CHEMISTRY

MDCAT
Lecture # 3
(Aromatic Hydrocarbons
and Alkyl Halides)
(A) Aromatic Hydrocarbons:
SUBTOPICS
1. Introduction 2. Properties
3. Nomenclature 4. Structure
5. Modern representation (Stability of Benzene)
(i) Resonance method (ii) Resonance energy
(iii) Atomic orbital treatment
6. Mechanism of electrophilic substitution in benzene.
7. Electrophilic Substitution Reactions of benezene and
methylbenzene
(i) Nitration (ii) Sulphonation (iii) Halogenation
(iv) Friedal-Crafts Alkylation and Acylation
(contd.)
8. Addition reactions of benzene and methylbenzene.
9. Oxidation of methyl benzene and ethyl benzene
(Side chain reactions of benzene)
10. Apply the knowledge of positions of substituents in the
electrophilic substitution of benzene.
11. Compare the reactivity of benzene with alkanes and alkenes.
(B) Alkyl Halides (Halogenoalkanes)
SUBTOPICS
1. Nomenclature
2. Classification of alkyl halides
3. Structure and reactivity of RX.
4. Reactions
(a) SN reaction (Nucleophilic substitution reactions)
• Mechanism and types of nucleophilic substitution reactions
(SN1 and SN2)
(b) -Elimination reaction
• Mechanism and types of elimination reactions.
(E1 and E2)
 (A) Aromatic Hydrocarbons
1. Introduction
• Aromatic hydrocarbons are unique in having conjugated
double bonds throughout their rings.
• Benzene and its derivatives are part of an essential
chemical community known as aromatic compounds.
• The term aromatic was derived from the Greek word
‘aroma’ meaning “fragrant” (Pleasant odour) and was used
in organic chemistry for a special class of compounds.
These compounds have a low hydrogen to carbon ratio (or
high carbon to hydrogen ratio) in their molecular formulas
and have a characteristic odour. These are called aromatic
compounds.
 2. Properties of Benzene
• Benzene was discovered by Michael Faraday in 1825 in the gas
produced by the destructive distillation of vegetable oil.
• The word benzene derives historically from gum benzoin,
sometimes called ‘Benjamin’. Gum benzoin was known as an
aromatic resin.
• The name benzene was given by German Chemist Mitscherich in
1833.
• It is the simplest organic, aromatic hydrocarbon.
• Its molecular formula is C6H6 and its molar mass is 78g.
• It has cyclic hexagonal planar structure.
• It is a closed ring of six carbon atoms linked by bonds
that alternate between single and double bonds.
• It is a colourless, mobile, volatile, toxic and inflammable liquid.
• Its boiling point is 80.1oC.
• It is non-polar, immiscible with water but miscible with organic
 3. Nomanclature
(Monosubstituted benzene, Polysubstituted benzene)
Some important rules of naming are given below.
1) Mono-substituted benzene derivatives are named by
prefixing benzene with the name of the substituent. The
whole name is written as one word,
e.g.
 2) There are certain monosubstituted benzene derivatives
which are given the special names, like methylbenzene as
toluene, hydroxybenzene as phenol, etc.
e.g.

All the six positions in benzene are exactly equivalent so

there is only one monosubstituted benzene.
 3) The second substituent in benzene would give rise to
three isomeric products designated as ortho (1, 2), meta (1,
3) and para (1, 4), e.g.
e.g.

4) If two or more substituents are different, then the

substituent that is treated as a high priority group, is given
the number 1 position in the benzene ring. Other groups are
numbered by counting from position 1 in the manner
which gives them the lowest number.
The order of priority of the groups (left to right):
– COOH, – CN,  CHO – COCH3, – OH, – NH2, – OR, – R.
e.g.

5) (a) If two substituents are different and they are not

present in priority order list, they are named in alphabetical
order. The last named substituent will be at position 1, e.g.
 b) If there is a substituent on the ring which gives a special name to the
molecule, then special name is used as parent name to the molecule
e.g.

c) When three or more substituents on the ring are different, the order
of numbering is in the alphabetic order. The last name of substitutent is
assumed to be in position 1. e.g.

4-bromo-3-chloroiodobenzene 3-bromo-5-fluronitrobenzene 2,4-dichloro-5-iodonitrobenzene

4. Structure of Benzene
• The X-ray studies of benzene have confirmed
that:
• Benzene has regular hexagonal structure.
• All the carbon and hydrogen atoms are in the
same plane (co-planer).
• All the angles are of 1200.
• All C  C and C  H bond lengths are 1.397Å
and 1.09 Å, respectively.

5. Modern representation (Stability of Benzene)

The stability of benzene structure can be
explained by the following ways:
(i) Resonance Method
(ii) Resonance Energy
(iii) Atomic orbital Treatment of Benzene
 (i) The Resonance Method: “The possibility of different pairing
schemes of valence electrons of atoms is called resonance and the
different structure thus arranged are called resonance structure. The
resonance is represented by (↔) arrow. or
The representation of a real structure as a weighted average of two and
more contributing structures is called resonance.
MCQ
Benzene is an extra ordinary stable molecule. This stability is due the extensive
delocalization of electron cloud. Which of the following methods/techniques does not
explain the stability of benzene:
A) Resonance method C) Crystal field theory
B) Atomic orbital treatment of benzene D) Resonance energy
Answer Explanation: (C)
Crystal field theory does not explain the stability of benzene. It explain colours
shown by the coordination compounds of transition elements.
15
 16
(ii) Resonance Energy: It is the difference between amount of heat actually
released on hydrogenation of benzene and that calculated on the hydrogenation
of 1,3,5-Cyclohexatriene(hypothetical structure).
MCQ
In benzene electrons are delocalized making it a very stable molecule. Greater is the resonance
energy, greater is the stability. The resonance energy of benzene is:
A) -152 kJmol-1 C) -358kJmol-1
B) +150.5kJmol-1 D) +358kJmol-1

Answer Explanation (B)

The resonance energy of benzene is +152.0 kJmol-1.
Calculation for resonance energy:
 Heat of hydrogenation of 1,3,5-cyclohexatriene = 3 x -119.5 = -358.5 kJmol-1
 Heat of hydrogenation of benzene = -208.0kJmol-1
 According to the definition of resonance energy
= Actual heat of hydrogenation of benzene – Heat of
hydrogenation of 1,3,5-cyclohexatriene (hypothetical)
= -208.0 – (-358.5)
= +150.5 kJmol-1
 17

(iii) Atomic orbital treatment

This is the most accurate concept of the structure of benzene. The structure of benzene molecule is
best described using hybridization opproach.
According to this concept, all the C-atoms in benzene are sp2-hybridized. Two sp2-hybrid
orbitals of each C-atom overlap with two sp2-hybrid orbital of two other C-atoms to form
sigma bonds. In this way there are six sigma bonds are formed between six C-atoms which
are 120o apart. Remaining six sp2-orbital of six C-atoms overlap with 1s orbital of six H-
atoms individually to form six sigma bonds. Since sigma bond results from the overlap of above
said planar orbital, all H and C atoms are in the same plane and they generate a hexagonal ring of
C-atoms.
sp2 orbital hybridization
(i)
 Each C-atom in benzene also has an unhybrid 2pz-orbital containing one electron. These
2pz-orbitals are perpendicular to the plane of sigma bonds. pz orbital in benzene as shown in
the diagram:

unhybrid 2pz-orbital
(ii)

These 2pz-orbitals by lateral overlapping form three alternate pi-bonds in benzene ring. There are
two possibilities of pi-bond formation in benzene.

(iii)
Lateral overlapping of 2pz-orbitals
Two possibilities of pi bond formation
 19

Actually these 2pz-orbitals produce a pi-molecular orbital containing six electrons. One half
of this pi-molecular orbitals lie above the plane of hexagonal ring and remaining half below the
ring like a sandwich. The overlap of these 2pz-orbitals result in the formation of a fully delocalized
pi-bonds, which extend all over the six C-atoms of benzene nucleus. This hybridization approach
clearly indicates that these six electrons could be found anywhere in highly delocalized manner. As
a result of delocalization, a stronger pi-bond and a more stable benzene molecule is obtained
which undergo substitution reactions more frequently than addition reactions.

• One half of this pi-molecular orbital lies above

Sandwich structure (iv)

• and remaining half below the ring

 20

Q: Benzene has number of

A. 12 σ bonds and 6  electrons C. 8 σ bonds and 8  electrons
B. 10 σ bonds and 4  electrons D. 14 σ bonds and 8  electrons
Reactions of benzene
• The highly stable delocalized electrons of benzene are not easily available.
• It means that powerful electrophile is required .
• In benzene two type of reactions take place
• (a) Electrophilic substitution reaction (Benzene ring is not affected)
• (b) Addition reactions (oxidation reaction, ozonolysis, reduction reaction) In this reaction
benzene ring is affected .
 6. Mechanism of electrophilic substitution in benzene.
In the electrophilic substitution of benzene which of the following
steps is/are involved in the mechanism of the reaction:
A) Generation of electrophile (E+)
B) Formation of arenium ion
C) Regeneration of catalyst and formation of product
D) All of these
ANSWER EXPLANATION: (D)
Nitration of Benzene
General Reaction:
 7. Electrophilic Substitution Reactions 23

Q: Benzene shows the following reactions:

Type of reactions Reagents Chemical reaction
Nitration
I (introduction of Conc. HNO3 , Conc. H2SO4 50° - 55° C
 NO2 group)
Sulphonation
II Conc. H2SO4 80°C
( SO3 H group)

Alkylation
III CH3Cl , AlCl3
(R ) group

Acylation O
IV CH3COCl, AlCl3
(
R-C
-)
The mechanism shown in the given reactions is:
A) Electrophilic substitution reaction C) Nucleophilic substitution reaction
B) Acid base reaction D) β-elimination reaction
Explanation: (A) Overall reaction is electrophilic substitution
reaction as shown in the mechanism below.
Overall reaction
 7. Electrophilic Substitution Reactions of Benzene at a glance
Cl
FeCl3 or AlCl3
+ Cl2 + HCl
1) Halogenation
Chlorobenzene
NO2
H2SO4 (conc.)
+ HONO2 (conc.) + H2O
2) Nitration 50 – 55oC

Nitrobenzene
SO3H
SO3
H2SO4 (conc.) + H2O
3) Sulphonation
Benzene sulphonic acid
CH3
AlCl3
+ CH3Cl + HCl
4) Alkylation
Toluene
O
COCH3
AlCl3
+ CH3C-Cl + HCl
5) Acylation Acetophenone
 26
8. Addition Reactions of Benzene
(a) Reduction of Benzene
Benzene is reduced to cyclohexane on heating at high
temperature with hydrogen in the presence of Pt in an
acidic solvent (acetic acid) or Ni at 200oC as a catalyst.
 27

(b) Halogenation of Benzene

Benzene reacts with chlorine and bromine in the presence of
sunlight to give addition products, hexachlorocyclohexane
and hexabromocyclohexane flurination is too vigorous
while iodination is slow.

1,2,3,4,5,6-Hexachlorocyclohexane
 Free Radical Substitution of Methylbenzene 28
Halogenation of Toluene
 29

9. Oxidation of methyl benzene and ethyl benzene

Side chain reactions of benzene
Q: Alkyl benzene are readily oxidized by acidified KMnO4 or K2Cr2O7. In
these reactions, alkyl groups are oxidized keeping the benzene ring intact.
On oxidation of methyl benzene under such conditions the main product
obtained is:
A) Phthalic acid C) Benzoic acid
B) Propanoic acid D) Ethanoic acid

Note: Whatever the length of an alkyl group may be, it gives only carboxyl
group. This reaction is used as a test for alkyl benzene.
 30

Explanation: (C) Methyl benzene (toluene) are readily oxidized by acidified KMnO4 or
K2Cr2O7. In these reactions, the methyl groups are oxidized into carboxylic acid keeping the
benzene ring intact. CH 3 COOH - Benzyl alcohol
- Benz aldehyde
- Benzoic acid
+3 O     H 2O
KM nO4
dil.H 2SO 4

 K 2SO 4 + 2MnSO 4 + 3H 2O + 5 O 
2KMnO 4 + 3H 2SO 4 
 K 2SO 4 + Cr2 SO 4 3 + 4H 2O + 3[O]
K 2 Cr2 O7 O.A  + 4H 2SO 4 
 Q: During the nitration of benzene, a nitro group (-NO2) 31
substitutes at a carbon atom. Which one of the following
gives the arrangement of the bonds at this carbon atom
during the reaction?
At the start of In the intermediate At the end of
Options
reaction complex reaction
A) Planar Planar Planar
B) Planar Tetrahedral Planar
C) Planar Tetrahedral Tetrahedral
D) Tetrahedral Planar Tetrahedral
Explanation: (B) Option B gives the arrangement of the bonds at this carbon atom
during the reaction.
At the start of In the intermediate At the end of
Options
reaction complex reaction
B) Planar (sp2) Tetrahedral (sp3) Planar (sp2)
Q: AlCl3 catalyzes certain reactions by forming carbocation 32
(carbonium ion) with chloroalkane as shown in the
following equation:
R - Cl + AlCl 3  R + + AlCl - 4
This can occur because: Electrophile
A) AlCl3 is a covalent molecule
B) AlCl3 exists in the dimeric form (Al2Cl6)
C) Al-atom in AlCl3 has an incomplete octet of electrons
D) Cl-atom in R-Cl has a vacant p-orbital
Explanation: (C) Al-atom in AlCl3 has an incomplete octet of electrons.
 10. Apply the knowledge of positions of substituents in the electrophilic
substitution of benzene. (Orientation and Reactivity)
The positioning of a new incoming group in the mono-
substituted benzene ring is called orientation in substitution
reaction.
e) Direct influence of substituents on the benzene ring by 2,4
directing and 3,5-directing groups (orientation in Electrophilic
Substitution reactions of Benzene)
- A substituent already present on the benzene ring affects the reactivity of
aromatic ring .
- (a) Some substituents activate the benzene ring and thus reactivity
increases (by 2-4 direacting groups)
- (b) some substituents deactivate the benzene ring and thus reactivity
decreases (by 3-5 directing groups)
 34

Q: Which one of the following statements is incorrect about 2,4-

directing and 3,5-directing groups?
2,4-directing groups 3,5-directing groups
Opt
(ortho- and para- directing groups) (meta-directing groups)
A) They are electron donating groups They are electron withdrawing groups
B) They decrease reactivity of benzene They increase reactivity of benzene
C) They have lone pair at the central atom except They have multiple bonds
alkyl group
D) e.g. –NH2, –OCH3 e.g. –C N, –COOH
 35
Explanation: (B) In fact, the correct statement is as follow:

2,4-directing groups 3,5-directing groups

Option
(ortho- and para- directing groups) (meta-directing groups)
B) They increase reactivity of benzene They decrease reactivity of benzene

NO 2 NO2


NO
-H

2
+

-CH3 increases reactivity of benzene -NO2 decreases reactivity of benzene

Nitration of toluene take place at 30-40oC Nitration of nitro-benzene take place at 95oC.
 Effect of Substituents on Reactivity of Benzene
Substituents Effect on Reactivity
ortho- and para- directing
groups
-OH, -NH2, -NHR, -NR2 Strongly activating
-R, -CH3, -C2H5 Weakly activating
-F, -Cl, -Br, -I Deactivating
meta- directing groups
-NO2, -CHO, -COR Strongly deactivating
-SO3H, -CN, -COOH
 Anomalous Behaviour of Halogens 37
We have seen above that the o-p directing substituents are, in general
activation as well. However, it has been observed experimentally that
Halogen, although ortho-para directors, are ring deactivators. This
anomalous behaviour of halogens is attributed to the fact that there are
two opposing effects operating.
A halogen substituent is electron-releasing by resonance but, electron withdrawing
because of its high electronegativity (inductive effect). The inductive effect dominates
the resonance effect, and the net result is that the ring is rendered electron-deficient
and less liable to electrophile attack.

Fig. Cl releases electrons into the Fig. Higher electronegativity of

ring by resonance and increases Cl, decreases the electron-
its electron density density of the ring by inductive
effect.
The o-p-directing substituents are also called ring activators.
General effect Example

The m-directing substituents groups are also called ring-deactivators

General effect Example
 11. Comparison of Reactivity of
Alkanes, Alkenes and Benzene
Order of Reactivity: Alkenes > Benzene > Alkanes

Properties / Tests Alkanes Alkenes Benzene

General formula CnH2n+2 CnH2n CnHn
Hybridization of C- sp3 (saturated) sp2 (unsaturated) sp2 (unsaturated)
atoms
Bond angles 109.5o 120o 120o
Reaction with Br2/CCl4 No reaction Reddish brown colour No reaction
of Br2 is discharged
Reaction with Alkaline No reaction Purple colour of KMnO4 No reaction
KMnO4 is discharged
Reaction with O3 No reaction Ozonide is produced Gives glyoxal through
which on reduction benzene triozonide
gives carbonyl
compounds
 (B) Alkyl Halides (Halogenoalkanes)
Halogen derivatives of alkanes are called alkyl
halides (haloalkanes or halogenoalkanes)

1. Nomenclature of Haloalkanes (Alkyl halide) (R-X)

• Alkyl halides are formally derived from alkanes by exchanging

hydrogen for halogen (fluorine, chlorine, bromine, and iodine)
• Depending on the degree of substitution at the carbon atom
carrying the halogen, alkyl halides are classified into primary,
secondary and tertiary alkyl halides
 41
Examples:
 42
Q: Consider the following structural formula of an alkyl halide:
CH3 Br

CH CH CH CH3
CH3 CH3
The correct name according to IUPAC rules is:
A) 2,3-Dimethyl-4-bromopentane C) 2-Bromo-3,4-dimethylpentane
B) 2-Bromo-2,2-dimethylpentane D) 3-Bromo-3,4-dimethylpentane
Explanation: (C) The correct name of the above structure according to IUPAC is
2-Bromo-3,4-dimethylpentane.
C H3 B
r
4
3
21
C
H
C
H
C
H
C
H
3
5
C
H
3
C
H
3
 Q: Consider the following structure of halothane: 2017 43
Br
Cl CH CF3
The correct name of halothane according to IUPAC is:
A) 2-Bromo-2-chloro-1,1,1-trifluoroethane
B) 2,2,2-Trifluoroethane-1-bromo-1-chloroethane
C) 1,1,1-Trifluoro-2-chloro-2-bromoethane
D) 1-Chloro-1-bromo-2,2,2-trifluoroethane
Explanation: (A) The correct name of halothane according to IUPAC is
2-Bromo-2-chloro-1,1,1-trifluoroethane
 Q: The IUPAC name of the given compound is 2015 44
CH3
|
H3C  CH  CH 2  Cl
A) 1-Chloro-2-methylpropane C) Isobutyl chloride
B) 1-Chloro-2-methylbutane D) 2-Methyl-3-chloropropane

Explanation: (A) The correct name according to IUPAC of the given compound is
1-Chloro-2-methylpropane.
Q: In the below reaction, the configuration of product is 2015

A) 100% same of the configuration of reactant C) 50% inverted

B) 100% opposite from configuration of reactant D) 50% retained
Explanation: (B) In the above reaction, the configuration of product is
100% opposite from configuration of reactant.
 2. Classification of alkyl halides
Q. Consider the following statements for the classification
of alkyl halides:
I. A primary alkyl halide has the –X group at the end of
carbon chain
II. A secondary alkyl halide has the –X group in the body of
carbon chain
III. A tertiary alkyl halide has the –X group at the branch in
the carbon chain
IV. A neo- alkyl halide has the –X group at the 2nd last carbon of
the chain
Which of the given statement is incorrect?
A) I only C) IV only
B) II and III D) I, II, III and IV
 3. Structure and reactivity of RX.
The reactivity of alkyl halides depends upon the following factors,
i. C-X Bond energy (Reactivity order R-I > R-Br > R-Cl > R-F)
ii. C-X Bond polarity (Reactivity order R-I < R-Br < R-Cl < R-F)
 C-X Bond energy of R-X, greater will be the stability and lesser the reactivity.
 Greater electronegativity difference (bond polarity) of R-X, greater will be stability
and lesser the reactivity.

Conclusion
• Experiments have shown that the strength of carbon halogen bond is the
main factor which decides the reactivity of alkyl halides. R-I > R-Br > R-Cl >
R-F
Important
• If an electrophile is the attacking reagent then R-F with be the most reactive.
Conclusion:
• The overall order of reactivity of alkyl halides
for a particular alkyl group is -I > -Br > -Cl > -F
• In fact the C – F bond is so strong that the
alkyl fluorides do not react under ordinary
condition
 Q: Experiments have shown that the strength of carbon
halogen bond is the main factor which decides the reactivity
of alkyl halides. Which of the following alkyl halides is least
reactive:
A) R-F C) R-Cl
B) R-Br D) R-I
Explanation: (A) Alkyl halide (R – F) is the least reactive.
Reason:
• Greater electronegativity difference • Greater bond energy of C – F
• Greater polarity Atom Electronegativity Bond Bond Energy (kJ mol-1)
F 4.0 C–F 467
Cl 3.0 C–H 413
Br 2.8 C – Cl 346
I 2.5 C – Br 290
H 2.1 C–I 228
C 2.5
 • Discuss the types of reagents;
Nucleophile and electrophile

Nucleophile (Nucleus Loving) Electrophile (Electron Loving)

It is a specie which is rich in electrons It is a specie which is deficient in electrons
It is a specie which can donate an electron pair It is a specie which can accept an electron pair
It is denoted by NU- It is denoted by E+
(a) Molecule having lone pair of electrons at the (a) Molecule in which central atom is deficient
central atom H2O, NH3, ROR, ROH, in one electron pair
(b)Negatively charged species: F-, Cl-, Br-, I-, OH-, BF3, FeCl3, AlCl3, SO3, CO2
R-, CN-, CH3COO-, NH2-, OH-, C - (b)Positively charged species O
(c) Having pi electron H+, F+, Cl+, Br+, I+, NO2+, C + , R - C +
Alkene (C = C), Alkyne (C ≡ C), Benzene
 52

Q: Which of the following is comparatively weaker

nucleophile?
A) CH3- C) OH-
B) NH2- D) F-
Explanation: (D) Within any given row of the periodic table,
nucleophilicity decreases from left to right as polarizability decreases
(because electronegativity of the central atom is increasing).

CH3- > NH2- > OH- > F-

> NH3 > H2O > HF
electronegativity C = 2.5 N = 3.0 O = 3.5 F = 4.0
 53
Q: Select a nucleophile from the following examples: 2013
A) NH4+ C) NH3
B) BF3 D) NO2+

Explanation: (C) NH3 is a nucleophile because it has a lone pair of

electrons at the central atom of nitrogen in NH3

Q: All of the following are nucleophile EXCEPT:

A) H2O C) AlCl3
B) NH3 D) OH-
Explanation: (C) AlCl3 is an electrophile because in this neutral
molecule the central atom of Al is deficient of one electron pair. It is
also known as Lewis acid.
 Q: Which of the following is the most stable carbocation. 2015
A) (CH3)3C+ C) C6H5CH2+
B) (CH3)2CH+ D) CH3CH2+
Explanation: (C) Benzyl carbocation is the most stable
carbocation. The overall order of stability of carbocations is
Ph 3C+ > Ph 2CH + > PhCH 2 + > CH 2 = CH-CH 2 + > Me3C+ > Me 2CH + > MeCH 2 +
Q: Which of the following is a strong nucleophile: 2012
A) Cl– C) Cl2
B) Cl+ D) Cl
Explanation: (A) Chloride ion (Cl-) is a strong nucleophile.
Q: Select a nucleophile from the following examples: 2013
A) CO2 C) NO2+
B) NH2- D) N+H4
Explanation: (B) NH2- is an example of a nucleophile.
 Q: Alkyl halides are considered to be very reactive compounds 55
towards nucleophiles because:
A) They have an electrophilic carbon
B) They have an electrophilic carbon and good leaving group
C) They have a nucleophilic carbon and a good leaving group
D) They have an electrophilic carbon and bad leaving group
Explanation: (B) They have an electrophilic carbon and good leaving group:

Reason: In prim. alkyl halide ( R  C H 2  X  
) , halogen bears partial negative charge (𝛿 −)
because it has greater electronegativity than that of carbon. While carbon bears partial
positive charge (𝛿 +), so carbon atom in alkyl halide acts as electrophile while halogen acts as
leaving group as shown in the reaction.
 56

Good leaving groups Poor leaving groups

Greater size Smaller size
Greater polariziability Smaller polariziability
Low electronegativity Greater electronegativity
e.g. Cl-, Br-, I-, HSO4- e.g. OH-, OR-, NH2-
 57

4. Reactions
(a) SN reactions
The reactions in which a strong nucleophile (Nu-) displaces a weaker
nucleophile (X-) from a compound (by the combination with electrophilic
carbon atom of alkyl halides) are called nucleophilic substitution (SN)
reactions. A nucleophilic substitution reaction is represented as
 58
Examples of SN reactions
δ+
(i) CH 3 -CH 2 -Br δ- + OH - 
KOH(aqueous)
 C2 H 2OH + Br -

(ethanol)
δ+
(ii) CH 3 -CH 2 -Br δ- + OH - 
Alcoholic KOH
 C2 H 4 + H 2O + Br -

(ethene)
δ+
(iii) CH 3 -CH 2 -Br δ- + CN -  C 2 H 5CN + Br -
(Propanenitrile)
δ+
(iv) CH 3 -CH 2 -Br δ- + NH 3  C 2 H 5 NH 2 + HBr
(Ethylamine)
 59
Q: Which of the following statements is incorrect for SN1 and SN2
mechanism reaction w.r.t alkyl halide (two types of SN reactions)?

Options SN1 Mechanism Reaction SN2 Mechanism Reaction

A) It is uni-molecular reaction It is bimolecular reaction
SN reaction: B) It is second order reaction It is first order reaction
𝑅𝛿+ − 𝑋 𝛿− + 𝑌 − ՜ Order of ease of SN1 mechanism Order of ease of SN2 mechanism
𝑅−𝑌+𝑋 − C)
reaction R3C X > R2C HX > RC H2X reaction RC H2X > R2C HX > R3C X
It involves 50% inversion and
It involves 100% inversion of
D) 50% retention of configuration in
configuration in the product
the product
Explanation: (B) It is incorrect statement. The correct statement is as follow.
Options SN1 Mechanism Reaction SN2 Mechanism Reaction
B) It is first order reaction It is second order reaction
 b) SN2 mechanism reactions

rds

sp3 sp2 sp3

Bromomethane Transition state Methanol

rds = Rate determining step Bond breaking and Inverted molecule
bond making take 100% inversion
place simultaneously
 SN1 mechanism reactions 61
F
irstS
tep

C
H 3 H
3CC
H 3
Polarsolv
ent
+
C
H 3 C C
l (rds)Slowstep C l-
+C
C
H 3 C
H 3

S
eco
n dS
tep
H
3CC
H 3 C
H 3
+ -
Fast
CH
C + O
H 3 C O
H
C
H 3 C
H 3
 Q: During SN2 reaction, configuration of the alkyl halide 62
molecule: 2010
A) Remains same
B) Depends upon the carbon-atom
C) Gets inverted
D) Depends on the electronegativity of halogens
Explanation: (C) It gets inverted 100% inversion of configuration in the product as shown
in the reaction. rds

sp3 sp2 sp3

Bromomethane Transition state Methanol

Bond breaking and bond Inverted molecule
rds = Rate determining step making take place 100% inversion
simultaneously
 Q: Which of the following is correct order of decreasing SN2 63
reactivity:
A) R3C X > R2CH X > RCH2X C) R2CHX > R3CX > RCH2X
B) RCH2 X > R3C X > R2CH X D) RCH2X > R2CHX > R3CX
Explanation: (D) The correct decreasing order of SN2 chemical reactivity
in alkyl halides is as follow:
RCH2X > R2CHX > R3CX
(100% SN2) (50% SN2 & 50% SN1) (100% SN1)
Reason:
• From the comparison, it is clear that with the increase of alkyl groups, the rate of SN2
mechanism reaction decreases because steric hindrance (bulky group effect) increases.
• In such condition with the increase of alkyl groups, the attack of attacking nucleophile
becomes more and more difficult
• That is the reason, primary alkyl halides follow 100% SN2 mechanism reaction whereas
tertiary alkyl halides do not follow SN2 mechanism reaction
 Q: Which of the followings factors does not affect SN1 64
mechanism reaction:
A) Nature of leaving group C) Structure of alkyl halide
B) Nature of solvent D) Strength of attacking nucleophile
Explanation: (D) Strength of attacking nucleophile is also known as
nucleophilicity. Since SN1 mechanism reaction completes in two steps.
1. In the first step ionization of alkyl halide in the presence of polar solvent
takes place and attacking nucleophile does not involve in this step. Rate of
reaction is always determined by slow step.
2. In the second step attacking nucleophile attacks on carbocation of alkyl
halide. It is comparatively fast step
i  R  X polarsolvent
slow step
R   X   ionization step 

 ii  R   Y  fast step
R Y
attacking
nucleophile
 (b) -Elimination reaction 65
During nucleophilic substitution reactions (SN reactions), the attacking
nucleophilic attacks the electrophilic carbon atom of the alkyl halide.
i. There is another site present in the alkyl halide molecule where the
nucleophile can attack at the same time.
ii. Such a site is an electrophilic hydrogen atom attached to the -carbon
of the alkyl halide.
iii. When the attack takes place on -hydrogen, we get an alkene instead
of a substitution product.
iv. Such a type of reactions are called -elimination reactions.
electrophilic hydrogen atom
(-hydrogen)
 66
Types of -Elimination reaction

Mechanism of E2 elimination reaction

• In E2 elimination mechanism, the nucleophile attacks and the
leaving group leaves at the same time with the formation of
carbon carbon double bond.

+ KBr
Mechanism of E1 elimination reaction 67
• In E1 elimination mechanism, the first step is the ionization of
the substrate (alkyl halide) to give a carbocation. In the second
step, the nucleophile attacks on -hydrogen to give an alkene
as a product.
First step:

Second step:
 68

Difference between E2 and E1 mechanism of reactions

E1 Elimination E2 Elimination
It is unimolecular reaction It is bimolecular reaction
It is first order reaction It is second order reaction
It completes in two steps It completes in one step
Order of ease of E1 elimination in alkyl Order of ease of E2 elimination in alkyl
halides is 3o > 2o > 1o halides is 1o > 2o > 3o
 69

Q: Dehydration of alcohol to form an alkene is an example of ______ reaction:

A) Elimination C) Oxidation
B) Substitution D) Condensation

Explanation: (A) Dehydration of alcohol to form an alkene is an

example of β-elimination reaction.
 Q: Which one of the following alcohols does not involve 70
β-elimination reaction i.e. (dehydration of alcohols) when
treated with conc. H2SO4?

Explanation: (D) (2,2-Dimethyl-1-Propanol) does not give

β-elimination reaction because it does not have β-hydrogen.

 71

Difference between SN and elimination reaction

SN-Reaction -Elimination Reaction
SN reaction takes place in more polar -Elimination reaction takes place in less
solvent e.g. Water polar solvent e.g. Alcohol
δ+
CH 3 -CH 2 -Br δ- + OH -   C2 H 2OH + Br -
δ+
CH 3 -CH 2 -Br δ- + OH -   C2 H 4 + H 2O + Br -
KOH(aqueous) Alcoholic KOH

(ethanol) (ethene)

In SN reaction, attacking nucleophile attacks In -Elimination base attacks on the

the electrophilic carbon atom (-carbon) of -hydrogen atom attached to the -carbon
the alkyl halide. of the alkyl halide.
It takes place comparatively at low It takes place comparatively at high
temperature temperature
 72

Q: For which mechanism in case of alkyl halides, first step

involved is the same:
A) E1 and SN1 C) E2 and SN2
B) SN1 and E2 D) E1 and E2

Explanation: (A) For E1 and SN1 mechanisms in case of alkyl halide first step
involved is the same i.e. the ionization in the presence of polar solvent as
shown in the reaction:
 i  R  X polar solvent
slow step
R 
 X 
 ionization step  same for E1 and SN1 mechanism
Thank you!