f

1.
12 IIT–JEE Syllabus
Alkyl Halides
& Aryl Halides
2. Structure and Nomenclature
2.1 Alkyl Halide
2.2 Aryl Halides
3. General Methods of Preparation
3.1 Alkyl Halides
3.2 Aryl Halides
4. Physical Properties of Alkyl
Change in structure of alkane through replacing
Halide
5. Chemical Properties of Alkyl hydrogen by halogen brings about tremendous
Halide
6. Types of Nucleophilic Substitutions change in properties also. In alkyl halide, carbon
6.1 Mechanism & Kinetics of SN1
6.2 Bimolecular Mechanism bearing partial positive charge becomes
7. Factors Affecting Nucleophilic
Substitutions susceptible to attack by a nucleophile which leads
7.1 Alkyl Group
7.2 The Leaving Group to the formation of a lot many organic compounds
7.3 The Nucleophile
7.4 Effects of Solvent on Nucleophilicity
7.5 Effect of Solvent on Kinetics of
and thus making it a versatile compound, having a
Reaction
8. The Unreactivity of Vinyl and Phenyl very important niche in organic chemistry.
Halides
9. Summary of SN1 and SN2 Mechanism
10. Intramolecular Substitution Reaction If we a have family of organic compounds from
11. Competition between Substitution and
Elimination Reaction which we can remove an atom and attach another
11.1 SN2 vs E2
11.2 SN2 vs E1 atom, so that the functional group is changed, it
12. Overall Reaction of Alkyl Halides
12.1 Grignard Reagent will be very nice. Of course, we are having a family
13. Characteristic Reaction Chart for Alkyl
Halides and that is your alkyl halides.
14. Dihalides
15. Trihalides
16. Properties of Aryl Halides
16.1 Reactivity
Yes, the halogen atom in the alkyl halides can be
16.2 Nucleophilic Substitution Reaction
17. Solution to Exercise replaced by many other atoms, thus yielding other
18. Solved Problems
18.1. Subjective families of organic compounds. Interesting, isn’t it?
18.2. Objective
19. Assignments
Let us study more
(Subjective Problems)
20. Assignments
(Objective Problems)
21. Answers to Objective
Assignments
1. IIT-JEE Syllabus
Characteristic reaction of Alkyl halides (nucleophilic substitution reaction,
rearrangement of alkyl carbocations).

2. Structure and Nomenclature

2.1 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.

CH3––CH––CH3 CH3––CH––CH2––Cl
CH3––CH2Br
Br CH3
Ethyl Bromide
or Bromo ethane Isopropyl bromide Isobutyl chloride
or 2–bromo propane or 1–chloro – 2 methyl
propane

CH3 CH3
CH3––CH––CH2––CH—CH3
CH3––C––CH3 CH3––C––CH2––Br
Cl Br
Cl CH3
2-bromo-4-chloro
tert–Butyl chloride Neopentyl bromide pentene
or 2–chloro –2– methyl propane or 1–bromo –2,2-dimethyl propane

H2C = CH –– CH2Br H2C=CH––CC––CH=C––CH3

Allyl bromide or
3–bromo 1–propene Br
6––Bromo –1,5–heptadiene –3–yne

CH2––CH2
H2C =CHCl CH2––CH2
Vinyl Chloride
OH Br
Br Br
1,2–dibromoethane Ethylene bromohydrin
or 2–bromoethanol
H CH2Cl
Br

Cyclohexyl bromide Benzyl chloride

2.2 Aryl halides

Aryl halides are the compounds that contain halogen atom, directly attached to the
benzene ring. They have general formula ArX.
 Cl Cl Cl Cl
| | | |

NO2
| |
NO2 NH2
Chlorobenzene m-chloronitro benzene p-chloronitro benzene p-chloro aniline

Any halogen compound that contains a benzene ring is not classified as aryl halide. e.g.
Benzyl chloride is not an aryl halide, but is a substituted alkyl halide.

3. General Methods of Preparation

3.1 Alkyl halides

i) Photohalogenation of Alkanes: By direct halogenation of paraffins in the

presence of light or catalyst. The order of ease of substitution is tertiary hydrogen
atom > secondary hydrogen atom > primary hydrogen atom. During chlorination
every possible mono chloride is obtained and chlorination beyond mono
substitution may be suppressed by controlling the ratio of chlorine to paraffin .

CH4 + Cl2  CH3Cl + HCl

Methyl chloride

Direct chlorination occurs by free radical mechanism as explained in general

organic chemistry.

ii) By Addition of Halogen Acids to an Olefin

CH2 = CH2 + HI  CH3CH2I

Ethylene Ethyl iodide

iii) By the Displacement of One Halogen Atom by Another

For example, an iodide may be obtained, in many cases by treating the

corresponding chloride or bromide in acetone or methanol solution with sodium
iodide. This is possible because sodium iodide is soluble in methanol or acetone
whereas sodium bromide and sodium chloride is insoluble in these.

RCl + NaI  RI + NaCl

Alkyl chloride Alkyl iodide

iv) From alcohols

a) Grove’s process: This process is the replacement “OH” group in primary and
secondary alcohols with an “X’ atom by means of Hydrogen chloride or
bromide in presence of Zinc chloride. But for tertiary alcohol, it readily reacts
with concentrated hydrochloric acid in the absence of zinc chloride. Zinc
chloride is a lewis acid and consequently can co-ordinate with the alcohol
  SN 1 
ROH + ZnCl2  R—O—ZnCl2  R + [HO — ZnCl2]

The R–O bond is weekend and so the complex readily forms a carbonium ion
(SN1 mechanism). If the nature of R+ is such that it can undergo
rearrangement, the product will be mixture of isomeric alkyl chlorides.

The reaction also follows SN2 mechanism when the concentration of zinc
chloride is low, the reaction is still catalysed, but no rearrangement occurs.

SN
ZnCl 2  HCl  ROH  ZnCl 3  ROH 2  2  ZnCl  RCl  H O
2 2

Pyridine and dimethyl amine also catalyse the reaction between alcohols and
hydrochloric acid without rearrangement. The formation of the various halides
by rearrangement is one example of 1,2 shifts. In this type of rearrangement a
group migrates from a carbon atom (the migration origin) to an adjacent atom
(the migration terminal), which is usually carbon or nitrogen. The
rearrangement may be expressed in following general form.

Z Z Z
  Nucleophilic
A—B—Y  Y– + A — B  A— B product
reagent

When Y ionises, B is left only with six valence electron (open sextet) and
consequently carries a positive charge. Z migrates with its bonding pair of
electrons and A now has an open sextet. Attack now takes place at A by Y– or
some other nucleophilic reagent to form the products.

b) Darzen Process: Thionyl chloride reacts with straight-chain primary alcohols

without rearrangement in the presence or absence of pyridine. The reaction
proceeds via a chloro sulphite

SN
ROH + SOCl2  HCl + ROSOCl  Cl– + RO S O  2  RCl + SO
2

c) Any Alkyl Halide may be prepared by the action of a phosphorus halide on the
alcohol. Phosphorus penta chloride gives variable yields depending on the
alcohol.
ROH + PCl5  RCl + HCl + POCl3.
Straight chain primary alcohols react with phosphorus trihalides to give
unrearranged alkyl halides but many secondary alcohols undergo rearrangement

v) Hünsdiecker or Bonodine – Hünsdiecker Reaction

When silver salts of the carboxylic acids in carbon tetrachloride solution are
decomposed by chlorine or bromine then it forms the alkyl halide e.g..
RCO2Ag + Br2  RBr + CO2 + AgBr
The yield of halides is primary > secondary > tertiary and bromine is generally
used, as chlorine gives a poorer yield of alkyl chloride.
3.2 Aryl halides

3.2.1 Halogenation

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

Mechanism:
X—X + AlX3  X+ + AlX 4
Lewis acid
H + H
X
X
 H X X
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

3.2.2 From diazonium salts


N2 Cl
|
Ar – H   Ar – NO2 
HNO3
H SO
 Ar – NH2 
reduction
Sn/HCl

NaNO 2
HCl
2 4
0-5°

Cl

Cu powder(Gatterman
reaction) + HCl

I N2Cl
KI
HBF4 F

(Schiemann Reaction)

CuCl
(Sandmeyer reaction)

Cl
4. Physical Properties
1. Physical State: The lower members (CH3Cl, CH3Br and C2H5Cl) are gases. The rest
of the lower members are colourless, sweet – smelling liquids.

2. Solubility: 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. Boiling Point: Haloalkanes have considerably higher boiling points than alkanes
having same number of carbons because of greater molecular weight.

4. Density: 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

  R –– R + I
h
2RI  2

Illustration 1: Arrange RCl, RBr, RI, RCl in decreasing order of boiling point.

Solution: For a given alkyl group, the boiling points and densities are
proportional to the molecular weight hence show a regular gradation in
the order iodide > bromide > chloride > fluoride.

Exercise 1: Compare R—X and R—H (alkyl halide and alkane) in following respects:
a) dipole moment
b) solubility in H2O

5. Chemical Properties of Alkyl Halide

Reactions of alkyl halide: During the preparation of alkene we have studied that one of
the important reaction of alkyl halides is elimination followed by formation of alkenes. We
studied E1,E2,E1CB mechanism. (Do you remember?).

Beside these elimination reactions alkyl halide show another type of reactions, also
known as substitution reaction. First let’s see how this substitution takes place, what
exactly it means. Lets have an alkyl halide say R—X. In R—X, X is more electronegative
as compared to that of C with which it is attached, hence there is polarity in C—X bond
e.g.
RCH2—X

H
+

R — C  X-
H

Or we can say C is having small +ve charge or it is an attraction point for a nucleophile
(+ve loving) so as the nucelophile approaches, it replaces X atom.
 H H
R – C – X  Nu – C – R
H H
Nu
Since X atom has been replaced by a nucelophile the process is called nucleophilic
substitution, the versatile reaction for the formation of organic compounds.

6. Types of Nucleophilic Substitution

Nucleophilic substitution can take place in two ways
i) A nucleophile is attracted to the partially positively charged carbon. As the
nucleophile approaches to the carbon, it causes the carbon halogen bond to break
heterolytically e.g.
+ –
Nu + —C—X —C— Nu + X–

ii) The carbon – halogen bond breaks heterolytically without any assistance from the
nucelophile, forming a carbocation. The carbocation then reacts with the nucelophile
to form the substituted product.

| |
slow
 C X    C   X 

| |

| |
fast
 C   N u    C Nu
| |

The first type of reaction is called SN2 (substitution nucleophilic bimolecular) because
two molecules are involved in rate determing step.

The second type of reaction is called SN1 (substitution nucleophilic unimolecular)

since only one molecule i.e., alkyl halide is involved in the rate determining slowest
step.

The mechanism that predominates depends on several factors as

 The structure of alkyl halide
 The reactivity and structure of nucleophile
 The concentration of nucleophile
 The solvent in which the reaction is carried out

6.1 Mechanism and Kinetics of SN1

The reaction between tert-butyl bromide and hydroxide ion to yield tert-butyl alcohol
follows first order kinetics; i.e., the rate depends upon the concentration of only one
reactant, tert-butyl bromide.
 CH3 CH3

CH3—C—CH3 CH3—C—CH3 + Br–

r.d.s.
Br

CH3 CH3
fast
CH3—C—CH3 + OH CH3—C—CH3

OH

Rate = K[RBr]

SN1 reaction  follows first order kinetics.

6.1.1 Stereochemistry (SN1)

In SN1 reaction the rate determining step proceeds through the formation of carbocation
formation and carbocation is sp2 hybridised with the planar structure and since the
carbocation is planar, the nucleophile can attack from both the side. It means we will be
getting both the products with the same and the opposite configurations and hence
racemisation will occur but we can’t say that 100% racemisation will occur because there
is no surety that we will be getting both the products in equal amount. Still we can say
that racemisation will take place.
OH

— C
R' R" OH (a)
R sp
2
R attack R R' R" Both enantiomers
from top may be formed in
C+ R" equal amounts
C (b) (Inversion)
R' or one may exceed
attack R' R" the other.
Br from R
bottom
—
C
OH
OH
Retention.

In SN1 reaction the order of reactivity of alkyl halides is allyl, benzyl > 3°>2°>1°> CH3X.

6.2 Bimolecular Mechanism

This is one step process, two molecules simultaneously undergoing covalency change in
the rate – determining step. This type of mechanism is called bimolecular and is labelled
as SN2. Here the rate determining step is the formation of transition state.

6.2.1 Mechanism and Kinetics

The reaction between methyl bromide and hydroxide ion, to yield methanol follows
second order kinetics that is the rate depends upon the concentrations of both reactants.
 H
— – –
OH + CH3 –– Br Slow step OH ------C------Br CH3OH + Br
–

H H fast
transition state
Rate = K [CH3Br] [OH–]

Therefore it follows second order Kinetics

H
H
Transition State – –
HO ----C-----Br
Free Energy 

–
HO +CH3—Br
–
HO—CH3+Br

Reaction Coordinate 

6.2.2 Stereochemistry (SN2)

In SN2 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. The orbital of the N u
overlaps with the smaller lobe of the sp3 orbital of the electrophilic carbon. This lobe is
the side of the carbon directed away from C—X bond. Hence the best overlap of the
interacting orbitals is possible through back side attack.

The best way to visualize the movement of the groups bonded to the carbon at which
substitution occurs is to picture an umbrella that turns inside out. This is called inversion
of configuration or we can say that SN2 mechanism occurs with the inversion of
configuration.

—
— + Br
HO:
— C Br — HO C
HO C Br
(Inversion)

Hence we can say when SN2 mechanism is operating, then inversion must have
occurred. The process has often been likened to the turning inside out of an umbrella in
a gale.

7. Factors Affecting Nucleophilic Substitutions

In the nucleophilic substitution we are having only these substrate which can affect the
reaction.

i) Alkyl halide which constitute two parts (a) alkyl group (b) halide group, since during
the process halide group use to leave. This is also called the leaving group.
ii) The nucleophile
iii) The medium or we can say the solvent
Let’s start first with the alkyl group:

7.1 Alkyl group

If our alkyl group is like this, that it can form stable carbocation in that case the molecule
will be having the tendency to undergo SN1 reaction e.g. if we compare the rate of SN1
reaction between methyl halide and t-butyl halide, t-butyl halide is having higher rate
than that of methyl halide.

On the other hand since SN2 proceeds through a transition state in which carbon is
bonded to 5 groups or atoms less hindered carbon is favourable to avoid the steric
hinderence or we can say less hindered the carbon atom greater is its tendency to follow
SN2 mechanism. We can see the following as.

Methyl halide, 1° alkyl halide, 2° alkyl halide, 3° alkyl halide



increasin g reactivityin SN1reaction



increasin g reactivityin SN 2 reaction

Illustration 2: I) Give the possible reason for the relative reactivities when iodide ions in
acetone solution reacts with MeBr, EtBr, iso - prBr and t–BuBr under
conditions where only the SN2 mechanism operates. The relative
reactivities were found to be 10,000: 65:0.50 : 0.039.
ii) Also state that why these relative reactivities is not observed in SN1
condition.

Solution: i) In an SN2 reaction there are five groups attached to the carbon atom
at which reaction occurs (transition state). Thus there is crowding in
the transition state, and bulkier the groups, the greater will be the
compression energy and consequently the reaction will be hindered
sterically. Thus from MeBr to t–Bu Br the number of methyl groups on
the central carbon atom increases the steric retardation, therefore
relative reactivities is observed.

ii) In SN1 reaction the intermediate state does not contain more than four
groups attached to the central carbon atom, and hence one would
expect steric hindrance to be less important in the SN1. If, however,
the molecule contains bulky groups, then by ionizing, the molecule
can relieve the steric strains, since the carbonium ion produced is flat
(trigonal hybridisation) and so there will be steric acceleration.

Exercise 2: Predict the tendency of the undergoing possible mechanism for the
ethyl, isopropyl and t- butyl halides.

7.2 The leaving group

 Relative rates of reaction
–
HO + RCH 2I  RCH 2OH  I 30000

OH  RCH 2Br  RCH 2OH  Br  10000

OH– + R  CH 2  Cl  RCH 2OH  Cl  200

OH– + RCH2F  RCH2OH + F– 1

If we can observe these data we can say that the only difference among these four
reactions is the nature of the leaving group. We can say that I – is the best leaving group
and F– is the worst. Actually leaving ability depends on basicity, because a weak base
doesn’t share its electron as effectively as a strong base does. We can say that weak
bases are good leaving group.

So for halide ions

I–  Br–  Cl–  F–
Increasing basicity

  
increasin g leavingability

and rate of nucleophilic substitution will follow the order

RI  RBr  RCl  RF

The following two explanations have been put forward to explain this.

i) In the larger atoms (e.g. iodine), electrons are less tightly bound by the nucleus and
hence they are more readily available to the carbon atom undergoing displacement in
an SN2 process, i.e., the larger atoms serve as better nucleophiles.

ii) The nucleophile is surrounded by the solvent molecules through hydrogen bonding
i.e., it is solvated. However, before attacking a carbon atom some of these bond must
be broken away. Now since we know that solvation energies of smaller molecules
are always greater than those of the larger one, the latter (i.e., larger) reagents are
better nucleophiles. This has been confirmed by the observation that in non-
hydroxylic solvents such as dry acetone, iodide ion is less nucleophilic than bromide
ion.

Thus basicity, polarizability and solvation are all involved in determining nucleophilicity of
a given reagent. Steric factors also sometimes assume significant importance in an S N2
reaction.

The nature of the leaving group at least partly determines the reactivity of the substrate.
Now since the leaving group breaks away as a base, it is easier to displace weaker base
as compared to stronger bases. Thus the less basic the substituent, the more easily it is
displaced by the solvent (in SN1 reactions) or by an attacking nucleophilic reagent (in SN2
reactions). Some of the anions according to their decreasing basicity are.

H3 C  N H2  OR  OH  I  Br   Cl   F
Thus among halide ions, iodides are the most reactive and fluorides the least. This is in
accordance with the carbon - halogen bond strength which decreases from C—F to
C—I.

Before concluding the effects of leaving and entering groups it must also be noted that if
both the leaving as well as entering groups are base, then the strong nucleophilic
reagent (entering group) will displace the weaker base, e.g. alkaline hydrolysis of alkyl
halides. But if the case is reverse i.e., the leaving group is

R—X + OH–  R—OH + X–

more basic than the entering group then in such cases the more strongly basic groups
are not normally displaced under ordinary conditions but can be made to do so in acid
solution, which makes them less basic due to protonation e.g. cleavage of ethers to
alcohols by HI, and conversion of alcohols into alkyl halides.

H
H  I 
C6H5OR  C6H5OR 
 C6H5.OH + RI
( from acid) +

H
H  Br 
R—OH   R—OH   R—Br+H2O
( from acid) +

Illustration 3: The hydrolysis of methyl bromide takes place much faster in the presence
of NaI. Why this is so?

Solution: Iodide ion is a good nucleophile as well as a good leaving group, it can
rapidly convert an alkyl chloride or bromide into alkyl iodide, and the alkyl
iodide and can then react rapidly with another nucleoophile. This can be
shown as.
+
CH3OH2 + Br–
H2O alone faster
(slower)
CH3—Br CH3OH + H+
H2O containing CH3I 
HO faster
faster
CH3I 2 CH3 O H2 + I–   CH3OH + H+
faster

7.3 The Nucleophile

In nucleophilic substitution reaction only the better nucleophile can replace the halide ion
(or another nucleophile). For comparing the nucleophilicity we are having certain rules –
I) In comparing molecules with the same attacking atom, nucleophilicity is parallel to
basicity so,
RO–  –OH (nucleophilic nature)
ii) Always negatively charged species is a better nucleophile than the uncharged
species. e.g.
–
OH  H2O nucleophilic nature
–
NH2  NH3
iii) If the attacking atoms are of same size (approximately), the stronger bases are better
nucleophiles.

CH4  NH3  H2O  HF (acidic strength)

CH3  –NH2  –OH  F–

–

  
increasingbasicity and nucelophilicity

iv) If the attacking atoms are different in size, the nucleophilicity depends on the
solvents. However in gaseous phase nucleophilicity parallels basicity.

7.4 Effect of solvents on Nucleophilicity

Polarity of solvent plays a vital role in the nucleophilicity of atoms, polar solvents are of
two types (a) protic solvents (b) aprotic solvents.

a) Protic solvent: These solvents have a hydrogen atom attached to an atom of a

strongly electronegative element (e.g. oxygen). Molecules of protic solvent can,
therefore form hydrogen bonds to nucleophiles as -
H+
+
H H+

H+ X– H+

H+ H+
H+
A small nucleophilie which is having high charge density than the larger nucleophile
is strongly solvated and this solvation hinders the direct approach to the nucleophilic
centre. Hence the smaller nucleophile doesn’t act as a good nucleophile as the larger
one. Hence in protic solvent nucleophilicity is reverse of basicity.

F– Cl– Br– I–
 
increasing basicity
  
Increa sin g nucelophilicity

Relative nucleophilicity in protic solvent

SH–  CN–  I–  OH–  N3  Br–  CH3COO–  Cl–  F–  H2O

b) Aprotic solvents: There are the polar solvents that don’t have H atom, capable of
forming H – bonds e.g.
O
|| CH3 O O
H  C N || || CH3
CH3  S  CH3 CH3  C N
CH3
N,N-Dimethyl formamide Dimethyl sulphoxide CH3
(DMF) (DMSO) Dimethyl acetamide
(DMA)
 These solvents dissolve ionic compounds and these solvate the cations.

O=SMe2
Me2S=O
O=S(CH3)2
+
Na

Me2S=O O=S(CH3)2

O
S(CH3)2

Now the naked anions are highly reactive as nucleophile and now nucleophilicity
follows the basicity e.g.

F– Cl– Br– I–
 
increasin g basicity
  
increaseing nucleophilicity in aprotic solvents

Illustration 4: Compare the following displacement reactions and account for any
difference
a) ROH + NaBr 
b) ROH + HBr 

Solution: a) No reaction. The extremely weak base Br– cannot displace the very
strong base OH–.
b) This reaction occurs in two steps
ROH + HBr  ROH2+ + Br–  RBr + H2O
Displacement is on the onium ion of ROH whose good leaving group
is the very weakly basic H2O

Exercise 3: For the given reaction

R—Br + NaCN  R—CN + NaBr
Whether the Reaction will take place in DMSO or ethanol. Explain your
answer?

7.5 Effect of solvents on Kinetics of Reaction

The nature of the solvent in which reaction is carried out exerts a profound effect on the
mechanism of the reaction. For example, hydrolysis of a halide in a polar solvent
proceeds via SN1 mechanism and if more polar solvent is used, the greater are the
chances of the reaction to proceed by the SN1 rather than the SN2 mechanism.

This effect of polar solvent on the mechanism of the substitution reaction is due to two
factors: (i) a polar solvent (having high dielectric constant) always promotes the
ionisation of the halide, and (ii) the ions so produced are solvated, in suitable solvent viz.
water, with the liberation of a considerable amount of energy which further helps in the
initial ionisation of the halide.
The ionising power of a solvent is reflected in its dielectric constant. Higher the dielectric
constant, greater the ionizing power. Thus water with a dielectric constant of 81 is more
ionizing than methanol having a dielectric constant of only 31. The order of ionizing
powers of more common solvents is as follows:
H2O  HCOOH  CH3OH  C2H5OH  CH3COOH
SN1 reactions are given mainly by tert-halides which have a dipole moment due to
halogen atom. Due to the presence of dipole moment, the reactant forms dipole-dipole
bonds to solvents. However, the transition state has a stretched carbon-halogen bond
and well developed positive and negative charges and hence has a much greater dipole
moment than the reactant and thus forms much stronger dipole-dipole bonds to the
solvent. The solvent thus stabilizes the transition state more than it does the reactant,
lowers the Eact, and ultimately speeds up reaction.
 
R  X  R X  HS  R XHS 
HS:
Reactant Transition state solv e nt Solvated TS of S N
(more polar than reaction
reactant and hence
stabilized more by
solvation)

Thus note that higher is the polarity of the solvent, the stronger is the solvent forces and
hence faster will be the ionization of the halide and thus rate of SN1 reaction. This is
evident by the fact that the rate of hydrolysis of tert-butyl chloride in 50% aqueous
ethanol is 30,000 times faster than in 100% ethanol.

In case of SN2 reactions, there are two reactants, viz. R – X and OH– ion. The alkyl
halide has a dipole moment and forms weak dipole-dipole bonds to the solvent. But the
second reactant, the hydroxide ion carries a full negative charge and hence forms very
powerful ion-dipole bonds to the solvent. The transition state also carries a full negative
charge but here it is divided between the attacking hydroxyl and the departing halide.
Bonding of the
   
OH  R  X  H O  R   X 
(R eactants)concentrated
charge leads to powerful ion  
dipolebonds due to solvation Transitionstate of S N 2
Note the negative charge is dispered

solvent to this dispersed charge is much weaker than that of the concentrated charge of
the small OH– ion. The solvent thus stabilizes the reactants (nucleophile) more than it
does the transition state, raises the Eact and hence ultimately slows down the reaction.

Sometimes the nature of the solvent plays such a dominant role that it is possible to
alter the mechanism of the reaction, by choosing an appropriate solvent. Thus methyl
bromide undergoes SN2 reaction in aqueous alkaline medium but methyl alcohol
undergoes SN1 reaction in the presence of formic acid containing a small quantity of
water.
HCOOH,H O
OH 
CH 3OH  HBr 
2
 CH3Br  
 CH3OH
SN 1 SN 2

8. The Unreactivity of Vinyl and Phenyl Halides

X

C=C
X
These halides are unreactive toward either SN1 or SN2 since vinylic and phenyl cation
are highly unstable and are not formed, they can’t undergo SN1. Now question arises
what’s the problem with SN2 mechanism. Due to +M effect of halide ion C — X bond in
both the case acquire partial double bond character and the  -electrons present in both
the system repels the nucleophiles (either negatively charged on electron rich species)
and hinder the back side approach of the nucelophile and hence these are unreactive
towards SN2 also.
Illustration 5: Vinyl chloride does not give SN reaction but allyl chloride gives. Explain.

Solution: In vinyl chloride C—Cl bond is stable due to resonance (as in

chlorobenzene).
+
CH2=CH——Cl  CH2—CH=Cl
Hence SN reaction in which Cl is replaced by nucleophile is not possible.
In addition to this, sp2 hybridised carbon is more acidic than sp3 carbon,
hence removal of proton (H+) is easier than removal of halide (Cl–).
In allyl chloride, SN reaction is easier since allyl carbonium ion formed
after removal of Cl– is stabilised by resonance.

CH 2  CH  CH 2Cl  CH 2  CH  C H2  Cl 
allylcarboniumion
 
CH 2  CH  C H2  C H2  CH  CH 2

Exercise 4: 1-Bromobicyclo[2.2.1] heptane is allowed to react with OH –. Comment on

the product specifying its reason?

9. Summary of SN1 & SN2 Mechanism

SN1 SN2
(1) R:X  
 R + X
Slow + -
Two :
Carbonium ion One : R:X + Nu-  RNu + X-
Steps
(2) R+ + Nu-  RNu or
fast
or R:X + Nu  RNu+ X-
R+ + :Nu  RNu+
Rate =K [RX] (1st order) =K[RX] [:Nu-] (2nd order)

— —
Nu C X
T.S. of slow step C+......X-

Stereochemistry Inversion and racemization Inversion (backside attack)

Molecularity Unimolecular Bimolecular
CH3> 1o> 2o> 3o
Reactivity 3o> 2o> 1o> CH3
Steric hindrance in R group
structure of R Stability of R+
Determining Factor
RI> RBr> RCl> RF
Nature of X RI> RBr> RCl> RF
with Nu- there is a large rate
Solvent effect on rate Rate increases in polar solvent
increase in polar aprotic solvents.
No effect as it does not appear in Rate depends on nucleophilicity
Effect of nucleophile
the rate expression. I- > Br- > Cl- ; RS- > RO-
Catalysis Lewis acid, eg. Ag+, AlCl3, ZnCl2 None
 Elimination
Competitive reaction Elimination, rearrangement

10. Intramolecular Substitution Reaction

In the case of a molecule that contains both a nucleophile and a leaving group, two
reactions can take place e.g.
BrCH2(CH2)nCH2O– + Br—CH2—(CH2)n—CH2O–

Intermolecular reaction

BrCH2—(CH2)n—CH2—O—CH2(CH2)n—CH2O– + Br–
(CH2)n
intra
Br—CH2—(CH2)n—CH2O–  
 CH2 CH2 + Br–
molecular
O

If intramolecular reaction would form a five or six membered or any stable ring it would
highly be favourable over the intermolecular reaction.

Exercise 5: Write the mechanism of the following reactions

a) HOCH2CH2Br  OH

 CH2—CH2
H2O
O
b)
OH
H2NCH2CH2CH2CH2CH2Br 
H2O N
H

11. Competition between Substitution and

Elimination Reactions
Alkyl halides can undergo E1, E2, SN1 and SN2 reactions. Now the problem arises how to
determine that which reaction will take place? We can decide in a primary alkyl halide
because usually it can’t form carbocation hence usually undergo SN2 / E2 reaction.
If the reactant is secondary or tertiary alkyl halide whether it undergo SN2 or E2, SN1 or
E1 reaction depends on the reaction conditions as we have studied earlier

11.1 SN2 vs E2

Primary alkyl halide can undergo following two reactions.

CH3—CH2—Br  CH3—CH2—OH + Br–

Substitution
product
OH–
 CH2—CH2—Br  CH2=CH2 + H2O + Br–
Elimination
H product

OH–

Usually substitution reaction dominates elimination untill either primary alkyl halide or the
nucleophile is sterically hindered e.g.

 CH 3CH 2CH 2OCH 3 + CH 3  CH  CH 2

CH3—CH2—CH2Br + CH3O– 
CH3OH
90% 10%

CH3 CH3 CH3

CH3—CH—CH2—Br + CH3O–   CH3—CH—CH2—OCH3 + CH3—C=CH2

CH3OH
(Sterically hindered 40% 60%
alkyl halide)

CH3 CH3
–
CH3CH2CH2CH2CH2Br + CH3—C—O    CH3CH2CH2CH2CH2—O—C—CH3
(CH3 )3 COH
CH3 CH3
(nucleophile is 15%
sterically hindered)

CH 3CH 2CH 2CH  CH 2

85%

A secondary alkyl halide to conform both substitution and elimination product under SN2
/ E2 condition, depends on the strength of base and temp. e.g.

Cl OCH2—CH3
CH3—CH—CH3 + CH2CH2O–   CH3—CH—CH3 + CH3—CH=CH2
CH3CH2OH
Strongly basic 25% 75%

Cl O O—CO—CH3
–
CH3—CH—CH3 + CH3—C—O   CH3—CH—CH3
CH3COOH
Weakly basic 100%

High temperature favours elimination

A tertiary alkyl halide is least reactive in an SN2 reaction and most reactive in an E2
mechanism. Hence only elimination product is formed.

CH3
CH3—C—Br + CH3—CH2—O–     CH3—CH=CH2
CH3CH2OH
100%
CH3
11.2 SN1 vs E1

Alkyl halides have the same order of reactivity in SN1 and E1 reaction because they have
the same rate determining step i.e., ionization of the alkyl halide. But substitution is
favoured over elimination at lower temperature; increasing the temperature increases the
percentage of elimination product.

11.3 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 E1 reaction
halide or nucleophile in which case
elimination is favoured.
2° alkyl halide Both substitution and elmination, Both substitution and elimination,
the stronger and bulkier the base the higher the temperature the
and higher the temperature the greater the percentage of
greater the % of elimination elimination.
3° alkyl halide Only elimination Both substitution and elimination,
high temperature favours
elimination.

Illustration 6: When t-butyl bromide is treated with CH3O– in a mixture of CH3OH and H2O,
the rate of formation of t-butyl alcohol and t-butyl methyl ether doesn’t
change appreciably as the concentration of CH 3O– ion is increased.
However, increasing the concentration of CH3O– caused a marked
increased in the rate at which t-butyl bromide disappear from the mixture.
Why this is so?

Solution: t-butyl alcohol and t-butyl methyl ether are formed through an SN1
mechanism and the rate of the reactions is independent of the
concentration of CH3O–. This was the only reaction that causes t-butyl
bromide to disappear. But if we increase the concentration of CH3O– t-
butyl bromide starts disappearing through E2 mechanism. This reaction is
dependent on the concentration of CH3O–. Hence as we increase the
concentration of CH3O– the rate of disappearance of t-butyl bomide
increase.

Exercise 6: Write down the products of the following reaction. Can you think why this is so?
a) CH3
DMF
Cl—CH2—C—CH2—CH2—Cl + I–  

CH3
b) CH3
DMF
Cl—CH2—C—CH2—CH2—Cl + H2O  

CH3

12. Overall Reactions of Alkyl Halides

Nucleophilic substitution
i) Formation of alcohol (hydrolysis)
RX + OH–  ROH + X–

ii) Formation of ether when alkyl halides react with sodium alkoxide or dry silver oxide
RO Na + X R  ROR + NaX ( Williamson synthesis)
Sodium alkoxide Alkyl halide Ether

C2H5 I C2H5
+ Ag2 O O + 2AgI
C2H5 I C2H5
Ethyl Dry Diethyl
Iodide Silver oxide ether

iii) Reactions with sodio – Alkynides: Higher alkynes are produced when alkyl halides
react with sodium Alkynide

H—C  C — Na + I — CH3  H— C  C — CH3 + NaI

Sodium Methyl Propyne
acetylide iodide

iv) Reaction with potassium cyanide : Alkyl cyanides are obtained when alkyl halides are
heated with aqueous cyanide, a small amount of isocyanide is also obtained.

R X + K CN  RCN + KX
Alkyl halide Alkyl cyanide

v) Reaction with silver cyanides: Alkyl isocyanides are obtained when alkyl halides are
heated with aqueous ethanolic silver cyanides

C2H5 I + Ag CN  C2H5NC + Agl

Alkyl halide Alkyl isocyanide

vi) Reaction with silver salt of a fatty acid: Esters are obtained when alkyl halides are
heated with an ethanolic solution of the silver salt of fatty acid

CH3COO Ag + I C2H5  CH3COOC2H5 + AgI

Silver acetate Ethyl iodide Ethyl acetate

vii) Reaction with silver nitrite: On heating an alkyl halide with an aqueous ethanolic
solution of silver nitrite.

O
R–– X + Ag NO2  R––N + Ag X
Alkyl halide Silver nitrite O
Nitro alkane

viii) Reaction with potassium Nitrite: By heating an alkyl halide with potassium nitrite in an
aqueous ethanol solution.

C2H5 I + K –– O — N = O  C2H5 –– O –– N = O + KI

Ethyl Iodide Ethyl nitrite

ix) Preparation of alkyl benzene (Friedel craft reaction)

AlCl
CH3Cl + C6H6  3 C6H5––CH3
Methyl chloride Benzene Toluene

x) Malonic ester synthesis

CO2C2H5 CO2CH2CH3
CH3Cl + CH CH3—C—H
Methyl chloride CO2C2H5 CO2CH2CH3

xi) Acetoacetic ester synthesis

CH3
CO2CH3
CH3Cl + C—H CH3COCHCO2CH3
COCH3

xii) Reaction with ammonia: When alkyl halides are heated with ethanolic solution of
ammonia under pressure in a sealed tube, a mixture of amine is obtained.

C2H5 I + H NH2  C2H5NH2

Ethyl iodide Ammonia Ethyl amine

We can see that alkyl halides can be transformed into a variety of other functional
groups. We will study the reactions separately but they have been summarized here.

Reduction:

Alkyl halides are reduced by zinc-copper couple, sodium and ethanol or tin and
hydrochloric acid etc. to form the corresponding paraffins.

C2H5Br + Zn + C2H5OH  C2H6 + Br– + C2H5O– + Zn2+

Wurtz Reaction

An ethanol solution of the alkyl halide (preferably bromide or iodide) gives a paraffin
when heated with metallic sodium.

CH3I + 2Na + I — CH3  CH3 — CH3 + 2NaI

Methyl iodide Sodium Ethane

Dehydrohalogenation:
When alkyl halides are boiled with alcoholic potash, olefins are obtained , e.g. propyl
bromide gives propene

CH3.CH2.CH2Br + KOH  CH3––CH = CH2 + KBr + H2O

propyl bromide (alcoholic) Propene

It is an elimination reaction and is termed -elimination since hydrogen atom is

eliminated from the -carbon atom.
In fact, on heating an alkyl halide with an alkali (aqueous or alcoholic), two products are
obtained, alcohol and olefin. An alcohol is the main product with aqueous alkali or moist
silver oxide (Ag2O) and an olefin is the main product with alcoholic alkali.

slow
(CH3)3 CBr (CH3)3C+ + Br–

HO– + H – CH2 – C+(CH3)2  H2O + CH2 = C(CH3)2

fast

The yield of alkene is fair from primary alkyl halide but good form secondary and tertiary
alkyl halides.

The direction of elimination has described empirically by saytzeff’s rule. This rule
may be stated in two ways. The predominant product is the most substituted
alkene, i.e. the one carrying the largest number of alkyl substituents or hydrogen
is eliminated preferentially from the carbon atom joined to the least number of
hydrogen atoms.

12.1 Grignard Reagent

12.1.1 Preparation of Gignard Reagent

Grignard reagent can be prepared by treating alkyl halide with Mg in dry ether
Mg
R—X  R—Mg—X
ether
Grignard reagents are another good source with chemists to prepare different
compounds e.g. alcohols, carbonyls alkanes etc.

12.1.2 Reaction of Grignard reagents

i) With the compounds having active H- atom: Active H means the H atom attached
with O, N, or S, or which is acidic in nature. Grignard reagents react with these to
form alkanes e.g.

HO
OH
R—Mg—X 2 R—H + Mg
X
X
R—Mg—X + NH3  R—X + Mg
NH2
ii) With carbonyl compounds: Grignard reagent reacts with carbonyl compounds to
give various alcohols e.g. with HCHO, 1° alcohol, with RCHO, 2° alcohol with
O
||
R  C R 3° alcohols e.g.
O O—MgX OH
|| - + H3O X
R  C R  R—Mg—XR—C—R  R—C—R + Mg
R R OH
 O H
|| |
H  C H  CH 3  MgBr  CH 3  C OH (1o alcohol)
|
H

O OH
||
CH 3  C H + CH3—Mg—Br  CH3—C—CH3 (2° alcohol)
H

O CH3
||
CH 3  C CH 3 + CH3—Mg—Br  CH3—C—OH 3° alcohol)
CH3

iii) With cyanides: It gives carbonyl compounds

R
H3O C=O
R—CN + R—Mg—X  R—C=N—Mg—X 
R Ketone

iv) With esters: Grignard reagents react with esters to give 3° alcohol.
O—MgX O
RMgX
RCOOR + R—MgX  R—C—OR  R—C—R  

R
O—MgX OH
H3O
R—C—R   R—C—R
(3° alcohol)
R R

13. Characteristics Reaction Chart for Alkyl Halides

RCH2 CH2 OH RCH2 CH2 OR RCH2 CH2MgX
aq. '
KOH PX3 R OK Mg

R'X
RCH2 CH2 R'
Na
KNH2 Redn.
RCH2 CH2 - NH2 R-CH2-CH2-X RCH2CH3
X2,h
KSH KNO2
KOH
HX alc. AgCN
RCH2 CH2SH KCN
RCH2 CH2 NO2
RCH=CH2 RCH2 CH2 NC
R-CH2 CH2-CN

14. Dihalides
They are of two types
i) Vicinal Dihalides CH2Cl – CH2Cl, in which two Cl of 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—C  CH + HX R — CH = CHX   R  CH 2  CHX 2
Markonikov rule ethylidenechloride

ii) From alcohols

CH2OH CH2Cl
PCl5,PCl3 or SOCl2
CH2OH CH2Cl
Oxidation PCl5
CH3CH2CH2OH    CH3CH2CHO  CH3CH2CHCl2
H2
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
NaNH / Liq.NH 2 3

But action of aq. KOH is different:

aq.KOH
R—CHX — CH2X 
 R—CHOH—CH2OH(glycol)
aq.KOH
 CH 3CH(OH)2 
CH3CHX2   CH3CHO
H2O
unstable
aq.KOH
 R—C(OH)2—R 
R—CX2 — R   R— CO—R(ketone)
H2O

15. Tri Halides(Haloform)

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.
oxidationby Cl2 chlorination Ca(OH)
CH3CH2OH   CH3CHO   CCl3CHO    2
hydrolysis
CHCl3

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

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

Fefillingssteam
3. 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

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.

Chemical reactions:

1 air / sunlight
CHCl3 + O 2  HCl + COCl2 (phosgene)
2

Hydrolysis occurs on refluxing it with conc. NaOH giving HCOONa

CHCl3 + 4NaOH  HCOONa + 3NaCl + 2H2O

Carbyl amine reactions:

warm
CHCl3 + CH3NH2 + 3NaOH   CH3N C + 3NaCl + 3H2O

Methyl carbyl amine R—N C, gives a very bad characteristic odour (a test of rprimary
amine)

CHCl3 + HNO3 (conc)  H2O + Cl3C—NO2 (chloropicrin)

CH3 CH3 OH
CO + HCCl3  C
CH3 CH3 CCl3
acetone chloroform chloretone(a hypnotic and sedative)

heat
HC Cl 3  6Ag  Cl 3 CH   CH  CH + 6AgCl



Reaction with phenol and an alkali (Reimer - Tiemann reaction)

C6H5OH + CHCl3 + 3NaOH  ortho  HO.C6H4 .CHO + 3NaCl + 2H2O

salicylaldehyde

It is to be noted that yellow crystals of iodoform (CHI 3) is formed when an alcohol,

R – CH(OH) – CH3 or an aldehyde or a ketone with three  - hydrogen atoms are heated
with I2 + KOH. This provides a test for above type of alcohols and carbonyl compounds.

16. Properties of Aryl halides

16.1 Reactivity
Unlike alkyl halides, aryl halides are less reactive towards Nucleophilic substitution
reactions, this can be attributed to their electron release via. resonance.
  
Cl Cl Cl Cl  Cl
| | || H || ||
H

H
I II III IV V

Structures III, IV and V stabilise chlorobenzene molecule and give a double bond
character to the carbon-chlorine bond. Now because of this, the carbon-chlorine bond
has more strength and hence aryl halides are more stable towards nucleophilic
substitution reactions. In Alkyl halides the carbon atom attached to halogen is sp3
hybridized and in aryl halides it is sp2 hybridized, as sp2 hybridized carbon is more
electronegative it does not permit the chlorine atom to get displaced with the bonded pair
of electrons.

16.2 Nucleophilic Substitution reactions

Aryl halides undergo Nucleophilic substitution reactions when a strong electron

withdrawing group is present on the benzene ring. Electron withdrawing groups activate
the benzene ring towards nucleophilic substitution in aryl halides whereas electron
donating groups deactivate the ring.

16.2.1 Mechanism: Bimolecular displacement mechanism

Cl Z Cl Z Cl Z Cl Z Cl
|
– H H
Z

|
Fast H
Z
|
+ Cl–

Any factor that stabilizes the carbanion will increase the rate of Nucleophilic substitution
reaction by dispersing the charge present on resonating structures. An electron
withdrawing group present at meta position does not activate the ring as much as it does
from ortho and para position. This can be known by looking at following resonance
structures.
Z Cl Z Cl Z Cl

NO2 NO2 NO2 (Meta)

Z Cl Z Cl Z Cl

(Para)

NO2 NO2 NO2

Illustration-7: Complete the following reaction
Cl
NO2 NO2
OH 
 



NO2

Solution: Cl
OH
NO2 NO2 NO2
NO2
OH
 


NO2
NO2

Mechanism:
Cl OH Cl OH Cl OH
NO2 NO2 NO2 NO2 NO2 NO2

NO2 NO2 N
–
+
O O–
Very stable (same with two
o-nitrogroups)
Cl OH OH
NO2 NO2 NO2 NO2

NO2 NO2

17. Solutions to Exercise

Exercise 1: a) Dipole moment: X (halide) is more electronegative than carbon
hence bonding pair between carbon and X is
attracted towards X.

   
Hence R—X  R  X  is more polar than R—H.
 
Thus dipole moment of R—X is greater than R—H.
b) Solubility in H2O: R—X is more polar than R—H hence R—X can
have H-bonding with H2O that makes it more
soluble in it than R—H.
   
R  XH OH

Exercise 2: When the SN1 mechanism is favoured it means that the activation
energy for this path is less than that for the SN2; and vice versa. Since
 more stable the ion the lower is the activation energy and more
favoured will be the mechanism. As we know the order of stability of
carbonium ion is 1°  2°  3° and hence the tendency for the SN1
mechanism to operate will be t–BuX > iso propyl X EtX and the
reverse tendency for the SN2 mechanism.

Exercise 3: The rate of reaction will be faster in DMSO because DMSO is aprotic
solvent and hence it enhances the nucleophilic nature of CN–

Exercise 4: 1-Bromobicyclo[2.2.1] heptane is unreactive in an SN2 reaction

because it is tertiary halide and its ring structure makes the backside
of the carbon bearing the leaving group completely unapproachable to
the attack by a nucleophile.
Br

Nu

1-Bromobicyclo [2.2.1] heptane is unreactive in SN1 reaction because

in SN1 reaction formation of carbocation is the first step and since
bridge head carbocations are highly unstable not easy to form hence it
will not follow SN1 also hence its compound will be unreactive towards
SN1 or SN2 and hence no reaction will take place.
Exercise 5: a) OH – int ra molecular
OH—CH2—CH2—Br  O—CH2—CH2—Br      CH2—CH2 + Br–
H2O substituti on
O

OH int ra molecular
H2NCH2CH2CH2CH2CH2Br  NH—CH2—CH—CH2—CH2—CH2—Br      
H2O substituti on
N
H

Exercise 6: a) CH3

Cl—CH2—C—CH2—CH2—I
CH3
b) CH3

HO—CH2—C—CH2—CH2—I + some alkene

CH3
–
Since I is very polarisable only the substitution reaction takes
place.
 SOLVED PROBLEMS
OBJECTIVE
Problem 1: Alkyl halide reacts with an alcoholic solution of ammonia to give a mixture
of:
(A) 1° and 2° amine (C) 1°, 2°, 3° & quaternary
(C) 1°, 2° & 3° amines (D) 1° & 3° amine

Solution: Alcoholic solution of ammonia is heated in a sealed tube at 100°C

RI  RNH2 

NH3 RI
(R)2NH 
RI
(R)3N 
RI
(R)4 N+I–
1° amine 2° amine 3° amine 4° amine
 (B)

Problem 2: Product – I   C2H5Br 

aq KOH
 Product – II, the correct statement
alc KOH

is
(A) Product – I is obtained by the elimination reaction
(B) Product – II is obtained by the substitution reaction
(C) The molecular formula of Product – I is C2H4, while the molecular
formula of Product – II is C2H6O
(D) Product – I is the isomer of dimethyl ether, while Product-II is the
dehydrated compound of Product - I

Solution: C2H5Br   C2H5OH (Product-I)

aq KOH

(Nucleophilic substitution reaction)

C2H5Br   C2H4 (Product – II)
alc KOH

(elimination reaction)
C2H5OH (Product-I) isomer is CH3OCH3
C2H5OH   C2H4
dehydration

 (D)
Problem 3: Which one of the following compounds most readily undergoes
substitution by SN2 mechanism?
CH3
H3C H3C
(A) (B)
Cl
Cl
Cl CH3
H3 C
(C) H3C (D)
Cl
C 3H7 H3C

Solution: Less hindered carbon follows SN2 mechanism.

 (B)
Problem 4: Which of the following derivatives of benzene would undergo hydrolysis
most readily with aq. KOH
Cl Cl
O2N 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 5: 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 6: 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 7: 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 8: 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)

Problem 9: In the given reaction

H
H3C Br NaI
acetone
 [X]
C2 H5
[X] will be
H H

(A) H3C I (B) I CH3

C2 H5 C2 H5
H3C
(C) Mixture of (A) and (B) (D) CH3

Solution: (B)

Problem 10: Which of the following is fast debrominated?

Br Br Br Br

(I) (II) (III) (IV)

(A) IV (B) II
(C) III (D) I

Solution: (A) More the stability of the product, faster is debromination of the parent
compound.

Problem 11: F NO 2 

(CH3 )2 NH
 X 
H 2 / Pd
Y
DMF / 

Y is :
CH3
(A) H2N N (B) H NH2
CH3
NH2
H3 C
(C) (D) N NO 2
H3C
N H3 C
CH3
Solution: H3C
F F N CH3 H3C N CH3 H3C
N
CH3


(CH3 ) 2 NH
 
 H
 F

H 2 / Pd


NO2 NO2 NO 2 NH2

Problem 12: The organic compound (P) of the reaction:

Ph
Me H

alc. KOH

 P is
Br H
Ph
Ph Me Ph Me

(A) (B)
H Ph Ph H
Ph Ph
Me H Me H
(C) (D)
H H H OH
Ph Ph

Solution: (B)

CH3 NaF NaF H

+

Problem 13: (X) ; CH3 CHCl (Y) ; (X) + (Y) (Z)

H3C H2 O
Br S O
CH3
H3C
Compound (X) and (Z) are respectively
CH3 CH3
CH3
(a) (b) CH3 and
F
and
OCHMe2 OCHMe2
CH3
(d) CH3 and CH3
(c) CH2 and
OCHMe 2 OCHMe2

Solution: CH3
NaF
29 CH3
H3C [via E2 machanism]
Br S O
H3C (X)
NaF
CH3 CHCl
H2O
CH3 CH OH [F- is solvated ]
CH3 CH3
(Y)
+ CH3
H
CH3 + CH3 CH OH
OCHMe2
CH3
(Z)
Problem 14: When an alkylhalide is dissolved in ethanol the following reaction begins
to occur.
R – X + EtOH   R  O  Et  HCl
SN 2 Mechanism

The overall order of reaction is:

(A) One (B) Two
(C) Three (D) Zero

Solution: The concentration of solvent alcohol remains constant hence order w.r.t.

alcohol is not one but zero.

C
l C
l 
t-
B u
O
t-
B u
OH
A
Problem 15: A is

O
t-BuO

O
(A) (B)
O
Cl O-t-Bu

(C) (D)

O O
Solution: (B)

Problem 16: Sec. Butyl chloride undergo alkaline hydrolysis in the polar solvent by
hydrolysis
(A) SN2 (B) SN1
(C) SN1 and SN2 (D) None of these.
Solution: (A)

Problem 17: Me
SOCl2
Ph C—OH   
in C5H5N
H
Which statement is true for the above reaction?

(A) Retention of configuration (B) Inversion of configuration

(C) Inversion and Retention both (D) None

Solution: (B)

Problem 18: Halogenation of alkanes is

(A) A reductive process (B) An oxidative process
(C) An isothermal process (D) An indothermal process
 [KCET 2002]
Solution: (B)

Problem 19: On heating diethyl ether with conc. HI, 2 moles of which of the following is
formed
(A) Ethanol (B) Iodoform
(C) Ethyl iodide (D) Methyl iodide
[IIT-JEE 1983; MP PET 1990; AFMC 1993]
Solution: (C)
C2H5 – O – C2H5 + 2HI  2C2H5I + H2O

Problem 20: On treatment with chlorine in presence of sunlight, toluene gives the product
(A) o-chloro toluene (B) 2, 5-dichloro toluene
(C) p-chloro toluene (D) Benzyl chloride
[Orissa JEE 2003; MH CET 1999]
Solution: (D)

Problem 21: Ethylene reacts with bromine to form

(A) Chloroethane (B) Ethylene dibromide
(C) Cyclohexane (D) 1-bromo propane
[Pb. CET 2000]
Solution: (B)
When ethylene reacts with bromine, it forms ethylene dibromide.
H 2C  CH 2  Br2 
 H2 C  C H2
Ethylene Bromine | |
Br Br

Problem 22: Chlorobenzene is

(A) Less reactive than benzyl chloride
(B) More reactive than ethyl bromide
(C) Nearly as reactive as methyl chloride
(D) More reactive than isopropyl chloride

Solution: (A)
Cl CH 2 Cl

Chlorobenzene is less reactive than benzyl chloride

in chlorobenzene the lone pairs present on Cl atom get involved in resonance

with  electrons of benzene due to which C – Cl bond acquires double bond
character Hence, reactivity decreases
 .. .. ..
: Cl : Cl : + Cl : + Cl : +
.. ..
..
Problem 23: The reactivities of methyl chloride, propyl chloride and chlorobenzene are in the
order
(A) Methyl chloride > propyl chloride > chlorobenzene
(B) Propyl chloride > methyl chloride > chlorobenzene
(C) Methyl chloride > chlorobenzne > propyl chloride
(D) Chlorobenzene > propyl chloride > methyl chloride
[KCET 1988]
Solution: (A)
Cl

CH3 - Cl > CH3 - CH2 - Cl >

Problem 24: Carbylamine is liberated when . . . . is heated with chloroform and alcoholic
potash
(A) An aldehyde (B) A primary amine
(C) A secondary (D) A phenol
[KCET 1992]
Solution: (B)

Problem 25: Following equation illustrates

200 250 C
C6H5Cl + 2NaOH   C6H5ONa + NaCl
0

200 atm
+ H2O
(A) Dow’s process (B) Kolbe’s process
(C) Carbylamine test (D) Haloform reaction
[Bihar CEE 1995]
Solution: (A)

Problem 26: The set of compounds in which the reactivity of halogen atom in the ascending
order is
(A) Vinyl chloride, chlorethane, chlorobenzene
(B) Vinyl chloride, chlorobenzne, chloroethane
(C) Chloroethane, chlorobenzene, vinyl chloride
(D) Chlorobenzene, vinyl chloride chloroethane
[KCET(Engg.) 2002]
Solution: (D)
Problem 27: Alkyl halide on heating with alc. NH3 in a sealed tube results
(A) 10 amine (B) 20 amine
0
(C) 3 amine (D) all of these
[Orissa JEE2002]

Solution: (D)

OH
NaNH2 H+
Problem 28: [Intermediate] ? Product
liq. NH3
Br
Choose the correct statement (s)
OH

(a) is formed.
NH2
(B) Intermediate formed is aromatic
OH

(c) is formed involving non-aromatic intermediate

NH2

(d) is also formed

OH OH

Solution: (a, b)

O
O CH3
+ KCN C CH 2 CH 2CN
N CH3 EtOH H2O
Problem 29:
CH3 250C

Choose the correct statement (s)

(A) The reaction involves SN2 attack followed by conjugate addition.
(B) The reaction involves ECB1 path.
(C) It involves 1, 4-addition in , -unsaturated carbonyl compound.
(D) It involves nucleophilic attack on carbonyl carbon initially.

Solution: (b, c)

Problem 30: Amongst following the right statements are

(A) In SN2 reactions if reactant has R configurations the product is has S
configuration.
(B) In SN2 reactions the configuration of reactant gets inverted.
(C) In SN2 reactions if reactant is dextrorotatory the product is laevorotatory.
 (D) In SN2 reactions if reactant has R configuration the product can have R or S
configuration.

Solution: (b, d)
Problem 31: Match List – I with List – II

List – I (Metals) List – II (Ores)

CH3 OH CH3 Cl (p) SN1
(a) C + SOCl2 C
Ph H Ph H
(+) (+)

CH3 OH Pyridine CH3 Cl (q) SN2

(b) C + SOCl2 C
Ph H H5C6 H
(+) (-)

(C) CH3  C H  Br + - OC 2 H 5 (r) SNi

|
CH3
CH3 OH CH3 Cl (s) E2
(d) C + HCl C
H5C6 H C6H5 H
(+) 

Solution: (A - R), (B – Q), (C - S), (D – P)

Write–up – I
Nucleophilic substitution reactions generally expressed as
Nu   R — L 
 R — Nu  L
where Nu–  Nucleophile
R — L  substrate
L  leaving group
The best leaving groups are those that become the most stable ions after they
depart. Since most leaving groups leave as a negative ion, the best leaving
groups are those ions that stabilize a negative charge most effectively. A good
leaving group should be
i) electron-withdrawing to polarize the carbon atom
ii) stable once it has left (not a strong base)
iii) polarisable – to maintain partial bonding with the carbon in the transition state
(both SN1 and SN2). This bonding helps to stabilise the transition state and
reduces the activation energy.

1. Among the following which is feasible?

(A) X– + CH3—CH2—H  CH3—CH2—X + H–
(B) X– + CH3—OH  CH3 —X + OH

X  H3C OH 
 CH3 — X  H 2O
(C)
H
 (D) X– + CH3—CH3  CH3 — X + CH3
2. Among the following which is false statement?
(A) The weaker the base after the group departs, the better the leaving
group.
(B) A reactive leaving group would raise the energy of the product,
driving the equilibrium towards the reactants.
(C) Relative leaving group ability may vary with change of solvent.
(D) Better leaving group only increases SN2 rate, not SN1.

3. CH3Br CH3F CH3OH CH3OSO2CF3

I II III IV

The correct order of decreasing reactivity above compounds towards

CH3O– in an SN2 reaction is
(A) I  IV  II  III (B) IV  I  II  III
(C) IV  I  III  II (D) IV  II  I  III

4. Cl , CH3O , CH3S , I

I II III IV

The correct order of increasing leaving group capability of above

compound is
(A) III  IV  II  I (B) II  III  I  IV
(C) II  IV  III  I (D) I  III  II  IV

Solution: 1. (C) 2. (D) 3. (B) 4. (B)

Write–up – II

An organic compound A has molecular formula C10H17Br and it is non-resolvable. A does

not decolourize brown colour of bromine water solution. A on treatement with
(CH3)2COK/(CH3)3COH yields B as major product. B on treatement with H2/Pt yields
(C10H16) which on treatement with Cl2/hv yields three monochloro derivative. Also B on
boiling with acidic permanganate solution yields C(C10H16O3). C on heating with sodalime
yields D (C9H16O). D on reducing with LiAlH4 followed by heating the product with
concentrated H2SO4 yields E (C9H16) as major product. E on treatement with ozone
followed by work-up with Zn H2O yields 6-Ketononanal

1. Compound A is
Br Br

(A) (B)

Br

(C) (D) None of these

2. Compound B is
 (A) (B)

(C) (D)

3. Compound C is
COOH
O O
CH2
(A) (B)
CH2 O
CH2
O COOH

(C) O (D) H CH2

O C=
=C
H
4. Compound D is
O O
(A) (B)

COOH CH3
O
CH
(C) 3
(D)

Solution: 1. (A) 2. (C) 3. (A) 4. (C)

Subjective
Problem 1: It required 0.70 gm of hydrocarbon (A) to react completely with 2 gm Br2.
On treatment of (A) with HBr, it yielded monobromoalkane (B). The same
compound (B) was obtained when (A) was treated with HBr in the presence
of peroxide. Write down the structural formula for (A) and explain the
reactions involved.

Solution: i) (A) gives monobromoalkane (B)  (A) is alkene

ii)
C=C + Br2  C–C
(A)
1 mole Br Br

Since 2 gm Br2 reacts completely with = 0.70 g of (A)

0.70 160
 160 gm Br2 reacts completely with = = 56 gm of (A)
2
 Molecular weight = 56
CnH2n = 56 (since compound is alkene)
12n + 2n = 56
 n=4
Hence (A) is C4H8

iii) Since compound A gives same mono bromoderivative either in presence or

absence of peroxide hence A should be symmetrical alekene.
Hence A = CH3CH = CHCH3.
HO
Problem 2: (CH3)3CBr 
2
 (CH3)3C—OH ------------ (1)
SN1
HO
(C6H5)3C—Br 
2
 (C6H5)3C—OH --------- (2)
SN1
Equation (1) show no effect with the addition of Br– to the reaction but
equation (2) shows common ion effect if Br– is supplied from external
source. Why is
it so?
Solution: Both the reactions followed the formation of carbocation. In the first reaction the
carbocation formed is (CH3)3C+ and in second it is (C6H5)3C + needless to say
that second carbonium ion is much more stable than first one. or the carbonium
ion is highly reactive compared to second since (C6H5)3C+ is more stable
reversible reaction would take place

HO
(CH3)3C—Br (CH3)3C+ + Br– 2 (CH3)3C—OH + H+
fast
(C6H5)3C—Br + –
(C6H5)3C + Br
(stable)
H2O (not so fast)

(C6H5)3C—OH + H+

and since second reaction involves equilibrium it shows common ion effect in first
reaction in there is no equilibrium it is free from the concentration of Br–.

Problem 3: 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 H2SO4 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 LiAlH4 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?

Solution: (A) 

Cl2
(B) 
NaNH 2
(C) 
dil. H 2SO4
Hg 2
(D) 
Alkaline Hypochlorite
 (E)
Alkene Acid

2CH3CHO 
Ozonolysis
(G) 
Dehydration
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 
Cl2

NaNH 2
 H3C
H3C H3C Cl

(A) Cl Hg 2 / H 2SO 4
(B)
CH3 OK
H3C 
hypo
chloride
 H3C

O O

LiAlH 4

CH2 CH3
O3
2CH3CHO
H2O
 H3C 
Al2 O3
H O
 H3C
2
(G)
OH
(F)

Problem 4: A hydrocarbon (A) of molecular weight 54 reacts with excess of Br2 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.

Solution: Compound (A) 

Br2 / CCl4
 Compound (B)
excess
Molecular weight 54 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 =  = 2 mole
Molecular weight 160

i) As two moles of Br2 adds hence compound has two  bonds hence general
formula should (CnH2n–2)
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
CH 
Br2
CCl4
 H3C Br
H3C (A) Br
CH3CH2Br Br
in NaNH2 CH3

Catalytic
Hydrogenation
 H3C
C 2H5 (C)
H3C (D)
O3
O

H3C C 2 H5

O
(O)

2CH3CH 2 COOH

Problem 5: A hydrocarbon C8H10 (A) on ozonolysis gives compound C4H6O2 (B) only.
The compound (B) can also be obtained from the alkyl bromide C3H5Br (C)
upon treatment with magnesium in dry ether followed by CO2 and
acidification. Identify (A), (B) and (C) and also give equations for the
reactions.

Solution: i) (C) is an alkyl bromide  C – C  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.
Br 

Mg
MgBr  

i ) CO2
C –OH   
ozonolysis CC
ether ii) H3O ||
O
Cyclopropyl (C) Cyclopropane Dicyclopropyl
bromide (B) (A)
carboxylic acid acetylene

Problem 6: Comment on the following observation

 CO2 CO 2

Br  
OH
High concentration
HO  Br
H H
H3C CH3
Retention of configuration
Solution: (S)  Bromopropanoate ion (R) Lacate ion

Inversion of configuration
Ag 2 O
Low concentration of - OH

CO 2

H OH
H3C
(S) lacate ion

Problem 7: i)


CH3 CH2
ii) CH2 
 H C NH2
H3C 3

iii) CH2
H3C 
 H2C CH2

Solution: i) Br

Br2
h

alc. KOH

CH3 CH3 CH2
ii) CH2   H3C Br   H3C
HBr NH3
NH2
H3C H O
2 2

iii) Br2 / h
CH2 
alc. KOH
 H2C CH2
H3C

Problem 8: Identify A to D in the following sequence of reactions.

C4 H9 Br 
aq. NaOH
 C4 H10 
oxidation
 C4 H8O 
NaOI

 yellow ppt.
(A) (B) (C)

conc. H 2SO4 Tollens' reagent

CH3CHO 
O3 / H 2 O / Zn
D no reaction

Solution: Br OH
A=
B=
H3C CH3 H3C CH3
O

C= D=
H3C CH3
H3C CH3

Problem 9: Predict the product of each SN2 reaction below. Be sure to indicate the
stereochemistry of each product where appropriate.
 a) H3C Br
Br  +
CH3
H
b) RCO2  H3C  N2 

c) CH3
O O
H3C  ROH
R
H3C

Solution: a) H3C CH3

H  Br 

Br
b) RCO2CH3  N2 
c) CH3
H
H3C
OR  R CO2 H

H3C

Problem 10: 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.

Problem 11: 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
NC  R  Br  R Br   
 N  C  R  Br 
Transition State
Problem 12: A student prepared a pure sample of 1-chloro-2-(dimethylamino)
propane. After standing for several weeks in a sealed container he
opened it and found it was mostly 2-chloro-1-(dimethylamino) propane.
Resolve the students’ dilemma and explain what has happened.
Solution:

CH3  CH  CH 2  Cl 
 Cl
 CH 3  CH  CH 2 
Cl

N
N
CH3 CH3
CH3 CH3
Cl CH3
CH 3  CH  CH 2  N
CH3

Problem 13: 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

H3C  OH H3C

F CH3
CH3
d)
 OH

Br
Problem 14: 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
 OH - 
E2

H3C CH3

b) OH

H /

E1

H3C CH3
c) O O
S S Ph
 OH- 
ElcB


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 (H2O), 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
 H2O  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

Problem 15: Which SN2 reaction of each pair would you expect to take place more rapidly in
a protic solvent and why?
CH3 CH2 CH2Cl + CH3 CH2O CH3CH2CH2OCH2CH3 + Cl
(i)
or
CH3 CH2 CH2Cl + CH3 CH2OH CH3CH2CH2OCH2CH3 + HCl

CH3 CH2 CH2Cl + CH3 CH2O CH3CH2CH2OCH2CH3 + Cl

(ii) or
CH3 CH2 CH2Cl + CH3 CH2S CH3CH2CH2SCH2CH3 + Cl
1
(iii) Which SN reaction of each pair would you expect to take place more
rapidly and Why?
(CH3)3CCl + H2O  (CH3)3COH + HCl
or
(CH3)3CBr + H2O  (CH3)3COH + HBr

Solution: (i) CH3CH2O is a stronger nucleophile ; it undergoes more rapidly SN reaction.

(ii) CH3CH2S is a stronger nucloephile
(iii) Br is a better leaving group.

Assignments (New Pattern)

SECTION – I Single Choice Questions

Level - I
1. Which of the following represents sec-butyl bromide ?
CH3
(b) CHCH 2Br
(A) CH3CH2CH2CH2Br CH3
CH3
(c) CH 3 Br (d) CH 3CH 2 CHCH 3
CH3 Br

2. Which of the following represents tert-butyl bromide ?

(b) CH3CHCH 2Br
(A) CH3CH2CH2CH2Br CH3
CH3
(c) CH3 C Br
(d) CH3CH CHCH 3
CH3 Br

3. Which of the following represents isobutyl bromide ?

(b) CH3CHCH 2Br
(A) CH3CH2CH2CH2Br CH3
CH3
(c) CH 3 Br (d) CH3CH2CHCH 3
CH3 Br

4. In the reaction
anhydrous
ROH + HX ZnCl 2
RX + H2O
the order of reactivity of halogen acids is
(A) HI > HBr > HCl (B) HI < HBr < HCl
(C) HI > HBr < HCl (D) HI < HBr > HCl

5. The ease with which an alcohol can be halogenated by treating it with HX in the
presence of anhydrous ZnCl2 is
(A) tertiary alcohol < secondary alcohol < primary alcohol
(B) tertiary alcohol > secondary alcohol > primary alcohol
(C) tertiary alcohol > secondary alcohol < primary alcohol
(D) tertiary alcohol < secondary alcohol > primary alcohol

6. When toluene is treated with Cl2 at high temperature without the use of any catalyst, the
product obtain is
(A) o-chlorotolune
(B) m-chlorotoluene
(C) a mixture of orhto- and para-chlorotoluenes
(D) benzylchloride

7. For the same alkyl group, the order of boiling points of alkyl halides is
(A) chloride < bromide < iodide (B) chloride > bromide > iodide
(C) chloride < bromide > iodide (D) chloride > bromide > iodide
8. An organic compound X(C4H9Br) on treatment with alc. KOH gave isomeric product with
the formula C4H8. On ozonolysis one of these gave only product CH3CHO while the other
gave two different products. The compound X
(A) 2-Bromobutane (B) 2-bromopentane
(C) 1,2 dibromo butane (D) 3-Bromopentene

9. Which of the following is an example of Sandmeyer reaction ?

Cl
FeCl 3
(a) + Cl 2 low temperature
Cl
Cl Cl
uv light
(b) + Cl 2
high temperature
Cl Cl
Cl
CH3
CH2Cl
light, high temp.
(c) + Cl 2
no. catalyst

+
N NCl Cl

(d) CuCl, heat N2

+

10. Which of the following compounds represents gammexane?

(A) Hexachlorobenzene (B) Benzene hexachloride
(C) Dichlorobenene (D) Trichlorobenzene

11. The dipole moment of CH3X (where X is a halogen) following the order
(A) CH3F > CH3Cl > CH3Br (B) CH3F > CH3Cl < CH3Br
(C) CH3F < CH3Cl > CH3Br (D) CH3F < CH3Cl < CH3Br

12. The order of reactivity for the SN2 reaction involving replacement of –X by a nucleophile
in alkyl halide is
(A) CH3 < 10 < 20 (B) CH3 > 10 > 20
0 0
(C) CH3 < 1 > 2 (D) CH3 > 10 < 20

13. The Wurtz-Fittidg reactions involves

(A) two molecules of aryl halides
(B) two molecules of alkyl halides
(C) one molecule of each of aryl halide and alkyl halide
(D) one molecule of each of aryl halide and phenol

14. Which of the following compounds undergoes replacement of –Cl by –OH by merely
warming the compound with aqueous NaOH ?
 Cl Cl
NO 2
(a) (b)

Cl Cl
NO 2 O 2N NO 2
(c) (d)

NO 2 NO 2

15. Aryl halides are less reactive towards nucleophilic substitution reactions as compared to
alkyl halides due to
(A) the formation of less stable carbonium ion
(B) resonance stabilization
(C) longer carbon-halogen bond
(D) inductive effect

16. Which of the following has the highest nucleophilicity ?

(A) F- (B) OH-
(C) CH3- (D) NH2-

17. The order of reactivities of the following alkyl halides for a SN2 reaction is
(A) RF > RCl > RBr > RI (B) RF > RBr > RCl > RI
(C) RCl > RBr > RF > RI (D) RI > RBr > RCl > RF

18. Which of the following orders about nucleophilicity is correct ?

(A) MeO- > HO- > MeCOO- (B) MeO- < HO- < MeCOO-
- - -
(C) MeO > HO < MeCOO (D) MeO- < HO- > MeCOO-

19. Heating together of sodium ethoxide and ethyl iodide will give:
(A) ethyl alcohol (B) acetaldehyde
(C) diethyl ether (D) acetic acid

20. The compound formed in carbylamine test is

(A) C6H5C  N (B) C6H5N  C
(C) CH3 – O – C  N (D) CH3 – N = C = O
 Level - II

1. An alkyl halide of formula C6H13Cl on treatment with potassium t-butoxide gives two
isomeric alkenes (C6H12). Both alkenes on hydrogenation give 2, 3, dimethyl butane.
Isomeric alkenes are
H3C H3C

CH3 CH3
(A) and H3C
H2C
CH3 CH3
H3C
H3C
CH3
(B) H2C and
CH3
CH3
H3C CH3
CH3
(C) H3C
and
H3C CH3
H3C CH3

CH3
(D) and H2C
H2C
CH3 CH3

Br
2.


i) alc. KOH
ii) NaNH
A 
NaNH 2
CH CH Cl
B. A and B
2 3 2

Br

CH2 CH3
A B
(A)

CH2 CH3
A B
(B)

CH CH
A B
(C)
(D) None of these

3. Br

On treatment with aqueous KOH gives

H3C CH3
 OH OH
CH3 CH3
(B)
(A)
H3C CH3 H3C CH3

OH
CH3

(D)
(C) CH3
H3C OH CH3

4. 3-methyl -2-pentene on reaction with HOCl gives

(A) 3-chloro-3-methyl pentanol-2 (B) 2,3-dichloro-3-methyl pentane
(C) 2-chloro-3-methyl pentanol -3 (D) 2,3-dimethyl butanol-2

5. Silver benzoate reacts with bromine in acetone to form

Br
(A) (B)

COOAg O
(C) (D) C—Br

Br
6. 2, 2 Dichloro-3-methyl butane on hydrolysis forms
(A) Diethyl ketone (B) methyl isopropyl ketone
(C) 3-methyl butane 2,3 diol (D) 2-methyl butane 2, 3 diol

7. Which will be obtained by boiling CH2Cl2 with Caustic Soda

(A) Sodium oxalate (B) Sodium acetate
(C) Sodium formate (D) Ethyl alcohol

8. The order of reactivity of alkyl halides depends upon:

(A) nature of alkyl group only
(B) nature of halogen atom only
(C) nature of both alkyl group and halogen atoms
(D) none of these

9. The reaction described below is

CH3(CH2)5
–
H3C C Br Conc. OH
H
(A) SE1 (B) E2
(C) SN1 (D) SE2
10. Which of the following ether will give always SN2 mechanism in acidic as well as basic
conditions?
O CH2
(A) H3C CH3 (B) C6 H5 O CH3
H3C
(C) (D) All of these
O

SECTION – II More than one choice

1. Which of the following compound will be least reactive towards NaOH.

Cl
(A) CH3Cl (B)
CH3

H3C
(C) (D) Cl

O
H3C

2. Which one of the following compounds will undergo SN1 mechanism?

H3C
(A) O (B) O2N Br
Br

(C) H3C (D)

Br Br
3. Which one of the following compounds give SN1 and SN2 mechanism?
(A) H3C Br (B) H3C Br

(C) H5 C6 Br (D) H2C Cl

4. In the given reaction

H3C I 
HOH
[X]

[X] will be
HO

(A) H3C OH (B)

H3C

(C) CH3 (D) H3C

HO

5. In the given reaction

C6 H5  CH  CH  CH 2  Br 
HOH
[X]  [Y]
[X] and [Y] are
 OH
(A) H5C6 OH (B) CH2
H5 C6
CH2
(C) (B) H5C6
OH

6. Rate of SN1 reaction is increased based on by following facrors because:

(A) good leaving groups (more stable anions) lower the energy of the transition state
leading to carbocation formation thus increasing the reaction rate
(B) a nonbasic nucleophile (like H2O) will prevent a competitive E2 reaction
(C) polar solvents stabilize the carbocation intermediate by solvation, thereby increasing
the reaction rate
(D) none of the above

7. Which of the following on treatment with NaNH2 in liquid NH3 gives m-anisidine
(A) o-Bromoanisole (B) m-Bromoanisole
(C) p-bromoanisole (D) all the three

8. Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by chlorination with

(A) SO2Cl2 (B) SOCl2
(C) Cl2 (D) NaOCl

9. Which of the following statements are correct

(A) In SN2 reaction inversion of configuration would take place
(B) In SN2 hydrolysis on akyl halide having R configuration will convert into an alcohol of
S-configuration
(C) In SN1 reaction, 100% racemisation takes place
(D) In SN1 reaction, racemisation takes place with inversion of configuration.

O
18 dil OH-
10. HO C CH2 CH2 CH2 Br
Product of the above reaction
O18 O
C 18
(a) O (b) O

O
(c) O C CH2 CH2 CH2 OH
(D) none of these
 SECTION – III Other Engg. Exams Questions

1. Ethylidene chloride on hydrolysis with aq. KOH gives:

(A) CH3CHO (B) CH3COOH
(C) CHCl3 (D) CH3CH2OH

2. An alkyl halide reacts with metallic sodium in dry ether. The reaction is known as:
(A) Frankland’s reaction (B) Sandmeyer’s reaction
(C) Wurtz’s reaction (D) Wurtz-fitting reaction

3. Which one of the following will produce a primary alcohol by reacting with CH3MgI ?
(A) Acetone (B) Methyl cyanide
(C) Ethylene oxide (D) Ethyl acetate

4. Which of the following will not give iodoform test ?

(A) isopropyl alcohol (B) ethanol
(C) Ethanal (D) Benzyl alcohol

5. The reaction conditions leading to the best yield of C2H5Cl are:

(A) C2H6 (excess) + Cl2  
UV light
 (B) C2H6 + Cl2 Dark, Room temp.

(C) C2H6 + Cl2 (excess) 
UVlight
(D) C2H6 + Cl2  UV light

6. Among the following the molecule with highest dipole moment is :

(A) CH3Cl (B) CH2Cl2
(C) CHCl3 (D) CCl4

7. Identify the set of reagent and reaction conditions ‘X’ and ‘Y’ in the following set of
transformations,

CH3 CH 2 CH 2Br
X Y
Product CH3 CH CH3
Br
(A) X = Dilute aqueous NaOH, 200C
Y = HBr/acetic acid, 200C
(B) X = Concentrated alcoholic NaOH, 800C
Y = HBr/acetic acid, 200C
(C) X = Dilute aqueous NaOH, 200C
Y = Br2/CHCl3, 00C
(D) X = Concentrated alcoholic NaOH, 800C
Y = Br2/CHCl3, 00C

8. Silver benzoate reacts with bromine to

(A) C6H6 (B) C6H5COOBr
(C) m-Br-C6H4-COOAg (D) C6H5Br

9. 2-Bromopentane is heated with potassium ethoxide in ethanol. The major product

obtained is
(A) 2-Ethoxypentane (B) Pentene-1
(C) pent-2-ene (D) none
10. SN1 reaction of alkly halides leads to
(A) retention of configuration (B) racemisation
(C) racemisation and inversion both (D) none of these

11. Which of the following on treatment with NaNH2 in liquid NH3 gives m-anisidine
(A) o-Bromoanisole (B) m-Bromoanisole
(C) p-Bromoanisole (D) both (A) and (B)

12. Energy of activation is lowest for which reaction?

   
(A) RCH2 O H2 
 R C H2 (B) R 2CH O H 2 
R2 C H

 R 3C 
(C) R 3CO H 2  (D) All have same Eact

13. Order of hydrolysis of the following in increasing order is

Br , Br , Br , (CH3)3CBr

(I) (II) (III) (IV)

(A) I < II < III < IV (B) I < IV < II < III
(C) IV < III < II < I (D) I < II < IV < III

14. When chlorine is passed through propene at 4000C, which of the following is formed ?
(A) PVC (B) Allyl chloride
(C) Vinyl chloride (D) 1, 2-Dichloroethane

15. The addition of HBr is easiest with

(A) CH2 = CHCl (B) ClCH = CHCl
(C) CH3 – CH = CH2 (D) (CH3)2C = CH2
 SECTION – IV Match the Column

1. Match List – I with List – II and select the correct answer from the codes given below the lists:

List – I List – II
Br
(A) (p) Ether
H3C  HOH 

CH3 CH3
CH3
(B) (q) Sec alcohol
H3C O  CH 3  Br
CH3 Na
Br
(C) (r) Tert alcohol
H3C CH3  NaOH (aq)
OH
(D) 
(s) Alkene
H3C CH3 
H


CH3

2. Match the following

Column I (Substrate) Column II

(Relative rate of solvolysis in 50% aqueous
ethanol at 450C)
(p) 7700
(a)
Cl
(q) 1
(b) Cl
H3C (r) 91
(c) Cl
H3C
(s) 1,30,000
(d) Ph Cl

3. Match: A student studied the rate of SN2 reaction of many organic halide (given in
column I) with NaI in acetone solvent and measured the relative rates in each case
(given in column II). Now, match column I with column II to get meaningful result.

Column I (Organic Substrate) Column – II Relative rate

(a) Me (p) 80
O Cl
Cl
(b) (q) 105

(c) H2C
(r) 103
Cl
 O
Cl
(d) (s) 200

SECTION – V Comprehension Type Questions

 Write-up I
Nucleophilic substitution reaction is given by those compounds which has nucleophilic
group as a good leaving group is a electron withdrawing group, it should be stable after
leaving with bonding pair of electrons and it should have high polarisability.

1. Which of the following compound will give nucleophlic substitution reactions?

(A) R – Br (B) R – N3

(C) R  O H 2 (D) all of these

2. Leaving power of which leaving group will be maximum

O O
O O
(A) H3C S (B) H3C S
C 2 H5 CH3
O O
O
O F O O
H3C S H3C
(C) (D)
O F CH3
F

3. Nucleophilic substituion reaction is given by

(A) R – NH2 (B) R – OH
(C) R – OR (D) R – Br

 Write-up II
Nucleophilic aliphatic substitution reaction is mainly of two types: SN1 and SN2. The SN1
mechanism is a two step process. Reaction velocity of SN1 reaction depends only on the
concentration of the substrate. Since product formation takes place by the formation of
carbocation, optically active substrate gives (+) and (–) forms of the product. In most of
the cases the product usually consits of 5-20% inverted product and 80-95%racemised
species. The more stable the carbocation, the greater is the proportion of racemisation.
In solvolysis reaction, the more nucleophilic the solvent, the greater is the proportion of
inversion.
4. Which one of the following compound will give SN1 reaction?
CH3
H3C
(A) H5 C6 Br (B) Br
CH3
(A) H3C Br (B) All of these

5. Which of the following compounds will give SN1 reactions?

I. C6H5 – CH2 – Br
II. CH2 = CH – CH2 – Br
III. CH3 – CH2 – Br
 CH3

IV. H3C
CH3 Br

Select the correct answer from the codes given below:

(A) I, II and III (B) I, II and IV
(C) II, III and IV (d I, III and IV

6 For the given reaction

R1 R1
X 
 R
HOH
R OH
R2 R2
Which substrate will give maximum racemisation?
CH3 H2C CH3

(A) H5 C6 Br (B) Br
C2 H5 C2 H5
Br Br
H5 C6 O H5 C6 NO 2
CH3
(C) (D)

+
CH3 NH3

 Write-up III
SN2 reaction is bimolecular reaction which takes place by formation of transition state.
Velocity of the reaction depends on the concentration of substrate as well as nucleophile.
The reaction is favorable by strong nucleophile in the presence of polar aprotic solvent.
Optically active halides gives. Walden inversion by SN2 mechanism. Presence of hetero
atom at -carbon, unsaturation as -carbon and carbonyl group at -carbon favours SN2
mechanism.

7. Which of the following will give SN2 mechanism?

(A) CH3 – Br (B) CH2 = CH – CH2 – Br
(C) C6H5 – CH2 – Br (D) All of these

8. Which of the following compound will give Walden inversion?

(A) C4H9 – CHD – Br (B) C6H5 – CH2 – Br
(C) CH2 = CH – CH2 – Br (D) All of these

9. Which of the following compounds will give SN2 reaction?

H3C H3C O
I. II
Br Br
O CH3
H5C6
III. IV. H3C
CH3 Br
Br
Select the correct answer from the codes given below:
 Codes:
(A) I and II (B) I and III
(C) I, II and III (D) I, II, III and IV

SECTION – VI Subjective Questions

LEVEL – I

1. Identify A, B, C, D, E and F in the following series of reaction.

Br2 aq.KOH Na
  A   B  C
h
alc. KOH
NBS C
D   E   F

2. Explain why an SN2 solvolysis (where solvent is the nucelophile) appears to follow a first
order rate law, rather than a second order one?

3. Suggest the mechanism

CH3
CH3 
aq. AgNO3
 OH
CH2Cl

4. R-CI is treated with Li in ether to form R – Li, R – Li reacts with water to form
isopentane. R – Cl also reacts with sodium to form 2, 7–dimethyl octane. What is
the structure of R – Cl.
O
5. (a) CH 2 C CH 2 CH 2 CH 2 Br base
?

Br2/H2O base CH3OH

(b) CH3 CH CH Ph A B C
Identify A, B and C.

6. A chloroderivative ‘X’ on treatment with zinc and hydrochloric acid gave a hydrocarbon
with five carbon atoms in the molecule. When X is dissolved in ether and treated with
sodium, 2, 2, 5, 5-tetramethyl hexane is obtained. What is compound X.

7. A hydrocarbon C5H10 does not react with chlorine in dark but gives a single monochloro
compound C5H9Cl in bright sunlight. Identify the hydrocarbon.

8. A hydrocarbon C5H12 gives only one monochlorination product. Identify the hydrocarbon.

9. Which compound in each of the following pairs will react faster in SN 2 reaction with HO–
?
a) CH3Br or CH3I
b) (CH3)3 CCl or CH3Cl
 c) CH2 = CHBr or CH2 = CHCH2CH2Cl.

10. Predict the order of reactivity of the following compounds in dehydrohalogenation :

a) CH3CH2CH2CH2Cl,(CH3)2CHCH2Cl,
(CH3)2CH–CH2Br,CH3CH(Br)CH2CH3. (CH3)3C—Br
b) CH3CH(Br)CH3, CH3CH2CH2Br, (CH3)2CH—CH2Br, (CH3)3 C—CH2Br.

LEVEL – II

1. An organic compound (A) C7H15Cl on treatment with alcoholic caustic potash gives a
hydrocarbon (B) C7H14. (B) on treatment with ozone and subsequent hydrolysis gives
acetone and butyraldehyde. What are (A) and (B).
2. Treatment of 2-bromobutane with hot alcoholic KOH gives a mixture of three isomeric

butenes (A), (B) and (C). Ozonolysis of the minor product (A), gives formaldehyde and

another aldehyde in equimolar amounts. What are the structural formulae of (A), (B)

and (C)?

3. What are the products of the following reactions?

CH3
(a) H3C—C—Cl + O CH3 

CH3
CH3

(b) CH3—C—O– + CH3—X

CH3

4. What would be the major products in each of the following reactions.

CH3
+
CH3 C OK

CH3 (CH 2)4 CH 2 CH 2 Br CH3

(i) ?
CH 2 Br
OC2H5
(ii) ?
CH3

5. The alkyl halide C4H9Br (A) reacts with alcoholic KOH and gives an alkene (B), which
reacts with bromine to give dibromide (C). (C) is transformed with sodamide to a gas (D)
which forms a precipitate when passed through an ammonical silver nitrate solution.
Give the structural formulae of the compounds (A), (B), (C) and (D) and explain reactions
involved.
6. A primary alkyl bromide (A), C4H9Br, reacted with alcoholic KOH to give compound (B).
Compound (B) reacted with HBr to give an isomer of (A), (C). When (A) was reacted with
sodium metal it gave compound (D), C8H18, which was different from the compound
produced when n-butyl bromide was reacted with sodium. Draw the structure of (A) and
write equations for all the reactions.
7. (A) What would be the major products in the following reaction
F
NaOCH3
(i) ?

NO 2
CH3
(ii) HBr
Peroxide
?

(B) Explain briefly the formation of the product giving the structure of the intermediate
OCH3
OCH3
Br
NaNH2

H NH3 NH2

8. Identify unknown compounds A, B …H in the following series of reactions:

OH 
H 2SO4
A 
NBS
 B 
LiAlD4
C

PBr5

D 
1. Li
2. CuI
 E 
NBS
 F 
H 2 / Ni
 G 
alcoholic KOH
H
3.B

9. CH3

C  B 
C2 H5 OH
 H3C 

C2 H5 O
A
CH3 Br

10. Compound A (C6H14) gives three different monochlorides on photochemical chlorination.

One of these monochlroides is inert to E2 elimination. The other two monochlorides yield
the same alkene B (C6H12) on being heated with potassium tert-butoxide in tert-butyl
alcohol. Identify compound A, the three monochlorides and alkene B.
ANSWERS TO ASSIGNMENTS

SECTION - I
Level - I

1. (D) 2. (C) 3. (B) 4. (A)

5. (B) 6. (D) 7. (A) 8. (A)
9. (D) 10. (B) 11. (C) 12. (B)
13. (C) 14. (D) 15. (B) 16. (C)
17. (D) 18. (A) 19. (C) 20. (B)

Level - II

1. (A) 2. (C) 3. (C) 4. (C)

5. (B) 6. (B) 7. (C) 8. (C)
9. (B) 10. (A)

SECTION - II

1. (c, d) 2. (a, b, c, d) 3. (a, c) 4. (a, b)

5. (a, b) 6. (A), (B), (C) 7. (a, b) 8. (a, c)
9. (a, d) 10. (a, b)

SECTION - III

1. (A) 2. (C) 3. (C) 4. (D)

5. (A) 6. (A) 7. (B) 8. (D)
9. (C) 10. (C) 11. (D) 12. (C)
13. (A) 14. (D) 15. (D)

SECTION - IV

1. (A - R), (B - P), (C - Q), (D - S)

2. (A - Q), (B - R), (C - S), (D - P)
3. (A - R), (B - S), (C - P), (D - Q)

SECTION - V
1. (D) 2. (C) 3. (D) 4. (A)
5. (B) 6. (C) 7. (D) 8. (A)
9. (C)

SECTION - VI

LEVEL – I

1. Br OH ONa
Br2
  aq.KOH
hv   Na
 
A B C
alc. KOH

NBS
 
D E Br
ONa Br

Williamson
+   —O—
synthesis
C E F

2. Because of SN2 solvolysis reaction is bimolecular, it would follow the following rate law.
Rate – k[RX] [solvent]
However, the concentration of solvent is very large and greatly exceeds the amount of
RX. For this reason, its concentration is effectively constant and therefore the reaction
will follow pseudo first order Rate Law.
Rate = k [R] where k = K [Solvent]
3. CH3 CH3
+ Ag+ + AgCl
CH3Cl CH2+

Ring expansion

+
CH3
+
CH3

H2O
OH
CH3

CH3—CH—CH2—CH2—Cl
4.
CH3

5. B reacts with Schiff’s reagent so it contains a carbonyl group but it does not reduce
Fehling solution so it is a ketone. Hence A is CH3 – CCl2CH3.
6. CH3 CH3 CH3

CH3 – C – CH2 – CH2 – C – CH3 – CH3 is formed from CH3 – C – CH2Cl

(X)
CH3 CH3 CH3 CH3

On reduction with Zn and HCl CH3 – C – CH3

CH3
7.

8. CH3

H3C CH3

CH3
9. a) CH3I
b) CH3Cl
c) CH2 = CH—CH2CH2Cl.

10. a) (CH3)2 CHCH2Cl > CH3CH2CH2CH2Cl.

b) (CH3 )3 C  CH 2  Br  (CH3 ) 2 CH  CH 2 Br  CH3CHCH 2CH3 > CH3 CH2 CH2
Br
Br

LEVEL – II

1. (A) (CH3)2CClCH2CH2CH2CH3 (B) (CH3)2C=CHCH2CH2CH3

2. (A) CH3—CH2—CH = CH2 (B) CH3—CH=CH—CH3 (cis)

(C) CH3 CH CH CH 3
(trans)
3. a) CH3 CH3

CH3—C—Cl + OCH3  CH3—C=CH2

CH3
OCH3 (nucleophile) can't attack 3° carbon having high electron - density hence
elimination takes place giving alkene.
b) CH3 CH3

CH3—C—O– + CH3X  CH3—C—CH3

CH3 CH3
Nucleophilic attack on methyl carbon is possible giving ether (Williamson synthesis).
4. a) slow
CH3—CH—CH—CH3   CH3—CH—CH—CH3
SN1
Br CH3 CH3
2° carbonium ion (A)
OC2H5
1,2 hydride shift OC2H5
  CH3—CH2—C—CH3   CH3—CH2—C—CH3
CH3 CH3
3° carbonium ion major

no shift OC H
A   , 
2 5
 CH5CH——CH—CH3
OC2H5 CH3
minor
Note: There can be elimination from 2° and 3° carbonium ion to give alkene, and alkene
predominates over substitution in 3° cation.
H 
CH3—CH—CH—CH3   CH3—CH=C—CH3
CH3 CH3
(A) (due to elimination)
slow
b) —CH3   —CH3

Cl 2° carbonium ion (A)

1,2 hydride shift —CH3

(A)  
3°carbonium ion (B OC2 H5
OC2H5
(B)   CH3
OC2H5
—CH3
major

OC2H5
minor

c) CH2Br +
CH2
slow

CH3 CH3
1° carbonium
1,2 methyl shift CH2CH3
OC2H5 CH2CH3
+  
(3° carbonium ion)
OC2H5
major

5. (A) CH3CH2CH2CH2Br (B) CH3CH2—CH = CH2

(C) CH3CH2CHBrCH2Br (D) CH3CH2C  CH

6. (A) 1–Bromo-2-methylpropane;
(B) 2-Methylpropene
(C) 2-Bromo-2- methylpropane
(D) 2,5-Dimethylhexane
 OCH 3
CH3
7. (a) (i) (ii)
Br
NO 2
OCH3
OCH3 OCH3 OCH3
Br
NH 2 NH 2 NH 3
(b)
H NH2
NH2

8.
A= B= Br

C= D D= Br

E= F=
Br

G= H=
Br

9. H3C
CH3 CH3
H3C
H3C (no rearrangement)
A= B= (by 1, 2-methyl shift)
O H5C 2 O
CH3
C 2 H5
CH3
H3C (due to elimination)
C=
H3C
10. Cl

CH3 H3C
CH3 CH3 CH3
H3C
B: CH2
A: monochlorides H3C Cl H3C H3C
H3C CH3 CH3
CH3 Cl
(inert to E2 elimination)
give same alkene B