Alkyl Halide and Aryl Halide

ALKYL & ARYL HALIDE
NOMENCLATURE
The general formula of saturated mono substituted alkyl halide is CnH2n+1X, where X is a halogen
atom. Alkyl halides are usually represented by R X where R is an alkyl group. For example
CH3 CH3
H 3C H 3C
H3C
Br
H 3C
1-bromopropane
Cl I
1-chloro-2-methylpropane 1-iodo-2,2-dimethylpropane
Some examples of substituted alkyl and aryl halides are:

OH
Cl H2C
Br Br
(bromomethyl)benzene 2-(chloromethyl)phenol bromoethylene
Cl
CH3
Cl
Cl
1-chloro-1-methylcyclopentane
1,3-dichlorocyclohexane
Classification: Alkyl halides can be classified as methyl halide, primary alkyl halide,
secondary alkyl halide (2) and tertiary alkyl halide (3), according to the number of other carbon
atoms attached to the carbon bearing the halogen atom.
H H R' R'
H X R X R X R X
H H H R"
Methyl halide Primary alkyl Secondary alkyl Tertiary alkyl
halide (1) halide (2
) halide (3 )
R, R and R may be same or different.
As we know that the alkyl halides contains halogen atom which is the functional group, which is
responsible for the characteristic reactions viz. nucleophilic substitution and elimination
reactions, of alkyl halides. So, it is functional group (X) which will decide the nature of the
reaction (i.e. substitution and elimination) and not the alkyl group. The nature of alkyl group (i.e.
1, 2, 3) will decide the mode (whether SN2 or SN1 and E2 or E1).
Methods of Preparation
1. From halogenation of Alkanes: Alkanes can be halogenated to give alkyl halide.
EXCELLENCE EDUCATION
h
CH 4 X 2 CH3X HX
or high
temp
(Where X = Cl, Br and I)
On further halogenation, di, tri or tetrahalomethane can be obtained. This can be

achieved by increasing the concentration of halogen (X2).
CH3X X 2 h CH2X HX
or high
temp
CH 2X2 X 2 h CH3X HX
or high
temp
CHX3 X2 h CX4 HX
or high
temp
2. From addition of halo acids on alkenes and alkynes: Electrophilic addition of

HX on alkenes and alkynes give the alkyl halides.
R
R + HX CH3
CH3 X
(Where HX = HCl, HBr and HI)
X
R
H3 C 2HX
+
CH3
CH X
Example
CH3
H3C + 2HCl H3C
CH2 Cl
Cl
H3 C
H3 C + HCl
CH3
CH Cl
Free radical addition of HBr on alkenes will give the anti-Markovnikov product.
H3 C Peroxide H3 C
+ HBr
CH2 Br
3. From addition of X2 on alkenes and alkynes: Addition of X2 on alkenes give

dihalo and that on alkyne give tetrahalo alkane.
R X
R + X2 dihaloalkane
CH2 X X
X X
R + 2X2 H3C CH3 Tetrahaloalkane
CH
X X
Example
Br
H3C + Br2 H3C

CH2 Br
1,2-dibromopropane
Cl Cl
H3C + 2Cl2 H3C H
CH Cl Cl
1,1,2,2-tetrachloropropane
4. From alcohols: When alcohols are treated with PX3 or HX they give alkyl halides.
RCH 2 OH PX

3 RCH 2 X
or HX
Example
H3C conc

. HBr or
H3C
NaBr , H 2SO 4
OH Br
CH3 CH3

PCl3
OH Cl
For the preparation of iodoalkane, we take a mixture of red phosphorus and I2.
P I 2
CH 3 CH 2 OH Re
d CH 3 CH 2 I
Alkyl chlorides can also be prepared from alcohols by treating it with PCl5 or SOCl2.
CH3CH2OH + PCl5 CH3CH2Cl + POCl3 + HCl

CH3CH2OH + SOCl2 CH3CH2Cl + SO2 + HCl
Preparation of alkyl chloride from alcohols by treating it with SOCl2 is the best method as
it gives almost pure alkyl chloride since the by products of the reaction i.e. SO 2 and HCl
are in gaseous phase.
5. From free radical substitution of alkyl benzenes

CH3
CH3 , h
Cl
Cl
2
Br
CH3
NBS

6. Halide Exchange: Alkyl iodides can be prepared from the corresponding alkyl
chlorides or alkyl bromides by reacting it with a solution of sodium iodide in acetone.
R Cl + I acetone
R I + Cl
As NaCl and NaBr are less soluble in acetone, they precipitate and can be removed from
solution by filtration.
Physical Properties of Alkyl Halides: Lower members of alkyl halides (CH 3F, CH3Cl,
CH3Br and C2H5Cl) are colourless gases at room temperature. The higher members up C 18 are
coloulress liquids where as other members are colourless solids. Despite of polar nature of alkyl
halides, they are insoluble in water due to inability to form hydrogen bond but they are soluble in
non-polar solvents. Alkyl bromides and iodides are heavier than water whereas alkyl fluorides
and chlorides are lighter than water. For a particular alkyl group, the boiling points of alkyl
halides follows order. RI RBr RCl RF and for a particular halogen the boiling points of
alkyl halides increase with the increasing size of the alkyl group. Alkyl halides are usually
poisonous compounds and causes unconsciousness when inhaled in large amounts.
Nucleophilic Substitution Reactions

A halogen is more reactive than a carbon consequently, the two atoms do not share their bonding
electron pairs equally. Because the more electronegative halogen has a larger share of electrons,
it has a partial ve charge and the carbon to which it is bonded has a partial ve charge.

R CH 2 X X = Cl, Br, I, F
This unequal sharing of electrons causes alkyl halides to undergo substitution and elimination
reactions. There are two important mechanisms of substitution reaction.
1. A nucleophile is attracted to the partially positively charged atom of carbon. As the

nucleophile approaches the carbon, it causes the C X bond to break heterolytically.
H H
X
Nu H
H H
H H
2. The C X bond breaks heterolytically without any assistance from the nucleophile,
forming a carbocation. The carbocation then reacts with nucleophile to form the
substitution product.
X -
+ X
+ Nu Nu
Regardless of the mechanism by which such a substitution reaction occurs, it is called a

nucleophilic substitution reaction because a nucleophile is substituted for the halogen.
The mechanism that predominates depends on
the structure of the alkyl halide.
the reactivity and the structure of the nucleophile.
the concentration of the nucleophile.
the solvent in which the reaction is carried out.
Mechanism of SN2 Reactions
The rate of nucleophilic substitution reaction such as the reaction of methyl bromide with
hydroxide ion depends on concentration of both the reagents. If the concentration of the methyl
bromide in the reaction mixture is doubled, the rate of SN reaction doubles. If the concentration of
OH is doubled the rate of reaction also doubled. If the concentration of both the reactants are
doubled, the rate of reaction quadruples.
CH3Br + HO CH3OH + Br
Rate [Alkyl halide] [Nucleophile]
Thus it is the second order reaction, first order with respect to substrate and 1 st order with respect
to nucleophile. The rate law tells us what molecules are involved in the transition state of the rate
determining step of the reaction. From the rate law for the reaction of methyl bromide with
hydroxide ion, we know that both methyl bromide and hydroxide ion, are involved in the rate
determining transition state. The transition state is BIMOLECULAR; i.e. it involves two
molecules. The rate constant k describes how difficult it is to overcome the energy barrier of the
reaction (how hard it is to reach the transition state). The larger the rate constant, the easier it is to
reach the transition state.
The mechanism proposed by Hughes and Ingold for an S N2 reaction has one step. The
nucleophile attacks the carbon bearing the leaving group and displaces the leaving group.
Because the nucleophile hits the carbon bearing the leaving group and displaces the leaving
group. Because the nucleophile hits the carbon on the side opposite to the side bonded to the
leaving group, the carbon is said to undergo back side attack. Backside attack occurs because the
orbital of the nucleophile that contains its non-bonding electrons interacts with the empty anti
bonding molecular orbital associated with the C Br bond. This orbital has its larger labe on the
side of the carbon directed away from the C Br bond. Consequently, the best overlap of the
interacting orbitals is achieved through backside attack. An S N2 reaction is also called direct
displacement reaction because the nucleophile displaces the leaving group in a single step. A
reaction co-ordinate diagram is shown in figure.
-
HO + H3C Br H3C OH + Br
Relative Rates of SN2 reactions for several alkyl halides with OH

Alkyl Bromide Class Relative Rate
H3C Br Methyl 1200 H H

HO C Br
H3C
Primary 40 H
Br
T.S.
H3C G
Primary 16
Br G
Br
H3C Secondary 1
CH3
CH3 CH 3OH Br
H3C
Too slow to Progress of reaction
Tertiary
Br measure
H3C
Because the nucleophile attacks the backside of the carbon that is bonded to the halogen, bulky
substituents attached to this carbon will make it harder for the nucleophile to get to the back side
and therefore will decrease the rate of reaction. Thus the mechanism explains why substituting
methyl groups for the hydrogens in methyl bromide progressively slows the rate of the
substitution reaction.
Effects due to groups occupying a certain volume of space are called steric effect. A steric effect
that decreases the reactivity is called steric hindrance. Steric hindrance results from groups
getting in the way at the reaction site. As a consequence of steric hindrance, alkyl halides have
the following, relative reactivities in an SN2 reaction. The steric crowding in tertiary alkyl halide,
is to great that they are unable to undergo SN2 reactions.
Relative reactivities of alkyl halides in an SN2 reaction:
Methyl halide 1 alkyl halide 2 alkyl halide 3 alkyl halide.
It is not just the number of alkyl groups attached to the carbon undergoing nucleophilic attack
that determines the rate of an SN2 reaction; the size of the alkyl group is also important. For
example, ethyl bromide and n-propyl bromide are both primary alkyl halide, but ethyl bromide is
more than twice as reactive in an S N2 reaction because the methyl group of the ethyl bromide
provides less steric hindrance to back side attack than does the ethyl group of n-propyl bromide.
As the nucleophilic approaches the backside of the carbon of methyl bromide the C H bond
begins to move away from the nucleophile and its attacking electrons. By the time transition state
is reached the C H bonds are all in the same plane and the carbon is pentacoordinate (fully
bonded to three atoms and partially bonded to two) rather than tetrahedral. As the nucleophile
gets closer to the carbon and the bromine moves further away from it, the C H bonds continue
to move in the same direction. Evidently the bond between the carbon and the nucleophile is
fully formed and the bond between the carbon and the bromine is completely broken, and thus
the carbon is once again tetrahedral.

HO + Br HO C Br HO + Br
The best way to visualize the movement of groups bonded to the carbon at which substitution
occurs is to picture on umbrella that turns inside out. This is called inversion of configuration.
The carbon at which substitution occurs have inverted its configuration during the course of the
reaction just as an umbrella has a tendency to invert in a windstorm. The inversion is known as
WALDEN INVERSION, since Paul Walden was the first to discover that compounds could
invert their configuration as a result of substitution reactions.
Because an SN2 reaction takes place with inversion of configuration, only one product is formed
when an alkyl halide that has the halogen leaving group bonded to a chiral centre undergoes on
SN2 reaction. The configuration of that product is inverted compared with the configuration of the
alkyl halide. Therefore, proposed mechanism accounts for the observed configuration of the
product.
R' R'
+ HO + Br
H H H R
Br HO
R' R'
R Br HO R
H H
Leaving Group: If an alkyl iodide, alkyl bromide, an alkyl chloride, and an alkyl fluoride (all
having the same alkyl group), were allowed to react with the same nucleophile under the same
conditions, we would find that the alkyl iodide is the most reactive and the alkyl fluoride is the
least reactive.
Relative Rates
HO + RCH2I RCH2OH + I 30,000
HO + RCH2Br RCH2OH + Br 10,000
HO + RCH2Cl RCH2OH + Cl 200
HO + RCH2F RCH2OH + F 1
The only difference among these four reactions is the nature of the leaving group. Apparently I
is the best leaving group and the F ion is the worst. This brings us to an important rule in organic
chemistry that will keep reappearing.
The weaker the base, the better is the leaving group.
The leaving ability depends on basicity because a weak base does not share its electrons as well
as a strong base does. Consequently, a weak base is not bonded as strongly to the carbon as a
strong base would be. Thus a bond between a carbon and a weak base is more easily broken than
a bond between a carbon and a strong base.
We know that the hydrogen halides have the following relative acidities.
HI HBr HCl HF
Because we know that stronger the acid weaker is its conjugate base, the order of basicities of
halide ions is
I Br Cl F
Further, because weaker bases are better leaving groups, the halide ions have the following
relative leaving abilities.
I Br Cl F
As a consequence of relative leaving abilities of the halides, alkyl halides have the following
relative reactivities in an SN2 reactions.
RI RBr RCl RF
Nucleophile: When we talk about atoms or molecules that have lone pair of electrons,
sometimes we call them bases and sometimes we call them nucleophiles. What is the difference
between a base and a nucleophile?
A base shares its lone pair with a proton. Basicity is a measure of how strongly the base shares
those electrons with a proton. The stronger the base the better it shares its electrons. Basicity is
measured by the acid dissociation constant (Ka) that indicates the tendency of the conjugate acid
of the base to lose a proton.
A nucleophile uses its lone pair of electrons to attack on electron deficient atom, other than a
proton. NUCLEOPHILICITY is a measure of how readily the nucleophile is able to attack such
an atom. It is measured by rate constant (k). In the case of an S N2 reaction, nucleophilicity is a
measure of how readily the nucleophile attacks an sp3 hybridised carbon bonded to a leaving
group.
In comparing molecules with the same attacking atom, there is generally a direct relationship
between basicity and nucleophilicity. Stronger bases are better nucleophiles. For example, a
compound with vely charged oxygen is a stronger base and a better nucleophile than a
compound with a neutral oxygen.
Stronger base better nucleophile Weaker base, poorer nucleophile
HO H2O
CH3O CH3OH
NH 2 NH3
CH 3 CH 2 NH CH3CH2NH2
In comparing molecules with attacking atom of approximately the same size, the stronger bases
are again the better nucleophiles. The atoms across the second row of the periodic table have
approximately the same size. If hydrogens are attached to the second row elements the resulting
compounds have the following relative acidities.
CH4 NH3 H2O HF
Consequently, the conjugate bases have the following relative basicities and nucleophilicites. For
example, the methyl anion is the strongest base as well as the best nucleophile.
CH3 NH2 OH F
In comparing molecules with attacking atoms that are very different in sizes, the direct
relationship between basicity and nucleophilicity is retained if the reaction occurs in the gas
phase. If, however, reaction occurs in solvent the relationship between basicity and
nucleophilicity depends upon the solvent.
If the solvent is a protic, the direct relationship between nucleophilicity and basicity holds. For
example, both the nucleophilicities and the basicities of halide decreases with increasing size in
the aprotic solvent such as N.N-dimethyl formamide (DMF), Dimethylsulphoxide (DMSO),
N,N-dimethylacetamide (DMA).
If the solvent is protic, the relationship between basicity and nucleophilcity becomes inverted,
as basicity increases, nucleophilicity decreases. Thus I ion which is the weakest base of the
halogen family. Is the poorest nucleophile of the family in an aprotic solvent and best nucleophile
in a protic solvent.
-
F- Size increases Basicity increases increases nucleophilicity increases nucleophilicity
Cl- in an aprotic solvent in a protic solvent
Br-
I
How does a solvent ability to be hydrogen bonded does not affect the relationship between
nucleophilicity and basicity? When a vely charged species is placed in a protic solvent, the
solvent molecules arrange themselves so that their partially positively charged hydrogen points
towards the vely charged species. An aprotic solvent does not have a partially positively charged
hydrogen.

H

O
O

H H

H

Y
H H

O O

H H
Ion-diopole interaction between a
nucleophile and water (protic solvent)
The interaction between the ion and the dipole of the protic solvent is called an ion-dipole
interaction. The change from a direct relationship between basicity and nucleophilicity in an
aprotic solvent to an inverse relationship in a protic solvent results from the ion-dipole
interactions between the nucleophile and the protic solvent. This occurs because at least one of
the ion dipole interactions must be broken before the nucleophile can participate in an S N2
reaction. Weak bases interact before the nucleophile can participate in an SN2 reaction weak bases
interact weakly with protic solvents, strong bases interact more strongly because they are better
at sharing their electrons. It is, therefore, easier to break the ion-dipole interactions between an
iodide ion and the solvent than between the more basic fluoride ion and the solvent, because the
latter is a stronger base. As a result, iodide ion is a better nucleophile in a protic solvent.
Relative Nucleophilicity towards CH3I in Methanol

-
RS
-
I
-
CN increasing nuleophilicity
-
CH3O
-
Br
NH3
-
Cl
-
F
CH3OH
Because there are many different kinds of nucleophiles, a wide variety of organic compounds can
be synthesized by means of SN2 reactions. The following reactions show just a few of the many
kinds of organic compounds that can be synthesized in this way.
CH3CH2Cl + HO CH3CH2OH + Cl
CH3CH2Br + HO CH3CH2OH + Br
CH3CH2I + RO CH3CH2OR + I
CH3CH2Br + RS CH3CH2SR + Br
CH3CH2F + NH2 CH3CH2NH2 + F
CH3CH2Br + C CR CH3CH2C CR + Br
CH3CH2I + CN CH3CH2CN + I
Stereochemistry of SN2 Reaction

As we have seen that an S N2 reaction the nucleophilie attacks from the backside, that is, from the
side directly opposite the leaving group. This mode of attack causes a change in configuration of
the carbon atom that is the target of the nucleophile. As the displacement takes place, the
configuration of the carbon atom under attack inverts it is turned inside out in such a way that an
umbrella is turned inside out in a strong gale.
R R R

HO Br HO C Br HO + Br
R' R'
R" R' R" H
Inversion of Configuration
A compound that contains one stereocentre, and therefore, exists as a pair of enantiomers, is
2-bromooctane. These enantiomers have been obtained separately and are known to have the
configuration and rotation shown here.
H13C6 H13C6
H Br Br H
CH3 CH3
R(-)-2-bromooctane S(+)-2-bromooctane

[]25
D 34.25 []25
D 34.25
The S-2-octanol is also chiral. The configuration and rotation of the 2-octanol enantiomers have
also been determined.
H13 C6 H13C6
H OH HO H
CH3 CH3
R-(-)-2-octanol S-(+)-2-octanol

[]25
D 9.90 []25
D 9.90
When R-()-2-bromooctane reacts with NaOH, the only substitution product is obtained from the
reaction is S-(+)-2-octanol.
H3C H CH3

HO Br HO C Br HO Br
H H
H13C6 H C6H13 C6H13
R-(-)-2-bromooctane S-(+)-2-octanol
25
[] 34.25
D []25
D 9.90
Enantiomeric purity = 100% Enantiomeric purity = 100%
There still remains a problem. We need to relate the configuration of the reactant and the product.
We know that the direction of rotation (optical) and the configuration of two different compounds
are not necessarily related, for they may have the same sign of rotation but may have different
configurations. The experimental proof of Walden inversion was obtained by a series of
experiments in which optically active alcohol was converted into its enantiomer having a rotation
opposite in sign but nearly equal in magnitude to that of the original alcohol.
Thus in the series of reactions on an optically active (+) alcohol formation of an ester with
4-methylbenzenesulphonyl chloride (Tosyl chloride) is known not to break the C O bond of the
alcohol (that such as the case may be shown by using an alcohol labeled with O 18 in its OH
group, and demonstrating that this atom is not eliminated on forming the tosylate; it is, however,
eliminated when the tosylate; is reacted with MeCOO ) hence the tosylate must have the same
configuration as the original alcohol.
O
PhH2C H2 CPh O O
p MeC6 H4SO2Cl CH3 H C CH2 Ph
OH OSO 2 C6 H4 CH3 3
Me Me
H H O
Me
H
OH
O CH2 Ph
H3C HO
Me
OH H
Reaction of this ester with CH 3COO is known to be a displacement in which ArSO 3

(Ar = p MeC6H4) is expelled and MeCO2 is introduced, hence the C O bond is broken in this
step and inversion of configuration can thus take place in forming the acetate. Alkaline
hydrolysis of the acetate can be shown not to involve fission of the alkyl oxygen (C O) linkage,
so the alcohol must have the same configuration as the acetate. (Hydrolysis of an acetate in
which the alcohol oxygen atom is O 18 labelled fails to result in the latter replacement, thus
showing that alkyl oxygen bond of the acetate is not broken during its hydrolysis). As is found to
be the mirror image of the starting material opposite direction of the optical rotation an
inversion of configuration must have taken place during the series of reactions and can have
occurred only during reaction of MeCO2 with the tosylate. Reaction of this tosylate with a
number of nucleophiles showed that inversion of configuration occurred in each case; it may thus
be concluded with some confidence that it occurs on reaction with Br to yield the bromide, i.e.,
that the bromide like acetate has the opposite configuration to the original alcohol.
The general principle that bimolecular (SN2) displacement reactions are attended by inversion of
configuration has been established in an elegant and highly ingenious experiment, in which an
optically active alkyl halide undergoes displacement by the same though isotopically labeled
halide ion as a nucleophile e.g. 128I on (+) 2-iodooctane.
H13C6 C6H13 C6H13
128
128 + I 128
I C I I + I
I H3C CH3
H H3C H H
()
(+)-2-iodooctane
the displacement was monitored by observing the changing distribution of I128 between the
inorganic (sodium) iodide and 2-iodooctane and it was found under these conditions, to be
second order overall.
If the inversion takes place, as S N2 requires. The optically activity of the solution will decline
zero i.e., racemization will occur. This will happen because inversion of the configuration of a
molecule of (+) 2-iodooctane results in the formation of a molecule of its mirror image (-)-2-
iodooctane. Which pair off with a second molecule of (+)-2-iodooctane to form a racemate ();
the observed rate of racemisation will thus be twice the rate of inversion.
Illustration: Write the structure of the nucleophilic substitution products in each of the
following.
i) CH2
Br

CN

ii) CH3

PhS
H2C
Cl
H3C
CN
Solution: i)
ii) S CH3
Ph
CH3
SN1 Reactions
Given our understanding about SN2 reactions, if were to measure the rate of reaction of tert-butyl
bromide with water, we would expect a relatively slow substitution reaction since water is a poor
nucleophile and tert-butyl bromide is sterically hindered to attack by a nucleophile.. However, we
actually discover that the reaction is surprisingly fast. It is, in fact over one million times faster
than the reaction of methyl bromide a compound with no sterric hindrance with water. Clearly,
the reaction must be taking place by a mechanism different from that of the SN2 reaction.
As we have seen, a study of the kinetics of a reaction is one of the first step undertaken when
investigating the mechanism of a reaction. If we were to investigate the kinetics of the reaction of
tert-butyl bromide with water, we would find that doubling the concentration of the alkyl halide
doubles the rate of reaction. We would also find that changing the concentration of nucleophile
has no effect on the rate of the reaction.
CH3 CH3
H3 C H3 C
H 2O
Br H
Br OH
H3 C H3C
Rate = K [Alkyl Halide]
Because the rate of reaction depends upon the concentration of only one reactant, it is a first
order reaction.
An SN1 reaction has two steps, the carbon-halogen bond breaks heterolytically with the halogen
retaining the previously shared electron pair. In the second step, the nucleophile reacts rapidly
with the carbocation formed in the first step.
CH3 CH3
slow
H3C Br H3C Br -
CH3 CH3
CH3 CH3 CH3
H3C + OH 2
fast
H3C OH2 H3C OH H
CH3 CH3 CH3
From the observation that the rate of an S N1 reaction depends only upon the concentration of the
RX, we know that the first step is the slow and rate determining step. Because the nucleophile is
not involved in the r.d.s., its concentration has no effect on the rate of the reaction. If you look at
the reaction co-ordinate diagram, you will be able to see why increasing the rate of the second
step will not make an SN1 reaction go any faster.
0
G
G 0
CH3 -
Free Energy
Br CH3
H3C
CH3 H3C OH 2
H2 O
CH3 CH3
H3C Br
CH3 CH3
H3C OH H
CH3
Progress of Reaction
Second, a carbocation is formed in the slow step of an SN1 reaction. Because a 3 carbocation is
more stable and therefore, easier to form than a secondary carbocation which in turn is more
stable to from than a 1 carbocation. 3 alkyl halides are more reactive than a 2 alkyl halide
which in turn more reactive than a 1 alkyl halide in an SN1 reaction.
Relative rates of SN1 for several alkyl halides.
(Solvent and Nucleophile = H2O)
Alkyl Halide Class Relative Rate
CH3
H3C Br 3 1,200,000
CH3
H3C Br
2 11.6
CH3
H3C
1 1.00
Br
CH3 Br Methyl 1.05
Relative Rates of Alkyl Halides in an SN1 reaction
3RX 2RX 1RX CH3X
Actually 1 carbocation and CH3+ are so unstable that primary RX and CH 3X do not undergo SN1
reactions. (The very slow reaction reported for ethyl bromide and methyl bromide in table are
SN2 reaction).
The positively charged carbon of the carbocation is sp2 hybridised, and the three bond connected
to this carbon are in the same plane. In the 2 nd step of the SN1 reaction, the nucleophile can
approach the carbocation from either sider of the plane.
Br
(a) (b)
H2 O H2 O
(a) (b)
+ H H +
-H + + -H
HO + O O + OH
H H
H H
Inverted Same configuration
configuration (retention)
The SN1 reaction of an alkyl halide in which the leaving group is attached to the chirality centre
leads to the formation of two stereoisomers; attack of the nucleophile on one side of the planar
cabrocation forms one stereoisomer and attack on the other side produces the other isomer.
R' R' R'
H 2O
H R HBr
R H R H
Br HO OH
In the reaction of (S) 2-bromobutane with water two substitution products are formed one
product has the same relative configuration. In an SN1 reaction the leaving group leaves before
the nucleophile attacks. This means that the nulceophile is free to attack from either side of the
planar carbocation.
CH3 H3C CH3
H 2 O S
N 1 conditions
R H H R R H
Br HO OH
(R)-2-butanol inverted (S)-2-butanol retended
Although one might expect that equal amounts of two isomers would form in an S N1 reaction but
a greater amount of the inverted product is obtained in most cases. Typically, 50 70% of the
product of an SN1 reaction is the inverted produced. If the reaction leads to the formation of
equal amounts of the two products, the reaction is said to take place with complete racemization,
when more of the inverted product is formed, the reaction is said to take place with partial
racemization ions.
Paul Winstein first postulated that dissociation of alkyl halide initially results in the formation of
an intermate ion pair. In an intimate ion pair, the bond between the carbon and the leaving group
has broken but the cation and anion remains next to each other. This species then forms an ion
pair in which one or more solvent molecules have come between the cation and the anion. This is
called the solvent separated ion pair. Further separation between the two results in the
dissociated ions.

R Br R Br R Br R Br
Intimate ion pair Solvent separated ion
The nucleophile can attack any of these species. If the nucleophile attack on only the completely
dissociated carbocation, the product will be completely racemised. If the nucleophile attacks
either the intimate ion-pair or the solvent separated ion-pair, the leaving group will be in a
position to partially block the approach of the nucleophile to that side of the carbocation. As a
result, more of the product with the inverted configuration will be obtained. If the nucleophile
attacks the undissociated molecule, it will be an SN2 reaction, and all the product will have the
inverted configuration).
CH3 CH3
OH2 H2 O - OH2
H2 O Br
H3C H H3C H
Br- has diffused away giving H2O equal access Br- has not diffused away, so it blocks the approach
to both sides of the carbocation of H2O to one side of the carbocation
The difference between the products obtained from an S N1 reaction and from an SN2 reaction is a
little easier to visualize in the case of cyclic compounds. When cis-1-bromo-4-
methylcyclohexane undergoes an SN2 reaction, only the trans product is obtained because the
carbon bonded to the leaving group is attacked by nucleophile only on its back side.
H H H OH
HO
Br -
H3C Br SN 2 H3C H
1-bromo-4-methylcyclohexane 4-methylcyclohexanol
When however, cis-1-bromo-4-methylcyclohexane undergoes SN1 reaction, both the cis and the
trans products are formed because the nucleophile can approach the cabrocation intermediate
from either side.
H H H OH H H
HO
HBr
H3C Br SN 1 H3C H H3C OH
4-methylcyclohexanol cis-isomer
The Leaving Group: Because the r.d.s. of an SN1 reaction is dissociation of the alkyl halide
to form a carbocation, two factors affects the rate of SN1 reaction, the case with which the leaving
group departs from the carbon and the stability of the carbocation that is formed. In the preceding
section, we saw that the tertiary alkyl halides are more reactive than 2 and which in turn more
reactive than 1 alkyl halide. This is because more substituted carbocation is, more easily it is
formed. But about a series of alkyl halides with different leaving groups that dissociate to form
the same carbocation? The answer is same for the S N1 reaction as for as for the S N2 reaction. The
weaker the bases, the less lightly it is bonded to the carbon and the easier it is to break the C
halogen bond. So an alkyl iodide is the most reactive of the alkyl halides in both S N1 and SN2
reactions.
Relative reactivities of alkyl halides in an SN1 reaction.

RI RBr RCl RF
The Nucleophile: The nucleophile traps the carbocation that is formed in the r.d.s. of the S N1
reaction. Because the nucleophile comes into play after the r.d.s., the reactivity of the nucleophile
has no effect on the rate of the SN1 reaction.
In some SN1 reactions, the solvent is the nucleophile. For example, relative rates given in table
are for the reaction of alkyl halides with water serves as both the nucleophie and as the solvent.
When the solvent is the nucleophile the reaction is called the solvolysis reaction.
Illustration: Why is PhO a weaker nucleophile than RO
Solution: The nucleophilic pairs of electrons on oxygen are involved in resonance in the
case of PhO. This resonance interaction decreases their availability to
participate in nucleophilic processes.
O O O etc
No such resonance is possible in the case of the alkoxide ion. It is also this
resonance interaction that makes phenoxideless basic than alkoxide, as well as
making phenols more acidic than alcohols.
Illustration: RBr when treated with AgCN in a highly polar solvent gives RNC whereas
when it is treated with NaCN it gives RCN. Explain.
Solution: As[CN] is an ambident nuicleophile which have two nucleophile which have
two nucleophilic sites and can attack from either side. In a highly polar
solvent, AgCN promotes the formation of carbocation R+, by precipitation of
AgBr.
C N C N
R Br Ag + [CN ]
slow
R CN AgBr
fast
R N C
In the absence of such promotion by Ag+, with Na+[CN], the resulting SN2
reaction is found to proceed with preferential attack on the atom in the
nucleophile which is more polarisable i.e. C.
NC L R L Br
NC R Br N C R Br
Transition State
BRAIN TEASER:
5-Chloro-1, 3-cyclopentadiene (below) undergoes SN1 solvolysis in the presence of
silver ion extremely slowly even though the chlorine is doubly allylic and allylic halides
normally ionize readily. Provide an explanation for this behaviour.
SNi Mechanism: Retention of Configuration

Despite what has been said above about displacement reactions leading to inversion of
configuration, to racemisation, or to a mixture of both, a number of cases are known of reactions
that proceed with actual retention of configuration, i.e., in which the starting material and product
have the same configuration. One reaction in which this has been shown to occur is in the
replacement of OH by Cl through the use of thionyl chloride, SOCl2:
Me Me
SOCl 2
OH Cl SO 2 HCl
Ph Ph
H H
(I) (IIa)
The reaction has been shown to follow a second order rate equation, rate = k2[ROH][SOCl2], but
clearly cannot proceed by the simple SN2 mode for this would lead to inversion of configuration
in the product, which is not observed.
Carrying out the reaction under milder conditions allows of the isolation of an alkyl
chlorosulphite, ROSOCl (III), and this can be shown to be a true intermediate. The chlorosulphite
is formed with retention of configuration, the R O bond not being broken during the reaction.
The rate at which the alkyl chlorosulphite intermediate (III) break down to the product, RCl (II),
is found to increase with increasing polarity of the solvent, and also with increasing stability of
the carbocation R+: an ion pair, R e OSOCl (IV), is almost certainly involved. Provided collapse
of the ion pair to produce then occurs rapidly, i.e., in the intimate ion pair (V) within a solvent
cage, then attack by Cl is likely to occur on the same side of R + from which OSOCl departed,
i.e., with retention of configuration:
Me
Me O Me Me
O slow

Cl
Ph O S Cl
H S O Ph H Ph H Ph
Cl H
Cl
(III) (IV) (V) (IIa)
Whether the breaking of the C O and the S Cl bonds occurs simultaneously, or whether the
former occurs first, is still a matter of debate.
It is interesting that if the SOCl 2 reaction on ROH (I) is carried out in the presence of pyrine, the
product RCl is found now to have undergoing inversion of configuration (IIb). This occurs
because the HCl produced during the formation of (III) from ROH and SOCl 2 is converted by
pyridine into C5H5NH+Cl and Cl, being an effective nucleophile, attacks (III) from the back in
a normal SN2 reaction with inversion of configuration.
Me Me O Me

Cl + O Cl C S Cl SO 2 +Cl+
Ph Ph H Ph
H S O Cl H
(III) (IIb)
Cl
BRAIN TEASER:
Convert
HO CH2

O
Elimination Reactions of Alkyl Halides

The E2 Reaction: There are two important mechanism for elimination. The reaction of ethyl
bromide with hydroxide ion is an example of an E 2 reaction. It is a second-order reaction because
the rate of reaction depends on the concentration of both ethyl bromide and hydroxide ion.
CH3CH2Br + HO CH2 = CH2 + H2O + Br
Rate = K [Alkyl halide] [Base]
The rate law tells us that alkyl bromide and hydroxide ion both are involved in the transition state
of the rate determining step of the reaction. The following mechanism agrees with the observed
second order kinetic.

The E2 reaction is a concerted one step H O H
reaction. The proton and the bromide ion are H 2 O Br
removed in the same step.
Br
In an E2 reaction, a base removes a proton from a carbon adjacent to the carbon bonded to the
halogen. As the proton is removed, the electrons, the hydrogen shared with carbon moves
forward to the carbon bonded to the halogen. As there electrons move in the halogen leaves
taking its bonding electrons with it. The removal of the proton and the halide ion from alkyl
halide is known as dehydrogenation.
The carbon to which the halogen is attached is called the -carbon. An adjacent is called a -
carbon. Because the reaction is initiated by the removal of proton from the -carbon, on E2
reaction is sometimes called a -elimination reaction. It is also called a 1,2-elimination reaction
because the atoms being removed from adjacent carbon.
carbon
B
H R
R BH Br _
R Br R
carbon
2-bromopropane has two -carbon atoms from which a proton can be removed in an E2 reaction.
Because the two carbons are identical, the proton can be removed from either one. The product is
propene.
CH3
H3 C CH 3O
H3C CH 3OH Br
Br CH2
How one will known which product will be formed in greater yield? You must determine which
of the product is formed more easily that is, which product is formed faster.
One must know that alkenes stability depends upon the number of alkyl substituents bonded to
the sp2 carbons, the greater that number, the more stable the alkene. In the transition state leading
to an alkene, the C H and C Br bonds are partially, broken and the double bond is partially
formed giving the transition state an alkene like structure. Because the transition state has an
alkene like structure, the transition state leading to 2-butene is more stable than the T.S. leading
to 1-butene. The more stable transition state allows the formation of 2-butene faster than 1-
butene.
OCH OCH
3 3
H H
H3 C CH CH CH3 H2C CH CH2 CH3

Br Br
T.S. leading to 2-butene more stable T.S. leading to 1-butene less stable
The difference in rate of formation of two alkenes is not very great, consequently, both products
are formed but the more stable alkene is the major product of the elimination reaction. Thus an E2
reaction is regio-selective; i.e., more of one isomer is formed than the other.
The reaction of 2-bromo-2-methyl butane with
hydroxide ion produces both 2-methyl-2-butene
and 2-methyl-1-butene. Because-2-methyl-2-butene
has greater number of alkyl substitutents attached
to sp2 carbon. It is more stable alkene and is the
major product of the elimination reaction.
CH3 CH3 CH3

H 3C
H2O
HO H 3C H2C
Br
CH3
H 3C H3C
(70%) (30%)
Saytzeff Elimination vs Hoffmann Elimination: Alkyl halides have the following

relative reactivities in an E2 reaction, because elimination from a 3 alkyl halide typically leads to
a more highly substituted alkene. But one must exercise some care in using Saytzeffs rule to
predict the major product of the elimination reaction because the most substituted alkene is not
always the one that is easiest to form.
For example, if the base in an E2 reaction is sterically hindered, it will preferentially remove the
most accessible -hydrogen. In the following, it is easier for the bulky tert-butoxide ion to
remove one of the more exposed terminal hydrogens which leads to the less substituted alkene.
Because the less substituted alkene is the one that is the more easily formed, it is the major
product of the reaction.
CH3 CH3 CH3 CH3
H3C
H3C O
CH 3 ) 3 C OH
( H3C H2C
Br
CH3
CH3
sterically hindered base H3C H3C
(28%) (72%)
Saytzeff product Hofmann product
The data in table below show that when an alkyl halide undergoes an E2 reaction with a variety of
alkoxide ion, as the size of the base increases, the % of the less substituted alkene (i.e. Hofmann
product) increases.
Effect of steric properties of the base on the distribution of products in an E2 reaction.

CH3
H 3C
H3C CH3 H 3C CH3
Br
H3C RO

-
CH3 H3C CH3 H 3C CH2
Base Saytzeff Product More Hoffmann product Less

substituted product substituted product
H3C
79% 21%
O
CH3
H 3C
27% 73%
O
H 3C
CH3
H 3C
19% 81%
O
H 3C
H3C
H3C CH3 8% 92%

O
Although the major product of the E2 dehydrohalogenation of the alkyl chlorides, alkyl bromides
and alkyl iodides is normally the most substituted alkene, the major product of the E2
dehydrohalogenation of alkyl of fluorides is the least substituted alkene (i.e. Hofmann
elimination).
F
CH 3O CH
3 H2C CH3 H3C CH3
H3C CH3 OH
(70%) (30%)
When a hydrogen and a chlorine, bromine or iodine are eliminated from an alkyl halide, you have
seen that the halogen starts to leave as soon as the base begins to remove the proton. Departure of
the halogen and its bonding electrons prevents the build up of ve charge on the carbon that is
loosing the proton, giving the T.S. alkene character. Of the halogens ions, fluoride ion is the
strongest base and therefore, the poorest leaving group. So when a base begins to remove a
proton from an alkyl fluoride, the F ion has less tendency to leave than do the other halide ions.
As a result, -ve charge develops on the carbon that is losing a proton, giving the T.S. a carbanion
character rather than an alkene like T.S. Normally, carbanion T.S. are unstable, but in this case
the carbanion T.S. is stabilized by the strongly electron withdrawing fluorine.
OCH3 OCH
3
H H
H2C CH3 H2C CH3

F F
Carbanonic T.S. leading to 1-pentene CarbanonicT.S. leading to 2-pentene
(more stable) (less stable)
The T.S. leading to 1-pentene has the developing ve charge on a primary carbon. This is more
stable than the T.S. leading to 2-pentene which has the developing ve charge on the 2 carbon.
Because the T.S. leading to 1-pentene is more stable, 1-pentene is formed more rapidly and is
therefore major product of the reaction.
In the following reaction, Saytzeff rule does not lead to the more stable alkene, because the rule
does not take into account the fact that the conjugated double bonds are more stable than the
isolated double bonds. Since the conjugated alkene is the more stable alkene, it is the one that is
most easily formed and is therefore, the major product of the reaction. So, if there is a double
bond or a benzene ring in the alkyl halide, do not use Saytzeff rule to predict the major product of
the elimination reaction.
CH3
CH3 H2C
CH3 HO
H2C
H2C
Br CH3
CH3
CH3 Minor product
Major product
CH3 HO

CH3 CH3
CH3 CH3
Br CH3
Major product Minor product
We can summarise by saying that the major product of the E 2 reaction is the most substituted
alkene unless one of the following applies.
move
The base is sterically hindered.

The alkyl halide is alkyl fluoride.
The alkyl halide contains one or more double bonds.
Illustration: Give the major product of the elimination reaction each of the following
alkyl halides with OH ion.
a) CH3
H3C OH
Cl
b) CH3
H3C OH
F
c) CH3
H3C OH
F CH3
d)
OH
Br
Solution: a) CH3
H3C OH H3C
Cl CH3
b) CH3
H3C OH H2C
F CH3
c) CH3 CH3
H3 C OH H3C
F CH3
CH3
d)
OH
Br
Illustration: What are the major products of the following reactions?

a) CH3
H3C Cl OCH 3

CH3
b) CH3
H3C O CH3 X

CH3
Solution: a) CH3 CH3

H3C Cl OCH 3
H3C
CH3 CH2
OCH 3 (nucleophile) can't attack 3 carbon having high electron - density

hence elimination takes place giving alkene.
b) CH3 CH3
H3C O CH3 X
H3C O
CH3 CH3 CH3
Nucleophilic attack on methyl carbon is possible giving ether (Williamson

synthesis).
Illustration: Predict the major product of each reaction below, and describe your reasoning.
Note that the mechanism of each reaction is given.
a) CH3
H C 3 +
N
CH3
E2
OH -
H3C CH3
b) OH

H /

E1

H3C CH3
O O
c) ElcB
OH -
S S Ph
CH3 O
d) Ph Ph
H
CH3
E

1
H +
H3C N CH3
O
Solution: a) Because the leaving group (CH3)3N+ departs is an uncharged species, we

expect Hofmann orientation to be followed, giving the least hindered
alkene:
CH3
+
H3C N CH3
H3C

CH3 H CH2
OH
b) The acid (H+) converts the OH group to a better leaving group (H 2O), and
the heat (H) promotes elimination of a -hydrogen from the carbocation
intermediate. Saytzeff orientation (most stable alkene) will be followed.
H H
+ H H
OH O
H H3C
H3C H3C
H H H3C H2 O H

CH3 CH3
CH3 CH3
H H H H H
H H
c) The sulfonyl (S = O) group is a strong electron withdrawing group, and

will stabilize the carbanion formed in the first step.
O O
O
H3C S CH3 H3C S CH3
H3C S CH3

H 2O OPh

H OH O O
Ph Ph
Because there is no stereoelectronic preference in an ElcB mechanism, we

would expect both the cis and trans isomers of the product to be formed.
d) The (CH3)2N+ O (amine oxide) group will serve as the internal base in
this reaction, and a cis transition state geometry will give the product
below:
Ph Ph Ph Ph H3C
H H
CH3
N OH
E 1
+
H N CH3 H3C H H3C
The E1 Reaction
The reaction of tert-butyl bromide with water is the first order elimination reaction because the
rate of the reaction depends only on the concentration of the alkyl halide. It is called an E 1
reaction.
CH3 CH3
H3C Br H 2O H3C
CH3 CH2
Rate = K[Alkyl Halide]
We know that only the alkyl halide is involved in the T.S. of the r.d.s. of the reaction therefore,
there must be at least two steps in the reaction.
An E1 reaction is the two step reaction. In the first step, alkyl halide dissociates heterolytically.
This is the r.d.s. of the reaction. In the second step of the reaction, the base forms an elimination
product by removing a proton from a carbon adjacent to the +vely charged carbon. Because the
first step is the r.d.s., increasing the concentration of the base which comes into play in the
second step of the reaction, has no effect on the rate of the reaction.
Mechanism
CH3 CH3
slow -
H3C Br H3C Br
CH3 CH3
CH3 CH3
fast +
H3 C H3 C H3O
CH2
H
OH2
When two elimination products can be formed, the major product is generally the one obtained
by following Saytzeff rule.
CH3 H3C H3C
H3C OH
CH3 CH2
CH3
Cl H3C H3C
Major product Minor product
Because the first step is the r.d.s. of an E 1 reaction depends on both the ease with which the
leaving group leaves, and the stability of the carbocation that is formed. Thus the relative
reactivities of the series of alkyl halides with the same leaving group parallel the relative
stabilities of carbocations. 3 benzylic alkyl halide is the most reactive alkyl halide because the
3 benzylic carbocation, is the most stable carbocation, is the easiest to form.
Relative Reactivities of Alkyl Halides in an E 1 Reaction = Relative Stabillities of the

carbocations.
3 benzylic 3 allylic 2 benzylic 2 allylic 3 1 benzylic 1 allylic 2 1 vinyl.
Because the E1 reaction involves the formation of carbocation intermediate, the rearrangement of
the carbon skeleton can occur before the proton is lost. For example, the 2 carbocation that is
formed when a chloride ion dissociates from 3-chloro-2-methyl-2-phenylbutane undergoes 1,2-
methanide shift to form a more stable 3 benzylic carbocation.
CH3
CH3 CH3 CH3 CH3
1, 2 Methanide shift

CH 3OH

CH3
CH3 Cl CH3 CH3
+
-H
CH3
CH3
H3C
Aryl Halide
Benzene and its homologues react with halogens to produce either addition or substitution
products.
i) Addition Compounds: These compounds are obtained by exposing the mixture of

aromatic hydrocarbon and the halogen to direct sunlight, e.g., benzene hexachloride
(BHC), C6H6Cl6; benzene hexabromide, C6H6Br6 etc.
ii) Substitution products: Two types of halogen substituted products are known.
a) Nuclear halogen substitution product: In these products, the halogen is linked

directly to the carbon of the benzene nucleus. These products are generally called
arylhalides.
Cl Br CH3 Cl
chlorobenzene bromobenzene
Br Cl
1-bromo-4-methylbenzene 1,4-dichlorobenzene
b) Side chain halogen substitution products: In these products, the halogen is

linked to the carbon atom of the side chain.
Cl Cl
Cl
Cl Cl
Cl
(chloromethyl)benzene (dichloromethyl)benzene (trichloromethyl)benzene
These are also called side chain aryl halides. They have properties of alkyl halides.
Aryl Halides: According to IUPAC system, aryl halides are named as Haloarenes. If more
than one halogen is present their positions in the ring are indicated by numbers or appropriate
prefixes, ortho, meta, para.
CH3
Br CH3 Cl
Cl
Br CH3
1,3-dibromobenzene or 1-chloro-2-methylbenzene 2-chloro-1,4-dimethylbenzene
m-dibromobenzene or o-chlorotoluene
General Methods of Preparation
i) By direct halogenation: This method is used for the preparation of chloro and bromo
derivatives. Halgoens react with aromatic hydrocarbons in presence of catalysts or
halogen carriers such as iron, iodine or aluminium chloride at room temperature in
absence of direct sunlight.
C 6 H 6 Cl 2
Fe
C 6 H 5 Cl HCl
For further halogenation, more halogen is used
C6H 6Cl Cl2

Fe
C6H5Cl2 HCl
Chlorobenzene o and p-
Dichlorobenzene
Toluene in presence of iron reacts with Cl 2 or Br2 form a mixture of o- and p-chloro or
bromotoluenes, respectively.
CH3 CH3 CH3
Cl
Cl 2
Fe

Cl
Mixture of o- and p-chlorotoluene
Iodo derivatives cannot be obtained by direction reaction with iodine as the reaction is
reversible.
C6H5 + I2 C6H5I + HI
Iodo-derivative can be obtained if the reaction is carried out in presence of an oxidizing

agent, e.g., iodic acid, or nitric acid, etc. The oxidizing agent oxidizes HI to iodine and
thus, the reaction moves to proceed to the right
2HI + [O] H2O + I2
ii) From diazonium salts: Aryl halides can be obtained most satisfactorily by the
decomposition of aryl diazonium salts in presence of copper halide solution dissolved in
the corresponding halogen acid, the diazo group is replaced by a halogen atom
(Sandmeyer reaction).
Cl
CuCl

/ HCl
heat
chlorobenzene
Br
+ -
N2 Cl CuBr

/ HBr
heat
bromobenzene
I
Benzene
diazonium KI
chloride heat
iodobenzene
F
NaBF
4
heat
fluorobenzene
Iodo compounds may be obtained by boiling the diazonium salt solution with aqueous
potassium iodide.
iii) Hunsdiecker reaction: Aryl bromides are obtained by heating the silver salts of
aromatic acid (in CCl4 or xylene) with bromine.
O
- + Br
O Ag
Br2
AgBr CO 2
iv) Decarboxylation of halogenated acids: Sodium salts of halogenated acid when

heated with soda lime produce aryl halides.
BrC6H5COONa + NaOH C6H5Br + Na2CO3
Properties: Aryl halides are colourless stable liquids with pleasant odour. These are
insoluble in water but readily miscible with organic solvents. Most of them are steam
volatile, heavier than water. Their boiling points are higher than corresponding alkyl
halides. The boiling points rise gradually from fluoro to iodo compounds.
Nucleophilic Aromatic Substitution
Normally, alkenes are unaffected by treatment with nucleophiles, and it is no surprise to find that
benzene also survives treatment with strong nucleophiles. In particular, no reaction occurs when
simple substituted benzenes are treated with base.
+-
Nu Na OCH 3
No reaction No reaction
HOCH 3
Cl
But a few specially substituted benzenes do undergo reaction in base. For example, 2, 4-
dinitrochlorobenzene is converted into 2,4-dinitrophenol by treatment with sodium hydroxide in
water.
NO2 NO2
NaOH/H2O
warming
NO2 NO2
Cl OH
(95%)
The nitro group is essential, and it must be substituted in the right place relative to the chlorine.
Chlorobenzene and m-nitrochlorobenzene do not react under these conditions, but p-
nitrochlorobenzene does, although it substitutes much more slowly than the 2,4-dinitro
compound.
Relative Rate
NO2 NO2
+-
Na OCH3
HOCH3 , 50C 115,000
NO2 NO2
Cl OCH3
NO2 NO2
+-
Na OCH3
HOCH3, 50C 3.4
Cl OCH3
+-
Na OCH3
HOCH 3, 50 C
NO2 NO2
1.0
Cl OCH3
NO2 +-
Na OCH3
or No reaction
HOCH3, 50C 0
Cl Cl
Neither an SN2 nor an SN1 reaction seems likely. Attack from the rear is impossible, as the ring
blocks the path of any entering nucleophile, and ionization would produce a most unstable
carbocation.
SN2
C L the path of attack in the SN2
reaction is blocked.
Nu S N1
An unstable phenyl cation - the SN1

C
reaction will not be easy.
The mechanism of the reaction involves addition to the benzene ring by methoxide to generate a
resonance stabilized anionic intermediate.
NO 2 NO 2 NO 2 NO 2 NO 2
HOCH 3
NO 2 NO 2 NO 2 NO 2
NO 2
Cl H3CO Cl H3CO Cl H3CO Cl H3CO Cl
OCH 3
The nitro groups stabilize the negative charge through resonance, and therefore will exert their
effect only when they are substituted at a carbon that helps to bear the negative charge. This
stabilization by nitro is the reason that o- or p-nitrochlorobenzene undergoes the reaction, but the
meta isomer does not.
Para addition
O O O O
NO2 + +
N N
+-
Na OCH3
HOCH 3
Cl H3CO Cl H3CO Cl
NO 2
+-
Na OCH3
HOCH3 O O
+ +
NO 2 N N
Cl H3CO Cl H3CO Cl
O O
Meta addition here the nitro groups do not help stabilize the negative charge
NO2 NO2 NO2 NO2
+-
Na OCH3
HOCH3
Cl H3CO Cl H3CO Cl H3CO Cl
The aromatic system can be regenerated by reversal of the attack of methoxide or by loss of
chloride to give 2,4-dinitroanisole.
NO2 NO2 NO2
HOCH3 (b)
(a) HOCH3
NO2 NO2 NO2
Cl H3CO Cl OCH3
+-
Na OCH3
(a) (b)
There are similarities between nucleophilic aromatic substitution and its more usual electrophilic
counterpart. Each involves the formation of a resonance stabilized intermediate, and each
involves a temporary loss of aromaticity that is regained in the final step of the reaction. But the
similarities are only so deep. One reaction is cationic; the other involves anions. Use the differing
effects of a nitro group, strongly decelerating in the electrophiilc substitution and strongly
accelerating in the nucleophilic reaction, to keep the two mechanisms distinct in your mind.
Benzyne Mechanism
We mentioned the lack of reactivity of halobenzenes with bases. It look the activation of a nitro
group for substitution to occur for (fig). In truth, if the base is strong enough, even chlorobenzene
will react. In the very strongly basic medium potassium amide in liquid ammonia, chlorobenzene
is converted into aniline.
The mechanism is surely not an SN2 displacement, and there is no reason to think nucleophilic
addition would be possible to an unstabilized benzene ring.
Cl +- NH2
Na NH2
+
NH3
NH2
Which reactions of halides do you know besides displacement? The E1 and E2 reactions compete
with displacement reactions. If HCl were lost from chlorobenzene, a cyclic alkyne, called
dehydrobenzene or benzyne, would be formed. This bent acetylene might be reactive enough to
undergo an addition reaction with the amide ion. If this were the case, the labeled material must
produce two differently labeled products of addition.
Cl (a)
+-
Na NH 2
NH 3 NaCl NH 2
H (b)
Benzyne
(a) (b)
NH2 H NH2
NH 3

H NH2 NH2
NH 2
Benzyne is surely an unusual species and deserves a close look. Although this intermediate
retains the aromatic sextet, the triple bond is badly bent, and there must be very severe angle
strain indeed. Remember, the optimal angle in triple bonds is 180. Moreover, the third bond is
not composed of 2p-2p overlap like a normal alkyne, but of overlap of two hybrid orbitals.
One would therefore not be too surprised to find that this molecule is able to add strong bases
such as the amide ion. In fact, one would expect very high reactivity for this strained acetylene.
Solved Problems (Subjective)
Problem 1: An olefinic hydrocarbon (A) adds chlorine to give a compound (B) which when
treated with sodamide gives a hydrocarbon (C). (C) is treated with dilute H 2SO4
in the presence of mercuric sulphate and then (D) is obtained. (D) on reaction
with alkaline hypochlorite gives an acid (E). (D) on reduction with LiAlH 4 gives
(F) which on dehydration with alumina gives a hydrocarbon (G) which is isomeric
with (A) and which on ozonolysis gives two moles of acetaldehyde. How do you
account for these reactions?
Cl2 NaNH 2 dil. H 2SO 4 Alkaline Hypochlorite
(A) (B) (C) Hg 2
(D) (E)
Alkene Acid
Ozonolysis Dehydration
2CH 3CHO (G)
Alu min a
(F)
Isomeric with
(A)
i) (D) reacts with alkaline hypochlorite to form carboxylic acid hence (D) must
be methyl ketone.
ii) (G) on ozonolysis gives two moles of CH3CHO hence (G) must be
2-Butene
iii) 2-Butene (G) is obtained by the dehydration of (F) hence (F) must be butan-1-
ol or butan-2-ol.
iv) (F) is obtained by reduction of (D) methyl ketone. Hence (F) is definitely a
secondary alcohol (Butanol-2)
(A) is isomeric with (G) Hence (A) is butene-1 (from the above sequence of
reactions it could not be isobutene)
CH
CH2 Cl 2 NaNH2
H3C
H3C Cl
H3C
(A) Cl Hg 2 / H 2SO 4
(B)
CH3 OK
hypo
H3C
chloride
H3C
O O
LiAlH 4
CH2 CH3
O3 Al 2O3
2CH 3CHO
H2O
H3C
H 2O
H3C
(G)
OH
(F)
Problem 2: A hydrocarbon (A) of molecular weight 54 reacts with excess of Br 2 in CCl4 to
give a compound (B) whose molecular weight is 593% more than that of (A).
However on catalytic hydrogenation with excess of hydrogen (A) forms (C)
whose molecular weight is only 7.4% more than that of (A). (A) reacts with
CH3CH2Br in the presence of NaNH2 to give another hydrocarbon (D) which on
ozonolysis yields diketone (E). (E) on oxidation gives propanoic acid. Give
structures of (A) to (E) with reasons.
Compound (A) Br2 / CCl4
Compound (B)
Molecular weight 54 excess
Molecular weight
CH3CH2Br
(593% more than A)
in NaNH2
Catalytic

Hydrogenation
(C)
(D) Molecular weight 7.4% of (A)
O3
Diketone (E)
(O)
Diketone (E)
100 gm of (A) add Br2 and the new weight is 593 gm

593 54
\ 54 gm of (A) add Br2 and the new weight is = 320.2 gm
100
Weight 360.2
\ No. of moles of Br2 = Molecular weight 160 = 2 mole
i) As two moles of Br2 adds hence compound has two p bonds hence general
formula should (CnH2n2)
CnH2n-2 = 54
12n + 2n 2 = 54
n = 4 \ molecular formula = C4H6
ii) (A) reacts with CH3CH2Br in presence of NaNH2 Compound (A)

should be terminal alkyne i.e. 1-butyne
Br
Br2
CH H3C Br
CCl 4
H3 C (A) Br
CH3CH2Br Br
in NaNH2 CH3
Catalytic

Hydrogenation
H3 C
C 2H5 (C)
H3 C (D)
O3
O
H3 C C2H5
O
(O)
2CH 3CH 2 COOH
Problem 3: A hydrocarbon C8H10 (A) on ozonolysis gives compound C 4H6O2 (B) only. The
compound (B) can also be obtained from the alkyl bromide C 3H5Br (C) upon
treatment with magnesium in dry ether followed by CO 2 and acidification.
Identify (A), (B) and (C) and also give equations for the reactions.
Solution: i) (C) is an alkyl bromide C C p bond is absent in it.

ii) Molecular formula (C3H5Br) (C) shows (C) would be a cyclic compound
Br
iii) CO2 and on acidification would give carboxylic acid compound (A) would be
symmetrical alkyne (B) is obtained by ozonolysis of (A) C8H10.
Problem 4: How would you synthesize CH3CH2C CH from CH3CH2I
Solution: a) What are the connectivities of the two compounds? How many carbon atom
does each contain? Are there any rings? What are the position of branches and
functional groups on the carbon skeletons?
The starting material has a two-carbon chain, an ethyl group, with an iodine
atom bonded to one carbon. The product has a four-carbon chain in which the
two carbons that have been added to the ethyl group are bonded to each other
by a triple bond.
b) How do the functional groups change in going from starting material to
product? Does the starting material have a good leaving group?
The iodine atom in the starting material is a leaving group and has been
replaced in the product by an alkyne functional group.
c) Is it possible to dissect the structures of the starting material and product to see
which bonds must be broken and which formed?
H3C CH2 I H3C
CH
Bond to be broken new bond to be formed
H3C CH2 C CH
the pieces that have to be brought together
d) New bonds are created when an electrophile reacts with a nucleophile. Do we

recognize any part of the product molecule as coming from a good nucleophile
or an electrophilic addition?
The ethyl group is attached to a leaving group in the starting material and so
must serve as the electrophilic center. A check reminds us that the
CCH group is related to the nuclophile HC C:, the conjugate base of an
alkyne.
e) What type of compound would be a good precursor to the product?
A displacement of the iodine atom by the nucleophile will give us the product
we want.

H3C CH2 I H3C
CH
C CH I
f) After this last step, do we see how to get from starting material to product? If
not we need to analyze the structure obtained in step 5 by applying questions 4
and 5 to it. These steps are a restatement of the way of thinking about
problems. It will be helpful to you to ask yourself these questions in a
systematic way for each problems you work, on until this way of thinking
becomes familiar and easy.
Problem 5: Predict the product(s) of the reaction.

- +
Br S Na

H3C
a) To what functional group classes do the reactants belong?

b) Does either reactant have a leaving group?
c) Are any of the reactants acids, bases, nucleophiles, or electrophiles?
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?
Solution: 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
this reaction mixture so a protonation-deprotonation reaction is not probable.
Reaction of the nucleophilic sulfur atom with the electrophilic carbon atoms is
most likely.
S
Br H3C

H3C

Br
S
e) All species formed are stable. No further reaction will occur. The complete
equation is:
- +
S
Br S Na H3C
Na + Br
H3 C
Problem 6: Comment on the following observation

CO2 CO2
OH
Br
High concentration
HO Br
H H
H3C CH3
Retention of configuration
(S) Bromopropanoate ion (R) Lacate ion
Inversion of configuration
Ag 2 O
Low concentration of - OH
CO2
H OH
H3C
(S) lacate ion
Problem 7: Identify the compounds A to D

Nitric acid Sn / HCl NaNO2 (D)
(A)
sulfuric acid
p-nitro Toluene (B) HCl, 05oC (C) p-flouro toluene
Solution: A = Toulene B = p-toluidine

C = p-toluene diazonium chloride D = HBF4
Problem 8: Explain the fact that a small amount of NaI catalyzes the general reaction
RCl + RONa+ ROR + NaCl
Solution: With I the overall reaction occurs in two steps, each of which is faster than the
uncatalysed reaction.
Step 1: RCl + I RI + Cl
This step is faster because I, a soft base has more nucleophilicity than OR, a hard
base
Step 2: RI + RO: ROR + I
This step is faster because I is a better leaving group than Cl
Problem 9: i)

CH3 CH2
ii) CH2
H C NH2
H3C 3
iii) CH2

H2C
H3C CH2
Solution: i) Br
alc. KOH
Br2

h

CH3 CH3 CH2
ii) CH2 HBr NH3
Br H3C NH2
H3C
H3C H O2 2
iii) CH2
Br2 / h
H2C
alc. KOH
CH2
H3C
Problem 10: Explain the formation of the products in the following reaction :
H3C CH3 H3C
H2 O
Ag + H3C
H3C Cl CH2 H3C OH
OH
85% 15%
Solution: Both products are derived from the allylic action which has two resonance forms
and the product can be formed by attack of water at either electron deficient allylic
carbon. The major product (85%) is formed from the most stable tertiary cation.
Problem 11: Identify A to D in the following sequence of reactions.

aq. NaOH oxidation NaOI
C4 H9 Br C4 H10 C4 H8 O

yellow ppt.
(A) (B) (C)
conc. H 2SO 4 Tollens' reagent
O3 / H 2 O / Zn
CH3CHO D no reaction
Br OH
H3C CH3 H3C CH3

O
C=
H3C CH3
H3C CH3
Problem 12: Identify A to E in the following
CH3
CH3 MgBr
A
H3O
Ph CH3
OH

aq. NaOH/I2 H soda lime CH3CH 2CH 2Cl / AlCl3

B C
E
O O
CH3 ONa
O
OH
CH3
CH3
Objective
Problem 1: Which one of the following compounds most readily undergoes substitution by
SN2 mechanism?
CH3
H3C H3C
(a) (b)
Cl
Cl
Cl CH3
H3C
(c) H3C (d)
Cl
C 3 H7 H3C
Solution: Less hindered carbon follows SN2 mechanism.

\ (b)
Problem 2: Which of the following derivatives of benzene would undergo hydrolysis most
readily with aq. KOH
Cl Cl
O 2N NO2
(a) (b)
NO2 NO2
Cl Cl
NO2
(c) (d)
NO2
N
NO2 H3C CH3
Solution: NO2 group increases SNAR because of R and I effect.

\ (b)
Problem 3: CH3Br A
KCN
CH3CH2NH2
4H
I.U.P.A.C. name of A is
(a) Methyl cyanide (b) Methyl isonitrile
(c) Acetonitrile (d) Ethane nitrile
Solution: CH3Br CH3CN CH3CH2NH2

4H
CH3CN Ethane nitrile

\ (d)
Problem 4: In two separate experiments equal quantities of an alkyl halide, C 4H9Cl were
treated at the same temperature with equal volume of 0.1 molar and 0.2 molar
solutions of NaOH respectively. In the two experiments, the times taken for the
reaction of exactly 50% of the alkyl halide were the same. The most likely
structure of halide is:
(a) CH3CH2CH2CH2Cl (b) CH3CH(Cl) CH2 CH3
(c) (CH3)2 CHCH2Cl (d) (CH3)3 CCl
Solution: CH3
+
H3C Cl H3C
O (After rearrangement)
CH3 CH3
CH3
+
H3C C Cl
H3 C Cl
CH3 CH3
As we already mentioned that Hydrolysis of 3 alkyl halide is independent of
nucleophilic concentration.
\ (d)
Problem 5: Which of the following method cannot be considered suitable for the
preparation of alkyl halide:
(a) Halogenation of alkane (b) ROH and PX3
(c) ROH and HX (d) Alkene and HX
high temperature 400
Solution: R H X 2 UV light
R X HX
1.
This is most drastic method as it required High temperature or catalyst CuCl 2,
FeCl3, FeBr3 etc.
2. ROH + PX3 3RX + H3PO3
3. ROH + HX R X + H2O
4. R H R H
HX

H H X H
(2), (3) & (4) are very feasible process
\ (a)
Problem 6: The heterolytic bond dissociation energy of C Cl bond in vinyl chloride is 207
kcal/mol as compared to 191 kcal/mol in the case of C Cl bond in ethyl
chloride. One explanation for this observation is
(a) That in ethyl chloride the bond energy is decreased through resonance
involving lone pair of electrons on chlorine.
(b) The hyper conjugation stabilization in ethyl chloride
(c) That in vinyl chloride the C Cl bond gets partial double bond character
through resonance.
(d) That in vinyl chloride the chlorine atom is attached to sp hybridised carbon
whereas in ethyl chloride it is attached to sp3 hybridised carbon.
H2C
Solution:
Cl
Vinyl chloride
H2C H 2C
Cl +
Cl
As we can see that C = Cl bond is formed in vinyl chloride so its bond
dissociation energy 207kcal/mol as compared 191 kcal/mol for C Cl bond.
\ (c)
Problem 7: Identify Z in the following sequence

KCN Conc. HCl dil. HCl
CH3CH2I X Y
Z
(a) CH3COOCl (b) CH3CONH2
(c) CH3COOH (d) CH3CH2COOH.
Solution: X = CH3CH2CN, Y = CH3CH2CONH2, Z = CH3CH2COOH.

\(d)
Problem 8: When tert-butyl chloride is made to react with sodium methoxide, the major
product is
(a) Dimethyl ether (b) Di-tert butyl ether
(c) Tert-Butyl methyl ether (d) Isobutylene.
Solution: Tertiary halides on treatment with base, such as sodium methoxide, readily
undergo elimination resulting in the formation of alkenes.
\ (d)
Problem 9: Which of the following compounds would be hydrolysed most easily ?

(a) C2H5Br (b) CH3Br
(c) CH2 = CH Br (d) CH2 = CH CH2Br.
Solution: Allylic halides undergo substitution very easily.

\(d)
Problem 10: An alkyl halide on reaction with sodium in the presence of ether gives 2, 2, 5, 5-
tetramethyl hexane. The alkyl halide possibly is
(a) 1-Chloropentane (b) 1-Chloro-2, 2-dimethyl propane
(c) 3-Chloro-2, 2-dimethyl butane (d) 2-Chloro-2-methyl butane.
Solution: CH3 CH 3
CH3 C CH 2 CH 2 C CH3
CH3 CH3
Wurtz reaction
CH3 CH3
CH 3 C CH 2 Cl ClCH 2 C CH3
CH3 CH 3
Problem 11: An alkyl chloride produces a single alkene on reaction with sodium ethoxide
and ethanol. The alkene further undergoes bydrogenation to yield-2-
methylbutane. Identify the alkyl chloride from amongst the following.
(a) ClCH2 C(CH3)2CH3 (b) ClCH2CH2CH2CH2CH3
(c) ClCH2CH(CH3)CH2CH3 (d) CH3C(Cl)(CH3)CH2CH3.
Solution: Formation of 2-methylbutane indicates that the carbon chain skeleton in the
chloride is
CCCC
C
Hence, choice (a) and (b) are ruled out. Out of (c) and (d), compound (d) can yield
two products on dehydrohalogenation.
\ (c)
+
Problem 12: Cl ONa
NO2 NO2

Dil. NaOH
NO2 NO2
The above transformation proceeds through
(a) Electrophilic-addition (b) benzyne intermediate
(c) Activated nucleophilic substitution (d) Oxirane.
Solution: NO2 groups activate the molecule towards nucleophilic substitution by
stabilizing the intermediate carbanion.
\ (c)
Problem 13: o-Methoxybromobenzene is treated with sodamide and then with ammonia. The
product formed is
(a) o-Methoxyaniline (b) Aniline
(c) Methoxybenzene (d) m-methoxyaniline.
Solution: Reaction proceeds through benzyne.

\(d)

Alkyl Halide and Aryl Halide

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Alkyl Halide and Aryl Halide

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ALKYL & ARYL HALIDE

Some examples of substituted alkyl and aryl halides are:

R, R and R may be same or different.

1. From halogenation of Alkanes: Alkanes can be halogenated to give alkyl halide.

On further halogenation, di, tri or tetrahalomethane can be obtained. This can be

2. From addition of halo acids on alkenes and alkynes: Electrophilic addition of

3. From addition of X2 on alkenes and alkynes: Addition of X2 on alkenes give

H3C + Br2 H3C

CH3CH2OH + PCl5 CH3CH2Cl + POCl3 + HCl

5. From free radical substitution of alkyl benzenes

Nucleophilic Substitution Reactions

1. A nucleophile is attracted to the partially positively charged atom of carbon. As the

Regardless of the mechanism by which such a substitution reaction occurs, it is called a

the structure of the alkyl halide.

the reactivity and the structure of the nucleophile.

the concentration of the nucleophile.

the solvent in which the reaction is carried out.

Mechanism of SN2 Reactions

Relative Rates of SN2 reactions for several alkyl halides with OH

Relative reactivities of alkyl halides in an SN2 reaction:

Methyl halide 1 alkyl halide 2 alkyl halide 3 alkyl halide.

The weaker the base, the better is the leaving group.

CH4 NH3 H2O HF

Relative Nucleophilicity towards CH3I in Methanol

Stereochemistry of SN2 Reaction

Reaction of this ester with CH 3COO is known to be a displacement in which ArSO 3

CH3 CH3 CH3

Relative Rates of Alkyl Halides in an SN1 reaction

3RX 2RX 1RX CH3X

Relative reactivities of alkyl halides in an SN1 reaction.

Illustration: Why is PhO a weaker nucleophile than RO

SNi Mechanism: Retention of Configuration

Elimination Reactions of Alkyl Halides

CH3 CH3 CH3

Saytzeff Elimination vs Hoffmann Elimination: Alkyl halides have the following

Effect of steric properties of the base on the distribution of products in an E2 reaction.

CH3 H3C CH3 H 3C CH2

Base Saytzeff Product More Hoffmann product Less

H3C CH3 8% 92%

H2C CH3 H2C CH3

The base is sterically hindered.

Illustration: What are the major products of the following reactions?

Solution: a) CH3 CH3

OCH 3 (nucleophile) can't attack 3 carbon having high electron - density

CH3 CH3 CH3

Nucleophilic attack on methyl carbon is possible giving ether (Williamson

Solution: a) Because the leaving group (CH3)3N+ departs is an uncharged species, we

c) The sulfonyl (S = O) group is a strong electron withdrawing group, and

Because there is no stereoelectronic preference in an ElcB mechanism, we

Rate = K[Alkyl Halide]

Relative Reactivities of Alkyl Halides in an E 1 Reaction = Relative Stabillities of the

3 benzylic 3 allylic 2 benzylic 2 allylic 3 1 benzylic 1 allylic 2 1 vinyl.

i) Addition Compounds: These compounds are obtained by exposing the mixture of

a) Nuclear halogen substitution product: In these products, the halogen is linked

b) Side chain halogen substitution products: In these products, the halogen is

(chloromethyl)benzene (dichloromethyl)benzene (trichloromethyl)benzene

General Methods of Preparation

For further halogenation, more halogen is used

C6H 6Cl Cl2

Iodo-derivative can be obtained if the reaction is carried out in presence of an oxidizing

2HI + [O] H2O + I2

iv) Decarboxylation of halogenated acids: Sodium salts of halogenated acid when

BrC6H5COONa + NaOH C6H5Br + Na2CO3

Nucleophilic Aromatic Substitution