friedel-Craft’s
of halo alkanes with silver nitrite, the major product alkylation]: Alkyl halides react with benzene in
formed is nitro ethane and the minor product is alkyl the presence of anhydrous aluminium halides (Lewis
nitrite. acids) to form alkyl benzene.
AgNO2
C2 H 5Cl   CH 3  CH 2  NO2  CH 3  CH 2  O  N  O C6 H 6   anhy  AlCl3
C2 H 5Cl   C6 H 5CH 2  CH 3
ethyl benzene
(Major) (Minor)
 Action of CH3COOAg:Alkyl halides react with
Reaction with ammonia: On heating with silver acetate in alcoholic solution to form esters.
aqueous or alcoholic solution of ammonia in a sealed
tube at 100°C, alkyl halides yield a mixture of CH3COOAg
C2 H 5Cl   CH3  COOC2 H5
amines and quaternary ammonium salt. ethyl acetate
R–X + NH3 
 R–NH2 + HX Reaction with Metals:
C2H5Cl + NH3 
HCl
 C2H5NH2 Action of magnesium: Alkyl halides form
(Primary amine) Grignard reagents when treated with magnesium
C2H5NH2 + ClC2H5   (C2H5)2NH
powder in dry ether.
HCl
dry
(Secondary amine) R–X + Mg 
ether
 R–Mg–X
(C2H5)2NH + ClC2H5 
HCl
 (C2H5)3N
dry
C2H5Cl + Mg 
ether
 C2H5MgCl
(Tertiary amine)
–  Action of Sodium (Wurtz reaction ): Alkyl
 [(C2H5)4N]+ Cl
(C2H5)3N + ClC2H5  halides react with sodium in dry ether to give
hydrocarbons containing double the number of
 Action of NaBr or KI: Alkyl chlorides react
carbon atoms present in the alkyl halide. This
with sodium or potassium bromide or iodide to form
reaction is known as Wurtz reaction.
alkyl bromide or alkyl iodide. The reaction is
conducted with acetone as solvent. 2C2 H5Cl 
Wurtzreaction
 CH3CH2CH2CH3  2NaCl
Sodium/ Dryether

C2 H 5Cl  Na Br 
 C2 H 5 Br  NaCl  Reduction:Alkanes are formed when alkyl
C2 H 5Cl  KI 
 C2 H 5 I  KCl halides are reduced with nascent hydrogen obtained
by Zn and HCl or sodium and alcohol or lithium
 Action of Sodium ethoxide (Williamson’s aluminium hydride or hydrogen in the presence of
synthesis): Ethers are formed when haloalkanes Nickel or Palladium.
are treated with alcoholic sodium or potassium Re duction
C2 H 5Cl   CH 3CH 3
alkoxide. This reaction is known as “Williamson’s Ethane
synthesis”.

C2 H 5Cl 
CH 3  CH 2  ONa C2 H 5  O  C2 H 5 Elimination reaction;
 This reaction can also be carried with dry silver  Dehydrohalogenation: Ethyl chloride
oxide. undergoes dehydrohalogenation with alcoholic
KOH and forms alkenes. Alc.KOH acts as
R–X + Ag–O–Ag + X–R 
 R–O–R + 2AgX dehydrohalogenating agent.
C2H5Cl+AgOAg+ClC2H5 
 C2 H 5Cl alc . KOH
  CH 2  CH 2
C2H5–O–C2H5+2AgCl
NARAYANAGROUP 13
HALOGEN COMPOUNDS
MISCELLANEOUS SOLVED EXAMPLES
W.E-11: A 10 gm mixture of isobutane and
isobutene requires 20 gm of Br2 (in CCl4) for
complete addition. If 10 gm of the mixture is
catalytically hydrogenated and the entire
alkane is monobrominated in the presence of
light at 127ºC, which exclusive product and
how much of its would be formed? (At. Wt. of
bromine = 80).
Sol. isobutane + isobutene
ag bg
 a + b = 10 g
Br
|
CH3  C  CH 2  Br2  CH3 – C – CH 2 Br ;
| |
CH 3 CH3
CH 3  CH – CH3  Br2  No addition
| mixture so a protonation-deprotonation reaction is
CH3
(56) (80 × 2)
160 g of Br2 reacts with 56 g of isobutene
JEE-ADV CHEM-VOL-V
(d)What is the most likely first step for the
reaction? Most common reactions classified as
either protonation – deprotonation reactions
or reactions of a nucleophile with an
electrophile.
(e)What are the properties of the species
present in the reaction mixture after this first
step? Is any further reaction likely to occur?
Sol. (a) One reactant is an alkyl halide, the other is a
sulfur anion (remember that sodium ions are usually
spectator ions, they are to balance charge but not
to participate in the reaction).
(b) Yes, the bromine atom in 1-brompropane is a
leaving group.
(c)The sulfur anion is a nucleophile. The alkyl
halide contains an electrophilic carbon atom.
(d) No strong acids (pKa < 1) or bases (pKa of
conjugate acid > ~13) are present in reaction
not probable. Reaction of the nucleophilic sulfur
atom with the electrophilic carbon atoms is most
likely.

56  20 + – s
 20 g of Br2 reacts with = 7 g of isobutene  Br H3C
160
(b) H3 C
 amount of isobutane is = a = 10 – 7 = 3 g +
CH3  C  CH 2  H 2
–s Br –
 CH3  CH – CH 3
| |
CH3 CH 3
(e) All species formed are stable. No further
(56) (58) reaction will occur. The complete equation is:
Now 56 g of isobutene gives 58 g of isobutane.  Br + – + s
S Na H3C –
H3C + NaBr
58  7
7 g of isobutene gives = 7.25 g of isobutane
56

W.E-13:Treatment of 2-bromobutane with hot

W.E-12:Predict the product(s) of the reaction.
alcoholic KOH gives a mixture of three
– + isomeric butenes (A), (B) and (C). Ozonolysis
Br + S Na
H3C of the minor product (A), gives formaldehyde
(a) To what functional group classes do the and another aldehyde in equimolar amounts.
reactants belong? Both (B) and (C) gave the same single product
(D) on ozonolysis. What are the structural
(b) Does either reactant have a leaving group?
formula of (A), (B), (C) and (D) ?
(c) Are any of the reactants acids, bases, nucleo
philes, or electrophiles? Sol. CH 3 – CH – CH 2 – CH 3 
|
Br

14 NARAYANAGROUP
 JEE-ADV CHEM-VOL-V HALOGEN COMPOUNDS

CH3CH2Br in the presence of NaNH2 to give

Alc. KOH
CH3–CH2–CH = CH2 (A) another hydrocarbon (D) which on ozonolysis
(20%) yields diketone (E). (E) on oxidation gives
propanoic acid. Give structures of (A) to (E)
with reasons.

Compound (A) Compound (B)

Br2/CC14
Alc. KOH Molecular weight 54 Molecular weight
CH3–CH=CH–CH3 (Cis & Trans) excess (593% more than A)
(B and C) (80%) (Major product) CH3CH2Br
in NaNH2
Cataytic
(D) C  Molecular weight
O3 Hydrogenation 7.4% of (A)
CH3 – CH2 – CH = CH2 Zn
/ H 2 O CH3CH2CHO
O3
O3 Sol.
+ HCHO (B,C) CH3 – CH = CH – CH3 
Zn/H O
Diketone (E)
2
2CH3CHO (O)

Diketone (E)
W.E-14:Alkyl halide are most often prepared from
alcohols, rarely by direct halogenation, supply 100gm of (A) add Br2 and the new weight is 593gm
structure formulas for the alkyl halides  54 gm of (A) add Br2 and the new weight is
synthesized in the reactions.
593  54
= 320.2 gm  No. of moles of
NaBr, H 2SO4 100
(a) CH3CH2CH2CH2CH2OH 


Weight 360.2
Conc. HCl
(b) (CH3)3COH   Br2=  = 2 mole
Molecular weight 160
room temp.

(i) As two moles of Br2 adds hence compound

(c) CH3CH(OH)CH2CH2CH3 
PBr3
 has two p bonds hence general formula should
PI3 (form P  I2 )
(d) CH3CH2CH2OH   (CnH2n–2) CnH2n-2 = 54 ; 12n + 2n – 2 = 54;
n = 4  molecular formula = C4H6
SOCl2
(e) Me2CHCH2OH   (ii) (A) reacts with CH3CH2Br in presence of
Sol. (a) CH3CH2CH2CHBrCH3 NaNH2Compound (A) should be terminal
(b) (CH3)3 CCl alkyne i.e. 1-butyne
Br
(c) CH3 – CH – CH2CH2CH3 Br2
| CH Br
H3C
Br (A) CC14
Br
H3C CH3CH2Br
(d) CH3CH2CH2I Br
in NaNH2 CH3
Cataytic
(e) Me2CHCH2Cl C2H5 Hydrogenation H3C
C 
(D)
H 3C O3
W.E-15:A hydrocarbon (A) of molecular weight O
54 reacts with excess of Br2 in CCl4 to give a
compound (B) whose molecular weight is 593% H 3C C2H5
more than that of (A). However on catalytic O
hydrogenation with excess of hydrogen (A) (O)
forms (C) whose molecular weight is only 7.4%
more than that of (A). (A) reacts with 2CH3CH2COOH

NARAYANAGROUP 15
HALOGEN COMPOUNDS JEE-ADV CHEM-VOL-V
W.E-16:How will you bring about the following (g) Bromoethane to cis-hex-3-ene
conversions in not more than two steps ? 2C 2 H 5 Br + NaC  CNa   CH3 –
2NaBr
(a) Ethene to bromoethene bromoethane disodium
ethylide
(b) Propene to 1-nitropropane
 H 2 , Pd
(c) Propene to propyne CH2 – C  C – CH2 – CH3  
heat
(d) Ethanol to ethyl fluoride
H H
(e) Bromomethane to propanone
C=C
(f) But-1-ene to but-2-ene
(h) Bromoethane to cis-hex-3-ene CH3CH2 CH2CH3
(i) Benzyl alcohol to phenylethanenitrile (h) Benzyl alcohol to phenylethanenitrile
(j) Benzene to biphenyl
(k) Cyclopentene to cyclopenta-1, 3-diene CH2OH CH2C1
(l) Aniline to phenyl isocyanide KCN (alc.)
+ SOC12 

Sol. (a) Ethene to bromoethene heat

CH2= CH2+Br2(g)  500ºC BrCH = CH2 + HBr Benzyl alcohol

ethene bromoethene CH2CN

(b) Propene to 1-nitropropane
CH3 – CH = CH2 + HBr  + KC1
 CH3 – CH2
peroxide

AgNO2 (ethanol)
– CH2Br 
 AgBr
 CH – CH CH NO
3 2 2 2
Phenyl ethanenitrile

propene (i) Benzene to biphenyl

(c) Propene to propyne
2Cl , FeCl
3 Na (dry ether)
2  2 C1 
CH 3  CH  CH 2  Br2 
  HCl heat
propene

KOH (alc.)
CH3  CH  CH 2 
2HBr
 CH 3  C  CH
propyne
| |
Br Br biphenyl

(d) Ethanol to ethylfluoride (j) Cyclopentene to cyclopenta-1, 3-diene

C 2 H 5 OH  SOCl 2 
 C 2 H 5 Cl Br
ethanol chloroethane
CCl4
Br
KOH (alc.)
AgF, heat
+ Br2  
room temp.


 C2 H5 F  AgCl 2HBr
fluoroethane cyclopentene
(ethyl fluoride)
3
(e) Bromomethane to propanone 2
KCN (ethanolic)
CH 3 Br  CH3CN 1
bromomethane  KBr cyclopenta-1,
3-diene
CH MgI/H O
3 2  CH  C  O  NH  Mg(OH)I
 3 3 (k) Aniline to phenyl isocyanide
|
CH3
propanone NH2

(f) But-1-ene to but-2-ene +

CHCl3
chloroform
heat
+ 3KOH (alc.)  
CH 3  CH 2  CH  CH 2  HBr 

but 1 ene Aniline
N C
KOH (alc.)
CH3  CH 2  CH  CH 3  
| + 3KC1+3H2O
Br
Phenyl isocyanide
CH 3  CH  CH  CH 3
but  2  ene (phenyl carbylamine)

16 NARAYANAGROUP
 JEE-ADV CHEM-VOL-V HALOGEN COMPOUNDS

W.E-17:Which compound in each of the following  The C - X bond in aryl halides is shorter and
pairs will react faster in SN2 reaction with HO–? stronger than the C - X bond of alkyl halides.
(a) CH3Br or CH3I  The strength of the C - X bond causes arylhalides
(b) (CH3)3CCl or CH3Cl to react very slowly in reactions in which cleavage
(c) CH2 = CHBr or CH2 = CH – CH2Br of C - X bond is rate determining i.e. nucleophilic
Sol. (a) CH3I will react faster than CH3Br in SN2 substitution.
reaction with OH– because the leaving group I is
bigger than Br. Preparation Methods of Halo
(b) CH3Cl will react faster than (CH3)3CCl in SN2 Benzene:
reaction with OH–, because the CH3– group is 1) Direct Halogenation of Benzene: This reaction
smaller than the (CH3)3C - group. The smaller is carried out in absence of sunlight but in presence
group offers less steric hindrance. of halogen carrier.
(c) CH2 = CH – CH2Br will react faster than CH2  This reaction is an electrophilic substitution reaction.
= CHBr in SN2 reaction with OH–, because in
a) Chlorination:
vinylic halides (CH2 = CHBr), C – Br bond
develops a partial double bond character due to
resonance. This makes C – Br bond stronger and AlCl3 Cl
+ Cl2 + Hcl
less polar, and hence breaking of C – Br bond
becomes more difficult.
 In this reaction AlCl3 is halogen carrier which is an
– +
CH2=CH–Br CH2–CH=Br electron deficient species, and hence acts as Lewis
Primary allylic halides may react by both SN1 and acid.
SN2 depending upon the nature of nucleophile and  It is the tendency of halogen carrier that it will
the solvent. polarise chlorine molecule to produce electrophile
ARYL HALIDES chloronium ion.
+ –
 Aryl halides are the compounds having halogen Cl–Cl+AlCl3 Cl + AlCl4
atom directly attached to the sp2 carbon of
aromatic ring
 They are represented by the general formula Ar-
X, where Ar may be phenyl, substituted phenyl or ELECTROPHILE
other aromatic system.  This electrophile attacks the benzene ring giving an
Cl arenium ion which is stabilised by resonance.

H H
+ SLOW
Eg:- + Cl Cl Cl
+ +
CHLOROBENZENE
 In Benzyl halides, the halogen atom is attached to + H H
sp 3 carbon which is attached to aromatic ring Cl + Cl
CH2– Cl  This step is slow step and hence rate determining
step.
Eg:-  In the second step the carbocation looses a proton

BENZYL CHLORIDE to the base AlCl4  to give chlorobenzene.

 In aryl halides, halogen atom is bonded to sp2 Cl
carbon while in benzyl halides, halogen atom is
–
AlCl4 FAST Cl
bonded to sp3 carbon.
H + HCl
+

NARAYANAGROUP 17
HALOGEN COMPOUNDS JEE-ADV CHEM-VOL-V
 On using excess of chlorine then the products are  This benzene diazonium chloride when heated
ortho, para disubstituted benzene. wit h CuCl / HCl or CuBr / HBr produces
corresponding aryl halide.
Cl Cl Cl
AlCl3
+ Cl2 Cl2,AlCl3 + Cl
Cl Cl
ORTHO PARA
DICHLORO DICHLORO CuCl
BENZENE BENZENE
N2+Cl– HCl
b) Bromination:
AlCl3 Br
+ Br2 + HBr

Br
c) Iodination: Iodination of benzene is not
possible because of formation HI. This being strong CuBr
reducing agent reduces alkyl iodide back to alkane. HBr

I  This reaction is known as Sandmeyer’s reaction.

+ I2 + HI
Gattermann Reaction:
N2+Cl– Cl

Strong reducing agent

 To get iodo benzene strong oxidising agents like Cu/HCl
+ N2
HNO3 , HIO3 , HgO etc are used which destroy HI.
Preparation of Chlorobenzene from
d) Fluorination: Direct fluorination of benzene
Phenol:Chlorobenzene can be prepared by the
is not done as this reaction is highly explosive and
cannot be easily controlled and hence it is prepared action of PCl5 on phenol.
from benzene diazonium chloride.  The yield in this method is very poor because of
side product POCl3 which readily reacts with
2) Decarboxylation of Sodium Salt of
phenol to give triphenyl phosphate.
Chloro Benzoic Acid:
Raschig Process (Exclusive for Advance):
Cl Cl
CaO Cl
+ NaOH + Na CO2 3
CuCl2
2 + 2HCl + O2 2 + 2H O
2
COONa
 The acid salt may be ortho, meta or para derivative. Hunsdiecker Method:
3) From Benzene Diazonium Chloride: C6 H 5COOAg  Cl2  C6 H 5Cl  CO2  AgCl
 Benzene diazonium chloride is obtained on Physical properties: On going down the group
diazotisation of aniline. M.P. and B.P. increases because of increase in size
of atoms. Hence, decrease in B.P. follows the order
NH2 N2+Cl–
IODO ARENES > BROMO ARENES >
NaNO2+HCl, 0-5°C CHLORO ARENES > FLUORO ARENES
 With the same halogen atom these properties
BENZENE increase as size of the aryl group increases.
DIAZONIUM
CHLORIDE
 B.P. of isomeric dihalo benzenes are nearly the
same. But their M.P’s are quite different.
18 NARAYANAGROUP
 JEE-ADV CHEM-VOL-V HALOGEN COMPOUNDS
 Generally the M.P. of para isomer is always higher  Low reactivity of C - Cl bond in chlorobenzene as
than that of ortho or meta isomer because para compared to alkyl halide can also be explained on
isomers are more symmetrical and hence its the basis of polarity of C - Cl bond.
molecules are packed closely in the crystal lattice.  It is observed that C - Cl bond in chlorobenzene is
This results an increase in intermolecular attractions less polar than C - Cl bond in alkyl halide.
and finally increase in melting points than the  This is because in chlorobenzene carbon atom is in
corresponding isomers. sp2 hybridised which is more electronegative than
 M.P. for isomeric dichloro benzene is in the the sp3 hybridised carbon atom in case of alkyl
order of chloride.
Cl Cl Cl  Therefore, the sp2 hybrid carbon of C - Cl bond in
aryl halides is less willing to release electrons to the
Cl halogen than a sp3 hybrid carbon in alkyl chloride.
> <
Cl
Nucleophilic substitution reactions of
chloro benzene: It has been observed that
Cl electron withdrawing groups such as  NO2 groups
M.P. 256 K 249 K 325 K present at ortho and para positions (not at meta
Chemical properties: Chlorine of position) with respect to halogen greatly activates
chlorobenzene is inert nucleophile i.e., far less the halogen towards nucleo philic displacement i.e.,
reactive than halo alkanes towards nucleophilic these groups withdraw electrons from benzene ring
substitution reactions. as well as carbon atom of the C - Cl bond.
 This is because of lone pair of electrons present at  Also greater the number of such groups at ortho
chlorine atom will conjugate with  electrons of and para positions, more reactive is the halo arene.
benzene ring, as a result some double bond Examples:
character is developed between the C - Cl bond
Cl OH
and hence this bond becomes shorter and
stronger.
 This can be explained on the basis of following
resonance structures. 1) NaOH
3600C
+ + +
Cl Cl Cl Cl Cl
+
+
Cl OH

 Stronger C - Cl bond in chlorobenzene as NaOH

compared to alkyl chloride can also be explained 1600C

2)
on the basis of hybridisation.
 In chlorobenzene carbon atom bearing chlorine
is sp2 hybridised whereas in alkyl chloride it is NO2 NO2
in sp3 hybridised state.
 Since sp2 hybrid orbital is smaller in size as Cl OH
compared to sp3 hybrid orbital, therefore, C-Cl
bond in chlorobenzene should be shorter and hence NO2 NO2
stronger than alkyl halide. NaOH
0
0 96 C
Cl H 1.77 A
3
1.69 A0 sp2 sp 3)
C Cl NO2 NO2
H 2,4 dinitro 2,4 dinitro
chloro phenol
H benzene

NARAYANAGROUP 19
HALOGEN COMPOUNDS JEE-ADV CHEM-VOL-V
Cl OH Other reactions of Chloro Benzene:
O 2N NO2 O 2N NO2 1. Halogenation
H 2O Cl Cl Cl

FeCl3 dark
Cl
+ Cl2  Δ
 +
NO2 NO2
sym. trinitro sym. trinitro
chorobenzene phenol Cl
(Picric acid)
2. Nitration
W.E-18:Which of the following does not give Cl Cl Cl
white precipitate with acidified NO2
2 4 H SO
AgNO3 solution. + HNO3  +
60C
Cl
NO2
3. Sulphonation
Cl Cl Cl
a) b) CH 2  CH  Cl
SO3H
Δ
+ H2SO4  +


c) CH 2  CH  CH 2  Cl d) both a and b. SO3H

Sol. ‘d’. In ‘c’ chlorine containing carbon atom is in sp3 4. Friedel Crafts Reactions
hybridised state and it is more polar and also it easily (a) Alkylation
gives AgCl precipitate. In case of ‘a’ and ‘b’ there Cl Cl Cl
is double bond character between C - Cl bond and anhyd. R
carbon bearing chlorine atom is in sp2 hybridised + R–X

AlCl3

+
state i.e., C-Cl bond is stronger bond and hence Δ
chlorine cannot be easily replaced. R
(b) Acylation
W.E-19:Arrange the following in decreasing order Cl
of their reactivity towards nucleophilic
anhyd. AlCl3
substitution. + CH3COCl or CH3 C– O– C CH3 
Δ
O O

Cl O Cl
C–CH3

C=O

CH3

Sol. V > IV > III > II > I. More electron withdrawing (c) Benzoylation
groups at ortho and para positions, chlorine can Cl
easily be replaced by nucleophile.Resonance effect
is not observed at meta position. + C6H5COCl or C6H5 –C– O– C C6H5
O O
Reaction with NaOH (Dow’s process): AlCl3
Δ

Cl ONa OH Cl O Cl
C–C6H5
3600C dil. HCl
+ 2NaOH +

Sodium phenoxide Phenol C=O

 This reaction proceeds by the formation of benzyne C6H5
intermediate.
20 NARAYANAGROUP
 JEE-ADV CHEM-VOL-V HALOGEN COMPOUNDS

III. Miscellaneous Reactions Cl Cl

(a) Fittig Reaction +
H
+

dry ether +E E
2 Cl+2Na   +2NaCl
(b) Wurtz-Fittig Reaction
W.E-21:How will you prepare m-bromo iodo
dry ether
Cl+R–Cl+2Na  R+2NaCl

 benzene from benzene.
NO2 NO2
Here side products like R – R and are Sol.
also formed. HNO
3
 2

Br
H 2SO 4 Fe
W.E-20:Which one of the following structure of Br
NH2 N2Cl
C7 H 7 Cl has weakest C - Cl bond.
CH2–Cl Cl Cl Cl NaNO /HCl
2


Sn /HCl 
0ºC
Br Br
a) b) c) d)
I

CH3 KI

CH3 Br

Sol. ‘a’ W.E-21:Identify the compounds A to D

Nitric Acid
 Just as in chlorobenzene C - Cl bond in ortho, (A)  Sulphuric Acid
 p-nitroToluene
meta and para chloro toulene has double bond Sn / HCl NaNO 2 (D)
character due to resonance. Whereas in benzyl  (B)  (C)   p-flouro
HCl, 0  5 C 
chloride the C - Cl bond is pure single covalent toluene
bond . Sol. A= Toulene, B = p-toluidine, C = p-toluene
 Thus out of four isomers the C - Cl bond is diazonium chloride, D = HBF4
weakest in benzyl chloride.
Electrophilic substitution reactions of W.E-22: Which of the following derivatives of
Halo Benzene: Halo benzene undergoes benzene would undergo hydrolysis most
usual electrophilic substitution reactions. readily with aq. KOH
 Halogen atom being deactivating in nature, but Cl Cl Cl Cl
activates the benzene ring by increasing electron ON 2 NO 2
NO 2

density at ortho and para position. a) b) c) d)

 Therefore, during the electrophilic substitution NO

N
2

NO NO NO
reaction, electrophile will occupy ortho and para 2 2 2

H C CH
position. 3 3

 As halogen atom in halo benzene has -I effect hence Sol. B. – NO2 group increases reactivity because of –
its electrophilic substitution reactions occur slowly R and –I effect.
under more drastic conditions as compared to W.E-23: When all cis isomers of C 6 H 6 Cl 6
benzene. (1,2,3,4,5,6-Hexachlorocyclohexane) is heated
 Chlorine withdraws electrons through inductive with alc. KOH, the most probable product is
effect and releases electrons through resonance.
Cl Cl
 Through inductive effect, chlorine destabilises the a) Cl b) c) d)
intermediate carbocation formed during the Cl Cl
b) d)
electrophilic substitution. a)
 Through resonance, halogen tends to stabilise the Cl Cl Cl Cl
carbocation. Cl
Sol. B. It is an example of E2 elimination.

NARAYANAGROUP 21