Types of Reagent

GOC (Types of Reactions)

SYNOPSIS
ELIMINATION REACTIONS
The reaction in which loss of two atoms or two groups, or one atom and one group from
the substrate takes place, is known as elimination reaction. Elimination reactions are
generally endothermic and therefore require heating.
Types of elimination of reactions
Elimination reactions can be classified into two ways
i) -elimination reactions (or) 1,1-elimination reactions.
ii) -elimination reactions (or) 1,2-elimination reactions.
i) -elimination reactions
An elimination reaction in which either the two groups or atoms are lost from the same
carbon of the substrate is known as -elimination reaction. This reaction is mainly
observed in case of gemdihalides and trihalides.
•• Θ Å
CHX3 ⎯⎯⎯⎯
Alc.KOH/Δ
→ CX2 + X + H
Haloform Dihalocarbene

•• Θ Å
CH2X2 ⎯⎯⎯⎯
Alc.KOH/Δ
→CHX+X+H
••
CH3CHI2 +Zn ⎯⎯
Δ
→CH3CH+ZnI2
ii) -elimination reactions
-Elimination reactions may be divided into two types; one type taking place largely
in solution, the other (pyrolytic eliminations) mostly in the gas phase. In the reactions
in solution, one group leaves with its electrons and the other without, the latter most
often being hydrogen. In these cases, we refer to the former as the leaving group or
nucleofuge.
The -elimination reactions in solution can proceed by four mechanisms(paths).
a) E2 mechanism
b) E1 mechanism
c) E1cB mechanism
d) Ei mechanism

pg. 1
 Types of Reagent

a) E2 mechanism
In the E2 mechanism (elimination, bimolecular), the two groups depart
simultaneously, with the proton being pulled off by a base. The mechanism thus takes
place in one step and is a concerted process.

CH3 − CH2 − CH2 − Br + C2 H5 O → CH3 − CH = CH2 + C2 H5OH + Br 

Key Points:
➢ In 𝐸2 reaction product formation takes place by formation of TS.
➢ In 𝐸2 reaction, both the leaving groups should be antiperiplanar, i.e., both leaving
groups should be in the same plane but should have anti conformation (i.e., angle
is 180°)
➢ The elimination in six membered cyclic compounds proceeds best when leaving
groups are diaxial.
➢ Kinetic studies show that E2 elimination reactions exhibit second-order kinetics.
The rate equation is Rate = k [substrate] [base]
The rate is linearly dependent on the concentrations of the substrate and the
base.
➢ Order of reactivity: 3°R-X > 2°R-X > 1°R-X
➢ It shows primary kinetic isotopic effect.
➢ Good leaving groups are favour (Usually conjugative base of strong acid acts as
good leaving group).
➢ Generally polar aprotic solvents are favour
Examples of polar aprotic solvents:
i) Diethyl ether (𝐶2 𝐻5 − 𝑂 − 𝐶2 𝐻5 )

ii) Acetone
iii) DMSO (dimethyl sulphoxide) [(𝐶𝐻3 )2 𝑆𝑂]....
iv) DMF (dimethyl formide) [(𝐶𝐻3 )2 𝑁𝐶𝐻𝑂]....
v) Dichloro methane [(𝐶𝐻2 𝐶𝑙2 )]....

pg. 2
 Types of Reagent

The energy diagram of an E2 reaction

H
Br + Br + H2O
HO

b) The E1 mechanism
The E1 mechanism is a two-step process in which the rate-determining step is ionization
of the substrate to give a carbocation that rapidly loses a -proton to a base, usually the
solvent. This mechanism normally operates without an added base.
Reaction

Mechanism:
Step 1:

Step 2:

➢ Kinetic studies show that E1-elimination reactions exhibit first-order kinetics, with
a rate equation that has the following form Rate = k [substrate]

pg. 3
 Types of Reagent

The rate is linearly dependent on the concentration of only one compound (the
substrate).
➢ E1 reactions are not accompanied by a primary hydrogen isotope effect.
➢ Order of reactivity: 3° R-X > 2° R-X > 1° R-X
➢ Polar protic medium is usually favourable (Eg. H2 O, NH3 , CH3 COOH, …)
The rate of reactivity of various substrates in an E1 reaction

A comparison of energy diagrams for the E1 reactions of secondary and tertiary

substrates
Number of Products in β-Elimination Reactions
Number of products in a β elimination reaction = Number of different types of β
carbons having hydrogen/s.

CH3 − CH3 − CH2 − X → CH3 − CH = CH2

 

ORIENTATION IN ELIMINATION REACTIONS

Saytzeff Rule
According to this rule, major product is the most substituted alkene, i.e., major
⊕
product is obtained by elimination of 𝐻 from that β-carbon which has the least number
of hydrogens. Product of the reaction in this case is known as Saytzeff product.

pg. 4
 Types of Reagent

Hofmann Rule
According to this rule major product is always least substituted alkene, i.e., major
product is formed from β-carbon which has maximum number of hydrogens. Product of
the reaction in this case is known as Hofmann product.

HOFMANN ELIMINATION REACTIONS

Four cases are known where product formation takes place according to the Hofmann rule in
E2 reactions:
1) Dehydrohalogenation of alkyl halides when leaving group is very poor, i.e., alkyl fluoride
(primary or secondary).

2) Primary and sec. alkyl halides gives Hofmann elimination when the size of the base is
bulky, i.e., sodium or potassium salt of tert butoxide, LDA (lithium diisopropyl amide)....

3) Primary and sec-alkyl halides having quarternary -carbon gives Hofmann elimination

4) If leaving group is bulky, then compound gives Hofmann elimination reaction.

The most common type of large, bulky leaving groups which leads to Hofmann products
   
have positively charged nitrogen  N R 3  or positively charged sulphur  SR 2 
   

pg. 5
 Types of Reagent

Solved Examples E2 reaction:

1)

2)

3)

4)

pg. 6
 Types of Reagent

5)

Compare rate of E2 reaction:

Note: 1) H & X must be anti to each other
2) Alkene character in transition state
3) More acidic β-Hydrogen

1.

2.

3.
Solved Examples E1 reaction:

1.

2.

pg. 7
 Types of Reagent

3.

4.
➢ Carbocation rearrangement during an E1 mechanism
The E1 mechanism involves formation of a carbocation intermediate. The carbocations
are susceptible to rearrangement via either a hydride shifts or a methyl shift.
Ex:
Cl

1) H2O


Mechanism
Cl H H (solvent )
O
− Cl Methyl shift H

2 carbocation 3 carbocation

The carbocation rearrangement occurs between the two core steps of an E1-mechanism.

pg. 8
 Types of Reagent

3)
1.

X and are respectively

4)
*1)
(CH3 )2 C = C (CH3 )2 and (CH3 )3 CCH = CH 2
2) ( CH3 )3 CCH = CH 2 and ( CH3 )2 C = C ( CH3 )2 4. An alkyl chloride produces a single
alkene on reaction with sodium ethoxide
(CH3 )2 CH − C (CH3 ) = CH2 and and ethanol. The alkene further
3)
(CH3 )2 C = C (CH3 )2 undergoes hydrogenation to yield -2-
methylbutane Identify the alkyl chloride
(CH3 )2 C = C (CH3 )2 and from amongst the following
4)
(CH3 )2 CH C (CH3 ) = CH2 1) ClCH 2C ( CH3 )2 CH3
2. Which of the following reactions DO
2) ClCH 2CH 2CH 2CH 3
NOT represent the major product
*3) ClCH 2CH ( CH 3 ) CH 2CH 3

1)
4) CH 3C ( Cl )( CH 3 ) CH 2CH 3

5. When (1R, 2R)-1, 2-Dibromo-1, 2-

diphenyl ethane is treated with alcoholic
2) solution of KOH, the most probable
product would be

1) trans-1, 2-diphenyl ethene

*3) 2) A mixture of cis, trans alkenyl

bromide
3) cis-alkenyl bromide
*4) trans-alkenyl bromide
4) 6. In the following reaction, A and B
3. Major product of the reaction respectively are,
A ⎯⎯ ⎯
HBr
→C2H5Br ⎯⎯
B
→A

*1) C2 H 4 & alcoholic KOH / 

2) C2 H 4Cl & aqueous KOH / 

3) C2 H5OH and aq KOH / 

CH3 − CH = CH − CH3
1)
4) C2 H2 & Br2
CH3 − CH 2 − CH = CH 2
*2)

pg. 9
 Types of Reagent

7. Select the formula representing the

major product of the following reaction

i)

⎯⎯⎯⎯⎯⎯⎯→
CH3CH2OK / CH3CH2OH
 ii)
CH3 − CH 2 − Br

CH3 − CH 2 − CH 2 − Br
iii)

1) 1) i>ii>iii 2) iii>ii>i

3) ii>iii>i *4) i>iii>ii

10. Reaction of trans-2-phenyl-

2) 1bromocyclopentane on reaction with
alcoholic KOH produces (major)

1) 4-phenylcyclopentene
*3) 2) 2-phenylcyclopentene

*3) 1-phenylcyclopentene
4) 3 -phenylcyclopentene
4)
11. How many isomeric pentanols give 2-
8. When the all-cis isomer of C6 H6Cl6 (1, 2, methylbut-2-ene as the major product
, 3,4,5,6-Hexachlorocyclohexane) is on dehydration? (including stereo
heated with alc. KOH ,the most isomers)
probable product is: 1) 4 2) 5

3) 6 *4) 7
12. The major product of the acid catalyzed
dehydration of the following alcohol is
1) *2)

OH

3) 4)
1) 2)

9. Arrange the following alkyl halides in

decreasing order of the rate of  − *3) 4)
elimination reaction with alcoholic
KOH.

pg. 10
 Types of Reagent

13. CH3 H
CH3 CH3
CH3 H H H H Br D H CH3
H H
H Br CH3 Br CH3 H CH3 Br
(I) (II) (III) (IV)
3) D H 4) D H
Which of the following is correct
CH3
decreasing rate of dehydrobromination
on treatment with NaOEt/EtOH?
CH3 MeOK
1) I > II > III > IV *2) II > IV > III > I

3) II > III > IV > I 4) III  IV > II > I 15. H3C Cl

14. The following deuterated 1-bromo-2- Major product is

methyl cyclohexane undergoes E2 CH3 CH3
reaction. Then the product formed is CH3 CH3

1) H3C 2) H3C

CH3
CH3

CH3 CH3

*3) H3C 4) H3C

H H
CH3 CH3

H ANSWER KEY
Q.NO. 1 2 3 4 5 6 7 8 9 10
1) D *2) H
KEY 1 3 2 3 4 1 3 2 4 3
Q.NO. 11 12 13 14 15
KEY 4 3 2 2 3

pg. 11
 Types of Reagent

1) Addition reactions
A reaction in which two molecules combine to yield a single molecule of product is called
an addition reaction.

C C + Y Z C C
Y Z
A) Addition of halogen acids (HX) or Hydrohalogenation:
➢ Order of reactivity: HI > HBr > HCl > HF
➢ Order of reactivity of alkenes:

Mechanism:

Key points
➢ Attack of electrophile is slow step and rate determining step.
➢ Reaction intermediate: Carbocation, rearrangement is possible
➢ Attack of nucleophilic is fast step and attack on most stable carbocation (rearranged
carbocation)
➢ Attacking of nucleophilic occurs on both sides of carbocation

Addition Reactions of Alkenes:

Markovnikov’s Rule:
According to the Markovnikov’s rule the negative part of the reagent adds on that doubly
bonded carbon of the alkene which has least number of hydrogen(s).

pg. 12
 Types of Reagent

Anti-Markovnikov’s Rule:
Unsymmetrical alkenes having the following general structure give addition according to anti-
Markovnikov’s rule.
𝐶𝐻2 = 𝐶𝐻 − 𝐺
Where G is a strong –I group such as:

➢ When unsymmetrical Alkene reacts with unsymmetrical reagent, then we decide major
product through Markovnikov’s Rule / Anti-Markovnikov’s Rule.
Solved Examples:

pg. 13
 Types of Reagent

➢ Cl
Cl
Cl Cl
HCl
+ + +

Peroxide effect or Kharasch effect:

Kharasch observed that the addition of HBr to unsymmetrical alkene in presence of
peroxide follow an opposite course to that suggested by Markovnikov’s. This is termed as anti-
Markovnikov’s or peroxide of Kharasch effect.

pg. 14
 Types of Reagent

Mechanism:
Mechanism of reaction proceeds with three distinct parts: initiation, propagation and
termination.
Initiation: Abstraction of H from H-Br

Propagation: The  -bond is broken and the C-H and C- Br  -bonds are formed

Termination: Two radicals react to form a bond.

Note:
➢ Peroxide effect is effective only in case of HBr and not effective in case of H—F, H—Cl
and H—I
➢ For the radical reaction of H—F and H—Cl, the first propagation step is exothermic and
the second is endothermic, because H—F and H—Cl bonds are stronger than H—Br. So,
overall reaction with H—F and H—Cl is endothermic
➢ For the radical addition of HI the first propagation step is endothermic, because carbon-
iodine sigma bond is weaker than carbon-carbon π-bond.

Solved Examples:

pg. 15
 Types of Reagent

1. The intermediate during the addition of 2) HBr / C6 H 5COOH

HCl to propene in the presence of
peroxide is: *3) ( C6 H5CO )2 O2 / HBr
 +
1) CH3 CHCH2Cl *2) CH3 CHCH3 4) HBr / C6 H 5OH

 + 4. In which of the following will Kharasch

3) CH3CH2 CH2 4) CH3CH2 CH2
effect operate?
2. The reaction
1) CH3 − CH 2 − CH = CH 2 + HCl

*2) CH 3 − CH 2 − CH = CH 2 + HBr

with HBr gives 3) CH3 − CH = CH − CH3 + HBr

4) CH 3 − CH 2 − CH = CH 2 + HI
1)
5. H2C = CH − CH2 − CH3 ⎯⎯
x
→ C H 2 − CH 2 − CH 2 − CH3 .
|
Br
*2) Find the X

1) HBr / C6 H 5COOH
3)
2) Br2 / CCl4

*3) HBr / peroxide

4)
3. Anti Markovnikov’s addition takes 4) Br2 / H 2O
place in the presence of

1) HBr

pg. 16
 Types of Reagent

6.
4)
II) Ph- CH= CH-Ph
9. Which of the following compounds will
III. Ph − CH = CH − CH3 give in the presence of peroxide a
product different from that obtained in
IV) CH3 − CH = CH − CH3 the absence of peroxide

Correct order for electrophilic addition 1) 1-butene 2) 2-butene, HCl

reaction of given compound follows *3) 1-butene, HBr 4) 2-butene, HBr
*1) I>II>III>IV 2) I>III>II>IV 10. Arrange the following hydrogen halides
3) I>II>IV>III 4) I>IV>III>II in order of their decreasing reactivity
with propene.
7. CH3 − CH = CH2 + HCl ⎯⎯⎯
H2O2
→ Major
1) HCl  HBr  HI 2) HBr  HI  HCl
product
*3) HI  HBr  HCl 4) HCl  HI  HBr
*1) CH 3 − CH ( Cl ) − CH 3
11. Arrange the following reactions in
CH3 − CH 2 − CH 2 − Cl decreasing order of reactivity towards
2)
electrophilic addition
3) CH 2 = CH − CH 2 − Cl H3C
C CH2
HCl
H3C
C CH2
HCl
H3C
C CH2
HCl

H3C H3C O H3C NH

4) CH3 − CH ( OH ) − CH3 (P) (Q) (R)

1) P>Q>R 2) Q>R>P
*3) R>Q>P 4) P=Q=R
12. The reaction of 𝐶6 𝐻5 𝐶𝐻 = 𝐶𝐻𝐶𝐻3 with
8. HCl in presence and absence of
Major product X will be peroxides give the products having the
structures
H5C6 CH2 CH CH3 and H5C6 CH CH2 CH3

1) Cl Cl

H5C6 CH CH2 CH3 and H5C6 CH2 CH CH3

1)
2) Cl Cl

H5C6 CH CH2 CH3 and H5C6 CH CH2 CH3

*3) Cl Cl

CH CH CH3 CH2 CH CH3

2) and Cl

4) Cl

13. Predict the major product in the

following reaction?
*3)

pg. 17
 Types of Reagent

O Br O O
H3C HBr
H3C
O
O Br O
CH2

O O CH3 CH3
3) 4)
H3C
H3C
O
O
Br
CH3 ANSWER KEY
*1) 2) Br
Q.NO. 1 2 3 4 5 6 7 8 9 10
KEY 2 2 3 2 3 1 1 3 3 3
Q.NO. 11 12 13
KEY 3 3 1

Introduction to nucleophilic addition reactions

The electrophilicity of a carbonyl group derives from resonance effects as well as
inductive effects.

−
O O O

C C C
+
Resonance Induction

One of the resonance structures exhibits a positive charge on the carbon atom,
indicating that the carbon atom is deficient in electron density (  + ) . Inductive effects
also render the carbon atom deficient in electron density. As a result, this carbon atom
is particularly electrophilic and is susceptible to attack by a nucleophile. Molecular
orbital calculations suggest that nucleophilic attack occurs at an angle of approximately
107 to the plane of the carbonyl group, and in the process, the hybridization state of
the carbon atom changes.

pg. 18
 Types of Reagent

sp2 sp3
(Trigonal planar) (Tetrahedral)

The carbon atom is originally sp2 hybridized with a trigonal planar geometry. After the
attack, the carbon atom is sp3 hybridized with a tetrahedral geometry.

In general, aldehydes are more reactive than ketones towards nucleophilic attack. This
observation can be explained in terms of both steric and electronic effects.
a) Steric effects
A ketone has two alkyl groups (one on either side of the carbonyl) that contribute
to steric hindrance in the transition state of a nucleophilic attack. In contrast, an
aldehyde has only one alkyl group, so the transition state is less crowded and lower
in energy.
b) Electronic effects
A ketone has two electron-donating alkyl groups that can stabilize the + on the
carbon atom of the carbonyl group.
In contrast, aldehydes have only one electron-donating group.
O O

R + R R + H
a ketone an aldehyde

has two electron-donating alkyl groups has only one electron-donating alkyl
group that stabilize the partial positive charge that stabilizes the partial positive
charge
The + charge of an aldehyde is less stabilized than a ketone. As a result, aldehydes
are more electrophilic than ketones and therefore more reactive.
In general, the reactivity order of aldehyde and ketones towards nucleophilic
addition is
O O O O
  
R H Ph H R R Ph Ph

pg. 19
 Types of Reagent

Aldehydes and ketones react with a wide variety of nucleophiles. Some nucleophiles
require basic conditions, while others require acidic conditions.
Mechanism of nucleophilic addition under basic conditions

O O O OH
Nuc H H
Nuc Nuc

Aldehydes and ketones also react with a wide variety of other nucleophiles under acidic
conditions.

Mechanism of nucleophilic addition under acidic conditions

H
O O OH
H A Nuc
Nuc

In acidic conditions, the first step plays an important role. Specifically, protonating the
carbonyl group generates a very powerful electrophile.
H H
O O O
H A

Very powerful electrophile

It is true that the carbonyl group is already a fairly strong electrophile; however, a
protonated
carbonyl group bears a full positive charge, rendering the carbon atom even more
electrophilic. This is especially important when weak nucleophiles, such as H2O or ROH,
are employed.
When a nucleophile attacks a carbonyl group under either acidic or basic conditions,
the position of equilibrium is highly dependent on the ability of the nucleophile to
function as a leaving group.
Order of reactivity of carbonyl compounds towards nucleophilic addition
3. Order of reactivity of carbonyl compounds towards nucleophilic addition

pg. 20
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Solved Examples:

1. Reactivity of HCHO (I), CH3CHO (II) IV) p-Tolylaldehyde

and C6 H5CHO (III) is in order *1) I < IV < III < II 2) I < II < III < IV
(towards nucleophilic addition) 3) I > IV > III < II 4) III < I < II < IV
1) I > III > II 2) III > II > I 3. Arrange the following compounds in
decreasing order of nucleophilic
3) I = II > III *4) I > II > III
addition reaction
2. The correct order of reactivity of the
following towards nucleophilic
addition
I) Acetophenone
1) II > IV > III > I *2) I > II > III > IV
II) p-Nitrobenzaldehyde.
3) IV > III > II > I 4) II > III > IV > I
III)Benzaldehyde

pg. 21
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4. Arrange the following compounds in 5. Arrange the compounds in order of

decreasing order of nucleophilic decreasing reactivity for nucleophilic
addition reaction addition reaction

1) I > IV > II > III 2) I > II > III > IV

*3) II > III > I > IV 4) II > I > III > IV
*1) II > V > I > IV > III
2) III > IV > I > V > II
ANSWER KEY
3) II > I > V > III > IV Q.NO. 1 2 3 4 5
KEY 4 1 2 1 3
4) IV > III > V > I > II

(1) ELECTROPHILIC AROMATIC SUBSTITUTION REACTIONS

Most important reactions of aromatic compounds are those in which an electrophile
replaces one of the hydrogen atoms of the ring.
H E

+ E A + H A

This reaction is known as electrophilic aromatic substitution (EAS).

The cloud of  -electrons above and below the plane of its ring makes benzene a
nucleophile, so it reacts with an electrophile ( E ).
Arenium ion mechanism

E
+ − slow
+ E A H + A

Step-1
The carbocation formed in this step is an arenium ion or cyclohexadienyl cation,
Wheland intermediates and also known as a -complex. It is an allylic carbocation and
is stabilized by the electron delocalization represented by resonance.

pg. 22
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E
E E E
H
H H H 

Resonance
Arenium ion hybrid of
(a delocalized cyclohexadienyl cation) Arenium ion

Step-2

E E
fast
H + H A
A
If the carbocation intermediate that is formed from the reaction of benzene with an
electrophile were to react similarly with a nucleophile, then the addition product would
not be aromatic. But, if the carbocation loses a proton from the site of electrophilic
addition and form a substitution product, then the aromaticity of the benzene ring will
be restored.
The reaction leading from
benzene and an electrophile to the
arenium ion is highly endothermic,
because the aromatic stability of the
benzene ring is lost. The reaction
leading from the arenium ion to the
substituted benzene, by contrast, is
highly exothermic because it restores
aromaticity to the system.
Kinetics
Of the following two steps, step-1 (the formation of the arenium ion) is usually the
rate-determining step in electrophilic aromatic substitution because of its higher free
energy of activation. Step-2, the removal of a proton, occurs rapidly relative to step-1
and has no effect on the overall rate of reaction. It follows second order kinetics with the
rate equation.
Rate = k[substrate] [electrophile]
Isotope effects
If the hydrogen ion departs before the arrival of the electrophile or if the arrival and
departure are simultaneous, there should be a substantial isotope effect i.e., deuterated
substrates should undergo substitution more slowly than non-deuterated compounds
because, in each case, the C—H bond is broken in the rate-determining step. However,
in the arenium ion mechanism, the C—H bond is not broken in the rate-determining
step, so no isotope effect should be found.

pg. 23
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But, reactions in which energy difference between transition state-1 and transition
state-2 is negligible, isotopic effect is observed because arenium intermediate might get
rid of its positive charge by expelling H ( or ) E with equal ease.

Ex: Sulfonation and iodination of benzene.

REACTIVITY
The substituents that donate electrons to the benzene ring increase benzene
nucleophilicity and stabilize the partially positively charged transition state, thereby
increasing the rate of electrophilic aromatic substitution; these are called activating
substituents. In contrast, substituents that withdraw electrons from the benzene ring
decrease benzene nucleophilicity and destabilize the transition state, thereby decreasing
the rate of electrophilic aromatic substitution; these are called deactivating substituents.

G G # + G

+ E + +
+ +

H E H E
G releases Transition state Arenium ion is
electrons is stabilized stabilized

G G # + G

+ E + +
+ +
+
H E H E
G withdraws Transition state Arenium ion is
electrons is destabilized destabilized

If G is an electron-releasing group (relative to hydrogen), the reaction occurs faster

than the corresponding reaction of benzene.
If G is an electron-withdrawing group, the reaction is slower than that of benzene.
The electron-withdrawing and electron-releasing abilities of substituents affect the
relative free energies of activation of electrophilic aromatic substitution reactions.

Relative rates of electrophilic aromatic substitution

Z donates electrons Y withdraws electrons
to the benzene ring to the benzene ring

Z Y

> >

pg. 24
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The effects of substituents on the reactivity of benzene ring towards electrophilic

aromatic substitution

Activating substituetns Most activating

O-
NR2
NHR
Strongly
NH2 activating
OH
OR
O
NHCR Moderately
O activating

OCR
R Ortho/para
directing
Ar Weakly
CH CHR activating
Standard of comparison H
Deactivating substituents
F
Cl Weakly
Br deactivating
I
O
CH
O
CR
O
Moderately
COR deactivating
O
COH
O
CCl Meta directing
C N
SO3H
NH3 NH2R Strongly
deactivating
NHR2 NR3
NO2
Most deactivating

pg. 25
 Types of Reagent

Solved Examples:
Order of Reactivity of different compounds towards electrophilic aromatic substitution

pg. 26
 Types of Reagent

1. Which of the following carbocation 5. Arrange the following set of compounds

expected to be least stable in the order of their decreasing relative
reactivity with an electrophile

1) 2)
*1) I>II>III 2) I=II=III
3) I<II<III 4) I>II<III
6. Which of the following species is
expected to yield maximum percentage
of meta substituted product
*3) 4)
1) ArCH3 2) ArCH2Cl
2. What is the slow and rate determining
stage of electrophilic substitution of
3) ArCHCl2 *4) ArCCl3
benzene?
*1) Formation of carbocation

2) Loss of H  from carbocation

3) Attack of electrophile
7.
4) Formation of electrophile
*1) E  Attacks preferably at o-position
3. The number of hybrid orbitals in
to CH3
Arenium ion
1) 20 2) 24 2) E  Attacks preferably at o-position
3) 18 *4) 19 to CD3

3) E  Can attack equally at any of the

four positions
4) Not predictable here
4.
8. Which among the following is very
strong o-, p-directing group?

1) −Cl 2) - O R

3) − NH 2
( −)
*4) −O
Rate of reaction is

*1) r1  r2 2) r2  r1

3) r2 = r1 4) r2  r1

9.

pg. 27
 Types of Reagent

The correct arrangement for decreasing

order of reactivity towards electrophilic
substitution reaction is 3)
*1) III  I  II  IV 2) IV  I  II  III
3) III  IV  II  I 4) II  IV  III  I
10. The correct order of reactivity towards 4)
the electrophilic substitution of the 13. Amongst the following, the moderately
compounds Aniline (I), Benzene (II) and activating group is
Nitrobenzene (III) is,
1) -NHR *2) −𝑁𝐻𝐶𝑂𝐶𝐻3
*1) I  II  III 2) III  II  I
3) −𝑁𝑅2 4) −𝐶𝐻3
3) II  III  I 4) I  II  III
11. The correct order of rate of reaction of
the following compounds with E + will
be

14.
Identify the position where electrophilic
1) II  VI  III  V  I  IV aromatic substitution (EAS) is most
favorable
2) IV  I  V  VI  II  III
1) A *2) B
3) V  II  III  VI  I  IV
3) C 4) D
*4) V  III  II  VI  I  IV
12. Which of the following is major product
for the mono nitration of phenyl
benzoate,

15.
Correct order of rate of EAS
(electrophilic aromatic substitution) is
1) c  b  a  d 2) c  d  a  b
1)
3) a  b  c  d *4) c  d  b  a
16. Increasing order of rate of reaction with
*2) 𝐵𝑟2 /𝐴𝑙𝐶𝑙3 is

pg. 28
 Types of Reagent

1) I  II  III *2) III  II  I

3) III  I  II 4) I  III  II
20. Which position will be attacked most
( +
rapidly by the nitronium ion − NO2 )
when the compound undergoes
nitration with 𝐻𝑁𝑂3 /𝐻2 𝑆𝑂4
*1) iii  i  ii  iv 2) iv  ii  i  iii
3) ii  iv  iii  i 4) iv  ii  iii  i
17. Arrange the following in decreasing
order of reactivity towards EAS
(electrophilic aromatic substitution) 1) A 2) B
3) C *4) D
21. Which of the following will undergo
nitration slower than benzene

*1) A  B  C 2) C  B  A
3) A  C  B 4) C  A  B 1) 2)

18. *3) 4)
Arrange the decreasing order of rate of 22. Which of the following is the most
electrophilic aromatic substitution reactive towards electrophilic aromatic
1) A  B  C  D *2) A  C  B  D substitution?

3) B  A  C  D 4) B  C  A  D
19. Arrange in their decreasing order of
rate of electrophilic aromatic
substitution

pg. 29
 Types of Reagent

1) iii  ii  i 2) ii  iii  i
3) i  iii  ii *4) i  ii  iii
26. Rank in order of increasing rate of
reaction towards EAS with bromine in
23. In which case, EAS will not be in meta the presence of 𝐹𝑒𝐵𝑟3
position

1) 2)
*1) B  A  C 2) B  C  A

3) *4) 3) A  B  C 4) A  C  B

24. The major product formed in the

27.
reaction is Identify the position where EAS can
takes place
*1) 1 2) 2
3) 3 4) 4
1) *2)

ANSWER KEY
Q.NO. 1 2 3 4 5 6 7 8 9 10
KEY 3 1 4 1 1 4 1 4 1 1
3) 4) Q.NO. 11 12 13 14 15 16 17 18 19 20
KEY 4 2 2 2 4 1 1 2 2 4
25. Increasing order of rate of reaction with
Q.NO. 21 22 23 24 25 26 27
Conc HNO3 / H 2 SO4 is KEY 3 1 4 2 4 1 1

pg. 30
 Types of Reagent

ALIPHATIC NUCLEOPHILIC SUBSTITUTION

In nucleophilic aliphatic substitution the attacking reagent (the nucleophile) brings
an electron pair to the substrate, using this pair it forms a new bond and the leaving
group (the nucleofuge) comes away with an electron pair.

R X + Y R Y + X

Nucleophile Y may be neutral or negatively charged; RX may be neutral or positively

charged; so there are four charge types,

Type-1 R I + OH R OH + I

Type-2 R I + NMe3 R NMe3 + I

Type-3 R NMe3 + OH R OH + NMe3

Type-4 R NMe3 + H2S R SH2 + NMe3

When Y is the solvent, the reaction is called solvolysis.

The SN 2 mechanism

➢ The reaction is a one-step process with no intermediate.

➢ In this mechanism, there is backside attack. The nucleophile approaches the substrate
from a position 180 away from the leaving group.
➢ The C—Y bond is formed as the C—X bond is broken to generate transition state.

H H H # H
Y + H C X Y X Y C H + X
H H H

➢ The energy necessary to break the C—X bond is supplied by simultaneous formation of
the C—Y bond. The group X must leave as the group Y comes in, because at no time can
the carbon have more than eight electrons in its outer shell.
➢ When the transition state is reached, the central carbon atom has gone from its initial
sp3 hybridization to an sp3d state.

➢ Since both the nucleophile and the substrate are involved in the rate-determining step
(the only step, in this case), the reaction should be first order in each component, second
order overall and satisfy the rate expression.
Rate = k[RX][Y] (Order = 2, molecularity = 2)

pg. 31
 Types of Reagent

If the solvent is nucleophile, kinetics will be first order with respect to substrate and
with respect to nucleophile order is zero.
➢ The mechanism predicts inversion of configuration when substitution occurs at a chiral
carbon. This inversion of configuration that proceeds through transition state is called
the Walden inversion. (Stereo specific and stereo selective)
H H
Y + C X Y C + X
H H
➢ H H

An energy diagram of SN2 mechanism.

The SN 1 mechanism

➢ SN1 mechanism (substitutional nucleophilic unimolecular) consists of two steps.

slow
Step-1 R X R + X

fast
Step-2 R + Y R Y

➢ The first step is a slow ionization of the substrate and is the rate-determining step.
In the SN1 mechanism, ionization of a leaving group to form the carbocation is
always assisted by the solvent, since the energy necessary to break the bond is largely
recovered by solvation of R and of X .

–X Y
X Y
➢
➢ It is a first-order reaction following the rate law
Rate = k[RX] (order = 1, molecularity = 1)

pg. 32
 Types of Reagent

Since the slow step involves only the substrate, the rate should be dependent only on
the concentration of that. Although the solvent is necessary to assist in the process of
ionization, it does not enter the rate expression, because it is present in large excess.
➢ Non-stereo specific and non-stereo selective
➢ Experimentally product is partial racemic mixture (inverted form is 5-10% greater than
retention form) (extent of racemic mixture ∝ stability of carbocation)

An energy diagram of SN1 process

1. The reaction 4. For a nucleophillic substitution reaction

−
C2H5Cl + OH → C2H5OH + Cl is − the rate was found in the order RI > RBr
> RCl > RF then the reaction could be
1) S N 1 *2) S N 2
1) S N 1 Only
3) S E 1 4) S E 2
2) S N 2 Only
2. The absolute configuration of a
molecule changes during the reaction *3) Either S N 1 or S N 2

1) S N 1 4) Neither S N 1 nor S N 2

*2) S N 2 5. Which of the following alkyl halide is

hydrolysed by S N 1 mechanism
3) free radical substitution
1) CH3Cl
4) S E 2
2) CH3 − CH2 − Cl
3. S N 2 reaction leads to

*1) inversion of configuration 3) CH3 − CH 2 − CH 2 − Cl

2) retention of configuration *4) ( CH3 )3 CCl

3) partial racemisation
6. Which of the following is correct order of
4) no racemisation reactivity

pg. 33
 Types of Reagent

1) Vinyl chloride > Allyl chloride >

Propylchloride
2) Propylchloride > Vinyl chloride >
Allyl chloride
*1) 2)
*3) Allyl chloride > Propylchloride >
Vinyl chloride
4) Allyl chloride < Vinyl chloride >
Propylchloride
7. SN 2 reactions are 3) 4)
1) Stereospecific but not stereoselective 11. In SN 2 reactions the correct order of the
2) Stereoselective but not stereospecific reactivity for the following compounds
CH3 Cl, CH3 CH2 Cl, (CH3 )2 CHCl and (CH3 )3 CCl
*3) Stereoselective as well as
stereospecific 1) CH3 CH2 Cl > CH3 Cl > (CH3 )2 CHCl >
(CH3 )3 CCl
4) Neither stereoselective nor
stereospecific 2) (CH3 )2 CHCl > CH3 CH2 Cl >
CH3 Cl(CH3 )3 CCl
8. What is the order of reactivity of the
following compounds towards dilute 3) CH3 Cl > (CH3 )2 CHCl > CH3 CH2 Cl >
aqueous NaOH? (CH3 )3 CCl
*4) CH3 Cl > CH3 CH2 Cl > (CH3 )2 CHCl >
(CH3 )3 CCl
12. Which of the following halides would
undergo nucleophilic substitution more
readily
1) 1-Chloro-1-Butene
*1) I < III < II < IV 2) II < I < III < IV
2) 2-Chloro-1-Butene
3) IV < II < III < I 4) III < II < I < IV
*3) 3-Chloro-1-Butene
9. The correct order of decreasing S N 2
4) 4-Chloro-1-Butene
reactivity
13. Which one of the following compounds
*1) RCH2 X  R 2CHX  R 3CX will give enantiomeric pair on
treatment with HOH
2) RCH2 X  R 3CX  R 2CHX

3) R 2CHX  R 3CX  RCH2 X

4) R 3CX  R 2CHX  RCH2 X

1) 2)
10. Which one of the following compounds
will be most reactive for S N 1 reaction?

pg. 34
 Types of Reagent

*3) 4)
14. The correct order of reactivity of
following compounds in SN 1 reaction is

a) C6 H 5CH 2 Br 1) S>R>Q>P 2) R>S>Q>P

b) C6 H5CH ( C6 H5 ) Br 3) Q>R>S>P 4) P>Q>R>S

19. arrange the following compounds in
c) C6 H5CH ( CH3 ) Br decreasing order of 𝑆𝑁1 reaction

d) C6 H5C ( CH3 )( C6 H5 ) Br
*1) d > b > c > a 2) d > c > b > a
3) a > b > c > d 4) a > c > d > b
15. Which of the following species is most
reactive in an SN2 reaction? 1) P>Q>R>S 2) R>Q>P>S

1) CH 3CH 2 − Cl 2) CH3CH 2 − Br 3) Q>P>R>S 4) Q>P>S>R

20. Following is the list of four halides.
*3) CH3CH 2 − I 4) CH 3CH 2 − F Select correct sequence of decreasing
order of reactivity for SN 1 reaction using
16. arrange the following compounds in
the codes given below.
decreasing order of 𝑆𝑁2 reaction

I)
1) P>Q>R>S 2) R>P>Q>S
II) 𝐶6 𝐻5 − 𝐶𝐻2 − 𝐵𝑟
3) Q>R>P>S *4) R>Q>P>S
17. arrange the following compounds in
decreasing order of 𝑆𝑁2 reaction
III)
IV) 𝐶6 𝐻5 − 𝐶𝐻2 − 𝐼
Codes:
1) III>I>IV>II 2) III>I>II>IV
1) P>R>S>Q 2) P>Q>R>S
3) I>III>IV>II 4) I>III>II>IV
*3) P>R>Q>S 4) R>Q>S>P
21. Order of rate of reaction with 𝐴𝑔𝑁𝑂3 or
18. Arrange the following compounds in
rate of 𝑆𝑁 1
decreasing order of 𝑆𝑁1 reaction

pg. 35
 Types of Reagent

4) Neither stereoselective nor

stereospecific
25. Consider the following bromides

1) I > III > II 2) II > III > I 1)

3) I > II > III 4) III > I > II
22. Pick up the correct order of reactivity of
the following compounds in 𝑆𝑁1 2)
reactions

3)
1) The correct order of 𝑆𝑁 1 reactivity is
1) a > b > c 2) b > c > a
2)
3) b > a > c 4) c > b > a
26. Which of the following compounds
3) highly favours SN 2 mechanism
1) CH3 − CH2 − Br
4)
2) CH3 − O − CH2 Br
23. Which of the following will be the least
3) C6 H5 − CO − CH2 Br
reactive towards nucleophilic
substitution? 4) CH3 − C(CH3 )2 CH2 Br

ANSWER KEY
1) 𝐶2 𝐻5 𝐶𝑙 2) Q.NO. 1 2 3 4 5 6 7 8 9 10
KEY 2 2 1 3 4 3 3 1 1 1
Q.NO. 11 12 13 14 15 16 17 18 19 20
KEY 4 2 3 1 3 4 3 4 3 1
3) 4) Q.NO. 21 22 23 24 25 26
24. S N2 reactions are KEY 3 1 4 3 2 3

1) Stereospecific but not stereoselective

2) Stereoselective but not stereospecific
3) Stereoselective as well as
stereospecific

pg. 36