Reaction Mechanism

Topic Page No.
Theory 01 - 10
Exercise - 1 11 - 19
Answer Key 36 - 40
Contents
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Syllabus
REACTION MECHANISM
Organic Reagents, Alkyl halides : Nucleophilic substitution reactions, elimination reactions,
Alcohols : dehydration, reaction with sodium, phosphorus halides, ZnCl
2
/concentrated HCl,
Ethers : Preparation by Williamsons Synthesis; Nucleophilic substitution reactions.
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F-106, Road No.2 Indraprastha Industrial Area, End of Evergreen Motor,
BSNL Lane, Jhalawar Road, Kota, Rajasthan (324005) Tel. : +91-744-242-5022, 92-14-233303
REACTION MECHANISM # 1
REACTION MECHANISM
(Alkyl halides, Alcohols & Ethers)
KEY CONCEPTS
Types of solvents
Polar protic solvent Polar aprotic solvent
Capable of H-bonding Incapable of H-bonding
even thought polar protic solvents are not the best SN2 and E2, these reactions are often run in these
solvents because nucleophiles and bases are often easily prepared in these solvents.
Solvents Non Polar Polar Protic Aprotic
1. H
2
O ! !
2. CH
3
OH ! !
3. CH
3
CH
2
OH ! !
4. HCOOH ! !
5. CH
3
COOH ! !
6. NH
3
! !
7. ! !
8. ! !DMSODimethyl sulphoxide
9. ! !DMF Dimethyl formamide
10. ! !DMA Dimethyl acetamide
11. ! " !
12. ! " !
13. CCCCCC! " !
Organic Reagents
Organic reagents can be classified in two categories :
(1) Electrophile : Electron pair acceptor are electrophile.
(2) Nucleophile : Electron pair donor are nucelophile.
(1) Electrophiles
It can be classified into two categories :
(A) Charged electrophiles (E
) (B) Neutral electrophiles (E)

(A) Charged electrophiles : Positively charged species in which central atom has incomplete octet
is charged electrophile
H
, X

,

R
, , = O,
Note : Generally All cations are charged electrophiles except cations of IA, IIA group elements,
Al
+++
and .
(B) Neutral electrophiles : It can be classified into three categories :
(!B) Neutral covalent compound in which central atom has incomplete octet is neutral
electrophile, AlX
3
,
2

H C
,
2

X C
BF
3
, BCl
3
, BBr
3
, BI
3
(!!B) Neutral covalent compound in which central atom has complete or expended octet and
central atom has unfilled -d-shell is neutral electrophile
SnCl
4
, SiCl
4
, SbCl
5
Note :
(i) Cl
2
, Br
2
and I
2
also behave as neutral electrophiles.
(ii) Electrophiles are Lewis acids.
(2) Nucleophiles
Nucleophiles can be classified into three categories :
(A) Charged nucleophiles : Negatively charged species are charged nucleophiles.
, O , R , C
3
, , H, R
(B) Neutral nucleophiles : It can be classified into two categories :
Neutral covalent compound, in which central atom has complete octet, has at least one lone
pair of electrons and all atoms present on central atom should not be electronegative, is neutral
nucleophile.
, R , R
2
, R
3
, NH
2
(Nitrogen nucleophile)
H H, R H, R R (Oxygen nucleophiles)
H H, R H, R R (Sulphur nucleophiles)
H
3
, R H
2
, R
2
H, R
3
(Phosphorus nucleophiles)
(C) Ambident nucleophile : Species having two nucleophilic centres, one is neutral (complete
octet and has at least one lone pair of electrons) and other is charged (negative charge)
behaves as ambident nucelophile.
, = O ,
Note :
(A) Organometallic compounds are nucleophiles.
(B) Nucleophiles are Lewis bases.
Organic compounds which behave as electrophile as well as nucleophile :
Organic compound in which carbon is bonded with electronegative atom (O, N, S) by multiple bond/
bonds behaves as electrophile as well as nucleophile.
H C R
||
O

,
R C R
||
O

,
OH C R
||
O

,
Cl C R
||
O

OR C R
||
O
,
2
NH C R
||
O
, RCN,
R
Note : During the course of chemical reaction electrophile reacts with nucleophile.
NUCLEOPHILIC SUBSTITUTION REACTIONS (S
N
) AT SATURATED CARBON
NUCLEOPHILIC SUBSTITUTION REACTIONS (S
N
) :
Replacement (displacement) of an atom or group by an other atom or group in molecule is known as
substitution reaction. If substitution reaction is brought about by a nucleophile then it is known as nucleo-
philic substitution reaction. Generally substitution takes place at sp
3
carbon.
R!g + R Nu +
UNIMOLECULAR NUCLEOPHILIC SUBSTITUTION REACTIONS (S
N
1) :
Nucleophilic substitution which involves two step process
(a) First step : - Slow step involves ionisation to form carbocation
R!g R
+
+ !g
(b) Second step : - Fast attack of nucleophile on carbocation to result into product .
R
+
+ Nu

RNu
S
N
1

Reaction of Alkyl halide
Mechanism :
) rds ( step Slow
halide alkyl
of Ionisation

Characteristics of S
N
1 reactions :
1. It is unimolecular, two step process.
2. Carbocation intermediate is formed so rearrangement is possible in S
N
1 reaction.
3. It is first order reaction
4. Kinetics of the reaction Rate [Alkyl halide]
Rate of S
N
1 reaction is independent of concentration and reactivity of nucleophile.
5. Energetics of the S
N
1
Figure : Free energy diagram for the S
N
1 reaction.
S
N
1 Reaction of Alcohols
(A) Reaction with hydrogen halides
A common method is to treat the alcohol with a hydrohalic acid, usually HI or HBr. These acids are used
to convert alcohols to the corresponding alkyl halides.
(i) In acidic solution, an alcohol is in equilibrium with its protonated form. Protonation converts the
hydroxy group from a poor leaving group to a good leaving group (H
2
O). If the alcohol is
protonated all the usual substitution and elimination reactions are feasible, depending on the structure
(1, 2, 3) of the alcohol.
(ii) Halides are anions of strong acids, so they are weak bases. Solutions of HBr and HI contain nucleo-
philic and ions.
(iii) Concentrated hydrobromic acid rapidly converts t-Butyl alcohol to t-Butyl bromide. The strong acid
protonates the hydroxyl group, converting it to a good leaving group. The hindered tertiary carbon
atom cannot undergo S
N
2 displacement, but it can ionise to a tertiary carbocation. Attack by bromide
ion gives the alkyl bromide. The mechanism is similar to other S
N
1 mechanism.
(iv) 1-Butanol reacts with sodium bromide in concentrated sulfuric acid to give 1-Bromobutane by an S
N
2
displacement.
ol tan bu 1
OH CH ) CH ( CH
2 2 2 3

4 2
SO H , NaBr

%) 90 (
e tan bromobu 1
Br CH ) CH ( CH
2 2 2 3

Protonation converts the hydroxy group to a good leaving group, but ionization to a primary carbocation
is unfavourable. The protonated unbranched primary alcohol is well suited for the S
N
2 displacement.
(v) Secondary alcohols also react with HBr to form alkyl bromides usually by the S
N
1 mechanism.
e.g.

HBr

(vi) HCl (Hydrochloric acid) reacts with alcohols in much the same way that as the hydrobromic acid.
(vii) Chloride ion is a weaker nucleophlile than bromide ion because it is smaller and less polarizable.
Lewis acid, such as ZnCl
2
, is sometimes necessary to promote the reaction of HCl with primary and
secondary alcohols.
Mechanism :
R OH
2
H O R

RDS
O
2
H

R
R X
Reactivity of HX : HI > HBr > HCl
Reactivity of ROH : allyl " benzyl > 3 > 2 > 1
S
N
1

REACTIONS OF ETHERS
(A) Reaction with HX
Ethers are unreactive towards most bases, but they can react under acidic conditions. A protonated ether
can undergo substitution or elimination with the expulsion of an alcohol. Ethers react with conc. HBr and
HI because these reagents are sufficiently acidic to protonate the ether, while bromide iodide are good
nucleophiles for the substitution.
If R or R is 3 then mechanism will be S
N
1 otherwise S
N
2 .
Mechanism :
R O R`
ROH

O
X
R` X
S
N
2

Reaction of Alkyl halide :
Mechanism :

+
Characteristic of S
N
2
1. It is bimolecular, one step concerted process
2. It is second order reaction because in the rds both species are involved
3. Kinetics of the reaction # rate [alkyl halide] [nucleophile]
rate = k[alkyl halide] [nucleophile]
If the concentration of alkyl halide in the reaction mixture is doubled, the rate of the nucleophilic
substitution reaction is double. If the concentration of nucleophile is doubled the rate of reaction is also
double. If the concentration of both are doubled then the rate of the reaction quadriples.
4. Energetics of the reaction :
Figure : A free energy diagrams for S
N
2 reaction
5. No intermediates are formed in the S
N
2

reaction, the reaction proceeds through the formation of an
unstable arrangment of atoms or group called transition state.
6. The stereochemistry of S
N
2 reactions $ As we seen earlier, in an S
N
2 mechanism the nucleophile
attacks from the back side, that is from the side directly opposite to the leaving group. This mode
of attack causes an inversion of configuration at the carbon atom that is the target of nucleophilic
attack. This inversion is also known as Walden inversion.

Inversion

S
N
2 Reaction of Alcohol
(A) Reaction with HX : The protonated | unbranched primary alcohol is well suited for the S
N
2 reaction.
Mechanism :
R OH
2
H O R

O
X
R X + H
2
O
e.g
alcohol Pentyl n
OH CH CH CH CH CH
2 2 2 2 3

chloride Pentyl n
Cl CH CH CH CH CH
2 2 2 2 3
(B) Reaction with phosphorus trihalides

Several phosphorus halides are useful for converting alcohols to alkyl halides. PBr
3
, PCl
3
, & PCl
5
work
well and are commercially available.
Phosphorus halides produce good yields of most primary and secondary alkyl halides, but none works well
with tertiary alcohols. The two phosphorus halides used most often are PBr
3
and the P
4
/I
2
combination.
3R OH + PX
3
3R X + H
3
PO
3
Mechanism :
Step : 1
Step : 2 RCH
2
X+ HOPX
2
Remarks
The mechanism for the reaction involves attack of the alcohol group on the phosphorus atom, displacing
a halide ion and forming a protonated alkyl dihalophosphite
In second step a halide ion acts as nucleophile to displace HOPX
2
, a good leaving group due to the
electronegative atoms bonded to the phosphorus.
(C) Reaction with thionyl chloride in presence of pyridine
Thionyl chloride (SOCl
2
) is often the best reagent for converting an alcohol to an alkyl chloride. The by
products (gaseous SO
2
and HCl) leave the reaction mixture and ensure that there can be no reverse
reaction.
R OH + Cl S Cl
||
O

Pyridine
Heat
R Cl + SO
2
+ HCl
Mechanism :

+
H
R O S
O
Cl
:
..
.. ..
..
Chlorosulphite ester
+ HCl

R Cl + SO
2
In the first step, the nonbonding electrons of the hydroxy oxygen atom attack the electrophilic sulphur atom
of thionyl chloride. A chloride ion is expelled a proton and gives test of chloro sulphite ester.
Second step is an S
N
2 mechanism
e.g.
Py
SOCl
2

Reaction with thionyl chloride
ROH + SOCl
2

RCl + SO
2
+ HCl
In this mechanism an internal nucleophile attacks from the same side of leaving group , means retension
of configuration . It is an S
N
i mechanism , where i means internal
Mechanism :

+
H
R O S
O
Cl
:
..
.. ..
..
Chlorosulphite ester
+ HCl

R Cl + SO
2
e.g.
S
N
2 Reaction of Ether
(A) Reaction with HX
A protonated ether can undergo substitution reaction. Ether react with conc. HBr and HI because these
reagents are sufficiently acidic to protonate the ether. If R or R is 3 then mechanism will be S
N
1 otherwise
S
N
2.
Mechanism :
+

halide alkyl
R X
+
HX
X R + X R'
S
N
Reaction of Epoxide
Epoxides are much more reactive than ether because of angle strain in three membered ring therefore
epoxide readily undergo nucleophilic substitution reaction.
In basic medium mechanism is S
N
2. Nucleophile atacks on less hindered carbon.
Mechanism :

O
O
|
CH CH R
|
Nu
2

H

OH
|
CH CH R
|
Nu
2
e.g.
In acidic medium mechanism is S
N
1 type. Nucleophilic attacks on more substituted carbon.
Mechanism :

H

OH
|
CH CH R
|
Nu
2
ELIMINATION REACTIONS :
E
1
Reaction :
Proton and leaving group depart in two different step.
(a) First step : - Slow step involves ionisation to form carbocation
(b) Second step : Abstraction of proton
Mechanism :
Step 1 : Formation of the carbocation (RDS)

Step 2 : Base ( ) abstracts a proton (fast)
+ B H
E
2
Reaction :
Dehydrohalogenation is the elimination of a hydrogen and a halogen from an alkyl halide to form an
alkene.
(i) Hot alcoholic solution of KOH, EtO/EtOH
(ii) NaNH
2
(iii) t-BuO
+
K

in

t-BuOH
This is one step reaction, hydrogen and leaving group depart simultaneously
Mechanism :

+ BH
(iii) E
1

cB Reaction (Unimolecular conjugate base reaction) #
In the E
1
cB, H leaves first and then the X. This is a two step process, the intermediate is a
carbanion.
Mechanism :
Step - 1: Consists of the removal of a proton, , by a base generating a carbanion
| |
X C C
| |
H

Step - 2: Carbanion looses a leaving group to form alkene

| |
C C =
Condition : For the E
1
cB, substrate must be containing acidic hydrogens and poor leaving groups.
PART - I : OBJECTIVE QUESTIONS
* Marked Questions are having more than one correct option.
Section (A) Organic reagent
A-1. Which of the following molecules can behave both as a nucleophile and an electrophile ?
(A) CH
3
NH
2
(B) CH
3
Cl (C) CH
3
CN (D) CH
3
OH
A-2. Which one of the following statements is not correct for electrophile :
(A) Electron deficient species are electrophile (B) Electrophiles are Lewis acids
(C) All + ive charged species are electrophile (D) AlCl
3
and SO
3
are electrophiles
A-3. Which of the following is an electrophilic reagent ?
(A) H
2
O (B) OH
(C) NO
2
+
(D) none
A-4. Which of the following reaction intermediates are electrophilic in character ?
(a) Carbocation (b) Carbanion (c) Free radicals (d) Carbenes
(A) Only b (B) a and c (C) a and d (D) a, b, c and d
A-6. Which one of the following has maximum nucleophilicity ?
(A) (B) (C) (D)
A-7. Which one of the following has maximum nucleophilicity ?
(A)
!
S CH
3
(B) (C) Et
3
N (D)
A-8. Correct arrangement of the following nucleophiles in the order of their nucleophilic strength is -
(A) C
6
H
5
O

< CH
3
O
< CH
3
COO
< OH
(B) CH
3
COO
< C
6
H
5
O
< CH
3
O
< OH
(C) C
6
H
5
O
< CH
3
COO
< CH
3
O
< OH
(D) CH
3
COO
< C
6
H
5
O
< OH
< CH
3
O
A-9.* The correct nucleophilicity order is/are :

(A) (CH
3
)
3
!
O
>
!
3
CH (B) CH
3
S
!
> CH
3
SH
(C)

CH
3
CH
2
CH
2
O
!
> (CH
3
)
3
CO
!
(D) (CH
3
CH
2
)
3
N > (CH
3
CH
2
)
3
P
A-10. Which among the following species is an ambident nucleophile ?
(A) CH
3

2 H C
!
(B) CH
2
= CH
2
(C) N C
!
(D)
3

H N
A-11. Decreasing order of nucleophilicity of the following nucleophile is
(1) CH
3
O
-
(2)
CN
(3) (4)
3 2
CH CO
(A) 4 > 3 > 2 > 1 (B) 2 > 1 > 4 > 3 (C) 2 > 1 > 3 > 4 (D) 1 > 2 > 3 > 4
Section (B) S
N
1 Reactions
B-1. Following is the list of four halides. Select correct sequence of decreasing order of reactivity for SN
1
reaction using the answer codes given below :
(1) H
5
C
6
CH Br
CH
3
(2) C
6
H
5
CH
2
Br (3) H
5
C
6
CH I
CH
3
(4) C
6
H
5
CH
2
Cl
Answers codes :
(A) 3, 1, 2, 4 (B) 1,3, 2, 4 (C) 2, 4, 3, 1 (D) 4, 2, 3, 1
B-2. Which one of the following compounds will be most reactive for S
N
1 reactions:
(A)
O
I
(B)
O
Cl
(C)
O
Br
(D)
O
Cl
B-3. Arrange the following compounds in order of decreasing rate of hydrolysis for S
N
1 reaction:
(I) CH
2
Br (II) H
3
C CH
2
Br
(III) CH
3
CH
2
CH
2
Br (IV)
CH
C H
3
C H
3
CH
2
Br
(A) II > III > IV > I (B) IV > III > II > I (C) III > IV > II > I (D) I > II > III > I
B-4. Among the bromides IIII given below, the order of reactivity in S
N
1

reaction is:
(I) (II) (III)
(A) III > I > II (B) III > II > I (C) II > III > I (D) II > I > III
B-5. Which of the following compounds is most rapidly hydrolysed by S
N
1 mechanism.
(A) C
6
H
5
Cl (B) ClCH
2
CH = CH
2
(C) (C
6
H
5
)
3
CCl (D) C
6
H
5
CH
2
Cl
B-6. Which among the following will give S
N
1 reaction
(1) C H
3
CH Br
C
6
H
5
(2) C H
3
C Br
CH
3
CH
3
(3) CH
3
CH
2
I (4) H
5
C
6
C Cl
CH
3
C
6
H
5
Select the correct answer from the codes given below :
Codes :
(A) 1, 2 and 3 (B) 1, 2 and 4 (C) only 3 (D) 2 and 4
B-7. What will be the major product of the following reaction ?
Br CH H
| | |
CH CH C C CH
| |
CH H
3
3 3
3

" " " " " # "
$C 30 , OH CH
3
(A)
H H OCH
| | |
CH C C C CH
| | |
H C CH H
3
3 3
3 3
(B)
H CH H
| | |
CH C C C CH
| | |
OCH CH H
3
3 3
3 3
(C)
H OCH H
| | |
CH C C C CH
| | |
CH CH H
3
3 3
3 3
(D)
3 3
2 3
3
OCH H CH H
| | | |
CH C C C CH
| | |
H CH H
B-8. Which one of the following compounds will give (d) and (!) form in S
N
1 reaction (as major product)
(A) (B) (C) (D)
B-9. Product,
Identify the major product :
(A) (B) (C) (D)
B-10.
3
Aq.
AgNO
""""#
(B)
Which statement is correct about the above reaction ?
(A) Product (B) is (I) by SN
1
mechanism.
(B) Product (B) is (II) by SN
2
mechanism.
(C) Product (B) is (I) by SN
2
mechanism.
(D) Product (B) is (II) by SN
1
mechanism.
Section (C) : S
N
2 Reactions
C-1. The given compound CH
3
OCH
2
Br gives which one of the following reactions:
(A) Only S
N
1 (B) Only S
N
2
(C) S
N
1 as well as S
N
2 (D) E1
C-2.* In the given pair in which pair the first compound is more reactive than second to S
N
2 reaction.
(A)
Cl CH Cl
2
(B)
Cl
Cl
(C)
Cl Cl
(D)
Cl
Cl
C-3. The decreasing order of rate of S
N
2 reaction is :
CH
3
Cl
O
||
Cl CH C CH
2 3
% % %
CH
3
CH
2
Cl
(I) (II) (III) (IV)
(A) IV > III > II > I (B) II > III > I > IV (C) II > I > IV > III (D) none
C-4. In the following reaction the most probable product will be :

(A) (B) (C) (D)
C-5.
" " " # "
3
PBr
(X) , X is :
(A) (B) (C) (D)
C-6. " " " # "
2
SOCl
Product,
Identify the product
(A) (B) (C) (D)
C-7. Consider the following reaction.
ether
SOCl
2
" " " # "

In the above reaction which phenomenon will take place :
(A) Inversion (B) Retention (C) Racemisation (D) Isomerisation
C-8.* Which of the following conditions favour S
N
2 mechanism ?
(A) Strong nucleophile (B) High conc. of nucleophile
(C) 3 alkyl halide (D) Polar protic solvent
C-9.* Y
&
" " " " " '
H
OH CH
3

&
" " " # "
H
18
2
O H
X, Identify X & Y : Y :
(A) X = (B) Y = (C) X = (D) Y =
vkSj Y gSa %
Section (D) : E1 Reaction
D-1. Which one of the following compounds undergoes E1 reaction most readily ?
(A) (B) CH
3
CH
2
CH
2
Br
(C) CH
3
CH
2
CH
2
I (D)
D-2. Which of the following will be most reactive for E1 reaction ?
(A) (B) (C) (D)
D-3. In the given reaction,
(
" " " " # "
OH CH
3
[X]
[X] as the major product among the elimination products is :
(A) C = CH
2
|
CH
3
(B) (C) (D)
D-4.
" " " " # "
4 2
SO H

In the above reaction the major product is shown, which is formed through the intermediate (carbocation)
given below :
Which bond will migrate to form the above product ?
(A) p (B) q (C) r (D) s
D-5. Major product is :
(A) (B) (C) (D)
Section (E) : E2 Reaction
E-1. Which of the following cannot undergo E2 reaction ?
(A) (B) (C) (D) none of these
E-2. Arrange the following in decreasing order of stability of their transition state during elimination by strong
base
(A) II > I > III (B) II > III > I (C) I > III > II (D) I > II > III
E-3. 2-Bromopentane is heated with potassium ethoxide in ethanol. The major product obtained is
(A) 2-Ethoxypentane (B) pent-1-ene (C) cis-pent-2-ene (D) trans-pent-2-ene
E-4. In which of the following reaction, regioselectivity can be observed.
(A) CH CCH Cl
3 2
H
CH
3

" " " " # "
( / KOH . alc
(B) CH CCH
3 3
Cl
CH
3

" " " " # "
( / KOH . alc
(C)
CH CCH CH
3 2 3
Cl
CH
3

" " " " # "
( / KOH . alc
(D) CH CCH Cl
3 2
CH
3
CH
3

" " " " # "
( / KOH . alc
E-5. The most probable product in the following reaction is :

Trans
(A) (B) (C) (D)
E-6. Which one of the following hexachlorocyclohexane is least reactive and which one is most reactive for E2
reactions with a strong base for dehydrohalogenation.
(A) I least & II most (B) II least & I most (C) III least & I most (D) III least & II most
Section (F) : E
1
cB Reaction
F-1. E
1

cB reaction is given by which of the following :
(A) CF
3
CHCl
2
(B) (C) (D) All of these
PART - II : MISLLANEOUS QUESTIONS
Comprehensions Type Questions :
Comprehension # 1
Read the following passage carefully and answer the questions.
One of the most interesting and useful aspects of stereochemistry is the study of what happens to optically
acitive molecules when they react. The product isolated from the reaction of a chiral starting material can
tell us a great deal about the reaction mechanism . We observe
S
N
2 --------- Inversion of configuration
S
N
1 --------- Racemisation
S
N
i --------- Retention of configuration
1. In the given reaction, mention reaction mechanism respectively
())
"# "
())) "# " +
())))
"# "
()V) "# "
(A) S
N
2 , S
N
1

, S
N
2 , S
N
i (B) S
N
2 ,

S
N
1 , S
N
i , S
N
2
(C) S
N
1 ,

S
N
2

,

S
N
i , S
N
1 (D) S
N
2 ,

S
N
i ,

S
N
1 , S
N
2
2. The given reaction is an example of which type of Mechanism ?

" " " # "
Ether

+ SO + HCl
2
D Cl
C H
3 7
C H
6 5
(A) S
N
2
(B) S
N
1
(C) S
N
i
(D) None
3. In which of the following reaction retention of configuration is observed ?
(A) CH
3
Br
H
D
" " " " " # "
acetone / Nal
(B) "# "
(C)
+ HOH CH
3
Br
C H
2 5
C H
3 7
"# " (D) H OTs
CH
3
C H
2 5

" " # "
) Na
Comprehension # 2
Alcohols undergo acid catalysed elimination reactions to produce alkenes. Because water is lost in the
elimination , this reaction is called dehydration reaction. Secondary and tertiary alcohols always give E1
reaction in dehydration. Primary alcohols whose *-carbon is branched also give E1 reaction. The reactivity
of alcohol for elimination reaction is tertiary alcohol > Secondary alcohol > Primary alcohol.
4. In the given reaction :
(
" " " " " # "
4 2
SO H . conc
Alkenes
Total number of alkenes (Including stereo isomers) formed will be
(A) Two (B) Three (C) Four (D) Five
5. Which of the following dehydration product (major) is incorrect ?
(A)
(
" " " " " # "
4 2
SO H . conc

(B)
(
" " " " " # "
4 2
SO H . conc

(C) CH
3
CH
2
CH
2
CH
2
OH
(
" " " " " # "
4 2
SO H . conc
CH
3
CH=CHCH
3
(D)
(
" " " " " # "
4 2
SO H . conc

6. Identify the product in the given reaction :
Product
(A) (B) (C) (D)
Assertion / Reasoning Type Questions
DIRECTIONS :
Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
(E) Statement-1 and Statement-2 both are False.
7. Statement-1 : If the mixture of and reacts with the excess of NaSH in DMF,,
the molecuarity of the S
N
2 reaction will be two but not three.
Statement-2 : In the S
N
2 reaction two molecules e.g. R X and u N
. .
take part in the formation of transition
state.
8. Statement-1 : Iodide (I
) is the strongest nucleophile (in protic solvent) among the halide anions
Statement-2 : Iodide is the largest halide anion and is the most weakly solvated in a protic solvent
Match the column Type Questions
9. Match the following :
PART - I : MIXED OBJECTIVE
Single Choice Questions
1. Which one is the strongest nucleophilic site in the following species ?
(A) 1 (B) 2 (C) 3 (D) 4
2. Decreasing order of relative nucleophilicity of the following nucleophiles in protic solvent is -
, , , , H
2
O
(A) > > H
2
O > > (B) > > > > H
2
O
(C) > > > H
2
O > (D) > > > > H
2
O
3. Which of the following is not expected to be intermediate of the following reaction ?
" " # "
O H
2
(A) (B) (C) (D)
4. Which describes the best stereochemical aspects of the following reaction ?
" " # "
%Br H
Product
(A) Inversion of configuration occurs at the carbon undergoing substitution.
(B) Retention of configuration occurs at the carbon undergoing substitution.
(C) Racemization occurs at the carbon undergoing substitution.
(D) The carbon undergoing substitution is not stereogenic.
5. When the concentration of alkyl halide is tripled and the concentration of ion is reduced to half, the rate
of S
N
2

reaction increases by :
(A) 3 times (B) 2 times (C) 1.5 times (D) 6 times
6.
(
" " " # "
, pyridine
2
SOCl
Product
Product of the above reaction is :
(A) (B) (C) (D)
7. In the given reaction :
CH OH
2

" " " " " " # "
4 2
SO H . Conc
[X] as major product
[X] will be :
(A)
CH
2 (B)
CH
3 (C)
CH
3
(D)
8.

The product X and Y are respectively :
(A) &
(B) &
(C) &
(D) &
9. Which of the following will undergo fastest elimination reaction with alcoholic KOH.
(A) (B) (C) (D)
10.
X and Y are respectively :
(A) and (B) and
(C) and (D) and
More than one correct answer
11. Which of these statements are correct about nucleophiles :
(A) Nucleophiles have an unshared electron pair and can make use of this to react with an electron
deficient species.
(B) The nucleophilicity of an element (as electron donor) generally increases on going down a group in the
periodic table.
(C) A nucleophile is electron-deficient species
(D) All good nucleophiles are good bases when we deal across the period.
12. Which of the following is / are true for S
N
1 reactions ?
(A) They occur through a single step concerted reaction.
(B) They are favoured by polar solvents.
(C) 3 alkyl halides generally react through this mechanism.
(D) Concentration of nucleophile does not affect the rate of such reactions.
13. S
N
2 reaction will be negligible in
(A) (B) (C)
Br
(D)
14. Rate of S
N
2 depends on
(A) Conc of Nucleophile (B) Conc of substrate
(C) Nature of leaving group (D) Nature of solvent
15. Which of the following reaction is correct ?
(A) 1, 4-Dichlorohexane +
. eq 1
NaI " " " " # "
Acetone

I Cl
| |
CH CH CH CH CH CH
2 2 2 2 3
% % % % %
+ NaCl
(B) 1, 2-Dibromoethane + NaS CH
2
CH
2
SNa
"# "
+ 2NaBr
(C) 4-Chloro-1-butanol + NaH
" " " # "
O Et
2
C
4
H
8
ClONa "# "
(

(D) Propyne + NaNH
2
" " " # "
%
3
NH
C
3
H
3
Na " " " # "
I
3
CH
C
4
H
6
PART - II : SUBJECTIVE QUESTIONS
1. Arrange the given species in decreasing order of their nucleophilicity ?
H
2
O
2. Write nucleophilicity order in the following compound.
3. Of the following pairs, which is the faster SN
1
reactions?
(a) and (b) and CH
3
(CH
2
)
5
Cl
(c) and (d) and
(a) rFkk (b) rFkk CH
3
(CH
2
)
5
Cl
(c) rFkk (d) rFkk
4. Give the decreasing order of SN
1
reactions of the following compounds in H
2
O.
(a) (i) (ii) (iii)
(b) (i) (ii) (iii)
(c) (i) (ii) (iii)
5. (a) (b)
6. What effect do you expect due to following changes in S
N
1 reaction of (CH
3
)
3
CBr with CH
3
OH ?
(a) The Concentration of (CH
3
)
3
CBr is doubled and that of CH
3
OH is halved.
(b) The concentration of both (CH
3
)
3
CBr and CH
3
OH are tripled.
7. Which S
N
1 reaction of each pair would you expect to take place more rapidly ? Explain.
(a) (i) Me
3
CCl + H
2
O "# " Me
3
COH + HCl
(ii) Me
3
CBr + H
2
O "# " Me
3
COH + HBr
(b) (i) Me
3
CCl + H
2
O "# " Me
3
COH + HCl
(ii) Me
3
CCl + CH
3
OH "# " Me
3
COCH
3
+ HCl
8. Explain how AgNO
3
increases the rate of solvolysis in S
N
1 reactions of alkyl halide
9. Complete the following reactions and predict the nature of solution after product formation.
(a)
C 25
Acetone
O H
2
$
" " " " # " P + Q (b) R + S
10. Write the mechanism of the following reaction and mention the rate determining step.
(a)
(b)
11.
) eq 1 (
HI
"# " A + B,
Identify A and B.
12. Propose a mechanism for the following reaction
(a) CH CH CH CH
Cl
3 2
% % %
|
O
CH O CH OH
3 3
!
/
" # """" CH CH CH CH OCH
3 2 3
% % %
O
+ Cl
!
(b) HOCH
2
CH
2
CH
2
CH
2
OH
H
&
" # "
O
+ HOH
13. How many structural isomers of monobromo cyclohexene are possible. Which will react most readily with
NaCN?
14. Which of the following reactions (a) and (b) would give a better yield of the desired ether as product.
(a)
"# "
(b)
"# "
15. Explain why thionyl chloride is considered the best reagent for converting alcohols to alkyl chlorides.
16. Predict the product of the following reactions using one equivalent of HI.
(a) (b) (c) (d)
17. Give the products of the following reactions
(i) X (ii) YY
18. Few dialkyl ethers & cyclic ethers were allowed to react with excess of HBr with the following results.
Identify the ether in each case.
(P)
excess
HBr
" " # "
+ CH
3
CH
2
CH
2
CH
2
Br
(Q)
excess
HBr
" " # "

(R)
excess
HBr
" " # "

(S)
excess
HBr
" " # "

19. Observe the following reactions.
F C CH
||
O
3
1
2
r
O H
" " # "
Cl C CH
||
O
3
2
2
r
O H
" " # "
Br C CH
||
O
3
3
2
r
O H
" " # "
I C CH
||
O
3
4
2
r
O H
" " # "
Identify the order of the rate of reaction r
1
, r
2
, r
3
and r
4
, give reason.
20. Predict the products of the following reactions
(i) + !" ! (ii) Cl C Ph
||
O
# # + !" !
21. Explain the order of the rate of esterification of the following acid with MeOH :
MeCH
2
COOH > Me
2
CHCOOH > Me
3
CCOOH > Et
3
CCOOH >> (i-Pr)
2
CHCOOH
22. Write the correct reactivity order of nucleophilic substitution reaction for the following compounds.
23. Write the correct reactivity order with NaOH of following compounds.
24. When 1-Bromo-1-methylcyclohexane is heated in ethanol for an extended period of time, three products
result: one ether and two alkenes. Predict the products of this reaction, and propose a mechanism for their
formation. Also, mention the major elimination product.
25. Predict the major product of E1 elimination of the following compounds.
(a) (b) (c) (d)
26. Why dehydration of alcohol takes place in acidic medium but not in basic medium.
27. 1 alcohols are poor starting material for synthesis of 1-Alkene. Explain
28. What happens when ethanol is heated with conc. H
2
SO
4
at 453 K. Explain the mechanism of this reaction.
29. Predict the major product of the sulphuric acid catalysed dehydration of the following alcohols :
(a) (CH
3
)
2
C(OH)CH
2
CH
3
(b) CH
3
CH
2
CH
2
CH(OH)CH
3
(c) (CH
3
)
2
C(OH)CH(CH
3
)
2
(d) (CH
3
)
3
CCH
2
OH
30.
(
" " # "
&
H
Product,
Write the major product of the reaction
31.
(
" " " " " " # "
4 3
O H . Conc P
A (Major) + B (Minor),
Write structures of A and B
32. Among the various isomers of C
4
H
9
Br which would undergo elimination most readily and why ?
33. A halide with formula C
6
H
13
I is found to give two isomeric alkenes 2-methyl-2-pentene and 4-methyl-2-
pentene on dehydrohalogenation with alcoholic KOH. Suggest its structure.
34. Bromocyclodecane on heating with ethanolic KOH, produces two alkenes Write the two products also
mention the major one.
35. A compound (X) [mol formula (C
7
H
13
Br)] on dehydrohalogenation gives only vinylcyclopentane, Write the
strucuture of X.
36.
Explain why more alkylated alkene is formed predominatly if base is , while less alkylated alkene
is obtained majorly when base is used.
37. Give the product of elimination reaction with its stereochemistry
(a) (b) ?
38. Which alkyl chloride would yield following pure alkene on reaction with alcoholic KOH ?
(i)
2 3
3
CH C CH
|
CH
+ % (ii) CH
3
CH
2
CH
2
CH = CH
2
(iii)
3
2 2 3
CH
|
CH C CH CH + % %
39. The sum of molecular weights of the major products P and Q form at the followng reaction is
(i) + CH
3
I " " " " " " # "
( / KOH
P (organic product)
(ii) + CH
3
CH
2
OH " " " " # "
( / KOH
Q (organic product)
40. What are the essential conditons for any reaction to show E1cB mechanism ?
41. Write down the increasing order of reactivity of following compounds via E1cB mechanism in basic medium
(a) C
6
H
5
CH
2
CH
2
Br CF
3
CH
2
CF
3
(b) NO
2
CH
2
CH
2
Br
42. If ethanol containing EtOD is used as solvent, then deuterium exchange take place in E1cB mechanism.
Why?
43.

+

Write down the mechanism of the above reaction
PART - I : JEE PROBLEMS (PREVIOUS YEARS)
* Marked Questions are having more than one correct option.
1. An S
N
2 reaction at an asymmetric carbon of a compound always gives [JEE-2001, 1/135]
(A) an enantiomer of the substrate (B) a product with opposite optical rotation
(C) a mixture of diastereomers (D) a single stereoisomer
2. Explain why 7-bromo-1, 3, 5-cycloheptatriene exist as an ion while 5-Bromo-1, 3-cyclopentadiene does not
form any ion even in the presence of Ag
+
. Explain why ? [JEE 2004, 4/60]
3. Compound (X) is reacted with aqueous acetone it gives following
products. [JEE-(scr.)2005, 3/144]

(A) K, L (B) K, M (C) L only (D) M only
4. Explain the following observations [JEE(M)-05, 1/144]
Acidic solution
Neutral solution
5. Which is the best reagent to convert cyclohexanol into cyclohexene. [JEE-2005, 3/144]
(A) conc. HCl (B) conc. HBr (C) conc. H
3
PO
4
(D) HCl + ZnCl
2
6.
(
" " # "
,
H
X, Identify X. [JEE-2005, 2/144]
7. Match the following (one term in column-I may match with more than one terms in column-II)
[JEE-2006, 6/184]
8. The major product of the following reaction is [JEE-2008, 3/163]
(A) (B) (C) (D)
9. In the following carbocation; H/CH
3
that is most likely to migrate to the positiviely charged carbon is
[JEE-2009, 3/160]
(A) CH
3
at C-4 (B) H at C-4 (C) CH
3
at C-2 (D) H at C-2
10. In the reaction
OCH
3 " " # "
HBr
the products are : [JEE-2010, 3/163]
(A) Br OCH
3
and H
2
(B) Br and CH
3
Br
(C) Br and CH
3
OH (D) OH and CH
3
Br
11. The total number of alkenes possible by dehydrobromination of 3-bromo-3-cyclopentylhexane using alcoholic
KOH is : [JEE 2011 160/4]
12. The compound that undergoes decarboxylation most readily under mild condition is -[JEE-2012, 3/136]
(A)
COOH
CH
2
COOH
(B)
COOH
O
(C)
COOH
COOH
(D)
CH
2
COOH
O
PART - II : AIEEE PROBLEMS (PREVIOUS YEARS)
1. Following reaction
(CH
3
)
3
CBr + H
2
O
"# "
(CH
3
)
3
COH + HBr
is an example of : [AIEEE-2002]
(1) Elimination reaction (2) Free radical substitution
(3) Nucleophilic substitution (4) Electrophilic substitution
2. S
N
1
reaction is feasible in : [AIEEE-2002]
(1) + KOH (aq.)
"# "
(2) + KOH (aq.)
"# "
(3) + KOH (aq.)
"# "
(4) + KOH (aq.)
"# "
3. Maximum dehydration takes place that of : [AIEEE-2002]
(1) (2) (3) (4)
4. Tertiary alkyl halides are practically inert to substitution by S
N
2 mechanism because of [AIEEE-2005]
(1) steric hindrance (2) inductive effect (3) instability (4) insolubility
5. The decreasing order of nucleophilicity among the nucleophiles [AIEEE-2005]
(a) (b) (c) (d)
(1) (c), (b), (a), (d) (2) (b), (c), (a), (d) (3) (d), (c), (b), (a) (4) (a), (b), (c), (d)
6. The decreasing order of nucleophilicity among the nucleophiles [AIEEE-2005]
(a) (b) (c) (d)
(1) (c), (b), (a), (d) (2) (b), (c), (a), (d) (3) (d), (c), (b), (a) (4) (a), (b), (c), (d)
7. Fluorobenzene (C
6
H
5
F) can be synthesized in the laboratory [AIEEE-2006]
(1) from aniline by diazotisation followed by heating the diazonium salt with HBF
4
(2) by direct fluorination of benzene with F
2
gas
(3) by reacting bromobenzene with NaF solution
(4) by heating phenol with HF and KF
8. CH
3
Br

+ Nu

"# "
CH
3
Nu + Br
The decreasing order of the rate of the above reaction with nucleophiles (Nu) A to D is :
[Nu = (A) # PhO, (B) # AcO, (C) # HO, (D) # CH
3
O] [AIEEE-2006]
(1) D > C > B > A (2) A > B > C > D (3) B > D > C > A (4) D > C > A > B
9. The structure of the major product formed in the following reaction is [AIEEE-2006]

DMF
NaCN
" " " # "
(1)
CH Cl
2
)
CN
(2)
CH Cl
2
CN
(3)
CH CN
2
)
(4)
CH CN
2
CN
10. Reaction of trans 2-phenyl-1-bromocyclopentane on reaction with alcoholic KOH produces : [AIEEE-2006]
(1) 2phenylcyclopentene (2) 1phenylcyclopentene
(3) 3-phenylcyclopentene (4) 4-phenylcyclopentene
11.
The alkene formed as a major product in the above elimination reaction is : [AIEEE-2006]
(1) (2) CH
2
= CH
2
(3) (4)
12. Which of the following is the correct order of decreasing S
N
2 reactivity ? [AIEEE-2007, 3/120]
(1) RCH
2
X > R
3
CX > R
2
CHX (2) RCH
2
X > R
2
CHX > R
3
CX
(3) R
3
CX > R
2
CHX > RCH
2
X (4) R
2
CHX > R
3
CX > RCH
2
X
13. The organic chloro compound, which shows complete stereochemical inversion during an S
N
2 reaction, is
[AIEEE-2008, 3/105]
(1) (CH
3
)
3
CCl (2) (CH
3
)
2
CHCl (3) CH
3
Cl (4) (C
2
H
5
)
2
CHCl
14. Which of the following on heating with aqueous KOH, produces acetaldehyde ? [AIEEE-2009, 4/144]
(1) CH
3
CH
2
Cl (2) CH
2
ClCH
2
Cl (3) CH
3
CHCl
2
(4) CH
3
COCl
15. From amongst the following alcohols the one that would react fastest with conc. HCl and anhydrous ZnCl
2
,
is : [AIEEE-2010, 4/144]
(1) 2-Butanol (2) 2-Methylpropan-2-ol
(3) 2-Methylpropanol (4) 1-Butanol
16. Consider the following bromides : [AIEEE-2010, 4/144]
The correct, order of S
N
1 reactivity is
(1) B > C > A (2) B > A > C (3) C > B > A (4) A > B > C
17. In the chemical reactions : [AIEEE-2010, 4/144]
NH
2

K 278 , HCl
NaNO
2
" " " " # " A " " " # "
4
HBF
B
the compounds A and B respectively are
(1) nitrobenzene and fluorobenzene (2) phenol and benzene
(3) benzene diazonium chloride and fluorobenzene (4) nitrobenzene and chlorobenzene
18. The main product of the following reaction is : [AIEEE-2010, 4/144]
C
6
H
5
CH
2
CH(OH)CH(CH
3
)
2

" " " " " # "
4 2
SO H . conc
(1) (2)
(3) (4)
19. An unknown alcohol is treated with the Lucas reagent to determine whether the alcohol is primary, secondary
or tertiary. Which alcohol reacts fastest and by what mechanism : [JEE Mains 2013]
(1) secondary alcohol by S
N
1 (2) tertiary alcohol by S
N
1
(3) secondary alcohol by S
N
2 (4) tertiary alcohol by S
N
2
NCERT QUESTIONS
1. Write the isomers of the compound having formula C
4
H
9
Br.
2. Write the equations for the preparation of 1-iodobutane from
(i) 1-butanol (ii) 1-chlorobutane (iii) but-1-ene.
3. What are ambident nucleophiles? Explain with an example.
4. Which compound in each of the following pairs will react faster in S
N
2 reaction with OH?
(i) CH
3
Br or CH
3
I (ii) (CH
3
)
3
CCl or CH
3
Cl
5. Predict all the alkenes that would be formed by dehydrohalogenation of the following halides with sodium
ethoxide in ethanol and identify the major alkene:
(i) 1-Bromo-1-methylcyclohexane (ii) 2-Chloro-2-methylbutane (iii) 2,2,3-Trimethyl-3-bromopentane.
6. Write the structure of the major organic product in each of the following reactions:
(i) CH
3
CH
2
CH2Cl + NaI
acetone
heat
""""#
(ii) (CH
3
)3CBr + KOH
ethanol
heat
""""#
(iii) CH
3
CH(Br)CH
2
CH
3
+ NaOH
water
"""#
(iv) CH
3
CH
2
Br + KCN
aq.ethanol
""""#
(v) C
6
H
5
ONa + C
2
H
5
Cl "#
(vi) CH
3
CH
2
CH
2
OH + SOCl
2
"#
(vii) CH
3
CH
2
CH = CH
2
+ HBr
peroxide
""""#
(viii) CH
3
CH = C(CH
3
)
2
+ HBr "#
7. Write the mechanism of the following reaction :
nBuBr + KCN
2
EtOH H O
%
""""#nBuCN
8. Arrange the compounds of each set in order of reactivity towards S
N
2 displacement :
(i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
(ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 2-Bromo-3-methylbutane
(iii) 1-Bromobutane, 1-Bromo-2,2-dimethylpropane, 1-Bromo-2-methylbutane, 1-Bromo-3-methylbutane.
9. Out of C
6
H
5
CH
2
Cl and C
6
H
5
CHClC
6
H
5
, which is more easily hydrolysed by aqueous KOH.
10. p-Dichlorobenzene has higher m.p. and solubility than those of o- and m-isomers. Discuss.
11. The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but in the presence
of alcoholic KOH, alkenes are major products. Explain.
12. Primary alkyl halide C
4
H
9
Br
(a) reacted with alcoholic KOH to give compound(b).
Compound (b) is reacted with HBr to give (c) which is an isomer of (a).
When (a) is reacted with sodium metal it gives compound (d),
C
8
H
18
which is different from the compound formed when n-butyl bromide is reacted with sodium.
Give the structural formula of (a) and write the equations for all the reactions.
13. What happens when
(i) n-butyl chloride is treated with alcoholic KOH,
(ii) ethyl chloride is treated with aqueous KOH,
(iii) methyl chloride is treated with KCN?
14. Explain why propanol has higher boiling point than that of the hydrocarbon, butane?
15. Alcohols are comparatively more soluble in water than hydrocarbons of comparable molecular masses.
Explain this fact.
16. Show how will you synthesise:
(i) cyclohexylmethanol using an alkyl halide by an S
N
2 reaction.
(ii) pentan-1-ol using a suitable alkyl halide?
17. Give reason for the higher boiling point of ethanol in comparison to methoxymethane.
18. Write the names of reagents and equations for the preparation of the following ethers by Williamsons
synthesis:
(i) 1-Propoxypropane (ii) Ethoxybenzene
(iii) 2-Methoxy-2-methylpropane (iv) 1-Methoxyethane
19. Illustrate with examples the limitations of Williamson synthesis for the preparation of certain types of ethers.
20. How is 1-propoxypropane synthesised from propan-1-ol? Write mechanism of this reaction.
21. Preparation of ethers by acid dehydration of secondary or tertiary alcohols is not a suitable method. Give
reason.
22. Write the equation of the reaction of hydrogen iodide with :
(i) 1-propoxypropane (ii) methoxybenzene and (iii) benzyl ethyl ether.
23. Explain the fact that in aryl alkyl ethers
(i) the alkoxy group activates the benzene ring towards electrophilic substitution and
(ii) it directs the incoming substituents to ortho and para positions in benzene ring.
24. Write the mechanism of the reaction of HI with methoxymethane.
25. When 3-methylbutan-2-ol is treated with HBr, the following reaction takes place:
Give a mechanism for this reaction.
(Hint : The secondary carbocation formed in step II rearranges to a more stable tertiary carbocation by a
hydride ion shift from 3rd carbon atom.
Exercise # 1
PART - I
A-1. (C) A-2. (C) A-3. (C) A-4. (C) A-6. (A) A-7. (A) A-8. (D)
A-9.* (BC) A-10. (C) A-11. (B) B-1. (A) B-2. (A) B-3. (A) B-4. (A)
B-5. (C) B-6. (B) B-7. (C) B-8. (B) B-9. (A) B-10. (D) C-1. (C)
C-2.* (BD) C-3. (C) C-4. (B) C-5. (A) C-6. (A) C-7. (B) C-8.* (AB)
C-9.* (AD) D-1. (D) D-2. (A) D-3. (C) D-4. (B) D-5. (C) E-1. (C)
E-2. (A) E-3. (D) E-4. (C) E-5. (C) E-6. (B) F-1. (D)
PART - II
1. (B) 2. (C) 3. (B) 4. (C) 5. (B) 6. (C) 7. (A)
8. (A) 9. (A) - p, r, s ; (B) - r, s ; (C) - r, s ; (D) - p, q
Exercise # 2
PART - I
1. (D) 2. (B) 3. (A) 4. (C) 5. (C) 6. (A) 7. (B)
8. (A) 9. (A) 10. (A) 11. (ABD) 12. (BCD) 13. (ABC)
14. (ABCD) 15. (ABCD)
PART - II
1. > > > H
2
O 2. III > II > I > IV 3. (a) (i), (b) i, (C)i (d) i
4. a. (iii) > (ii) > (i) b. (iii) > (i) > (ii) c. (ii) > (i) > (iii) (allylic > 3 > 1)
5. (a) (b)
6. (a) Rate - doubled ; (b) Rate - tripled
7. (a) ii, (b) i
8. Ag
+
ion has strong affinity for X
than a solvent molecule, the precipitation of AgX accelerates the dissociation

of RX bond.
9. (a) P = , Q = pH is less than seven because acid HBr is formed.
(b) R = , S = pH is less than seven because acid HCl is formed
10. (a)
ol tan bu 2 Methyl 3
OH
|
CH CH CH CH
|
CH
3 3
3
! ! !
! ! !
rds
Slow
" " " # "

(b)
rds
O H
2
" " " # "
!

11. + CH
3
OH
12. (a)
CH O CH OH
S
N
3 3
2
$
/
" # """" CH CH CH CH OCH
Cl OH
S
N
3 2 3
2
! ! ! ! " # ""
| |
CH CHCHCH OCH
3 2 3
"# "
O
%
H
CH CHCHCH OCH
3 2 3
O
(b) HO(CH
2
)
3
CH
2
OH
H
%
" # "
H O CH CH O ( )
& &
& &
! ! !
2 3 2
H
H
%
!
" # ""
H O
2
O
H
%
!
%
" # "
H
O
13. Three will react most readily with NaCN.
14. (a) Give better yield, because in the (b) nucleophile attacks on more hindered 2 carbon. So along with
substitution, elimination also posible in the (b).
15. ROH + SOCl
2
"# " RCl + HCl ' + SO
2
'
gases
Pure RCl is obtained, as the by products (HCl and SO
2
) are gases and get evaporated from the reaction
mixture.
16. (a) IH
2
C CH
2
CH
2
CH
2
CH
2
OH (b) + CH
3
I
(c) (d)
17. (i) X = CH
3
CH(OH)CH
2
OH (ii) Y = CH
3
CH(OH)CH
2
OMe
18. P = Q = CH
2
OCH
2
R = S =
19. r
4
> r
3
> r
2
> r
1
rate of S
N
2 Th is inversly proportional to basicity of leaving group.
20. (i) (ii)
21. As the size of the substituents on the ( C increases, the tetrahedrally bonded intermediate becomes more
crowded. The greater the crowding, the larger is )H
+
of the TS and the slower is the reaction.
22. II > I > IV > III 23. II > III > I 24. +
25. (a) (b) (c) (d)
26. In basic condition very poor leaving group OH will eliminate but in acidic medium OH will be converted
into
2
H O
%
which is very good leaving group.
27. 1 carbocation
%
2
CH R would rearrange and 2-alkene would result. Even if 1-alkene is also formed but, it
would tend to rearrange in acidic medium to 2-alkene.
28. What happens when ethanol is heated with conc. H
2
SO
4
at 453 K. Explain the mechanism of this reaction.
Ans. (a) CH
3
CH
2
O
..
..
H + H
+
CH
3
CH
2
H
Ethanol Oxonium ion
(b) " " " # "
slow
CH
2
=CH
2
+ H
2
O
29. (a)
CH
3
C CH
CH
3
CH
3
(b) CH
3
CH
2
CH = CH CH
3
(c)
C C
CH
3
CH
3
CH
3
CH
3
(d)
CH
3
C CH
CH
3
CH
3
30.
" " # "
! O H
2

H C
3
+
CH
3
H

" " " # "
%
H
31. A : B :
32. Tert-butyl bromide would undergo elimination most readily as the alkene formed from it would be more
stable.
33. 34. +
35.
HBr
2 E
!
" "# "
The product is formed only by E2 elimination.
36. t- is bulky base so Hoffmann product is formed as major product.
37. (a) (b)
38. (i) or ; (ii) CH
3
CH
2
CH
2
CH
2
CH
2
Cl ; (iii)
3
2 2 3
CH
|
Cl CHCH CH CH
39. 196
P =
O
CH
3
CH
3
[M.F. C
7
H
14
O M.W. 84+14+16 = 114]
Q = CH
3
[M.F. C
6
H
10
M. W. 72 + 10 = 82]
M.W. (P + Q) = 114 + 82 = 196
40. Reactant should have acidic *-hydrogen and poor leaving group.
41. (a) C
6
H
5
CH
2
CH
2
Br < CF
3
CH
2
CF
3
(b) NO
2
CH
2
CH
2
Br <
42. In E1cB mechanism carbanion is formed as intermediate and 1st step is reversible.
43.

2
nd
step

In E1cB 1st step is reversible step so deuterium exchange take place
Exercise # 3
PART - I
1. (D)
2. 7-bromo-1, 3, 5-cycloheptatriene on ionisation gives tropylium ion which is aromatic & highly stable,
but ionisation of 5-bromo-1, 3-cyclopentadiene gives 1, 3-cyclopentadienyl cation which is anti aromatic
& unstable. (non existent)
3. (A)
4. + HBr (strong acid) + (S
N
1 product)
No reaction.
Because aryl halide have resonance stabilized C X bond, and do not give S
N
reaction.
5. (C) 6. 7. (A) - q ; (B) - q ; (C) - r, s ; (D) - p, s
8. (A) 9. (D) 10. (D) 11. 5 alkenes including stereoisomers 12. (B)
PART - II
1. (3) 2. (1) 3. (2) 4. (1) 5. (1) 6. (1) 7. (1)
8. (4) 9. (3) 10. (3) 11. (2) 12. (2) 13. (3) 14. (3)
15. (2) 16. (1) 17. (3) 18. (1) 19. (2)

Reaction Mechanism

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Reaction Mechanism

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Topic Page No.

) (B) Neutral electrophiles (E)

(B) Reaction with phosphorus trihalides

A-9.* The correct nucleophilicity order is/are :

than a solvent molecule, the precipitation of AgX accelerates the dissociation

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