Chemistry : Alkyl Halides & Aryl Halides
ALKYL HALIDES &
ARYL HALIDES
Syllabus
Alkyl halides (nucleophilic substitution reactions, rearrangement of carbocations).
CONTENTS
 Structure and nomenclature
 Preparation
 Physical Properties
 Chemical Properties
 Elimination
 Elimination versus substitution
 General type reactions
 Williamson’s synthesis of ethers
 Case of AgCN and NaCN
 Dihalides
 Tri halides (Haloform)
 Aryl halides
INTRODUCTION
Saturated hydrocarbons are the class of
compounds which are almost unreactive due
to presence of strong C—H bonds which are
non-polar. They undergo mainly free radical
substitution reactions with halogens and
combustion in air. However, if they are
converted to their halogen derivatives i.e.,
alkyl halide, they become very reactive due
to presence of polar C—X bonds. Once they
are converted into haloalkanes, they can be
transformed to any class of organic
compounds in one or more than one steps by
means of two important reactions i.e.,
nucleophilic substitution and/or elimination
reaction.
In this chapter we will discuss mainly the
nucleophilic substitution reaction and
elimination reaction of alkyl halide. Here we
will also discuss the halogen derivatives of
benzene. In contrast to alkyl halides, aryl
halides do not undergo nucleophilic
substitution reaction in normal conditions.
But, they can do so if they are suitably
substituted with an appropriate group in the
benzene ring.
 Chemistry : Alkyl Halides & Aryl Halides

1. STRUCTURE AND NOMENCLATURE

1.1 ALKYL HALIDES

The alkyl halides have the general formula CnH2n+1X or RX, where X denotes chlorine, bromine or
iodine. Fluorine is not included, since fluorides do not behave like other halides.
CH 3 ––CH 2 Cl CH 3–– CH–– CH 3 CH 3–– CH–– CH 2–– Br
Ethyl Chloride
or Chloro ethane Cl CH 3
Isopropyl Chloride Isobutyl Bromide
or 2 – or 1 –Bromo – 2 methyl
propane

CH 3 CH 3

CH 3––C––CH 2 –– CH 3 CH 3–– C–– CH 2––CH 2 –– Br

Cl CH 3

tert –Pentyl chloride Neohexyl bromide

or 2 –chloro –2– methyl Butane or 1 –bromo –3,3 -dimethyl propane

H2C = CH –– CH 2Cl H2C=CH –– CH = CH –– CH=C –– CH 3

Allyl Chloride or
3–Chloro 1 –propene Cl
6–– Chloro –1, 3, 5 –heptatriene

H2C =CHBr CH 2–– CH 2 CH 2–– CH 2

Vinyl Bromide
Cl Cl OH Cl
1,2 –dichloroethane Ethylene Chlorohydrin
or 2–Chloroethanol
H
Cl CH 2Br

Cyclohexyl Chloride Benzyl Bromide

2. PREPARATION

2.1 FROM ALCOHOLS

HCl
R OH 
R Cl
PCl3

PCl5

SOCl2

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Chemistry : Alkyl Halides & Aryl Halides

CASE OF HX :
Features :
(a) — OH group is not a good leaving group, that is why reaction occurs if HX is used but fails if

NaX is used, because in case of HX, — OH group is protonated and thus  O H 2 becomes a better
leaving group.
 —

H X
R  OH  R  OH 2   RX  H 2O
Mechanism :

  
H SN1
R  OH  R  O H 2   R  H 2O

SN2 X X

RX + H2O RX

Therefore both SN1 and SN2 pathway are possbile, 1° alcohols under SN2 pathway while 2° and 3°
alcohol undergo SN1 pathway. Consequently in case of 1° alcohols carboium ion re-arrangement
doesn’t occur but it occurs in the case of 2° and 3° alcohols.
HBr
H3 C  CH 2  CH 2  OH 
SN
 H3C  CH 2  CH 2  Br
2
(Only)

CH3 CH3 CH3

HBr
H3C CH CH CH3 
SN1
 H3C CH CH CH3 + H3C C CH2 CH3

OH Br Br
(Minor) (Major)
However it should be noted that crowded primary alcohols undergo SN1 reaction since steric crowding
suppresses the possibilities of SN2 pathway. e.g.
CH3 CH3 CH3
HBr
H3C C CH2 OH 
SN1
 H3 C C CH2 CH3 + CH3 C CH2 Br

CH3 Br CH3
(i) Note the fact n-alkanols undergoes only SN2 pathway.
(ii) Reactivity of alcohol.

3o  2o  CH 3OH  1o

i.e. 3o ROH  2o ROH  CH3OH  1o ROH

CH3  CH 2  OH  CH 3OH
(More Reactivity)

(iv) Reactity of HX
HI  HBr  HCl  HF
 Chemistry : Alkyl Halides & Aryl Halides

Because
(a) HI is strongest acid.
(b) I – is strongest nucleophile
However, HI is also a good reducing agent.
HI HI
R  OH   R  I   RH  I 2
R I 
 RH  I 2
HI
That is why preparation of RI through the direct use of HI is generaly avoided.

2.2 FINKELSTEIN REACTION

Actually RI is generally prepared through halogen exchange reaction also known as
Finkelstein Reaction.
Acetone (Solvent)
CH3CH 2 Br  KI   H3C  CH2  I  KBr

CH3 CH 2  Br 
SN
 H3 C  CH 2  I  KBr
2

This is an SN2 reaction. Therefore only 1° or 2° R – X is used.

2.3 GROOVE’S PROCESS

Since HCl is less reactive, ZnCl2 is added as a catalyst. Actually HCl/ZnCl2 mixture is called ‘Lucas-
reagent’.
HCl
ROH 
(Slow )
 R  Cl
HCl
R  OH 
ZnCl
 R  Cl
2
(Fast )

H
ZnCl2
R  OH   Cl R O ZnCl2
+
A good
leaving group
R  Cl   HOZnCl2 

H+

H 2 O  ZnCl2
ZnCl2 catalyses the reaction by converting – OH group into a very good leaving group.
Lucas reagent is used to distinguish 1º, 2º and 3º alcohols.

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Chemistry : Alkyl Halides & Aryl Halides

Polar (CH3)3 C — OH OH CH3 — CH2 — OH

HCl H3C CH CH3 HCl

ZnCl2 ZnCl2
HCl
ZnCl2
Non-Polar (CH ) C — Cl CH3 — CH2 — Cl
3 3
Precipitate
H3C No turbidity
CH Cl appear
H3C
Turbidity appear Turbidity appear in 5
immediately to 10 minutes

2.4 HUNSDIECKER REACTION

R — COOH

O NH4OH

AgNO3
NH4NO3 + R C O Ag   R — COONH4

Insoluble in water
Soluble in CCl4
O
Br2
R C OAg 
CCl
 R — Br + AgBr + CO2
4

Hunsdiecker reaction
Mechanism :
O

R C OAg + Br — Br

O
O
R+ C O + Br R C O Br + AgBr

R + Br + CO2
R — Br

COOH
1. NH 4OH Br
2. AgNO 3

3.Br2 / CCl 4


This is a good method for making alkyl or aryl halides. It is a free radical reaction.
 Chemistry : Alkyl Halides & Aryl Halides

2.5 REACTION WITH PX3

PX 3
R — OH   RX + H3PO3
Mechanism : Br

R — OH + P Br

Br
H
Br
R O P
Å
Br
Br
Br
R — Br + HO P
Br
2 ROH + HOPBr 2

2 RBr + H3 PO3
This is an SN2 reaction, therefore, only 1° or 2º ROH should be used.

2.6 CASE OF PX5

PX5
R — OH   R — X  POX 3  HX
Cl Cl

R — OH + P Cl

Cl Cl
H

R O PCl 4
Å

Cl
Cl Cl

R — Cl + H O P Cl (Not Stable)

Cl Cl

POCl3 + HCl

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Chemistry : Alkyl Halides & Aryl Halides

2.7 DARZEN’S PROCESS

SOCl2
Case of SOCl2 (Thionyl Chloride) R — OH   R — Cl  SO 2  HCl

Mechanism :
H Cl Cl
S
R O +
H O
Cl Cl

R O S R O S Cl + HCl
Å
O O

R O S

Internal nucleophilic Cl
substitution SNi SO2 is a good leaving group
R — Cl + SO2
Reaction with SOCl2 is SNi which leads to only retention of configuration.
However SNi become SN2 if pyridine is used as base.
O

R — OH + SOCl2 R O S Cl

O O

R O S Cl R O S N + Cl

N

O

R O S N

N
Cl
RCl + SO2 +
 Chemistry : Alkyl Halides & Aryl Halides

CH3 CH3
HBr
H Br + Br H

C 2H5 C 2H5
CH3
CH3
PBr 3
Br H
H OH PBr 5
C 2H5
C 2H5
CH3
SOCl2
Cl H
Pyridine
C 2H5
CH3
SOCl2
H Cl

C 2H5

3. PHYSICAL PROPERTIES
1. The lower members (CH3Cl, CH3Br and C2H5Cl) are gases. The rest of the lower members
are colourless, sweet – smelling liquids.
2. Although Alkyl Halide is polar in nature, they are generally insoluble in water. This is because
of their inability to form hydrogen bonds while existing in water, or even break the hydrogen
bond existing in water. These are, however, soluble in alcohol, ether and benzene.
3. Haloalkanes have considerably higher boiling points than alkanes having same number of carbons
because of greater molecular weight.
4. Bromides and iodides are heavier than water.
5. Alkyl iodides are sufficiently reactive to be decomposed by light. Liberation of iodine is
responsible for the darkening of alkyl iodides on standing.
h
2RI   R –– R + I
2

4. CHEMICAL PROPERTIES
An alkyl halide undergo only two type of reaction.
(i) Nucleophilic substitution
(ii) Dehydrohalogenation, making alkenes or alkynes

4.1 IONIC SUBSTITUTION REACTION

Features :
1. If a reaction involves replacement of group or atom by anothers group or atom then it is called
substitution reactions.

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Chemistry : Alkyl Halides & Aryl Halides

e.g. OH  CH3  I  CH 3OH  I 

2. In all substitution reactions one -bond is cleaved to form a new -bond.
3. Depending upon the attacking species substitutions can be divided as :
Nucleophilic substitution reaction
If attacking species is a nuclephile
Cl NH2

NaNH

 + Cl–
e.g. 2

4.2 NUCLEOPHILIC SUBSTITUTION REACTION

Substrate

R — L + Nu  
 R — Nu  L
Pr oduct Base

Leaving group
Since one bond is cleaved and other is formed. There can be only three possibilities for the mechanism
of this reaction.

SN1 : First C – Cl bond is cleaved and then C – Nu bond is formed.

H3C H3C
(Slow ) +
C Cl C + Cl–
H3C CH H3C CH
3 3

Nu
(CH 3 ) C 
(Fast)
 (CH3 )3 C — Nu

R—L R   L .... (I)

Since, valency rule is not violated so this pathway is acceptable
R  N u 
 R — Nu ....(II)
It is a two step pathway.
First step involves ionization of the substrate giving carbonium ion intermediate and second step
involves formation of bond between R+ and Nu–.
Naturally therefore first step is slower than second step. Consequently first step is rate determing
step. Hence, Rate  [substrate]
order = 1 and molecularity = 1
That is why this pathway is called unimolecular nucleophilic substitution (SN1).
It is clear from the rate low that rate of SN1. reactions depend only upon the concentration of
substrate and not nucleophile.

SN2 : Both cleavage of C – L bond and formation of C – Nu bond occurs simultaneously.

H H H
Nu  
e.g. C L  Nu C  Nu — CH 3  L
L 
H
H H
T.S.
 Chemistry : Alkyl Halides & Aryl Halides

This is one step pathway and acceptable because valency rule is not disobeyed.
Hence, Rate [substrate] [nucleophile]
molecularity = 2
order = 2 (Not always)
That is why, this pathway is called as biomolecular nucleophilic substitution (SN2).
From the rate law it is clear that rate of SN2 reaction depend upon the concentration of both nucleophile
and substrate.

STEREOCHEMISTRY OF SN1 REACTION

CH3 CH3 CH3
rds
+ Nu 
H Br  C   H OH + HO H
C 2 H5 C 2 H5 C 2 H5
Retention Product Inversion Product

(Racemic mixture)
In SN1 reaction, stereochemistry is controlled by the 2nd step. Since, carbocation is sp2 hybridized
and has a pz-orbital empty one lobe above and one lobe below the plane. It is possible that Nu– can
attack on either side with equal probability, leading to 50% retention and 50% inversion generally.
Hence, SN1 reactions are said to be leading racemization.
OH OH
Br
H CH3 H3C H
H CH3 Aq. NaOH
  +
SN1
H3C H H3C H
H3C H
C 2 H5 C 2 H5
C 2 H5
Retention Inversion

Disteromers

TRANSITION STATE OF SN2 REACTION

In SN2 reactions Nu– attack from back side of the leaving group because
(a) In front side attack Nu– is strongly repelled by the leaving group as well as by C – L, bond pair
electrons. Such repulsion doesn’t occur if Nu– attack from back side.
(b) Bigger lobe of sp3 orbitals of C is already occupied by the leaving group but its smaller lobe is
free.
+
C L
-
Nu
–
An Nu attack the smaller lobe begins to increase in size and bigger lobe tends to decrease in size. In
the practice a state comes in which both lobes are of equal size. i.e. p-orbital is generated .
Therefore hybridization of the site of reaction becomes sp2. This state is called T.S., in which nucleophile
is above the plane and leaving group is below the plane of sp2 orbital.

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Chemistry : Alkyl Halides & Aryl Halides

- +
Nu C L

T.S

STEREOCHEMISTRY OF SN2 REACTION

Since attack of nucleophile is described above occurs from the back side, inversion of the configuration
occurs.
CH3
H OH Only retention
C 2 H5

CH3 CH3
Aq. NaOH
H Br 
SN 2
 HO H Only inversion
C 2 H5 C 2 H5

CH3 CH3
H OH + HO H (retention + inversion)
C 2 H5 C 2 H5
Hence, SN2 reactions lead to inversion of configuration i.e., Walden inversion.

4.3 REACTIVITY CONTROLLING POWER IN SN1 / SN2 REACTION

1. Case of SN1 Reaction : rds of SN1 : R — X R   X

SN1 reactivity  stability of carbocation.
Since site of reaction is positive in the intermediate its stability is highly sensitive to electronic
effects of substituents. On the other hand, steric effect is not efficiently operating. In other
word SN1 reactivity is controlled mainly by electronic effects. However in some cases steic
factor becomes dominants.

2. Case of SN2 Reaction : rds of SN2 :

 
C L 
 Nu C L
Nu–
T.S.

SN2 reactivity  stability of T.S.

Since there is no loss or gain of electrons on the site of reaction (if C — L bond cleavage and C — Nu
bond formation occur at similar rates).
Stability of T.S. is almost insensitive to electronic effects of substituents.
 Chemistry : Alkyl Halides & Aryl Halides

On the other hand, on going from substrate to T.S. number of groups on the site of reaction increases
which increases the steric repulsion. Hence, stability of SN2 T.S. is sensitive to steric factors and not
to electronic factors.
However, unlike SN1 reaction probability of SN2 reaction depends also upon the fact that how fast a
nucleophile can attack on the substrate. That is why, many cases will be sensitive to electronic
effects of substituents playing in ground state of substrate itself.

4.4 EFFECT OF SOLVENTS

Case of SN1 Reaction :
 R   L (In gas phase)
R — L 

 R   L (In polar solvent)

R — L 
Note that in rds of SN1 reaction, the most polar species is carbocation intermediate. Therefore a
polar solvent (protic solvent) solvates the intermediate more effectively than the substrates. Therefore
activation energy is reduced and SN1 reactivity increases. This is also a reason that SN1 reaction
doesn’t occurs in gas phase.
In other words, a considerable portion of activation energy is compensated by solvation energy which
is not possible in gas phase.
Case of SN2 reactions : In this type of SN2 reaction nucleophile is most polar.
Therefore, a polar solvent decreases the chance of SN2 reactions by increasing the activation energy.
Since, nucleophile will be most solvated.
That is why SN2 reactions are highly favoured to DMSO or DMF. Because these solvents dissolve
nucleophile without much solvation.

H2 O H H H H
O Nu O
C 3OH Nucleophile is heavily solvated.
Polar protic This retards nucleophilicity to very
Solvents C2 H5 OH H high extent
CH3COOK O
H

SN2 reactions are not favoured by protic polar solvents.


O
Polar aprotic D.M.S.O.  S Nu–
solvents D.M.F.
H3C CH3

Nucleophile dissolved without much solvation. In these solvents, nucleophilicity are not much affected.
Hence SN2 reactions are highly favoured in these solvents.
 
R — L  NH 3 
 H 3 N—    R    L

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Chemistry : Alkyl Halides & Aryl Halides

In this type of SN2 reaction, T.S. is most polar. A polar solvent should fovoured this SN2 reaction.
Once again for similar reason DMSO and DMF are most suitable solvent.

NaOH
H3C CH CH3 
H 2O(SN1 )
 H3C CH CH3
Br OH
NaOH SN2

D.M.F.

4.5 EFFECT OF LEAVING GROUPS

SN1
R L 
rds
 R   L

SN1   

R L    N u  T.S.
R  L
 
Cleavage of C–L bond is involved in rds of both SN1 and SN2 reactions. Therefore a better leaving
group increases the chance of both SN1 and SN2 reactions.
If L– is a poor base then leaving group is a better leaving group.

EXERCISE - 1
Which alkyl halde would you expect to react more rapidly by an SN2 mechanism ?

Br

Br
(a) or

(b) or Cl
Cl

Br
(c) or Cl

5. ELIMINATION
1. Those reactions are called eliminations in which two atoms or groups, are removed without
adding any atom or group.

CH3 — CH— CH— CH3 

 RCH  CHR
| |
Br Br
 Chemistry : Alkyl Halides & Aryl Halides

2. Depending upon relative position of leaving groups, elimination can be classified as :

 
Zn
CH3 — C H— C H— CH 3 

 CH 3 — CH  CH — CH 3  ZnBr2
| |  e limination or (1,2 elimination)
Br Br
base
CHCl3 

 CCl 2  HCl
 -elimination or (1, 1-elimination)

CH2
 
 Zn
CH2 CH2 

 + ZnBr2

Br Br -elimination or (1,3 – elimination)

5.1 β -ELIMINATION
base / 
R — C H — CH— R   R — CH  CH — R  HBr
| |
H Br
Features :
1. In all  -elimination two  -bonds are cleaved to form  -bond as product.
2. Mechanism : since two  -bonds have to be cleavage they can be simultaneous or in two steps.
E2 – Simultaneous Cleavage
Br
Br
C C
C C -
C C + BH + Br–
H
H -
- B
B T.S.
This is acceptable mechanism. Now it is one step pathway.
 Rate  (substrate) [base]
 order = 1 + 1 = 2, molecularity = 2
Hence, this pathway is called bimolecular elimination (E2).
According to rate law, rate of E2 pathway is dependent on the concentration of both substrate
and base.
E1 – First C — Br bond is cleaved
Br
+
C C C C + Br– ...(i)
H H

+
C C C C + BH ...(ii)
H
-
B
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Chemistry : Alkyl Halides & Aryl Halides

First step is rds which produces carbocation intermediate.

... Rate  [RX]
... order = 1 and molecularity = 1
Hence, this pathway is called unimolecular elimination and it is acceptable.
Unlike E2 reaction, rate of E1 reaction is independent of the concentration of the base.
E1CB C — H bond is first cleaved :
Br Br
C C C C + BH
H ...(i)
-
B

Br
C C C C + Br– ...(ii)

This also seems to be acceptable mechanism.

In most of this kind of elimination,
2nd step is rds because first step is an acid-base reaction and is faster.
... rate  [carbanion]
 [RX]
This is called unimolecular elimination involving carbanion as intermediates (E1CB).

EXERSICE - 2

Write structural formulae of the alkenes from the reactions :

Br

CH3CH 2 OK
(a) 
 ?

Br

CH3CH2 OK
(b) 
?

CH CH ONa 

3 2
 ?
(c) 

CH2 CH2 CH3

Transition state of E1 pathway

Br
Br
C C
C C Anti elimination
  Antiperiplaner T.S.
H
H -
- B
B T.S.
 Chemistry : Alkyl Halides & Aryl Halides

C C
C C syn elimination
  Synperiplaner T.S.
H Br
H Br -
B
- T.S.
B
E2 may be antielimination or synelimination. However syn elimination occurs only if anti-elimination is
not possible. This is because :
(a) Antiperiplaner T.S. is more stable than that of syn. Since former is staggered and latter is
eclisped.
(b) Antiperiplaner T.S. provides better bonding situation. Since C—H bonds pairs electrons attack
on the orbital holding Br from backside.
Orientation of Elimination :
This equation stands only when molecule has more than one type of  – H atoms.
CH3
H2C CH CH Minor
CH3
CH3
H3C CH HC
CH3
Br CH3
CH2 CH CH Major
CH3
Question of orientation stands here since there are two types of  — H . In such situation following
rules are applied to predict the major product.
Saytzeff’s Rule : This rule states that more stable alkene should be the major product. Example
given below.
H3C CH CH3   CH3 CH CH2
No question of orientations because
Br
all 6 -H atoms are identical

The basis of this rule is that incipient double bond in transition state is more stable if it is more substituted.
CH3
CH2 CH HC
H Br CH3

Anti Saytzeff's Elimination Saytzeff's Elimination

-
B
- -
Br H
CH3 CH3
CH2 CH HC CH3 CH C
TS-1 - CH3
H CH3 Br
- TS-2
Incipient Br Incipient
double bond double bond
CH3 CH3
CH2 CH CH CH2 CH CH
Less-stable CH3 more-stable CH3

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Chemistry : Alkyl Halides & Aryl Halides

Note : T.S. II has more stable incipient double bond. In other world T.S. of Saytzeff’s-elimination in
product like. Saytzeff’s elimination is violated when base is sterically crowded.

CH3
-
H3C C crowded base
CH3
A crowded base can approach only a less crowded  — H . That is why anti Saytzeff’s elimination
predominates.
Hoffman’s Rule : This rule is applied when leaving group is cationic. In such cases acidity difference
betwen  — H atoms becomes much more. Therefore acidity factor controls the orientation. This is
in contrast with Saytzeff’s elimination, in which stability of alkene controls orientation.
Rule of Conjugation : This rule is applied when substrate has resonating group. In that cases  -
bond is dominantly formed at the position conjugated with that resonating group.

H3C
CH CH CH CH CH2
H3C
H3C Major
CH CH CH2 CH CH2
H3C H3C
Br
C CH CH2 CH CH2
H3C Minor

6. ELIMINATION Versus SUBSTITUTION

-
Br
Br
E2 : Base C C
E1 Vs SN1 : C C  
H
H
-
B
T.S.
-
Br
Br
SN2 : C C
C C 

H H Nu
-
T.S.
E2 and SN2 have different transition states (T.S.) for this reason they should not complete with each
other but they do competes for the reason that all nucleophile are base and vice-versa.
Hence in general substitution competes with elimination. Therefore dominance of elimination or
substitution can be obtained through following changes in condition.
1. The conditions which favour SN1 also favour E1. Similarly, the conditions which favours SN2
also favour E2. Therefore, at first it is a case of SN1/ E1 vs. SN2/ E2. A transition from SN1/ E1
 Chemistry : Alkyl Halides & Aryl Halides

to SN2/E2 can be obtained by following changes :

SN1/E1  SN2/E2
In either case, amount of elimination can be increased by
(a) taking 3o substrates

(b) taking a base which is less nucleophilic e.g. , (CH3)2 N etc.

N
(c) by keeping the temperature very high. High temperature favours elimination while low
temperature favour substitution.
H3C
Aq.NaOH
CH Cl   H3C CH CH 2 + H3C CH CH3
H3C OH
40o C 2% 98%
65o C 10% 90%
NaOH N 150o C 55% 45%

H3C
CH OH H3C CH CH2
H3C (Major)
(Major)

EXERCISE - 3
Explain the following reactions :
C 2 H5 OH  H2 O
(i) CH3CH 2CH 2 CH 2 Br  KCN  CH 3CH 2 CH 2CH 2 CN
CH3
|
C2 H 5OH  H 2 O
(ii) CH3 — C — Br  KCN  CH 3 — C — CH 2
| |
CH3 CH3

6.1 SUMMARY

Alkyl halide SN2 vs E2 SN1 vs E1

1° Alkyl halide Primarily substitution unless there Usually does not undergo SN1 or
is steric hindrance in the alkyl halide E1 reaction
or nucleophile in which case
elimination is favoured.

2° Alkyl halide Both substitution and elmination, the Both substitution and elimination,
stronger and bulkier the base and the higher the temperature the
higher the temperature the greater greater the percentage of
the % of elimination elimination.

3° Alkyl halide Only elimination Both substitution and elimination,

high temperature favours
elimination.

18
Chemistry : Alkyl Halides & Aryl Halides

EXERCISE - 4

Assuming only E2 elimination write structures for all the possible elimination products from
each of the following :
C(CH3 )2 Cl H3 C Cl
CH3

(a) (b)

Br
CH2 Cl

CH3
(c) (d)
CH3

7. GENERAL TYPE REACTIONS

Aq. NaOH
  R — OH
Ag 2O / H 2 O
  R — OH
dry Ag 2O
  R—O—R
NaOEt / EtOH
  R — O — Et

CH3C  C N a
  R — C º C — CH3
NaI
R Br 
acetone
R—I
NaCN
  R — CN
AgCN
  R — NC
NaSH
  R — SH
NH 3 (Excess)
  R — NH2
COOEt
H2 C COOEt
COOEt

Base
 H3C CH2
COOEt

8. WILLIAMSON’S SYNTHESIS OF ETHERS

Treatment of alkyl halide with alkoxide giving ether is called Williamson’s synthesis of ether.

R — Br + NaOEt 
 R — OEt + NaBr
 Chemistry : Alkyl Halides & Aryl Halides

Features :
1. This is an SN2 reaction (in 2º halide also) because nucleophile is very strong. So no carbonium
ion rearrangement occurs.
2. Tertiary halide, aryl halide and vinyl halide are not used.
NaOEt
CH3 — CH2 — Br   CH3 — CH2 — OEt
SN2

H3C CH3
CH Br NaOEt CH OEt
 
H3C H3C
SN2

CH3 H3 C CH3
H3C
C Br NaOEt
  H3C CH OEt
H3C (Major)

CH3

CH3 C O CH2 CH3 CH3

Possible
CH3 H3C C O + CH3 — CH2 — Br

CH3 CH3

H3C C Br + CH3 CH2 O

CH3

Br O CH3
+ CH3 ONa 


+
ONa
+ CH3 Br

CH3 CH3
NaOCH3
H I 
CH 3OH
 H3OC H

Ph Ph

20
Chemistry : Alkyl Halides & Aryl Halides

By using alkoxides both symmetrical and unsymmetrical ethers can be obtained.

CH3 — ONa + CH3 — Br 

 CH3 — O— CH3

However only symmetrical ethers can be prepared using dry Ag2O. On the other hand moist
Ag2O gives alcohols.
Br Ag Ag Br

CH3 + O + CH3 
 CH3 —O — CH3 + 2AgBr

H2O OH2
+ O +
CH3 
 2CH 3OH  2AgBr  H 2 O
CH3 Br Ag Ag Br

9. CASE OF AgCN AND NaCN

NaCN
R  X   R  CN
AgCN
R  X   R  NC
Reason : NaCN is polar which ionizes to produce free CN– easily.

C N donate (Ambident)

Carbon is more active than nitrogen as nucleophile.

that is why attach occurs from carbon of CN giving R — CN. On the other hand AgCN is covalent.

It doesn’t ionizes to produce free CN . So in this case, attack occur through nitrogen leading to
RNC.
Case of NH3
NH NH
R — Br 
3
 RNH2 + HBr 
3
 NH4Br
H+ Å
R — NH 2 
 R — NH3 
 R — Br

Br
Features :
1. This is a simple nucleophilic substitution. Side product is HX which should be destroyed otherwise
reverse reaction can occur.
HBr
R  NH 2    R  Br  NH 3
To prevent this, excess of NH3 or other base like pyridine is used to destroy HX.
 Chemistry : Alkyl Halides & Aryl Halides

2. Reaction need not stop at 1º RNH2. It can go on the way to produce tetra alkyl ammonium
halide. This is called exhaustive alkylation of amines.

+ HCl + Cl

N NÅ

H
R
R  Br R  Br
R — Br + NH3 
 R — NH2   NH  
(1º) R (2º)
R
Exhaustive alkylation
N—R
on Quaternization of amines
R (3º)
R — Br

R4N + Br
(4º)
NH (Excess)
R — Br 
3
 R — NH2 [R — NH2 in major]
1º

NH3 (Excess) +
R — Br   R4 NBr
3. Quaternary ammonium salts undergo Hoffman’s eliminations
CH3

CH2
+ Ag O / 
CH3   HC +
2
CH2 CH2 N CH2 or NaOH /  2 CH2 + (C 2 H 5 ) 3 N
(Major )

H CH2
Br
CH3
OH
If both elimination and substitution are possible then elmination dominates.

CH3

+ NaOH
Cl 
CH3 N CH3  CH3OH + Me3N + Cl
(Strong Base only elimination)
CH3


OH
CH3 S CH3 I   CH3OH + (CH3)2 S + I
(Poor Base)
CH3

22
Chemistry : Alkyl Halides & Aryl Halides

10. DIHALIDES
They are of two types :
i) Vicinal Dihalides, CH2Cl – CH2Cl, in which two Cl or Br atoms are attached to adjacent C -
atoms.
ii) Gem Dihalides, R — CCl2 – R in which both Cl are attached to same C - atom.
They can be prepared from alkenes or alkynes as given below:
i) R — CH = CH2 + X2  R — CHX — CH2X

HX R  CH2  CHX 2
R—C  CH + HX R — CH = CHX  
Markonikov rule ethylidene chloride

ii) From alcohols

CH2OH CH2Cl
PCl5,PCl3 or SOCl2
CH2OH CH2Cl

Oxidation
CH3CH2 CH2OH   
H2
 CH CH CHO
3 2
PCl5
 CH3CH2CHCl2
 

Reactions : Both give same product on dehalogenation and dehydrohalogenation

Zndust ,heat
R—CHX—CH2X or R — CH2 — CHX2      R—CH = CH2 + ZnX2

R—CHX— CH2X or R—CH2CHX2    R—C CH + 2HX

NaNH2 / Liq.NH3

But action of aq. KOH is different:

aq.KOH
R—CHX — CH2X    R—CHOH—CH2OH(glycol)

EXERCISE - 5

Suggest a mechanism for the reaction

Cl
heat

N CH2Cl N
| |
Et Et
 Chemistry : Alkyl Halides & Aryl Halides

11. TRI HALIDES(HALOFORM)

11.1 PREPARATION
A haloform can be prepared from any alcohol having –CH(OH)CH3 group or from the aldehydes and
ketones formed from above type of alcohols i.e, from a carbonyl compound having three  - hydrogen
atoms by the action of X2 and an alkali or Na2CO3.

1. In the laboratory, CHCl3 is prepared by the distillation of a mixture of ethanol or 2-propanol or

acetone with a paste of bleaching powder in water. Bleaching powder supplies Cl2 and Ca(OH)2
for the reaction.
HALOFORM REACTION
Mechanism :
O
I2 / NaOH
H3 C C CH3   CH3  COONa  CHI3
Iodoform
O
Br2 / NaOH
H3 C C H  HCOONa  CHBr3
Bromoform
O O
Base –
H3 C C CH3 
enolisation
 H3 C C CH2

O
–
O
I I
H3 C C CH2 I  H3 C C CH2
enolate
base O –
O O
I I
H3 C C CHI H3 C C CHI  H3 C C CHI2
– enolate

O O base
I I
–
H3 C C CI3  H3 C C C I2
base
–
O O
–
H3C C CI3 H3 C C OH + CI3

OH
O
– +
H3 C C ONa + CHI3

24
Chemistry : Alkyl Halides & Aryl Halides

This reaction involves three steps of enolisation and three steps of halogenation. Most importantly
each enolisation is followed by one halogenation.
1. First enolisation is r.d.s. since it is slowest step as it involves least acidic H-atoms.
2. Finally hydrolysis occur to produce haloform.

Note :
(a) Only those ketones can produce haloform which have at least one CH3 group on carbonyl
and the hydrogen atoms of CH3 group is more acidic than any other hydrogen.
(b) Among all aldehydes only CH3CHO gives haloform because only this has CH3 group on
carbonyl.

Haloform reaction can be performed with bleaching powder also.

O

H3C C CH2 Cl  Ca (OCl) Cl  H 2 O 

 (CH3COO) 2 Ca  CHCl3
CH3CHO + Ca(OCl) Cl + H2O  (HCOO)2 Ca + CHCl3
H 2O
CH3CH 2OH  Ca (OCl) Cl   (HCOO) 2 Ca  CHCl3
H 2O
H3C CH CH3  Ca (OCl) Cl   (CH3COO) 2 Ca  CHCl3

OH
I2 / NaOH
H3C CH CH3   CH 3COONa  CHI3
coloured

OH

Note : X2/NaOH is also a mild oxidising agent capable to oxidise a 2° alcohol into ketone and a
primary alcohol into aldehyde. Therefore haloform reaction is possible directly on 2° alcohols which
can produce suitable ketone. On the other hand among all primary alcohol only ethanol gives haloform
reaction.
O
[O]
1. H3C CH CH3  H3C C CH3

OH
Br2 / NaOH
H3C CH CH2 CH3  CH3CH 2COONa  CHBr3

OH
[O] O

H3C C CH2 CH3

2. Similarly, CH3COCH3 + 3Cl2  CCl3 — CO — CH3

CCl3 — CO — CH3 + KOH CHCl3 + CH3COOK

3. Fe fillings  steam

From CCl4: CCl4 + 2H   CHCl3 + HCl
4. Pure chloroform is formed from the hydrolysis of chloral hydrate
CCl3.CH(OH)2 + NaOH  CHCl3 + HCOONa + H2O
 Chemistry : Alkyl Halides & Aryl Halides

11.2 PHYSICAL PROPERTIES OF CHCl3

It is a colourless liquid with sweet smell and taste. It is heavier than water and insoluble in it but
soluble in alcohol and ether.

11.3 CHEMICAL REACTIONS

1. Oxidation
CHCl3 + ½O2  HCl + COCl2 (phosgene)
2. Hydrolysis occurs on refluxing it with conc. NaOH giving HCOONa
CHCl3 + 4NaOH  HCOONa + 3NaCl + 2H2O
3. CHCl3 + HNO3 (conc)  H2O + Cl3C—NO2 (chloropicrin)
4. 2CHCl3 + 6Ag  CH  CH + 6AgCl
5. Carbylamine Reaction or Isocyanide Reaction

base
 -
R — NH2 + CHCl3 

 R — NC : (or) R  N  C
Mechanism :
CHCl3 + NaOH  : CCl2
H Cl
  : CCl  + –
R  NH 2 2  R NH
 R NH C

CCl2 Cl
–
– Cl–

 –  Cl  –
  C
R  N  C   RN  Cl

This reaction is given by only 1° R—NH2 and haloform. So it is a characteristics test of these
compound. The bad smell of RNC indicates 1° RNH2 and CHCl3.

12. ARYL HALIDES

Aryl halides are compounds containing halogen attached directly to an aromatic ring. The general
formula of aryl halides is ArX, where Ar is phenyl, sustituted phenyl or aryl groups.

Cl F Cl

NO2
Chlorobenzene Floro Benzene m-Chloro nitro
benzene

26
Chemistry : Alkyl Halides & Aryl Halides

An aryl halide is not just any halogen compound containing an aromatic ring. For example, benzyl
chloride is not an aryl halide, because halogen is not directly attached to the aromatic ring. Its structure
and properties resemble substituted alkyl halide.
The aryl halides differ from alkyl halides in their preparation and properties. Aryl halides are
comparatively unreactive towards the nucleophilic substitution reactions, which are
characteristic of the alkyl halides.
(1) The bimolecular displacement mechanism–involving the carbanion as intermediate and applicable
to activated aryl halides.
(2) The elimination addition mechanism–involving the remarkable intermediate called benzyne
and applicable to unactivated and deactivated aryl halides.
Vinyl halides are the compounds in which halogen is attached directly to a doubly bonded
carbon.

C C X
A vinyl halide show an interesting parallelism to aryl haldies. Both are unreactive towards nucleophilic
substitution reactions, for basically the same reason. Moreover, this low reactivity is caused partly by
partial double bond character of the carbon-halogen bond.

12.1 STRUCTURE AND REACTIVITY OF ARYL AND VINYL HALIDES

The low reactivity of aryl and vinyl halides towards nucleophilic displacement has been attributed to
two different factors.
(a) delocalization of electrons by resonance and
(b) differences in bond energies due to difference in hybridization of carbon.

Cl Cl + Cl + Cl Cl
H H

H
(I) (II) (III) (IV) (V)

Chlorobenzene is consider to be hybrid of not only the two kekule structure I and II, but also structures,
III, IV, and V, in which chlorine is joined to carbon by a double bond. In structures III, IV, and V
chlorine bears a positive charge and the ortho and para positions bear a negative charge.

12.2 PREPARATION OF ARYL HALIDES

(1) From Diazonium Salts

BF 4 , 
  C6 H 5 F
CuCl2 , 
  C6 H5Cl
HNO3 redn. HONO
C6 H6 
H2SO4
C6 H5 NO 2 
Sn / HCl
 C6 H 5 NH 2 
0o C
C6 H 5 N 2 
CuBr, 
  C6 H 5 Br

I ,
 C6 H 5 I
 Chemistry : Alkyl Halides & Aryl Halides

Halogenation :
Lewis acid
Ar – H + X2    Ar – X + HX
(X = Cl, Br)

Mechanism:

X — X + AlX3  X+ + AlX4
Lewis acid

H + H
X
X X X
 H
slow
+ +

X H
fast X
  +
H

For introducing only the halogen at para position, the Lewis acid thallium acetate is used.
NH – CO – CH3 NH – CO – CH3
| |
Br2
Tl(OAc)3
Acetanilide |
Br
For example,
NO 2 NO 2

Cl2 , FeCl3
 
Cl
m-chloronitrobenzene

12.3 GENERAL CHEMICAL PROPERTIES OF THE ARYL HALIDES

(1) Formation of Grignard Reagent
dry ether
ArBr  Mg   ArMgBr
tetrahydrofuran
ArCl  Mg  ArMgCl
(2) Fitting Reaction
It is an extension of wurtz reaction and consists of heating an ethereal solution of bromobenzene
with metallic sodium.

Br + 2Na + Br + 2NaBr

28
Chemistry : Alkyl Halides & Aryl Halides

(3) Ulmann Biaryl Synthesis

Iodobenzene on heating with cooper in a sealed tube forms biphenyl.

I + 2Cu + I + 2Cul

Chloro– or bromobenzene fails to undergo this coupling reaction unless some strong electron
withdrawing group (e.g. NO2) is present in the ortho or para position.
(4) Electrophilic Aromatic Substitution
Although halogen is deactivating but still it directs the incoming electrophile to ortho and para
position.
For example,
Cl Cl Cl
NO 2
H 2SO 4
 HNO 3  +

NO 2
Cl Cl Cl
CH3
CH3Cl

AlCl3
 +

CH3
Cl Cl Cl
Br
Br2 / Fe
 +

Br
(5) Nucleophilic Aromatic Substitution
(i) Bimolecular S NAr Mechanism

ArX  Z 
 ArZ  X 
For facile reaction Ar must contain strongly electron withdrawing groups at ortho and/or para position
to the halogen atom. The reaction involves the formation of intermediate as carbanion.

Cl OC2H5
NO2 NO2
C2 H5 OH

300o C, 10 atm

 Chemistry : Alkyl Halides & Aryl Halides

Cl OC 2 H 5
NO 2 NO 2
C 2 H 5 OH

300o C, 10 atm


NO2 NO 2

Cl OEt
O2 N NO2 O2 N NO2
C H OH

2 5
75o C, 2 atm


NO2 NO2

Reaction proceeds by carbanion intermediate. The rate of the reaction increases with the increase in
number of electron withdrawing groups, since the carbanion formed would be stabilized more. The
mechanism of the reaction is of addition-elimination type.
Step : 1

X O
X Nu X Nu X Nu
NO2 NO 2 NO2 N

Nu

slow (RDS)
   O

X Nu O
N

Step : 2

Nu
X Nu
NO2 NO2

X

fast

It can be seen that the presence of –NO2 group at ortho or para position would facilitate to disperse
the negative charge of the carbanion, thus stabilizing it more and making the reaction to occur fast.
(ii) Benzyne or Elimination – Addition Mechanism
Strong base
ArX + : Z –     ArZ + :X– Ring not activated toward bimolecular displacement

30
Chemistry : Alkyl Halides & Aryl Halides

O–Na+ OH
Cl

o 
NaOH, 300 C H

High pressure
 
Drastic conditions

Cl NH2

KNH 2

in liq. NH

3

Cl NH2

o
NH 3 , Cu 2 O, 200 C

high pressure

Mechanism :

Br NH2 NH2
NH 2 NH2 NH3

 Br  ,  NH 3
 :
  
fast  NH 2 , fast
Slow step
H

For example :

OCH3 OCH3 OCH3

Br
 
NH 2 : NH 2 NH 3
(a) 
 HBr
    

NH2

NH2
14
Cl
14 14


NH 2
(b) 
 HBr
 14
NH2
 Chemistry : Alkyl Halides & Aryl Halides

CH3 CH3 CH3

Cl NH2
NH 2 NH 2 NH 3
(c) 
 Cl,  NH

  
3

OCH3 OCH3 OCH3

  NH 3
NH 2 NH 2
(d) 
 Cl,  NH
   
3

Cl NH2

CH3 CH3 CH3

 
NH 2 NH 2 NH 3
(e) 
 Cl,  NH
   
3

Cl NH2

OCH3 OCH 3 OCH3


NH 2 NH  NH3
(f) 
 Cl,  NH

2
  
3

Cl NH2

CH3 CH3 CH3

 
NH 2 NH2 NH3
(g) 
 Cl,  NH
   
3

NH2
Cl

32