Reaction Mechanism

REACTION MECHANISM
Contents
Topic Page No.
Theory 01 - 10
Exercise - 1 11 - 19
Answer Key 36 - 40
Syllabus
Organic Reagents, Alkyl halides : Nucleophilic substitution reactions, elimination reactions,
Alcohols : dehydration, reaction with sodium, phosphorus halides, ZnCl2/concentrated HCl,
Ethers : Preparation by Williamsons Synthesis; Nucleophilic substitution reactions.
Name : ____JYOT SILVER________________________

Contact No. __________________
JYOT SILVER
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.
JYOT SILVER
Physical & Inorganic By A-479 Indra vihar, kota Organic Chemistry By
NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir
REACTION MECHANISM # 1
B.Tech. IIT Delhi M.Sc. IT-BHU
Solvents Non Polar Polar Protic Aprotic
1. H2O
2. CH3OH
3. CH3CH2OH
4. HCOOH
5. CH3COOH
6. NH3
7.
8. DMSODimethyl sulphoxide
9. DMF Dimethyl formamide
10. DMA Dimethyl acetamide
11.
12.
CCCCCC
JYOT SILVER
13.

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 A, A 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, AlX3, C H2 , C X 2 BF 3, BCl 3, BBr3, 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) Cl2, Br2 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 , R2 , R3 , NH2 (Nitrogen nucleophile)
H H, R H, R R (Oxygen nucleophiles)
H H, R H, R R (Sulphur nucleophiles)
H3, R H2, R2 H, R3 (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.
Note :
JYOT SILVER
(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.
O O O O
|| || || ||
R CH, R CR, R C OH , R C Cl
O O
|| ||
R C OR , R C NH2 , RCN,
R
Note : During the course of chemical reaction electrophile reacts with nucleophile.
NUCLEOPHILIC SUBSTITUTION REACTIONS (SN) AT SATURATED CARBON
NUCLEOPHILIC SUBSTITUTION REACTIONS (SN) :

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 sp3 carbon.
Rg + R Nu +
UNIMOLECULAR NUCLEOPHILIC SUBSTITUTION REACTIONS (SN1) :

Nucleophilic substitution which involves two step process
(a) First step : - Slow step involves ionisation to form carbocation
Rg R+ + g
(b) Second step : - Fast attack of nucleophile on carbocation to result into product .
R+ + Nu RNu
SN1 Reaction of Alkyl halide
Mechanism :
Ionisation of
alkyl halide

Slow step (rds)
Characteristics of SN1 reactions :

1. It is unimolecular, two step process.
2. Carbocation intermediate is formed so rearrangement is possible in SN1 reaction.
3. It is first order reaction
4. Kinetics of the reaction Rate [Alkyl halide]
Rate of SN1 reaction is independent of concentration and reactivity of nucleophile.
JYOT SILVER
5. Energetics of the SN1
Figure : Free energy diagram for the SN1 reaction.
SN1 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 (H2O). 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 SN2 displacement, but it can ionise to a tertiary carbocation. Attack by bromide
ion gives the alkyl bromide. The mechanism is similar to other SN1 mechanism.
(iv) 1-Butanol reacts with sodium bromide in concentrated sulfuric acid to give 1-Bromobutane by an SN2
displacement.
NaBr, H SO
2 4
CH3 (CH2 )2 CH2OH
CH3 (CH2 )2 CH2Br
1 bu tan ol 1 bromobutane
( 90%)
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 SN2 displacement.
(v) Secondary alcohols also react with HBr to form alkyl bromides usually by the SN1 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 ZnCl2, is sometimes necessary to promote the reaction of HCl with primary and
secondary alcohols.
JYOT SILVER
Mechanism :
RDS
R OH R O H2 R
H2O R X
Reactivity of HX : HI > HBr > HCl
Reactivity of ROH : allyl benzyl > 3 > 2 > 1
SN1 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 SN1 otherwise SN2 .
Mechanism :
X
R O R` R` X
ROH
SN2 Reaction of Alkyl halide :
Mechanism : +
Characteristic of SN2
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 :
JYOT SILVER
Figure : A free energy diagrams for SN2 reaction
5. No intermediates are formed in the SN2 reaction, the reaction proceeds through the formation of an
unstable arrangment of atoms or group called transition state.

6. The stereochemistry of SN2 reactions As we seen earlier, in an SN2 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

SN2 Reaction of Alcohol

(A) Reaction with HX : The protonated unbranched primary alcohol is well suited for the SN2 reaction.
Mechanism :
X
R OH R O H2 R X + H2O
CH3 CH2 CH2CH2CH2Cl

e.g CH3 CH2 CH2CH2CH2 OH
n Pentyl alcohol n Pentyl chloride
(B) Reaction with phosphorus trihalides

Several phosphorus halides are useful for converting alcohols to alkyl halides. PBr3, PCl3, & PCl5 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 PBr3 and the P4/I2 combination.
3R OH + PX3 3R X + H3PO3
Mechanism :
Step : 1
Step : 2 RCH2X+ HOPX2
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 HOPX2, a good leaving group due to the
electronegative atoms bonded to the phosphorus.
(C) Reaction with thionyl chloride in presence of pyridine

Thionyl chloride (SOCl2) is often the best reagent for converting an alcohol to an alkyl chloride. The by
products (gaseous SO2 and HCl) leave the reaction mixture and ensure that there can be no reverse
reaction.
O
JYOT SILVER
||
Heat
R OH + Cl S Cl R Cl + SO2 + HCl
Pyridine

Mechanism :
..
.. .. O:
H + HCl
R O
.. S
Cl
Chlorosulphite ester
R Cl + SO2
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 SN2 mechanism
SOCl 2
e.g.

Py
Reaction with thionyl chloride

ROH + SOCl2 RCl + SO2 + HCl
In this mechanism an internal nucleophile attacks from the same side of leaving group , means retension
of configuration . It is an SNi mechanism , where i means internal
Mechanism :
..
.. ..
O:
H + HCl
R O
.. S
Cl
Chlorosulphite ester
R Cl + SO2
e.g.
SN2 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 SN1 otherwise
JYOT SILVER
SN2.

Mechanism :
HX
+ X R + X R + X R
alkyl halide
SN 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 SN2. Nucleophile atacks on less hindered carbon.
Mechanism :
Nu
Nu
|
R CH CH2
H |
R CH CH2
|
|
O OH
e.g.
In acidic medium mechanism is SN1 type. Nucleophilic attacks on more substituted carbon.
Mechanism :
Nu

|
H

R CH CH2
|
OH
ELIMINATION REACTIONS :
E1 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)
JYOT SILVER
Step 2 : Base ( ) abstracts a proton (fast)
+ B H
E2 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) NaNH2

(iii) t-BuO K in t-BuOH
This is one step reaction, hydrogen and leaving group depart simultaneously
Mechanism :
+ BH
(iii) E1 cB Reaction (Unimolecular conjugate base reaction)

In the E1 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
H
| |
CC X
| |
Step - 2: Carbanion looses a leaving group to form alkene
C C
| |
Condition : For the E1 cB, substrate must be containing acidic hydrogens and poor leaving groups.
JYOT SILVER
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) CH3NH2 (B) CH3Cl (C) CH3CN (D) CH3OH
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) AlCl3 and SO3 are electrophiles
A-3. Which of the following is an electrophilic reagent ?

(A) H2O (B) OH (C) NO2+ (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) CH3 S (B) (C) Et3N (D)
A-8. Correct arrangement of the following nucleophiles in the order of their nucleophilic strength is -
(A) C6H5O < CH3O < CH3COO < OH (B) CH3COO < C6H5O < CH3O < OH
(C) C6H5O < CH3COO < CH3O < OH (D) CH3COO < C6H5O < OH < CH3O
A-9.* The correct nucleophilicity order is/are :

(A) (CH3)3 O > CH3 (B) CH3S > CH3SH
(C) CH3CH2CH2O > (CH3)3CO (D) (CH3CH2)3N > (CH3CH2)3P
A-10. Which among the following species is an ambident nucleophile ?

(A) CH3 C H2 (B) CH2 = CH2 (C) C N (D) NH3
A-11. Decreasing order of nucleophilicity of the following nucleophile is

(1) CH3O - (2) CN (3) (4) CH3 CO2
JYOT SILVER
(A) 4 > 3 > 2 > 1 (B) 2 > 1 > 4 > 3 (C) 2 > 1 > 3 > 4 (D) 1 > 2 > 3 > 4

Section (B) SN1 Reactions
B-1. Following is the list of four halides. Select correct sequence of decreasing order of reactivity for SN1
reaction using the answer codes given below :
(1) H5C6 CH Br (2) C6H5CH2Br (3) H5C6 CH I (4) C6H5CH2Cl

CH3 CH3
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 SN1 reactions:
I Cl Br Cl
O O O
(A) (B) (C) (D)
B-3. Arrange the following compounds in order of decreasing rate of hydrolysis for SN1 reaction:
(I) CH2Br (II) H3C CH2Br
H3C
(III) CH3CH2 CH2Br (IV) CH CH2Br
H3C
(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 SN1 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 SN1 mechanism.
(A) C6H5Cl (B) ClCH2CH = CH2
(C) (C6H5)3CCl (D) C6H5CH2Cl
B-6. Which among the following will give SN1 reaction
CH3 C6H5
(1) H3C CH Br (2) H3C C Br (3) CH3CH2I (4) H5C6 C Cl
C6H5 CH3 CH3
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
JYOT SILVER
B-7. What will be the major product of the following reaction ?
H CH3
| |
CH3 C C CH CH3 3CH OH, 30C

| | |
H CH3 Br
H CH3 C H3 H CH3 OCH3

| | | | | |
(A) CH3 C C C CH3 (B) CH3 C C C CH3
| | | | | |
OCH3 H H H CH3 H
H CH3 CH3 H CH3 H

| | | | | |
(C) CH3 C C C CH3 (D) CH3 C C C CH2
| | | | | | |
H OCH3 H H CH3 H OCH3
B-8. Which one of the following compounds will give (d) and () form in SN1 reaction (as major product)
(A) (B) (C) (D)
B-9. Product,
Identify the major product :
(A) (B) (C) (D)
Aq.
B-10.
AgNO3
(B)
Which statement is correct about the above reaction ?
(A) Product (B) is (I) by SN1 mechanism.
(B) Product (B) is (II) by SN2 mechanism.
(C) Product (B) is (I) by SN2 mechanism.

(D) Product (B) is (II) by SN1 mechanism.
JYOT SILVER
Section (C) : SN2 Reactions
C-1. The given compound CH3OCH2Br gives which one of the following reactions:
(A) Only SN1 (B) Only SN2
(C) SN1 as well as SN2 (D) E1
C-2.* In the given pair in which pair the first compound is more reactive than second to SN2 reaction.
Cl
(A) Cl CH2Cl (B)
Cl
Cl Cl
(C) (D)
Cl Cl
C-3. The decreasing order of rate of SN2 reaction is :
CH3Cl CH3 C CH2 Cl CH3CH2Cl

||
O
(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)
3 PBr
C-5.
(X) , X is :
(A) (B) (C) (D)
JYOT SILVER
C-6. SOCl
2
Product,
Identify the product
(A) (B) (C) (D)
C-7. Consider the following reaction.
SOCl
2

ether
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 SN2 mechanism ?

(A) Strong nucleophile (B) High conc. of nucleophile
(C) 3 alkyl halide (D) Polar protic solvent
H O18
C-9.* Y CH OH
3 2
X, Identify X & Y :
H H
(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) CH3 CH2 CH2 Br
(C) CH3 CH2 CH2 I (D)
D-2. Which of the following will be most reactive for E1 reaction ?
(A) (B) (C) (D)
JYOT SILVER
CH3OH
D-3. In the given reaction,
[X]

[X] as the major product among the elimination products is :

CH3
|
(A) C = CH2 (B) (C) (D)
D-4. H SO 4
2

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.
CH3 CH3
alc. KOH /
(A) CH3CCH2Cl alc. KOH /
(B) CH3CCH3

H Cl
JYOT SILVER
CH3 CH3
alc. KOH /
(C) CH3CCH2CH3 alc. KOH /
(D) CH3CCH2Cl

Cl CH3

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) : E1cB Reaction

F-1. E1 cB reaction is given by which of the following :
(A) CF3 CHCl2 (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
SN2 --------- Inversion of configuration
SN1 --------- Racemisation
SNi --------- Retention of configuration
1. In the given reaction, mention reaction mechanism respectively
() () +
() (V)
JYOT SILVER
(A) SN2 , SN1 , SN2 , SNi
(C) SN1 , SN2 , SNi , SN1
(B) SN2 , SN1 , SNi , SN2
(D) SN2 , SNi , SN1 , SN2

2. The given reaction is an example of which type of Mechanism ?
C3H7
Ether

D Cl + SO2 + HCl
C6H5
(A) SN2 (B) SN1 (C) SNi (D) None
3. In which of the following reaction retention of configuration is observed ?

H
Nal / acetone
(A) CH3 Br (B)
C2H5 CH3
Na
(C) CH3 Br + HOH (D) H OTs
C3H7 C2 H5
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.
conc .H2SO 4
4. In the given reaction : 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 ?
conc .H2SO 4
(A)

conc .H SO
2
4
(B)

2 4 conc .H SO
(C) CH3 CH2 CH2CH2OH CH3CH=CHCH3

conc .H2SO 4
(D)

6. Identify the product in the given reaction :
Product
(A) JYOT SILVER (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 SN2 reaction will be two but not three.
..
Statement-2 : In the SN2 reaction two molecules e.g. R X and N u 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 :
JYOT SILVER
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 -

, , , , H2O
(A) > > H2O > > (B) > > > > H2O
(C) > > > H2O > (D) > > > > H2O
3. Which of the following is not expected to be intermediate of the following reaction ?
H O
2
(A) (B) (C) (D)
4. Which describes the best stereochemical aspects of the following reaction ?
HBr
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 SN2 reaction increases by :
(A) 3 times (B) 2 times (C) 1.5 times (D) 6 times
JYOT SILVER
SOCl 2
6. Product
pyridine,
Product of the above reaction is :
(A) (B) (C) (D)
CH2 OH
7. In the given reaction : Conc. H2SO 4

[X] as major product
[X] will be :
(A) CH2 (B) CH3 (C) CH3 (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)
JYOT SILVER
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 SN1 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. SN2 reaction will be negligible in

Br
(A) (B) (C) (D)
14. Rate of SN2 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 ?

Acetone
(A) 1, 4-Dichlorohexane + NaI CH3 CH2 CH CH2 CH2 CH2 + NaCl
1eq. | |
Cl I
(B) 1, 2-Dibromoethane + NaS CH2 CH2 SNa + 2NaBr
2 Et O
(C) 4-Chloro-1-butanol + NaH
C4H8ClONa
JYOT SILVER
3
(D) Propyne + NaNH2
NH CH3 I
C3H3Na
C4H6

PART - II : SUBJECTIVE QUESTIONS
1. Arrange the given species in decreasing order of their nucleophilicity ?

H2O
2. Write nucleophilicity order in the following compound.
3. Of the following pairs, which is the faster SN1 reactions?
(a) and (b) and CH3(CH2)5Cl
(c) and (d) and
(a) r Fkk (b) r Fkk CH3(CH2)5Cl
(c) r Fkk (d) r Fkk
4. Give the decreasing order of SN1 reactions of the following compounds in H2O.
(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 SN1 reaction of (CH3)3CBr with CH3OH ?
(a) The Concentration of (CH3)3CBr is doubled and that of CH3OH is halved.
(b) The concentration of both (CH3)3CBr and CH3OH are tripled.
JYOT SILVER
7. Which SN1 reaction of each pair would you expect to take place more rapidly ? Explain.
(a) (i) Me3CCl + H2O Me3COH + HCl
(ii) Me3CBr + H2O Me3COH + HBr
(b) (i) Me3CCl + H2O Me3COH + HCl
(ii) Me3CCl + CH3OH Me3COCH3 + HCl
8. Explain how AgNO3 increases the rate of solvolysis in SN1 reactions of alkyl halide
9. Complete the following reactions and predict the nature of solution after product formation.
2 HO
(a) P + Q (b) R + S
Acetone
25C
10. Write the mechanism of the following reaction and mention the rate determining step.
(a)
(b)
HI
11. A + B,
(1eq)
Identify A and B.
12. Propose a mechanism for the following reaction
O O

(a) CH 3 CH CH CH 2 CH CH CH CH OCH + Cl
CH 3 O / CH 3OH
3 2 3
|
Cl

H
(b) HOCH2CH2CH2CH2OH + HOH
O
13. How many structural isomers of monobromo cyclohexene are possible. Which will react most readily with
NaCN?
JYOT SILVER
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) Y
18. Few dialkyl ethers & cyclic ethers were allowed to react with excess of HBr with the following results.
Identify the ether in each case.
HBr
(P) excess
+ CH3 CH2 CH2 CH2 Br
HBr
(Q) excess

HBr
(R) excess

HBr
(S) excess

19. Observe the following reactions.

O O
|| HO ||
2 H O
CH3 C F CH3 C Cl 2
r1 r2
O O
|| ||
H O
CH3 C Br HO
2 CH3 C I 2
r4
r3
JYOT SILVER
Identify the order of the rate of reaction r1, r2, r3 and r4, give reason.

20. Predict the products of the following reactions
O
||
(i) + (ii) Ph C Cl +
21. Explain the order of the rate of esterification of the following acid with MeOH :
MeCH2COOH > Me2CHCOOH > Me3CCOOH > Et3CCOOH >> (i-Pr)2CHCOOH
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. H2SO4 at 453 K. Explain the mechanism of this reaction.
JYOT SILVER
29. Predict the major product of the sulphuric acid catalysed dehydration of the following alcohols :
(a) (CH3)2C(OH)CH2CH3 (b) CH3CH2 CH2CH(OH)CH3
(c) (CH3)2C(OH)CH(CH3)2 (d) (CH3)3CCH2OH
30. H
Product,

Write the major product of the reaction
Conc. H3PO4
31. A (Major) + B (Minor),

Write structures of A and B
32. Among the various isomers of C4H9Br which would undergo elimination most readily and why ?
33. A halide with formula C6H13I 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 (C7H13Br)] 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. JYOT SILVER

Which alkyl chloride would yield following pure alkene on reaction with alcoholic KOH ?

CH3
|
(i) CH3 C CH2 (ii) CH3 CH2 CH2 CH = CH2 (iii) CH3 CH2 C CH2
|
CH3
39. The sum of molecular weights of the major products P and Q form at the followng reaction is
(i) + CH3I KOH /

P (organic product)
(ii) KOH / Q (organic product)

+ CH3CH2OH
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) C6H5 CH2 CH2 Br CF3 CH2 CF3
(b) NO2 CH2 CH2 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
JYOT SILVER
PART - I : JEE PROBLEMS (PREVIOUS YEARS)
* Marked Questions are having more than one correct option.
1. An SN2 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. H3PO4 (D) HCl + ZnCl2
H
6. X, Identify X. [JEE-2005, 2/144]

JYOT SILVER
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/CH3 that is most likely to migrate to the positiviely charged carbon is
[JEE-2009, 3/160]
(A) CH3 at C-4 (B) H at C-4 (C) CH3 at C-2 (D) H at C-2
HBr
10. In the reaction OCH3 the products are : [JEE-2010, 3/163]
(A) Br OCH3 and H2 (B) Br and CH3Br
(C) Br and CH3OH (D) OH and CH3Br
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]
COOH COOH COOH CH2 COOH
JYOT SILVER
CH2COOH O COOH O
(A) (B) (C) (D)

PART - II : AIEEE PROBLEMS (PREVIOUS YEARS)
1. Following reaction
(CH3)3CBr + H2O (CH3)3COH + HBr
is an example of : [AIEEE-2002]
(1) Elimination reaction (2) Free radical substitution
(3) Nucleophilic substitution (4) Electrophilic substitution
2. SN1 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 SN2 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 (C6H5F) can be synthesized in the laboratory [AIEEE-2006]

(1) from aniline by diazotisation followed by heating the diazonium salt with HBF4
(2) by direct fluorination of benzene with F2 gas
(3) by reacting bromobenzene with NaF solution
(4) by heating phenol with HF and KF
JYOT SILVER
8. CH3Br + Nu CH3 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) CH3O] [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]
NaCN

DMF
CH2Cl CH2Cl CH2CN CH2CN

(1) (2) (3) (4)
CN
CN 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) CH2 = CH2 (3) (4)
12. Which of the following is the correct order of decreasing SN2 reactivity ? [AIEEE-2007, 3/120]
(1) RCH2X > R3CX > R2CHX (2) RCH2X > R2CHX > R3CX
(3) R3CX > R2CHX > RCH2X (4) R2CHX > R3CX > RCH2X
13. The organic chloro compound, which shows complete stereochemical inversion during an SN2 reaction, is
[AIEEE-2008, 3/105]
(1) (CH3)3CCl (2) (CH3)2CHCl (3) CH3Cl (4) (C2H5)2CHCl
14. Which of the following on heating with aqueous KOH, produces acetaldehyde ? [AIEEE-2009, 4/144]
(1) CH3CH2Cl (2) CH2ClCH2Cl (3) CH3CHCl2 (4) CH3COCl
15. From amongst the following alcohols the one that would react fastest with conc. HCl and anhydrous ZnCl2,
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]
JYOT SILVER
The correct, order of SN1 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]
NH2
NaNO 2 HBF4
A B
HCl, 278 K
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]
conc. H2SO4
C6H5CH2CH(OH)CH(CH3)2
(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 SN1 (2) tertiary alcohol by SN1
(3) secondary alcohol by SN2 (4) tertiary alcohol by SN2
JYOT SILVER
NCERT QUESTIONS
1. Write the isomers of the compound having formula C4H9Br.
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 SN2 reaction with OH?
(i) CH3Br or CH3I (ii) (CH3)3CCl or CH3Cl
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:
acetone
(i) CH3CH2CH2Cl + NaI
heat
ethanol
(ii) (CH3)3CBr + KOH
heat
(iii) CH3CH(Br)CH2CH3 + NaOH water

(iv) CH3CH2Br + KCN aq.ethanol

(v) C6H5ONa + C2H5Cl
(vi) CH3CH2CH2OH + SOCl2
(vii) CH3CH2CH = CH2 + HBr peroxide

(viii) CH3CH = C(CH3)2 + HBr
7. Write the mechanism of the following reaction :

EtOH H2 O
nBuBr + KCN nBuCN
8. Arrange the compounds of each set in order of reactivity towards SN2 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 C6H5CH2Cl and C6H5CHClC6H5, 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 C4H9Br

(a) reacted with alcoholic KOH to give compound(b).
Compound (b) is reacted with HBr to give (c) which is an isomer of (a).
JYOT SILVER
When (a) is reacted with sodium metal it gives compound (d),
C8H18 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 SN2 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.
JYOT SILVER
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. > > > H2O 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 =
JYOT SILVER
, S= pH is less than seven because acid HCl is formed

CH3
|
Slow
10. (a) CH3 CH CH CH3

| rds
OH
3 Methyl 2 butanol
H O
(b) 2

rds

11. + CH3OH
12. (a) CH
3 O / CH 3OH
CH 3 CH CH CH 2 OCH 3 S
N2
CH3CHCHCH2OCH3
CH3CHCHCH2OCH3
SN 2
| |
Cl OH O
O
H

H
H
(b) HO(CH2)3CH2OH HO

(CH 2 ) 3 CH 2 O
H 2O
O H

H O
H
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 + SOCl2 RCl + HCl + SO2

gases
Pure RCl is obtained, as the by products (HCl and SO2) are gases and get evaporated from the reaction
mixture.
16. (a) IH2C CH2 CH2 CH2 CH2OH (b) + CH3I
(c) (d)
17.
JYOT SILVER
(i) X = CH3CH(OH)CH2OH (ii) Y = CH3CH(OH)CH2OMe

18. P= Q= CH2OCH2
R= S=
19. r4 > r 3 > r 2 > r 1 rate of SN2 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 O H2 which is very good leaving group.

27. 1 carbocation R CH2 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. H2SO4 at 453 K. Explain the mechanism of this reaction.
.. +
Ans. (a) CH3CH2 O
.. H + H CH3CH2 H
Ethanol Oxonium ion
slow
(b) CH2=CH2 + H2O

CH3
29. (a) CH3 C CHCH3 (b) CH3 CH2 CH = CH CH3
CH3 CH3 CH3
(c) C C (d) CH3 C CHCH3
CH3 CH3
CH3
H
+
30.
H O
H3C
H
2
31. A:
JYOT SILVER B:

32. Tert-butyl bromide would undergo elimination most readily as the alkene formed from it would be more
stable.
33. 34. +
E2
35.
The product is formed only by E2 elimination.
HBr
36. t- is bulky base so Hoffmann product is formed as major product.
37. (a) (b)
38. (i) or ; (ii) CH3CH2CH2CH2CH2Cl ; (iii) CH3CH2CHCH2 Cl

|
CH3
39. 196
O
P= CH3 [M.F. C7H14O M.W. 84+14+16 = 114]
CH3
Q= CH3 [M.F. C6H10 M. W. 72 + 10 = 82]

M.W. (P + Q) = 114 + 82 = 196
40. Reactant should have acidic -hydrogen and poor leaving group.
41. (a) C6H5 CH2 CH2 Br < CF3 CH2 CF3 (b) NO2 CH2 CH2 Br <
42. In E1cB mechanism carbanion is formed as intermediate and 1st step is reversible.
43.
2nd step
In E1cB 1st step is reversible step so deuterium exchange take place
JYOT SILVER
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) + (SN1 product)
No reaction.
Because aryl halide have resonance stabilized C X bond, and do not give SN 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)
JYOT SILVER

Reaction Mechanism

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REACTION MECHANISM

Name : ____JYOT SILVER________________________

Polar protic solvent Polar aprotic solvent

9. DMF Dimethyl formamide

10. DMA Dimethyl acetamide

Physical & Inorganic By A-479 Indra vihar, kota Organic Chemistry By

(B) Neutral nucleophiles : It can be classified into two categories :

H3, R H2, R2 H, R3 (Phosphorus nucleophiles)

Physical & Inorganic By A-479 Indra vihar, kota Organic Chemistry By

NUCLEOPHILIC SUBSTITUTION REACTIONS (SN) AT SATURATED CARBON

NUCLEOPHILIC SUBSTITUTION REACTIONS (SN) :

UNIMOLECULAR NUCLEOPHILIC SUBSTITUTION REACTIONS (SN1) :

Characteristics of SN1 reactions :

Rate of SN1 reaction is independent of concentration and reactivity of nucleophile.

Figure : Free energy diagram for the SN1 reaction.

SN1 Reaction of Alcohols

Reactivity of ROH : allyl benzyl > 3 > 2 > 1

SN1 REACTIONS OF ETHERS

SN2 Reaction of Alkyl halide :

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SN2 Reaction of Alcohol

CH3 CH2 CH2CH2CH2Cl

(B) Reaction with phosphorus trihalides

Step : 2 RCH2X+ HOPX2

(C) Reaction with thionyl chloride in presence of pyridine

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Reaction with thionyl chloride

SN2 Reaction of Ether

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In basic medium mechanism is SN2. Nucleophile atacks on less hindered carbon.

Step 1 : Formation of the carbocation (RDS)

(iii) E1 cB Reaction (Unimolecular conjugate base reaction)

Step - 1: Consists of the removal of a proton, , by a base generating a carbanion

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

* Marked Questions are having more than one correct option.

A-3. Which of the following is an electrophilic reagent ?

A-4. Which of the following reaction intermediates are electrophilic in character ?

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

A-10. Which among the following species is an ambident nucleophile ?

A-11. Decreasing order of nucleophilicity of the following nucleophile is

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(1) H5C6 CH Br (2) C6H5CH2Br (3) H5C6 CH I (4) C6H5CH2Cl

(I) CH2Br (II) H3C CH2Br

(I) (II) (III)

B-6. Which among the following will give SN1 reaction

Select the correct answer from the codes given below :

H CH3 C H3 H CH3 OCH3

H CH3 CH3 H CH3 H

(A) (B) (C) (D)

Identify the major product :

(A) (B) (C) (D)

Which statement is correct about the above reaction ?

(A) Product (B) is (I) by SN1 mechanism.

(B) Product (B) is (II) by SN2 mechanism.

(C) Product (B) is (I) by SN2 mechanism.

C-3. The decreasing order of rate of SN2 reaction is :

Name : JYOT SILVER____________________