ORGANIC REACTION MECHANISMS-III

CONTENTS
Particular Page No.

Theory 01 – 10
Exercise - 1 11 – 17
Part - I : Subjective Questions
Part - II : Only One Option Correct Type
Part - III : Match the Columns
Exercise - 2 17 – 24
Part - I : Only One Option Correct Type
Part - II : Single or Double Digit Integer Type Questions
Part - III : One or More Than One Options Correct Type
Part - IV : Comprehensions
Exercise - 3 24 – 30
Part - I : JEE(ADVANCED) / IIT-JEE Problems (Previous Years)
Part - II : JEE(MAIN) / AIEEE Problems (Previous Years)
Answers 31– 34

Additional Problems for Self Practice (APSP) 35 – 52

Part - I : PRACTICE TEST-1 (IIT-JEE (MAIN Pattern))
Part - II : NATIONAL STANDARD EXAMINATION IN CHEMISTRY (NSEC) STAGE-I
Part - III : PRACTICE TEST-2 (IIT-JEE (ADVANCED Pattern))
APSP Answers 53
APSP Solutions 53 – 58

JEE (Advanced) Syllabus

Alkyl Halide : Nucleophilic substitution reactions of alkyl halides; Rearrangement reactions of alkyl
carbocation, Preparation of alkenes and alkynes by elimination reactions.
Haloarenes : Nucleophilic aromatic substitution in haloarenes and substituted haloarenes (excluding
Benzyne mechanism and Cine substitution).
Alcohols: Esterification, dehydration, reaction with sodium, phosphorus halides, ZnCl2/concentrated HCl.
Ethers : Preparation by Williamson’s Synthesis.

JEE(Main) SYLLABUS
Organic Reaction Mechanisms : Organic Compounds with functional groups Containing
Halogens (x):
Alkyl halides : Nature of C-X bond in haloalkanes, physical and chemical properties, mechanism of
substitution reactions, elimination reactions and rearrangement reactions , reactivity of C-X bond in
haloalkanes.
Some commercially important compounds : Dichloro, trichloro and tetrachloromethanes; freons, BHC,
DDT, their uses and important reactions.
Organic compounds with functional groups containing oxygen
Alcohols & Ethers : Methods of preparation, physical and chemical properties;
Electronic structure, Structure of functional group, some commercially important compounds.

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Organic Reaction Mechanisms-III

Nucleophilic substitution reaction (SN) :

Replacement (displacement) of an atom or group by an other atom or group in a molecule is known as
substitution reaction. If substitution reaction is brought about by a nucleophile then it is known as
nucleophilic substitution reaction. Generally substitution takes place at sp 3 carbon.
R–g + Nu–  R–Nu + g–
Types of nucleophilic substitution reaction :
(I) SN1 (II) SN2 (III) SNi

Section (A) : Unimolecular nucleophilic substitution reaction (SN1)

Nucleophilic substitution which involves two step process
(a) First step : Slow step which involves ionisation (to form carbocation)
R–g  R+ + g –
(b) Second step : Fast attack of nucleophile on carbocation results into product.
R+ + Nu–  R–Nu
(1) 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.
5. Energetics of the SN1 reaction :
Intermediate
 –
TS-1 (R---X)  –
TS-2 (R---Nu)

Figure : Free energy diagram for the SN1 reaction.

6. Factors affecting the rate of SN1 reaction :
(i) The structure of the substrate : The rds of the SN1 reaction is ionization step, a carbocation is
formed in this step. This ionisation is strongly endothermic process, rate of S N1 reaction depends
strongly on carbocation stability because carbocation is the intermediate of SN1 reaction which
determines the energy of activation of the reaction.

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Reactivity of SN1  stability of carbocation.

SN1 reactivity : 3° > 2° > 1° > CH3–X

(ii) Concentration and reactivity of the nucleophile  The rate of SN1 reaction is unaffected by the
concentration and nature of the nucleophile.
Weak and neutral nucleophile favours SN1 reaction.
Mostly solvents (protic) itself functions as nucleophiles in S N1 reaction, so SN1 reaction is termed as
solvolysis reaction.
water  hydrolysis ; C2H5OH  ethanolysis
CH3COOH  acetolysis ; NH3  ammonolysis
(iii) Effect of the solvent : (Ionising ability of the solvent)
The use of a polar protic solvent will greatly increase the rate of ionisation of an alkyl halide in any S N1
reaction because it solvate cations and anions so effectively and stabilises the transition state leading
to the intermediate carbocation and halide ion, thus the energy of activation is lower.
R–X (Solvolysis)

Solvated ions

Table - : Dielectric constants () and ionisation rate of t-Butylchloride in few common solvents
Solvent  Relative rate
H2O 80 8000
CH3OH 33 1000
C2H5OH 24 200
(CH3)2CO 21 1
CH3CO2H 6 –
(iv) The nature of the leaving group  In the SN1 reaction the leaving group begins to acquire a
negative charge as the transition state is reached` stabilisation of this developing negative charge at the
leaving group stabilises the transition state and this lowers the free energy of activation and there by
increases the rate of reaction. Leaving ability of halogen is F¯ < Cl¯ < Br¯ < I¯
7. Stereochemistry of SN1 reactions  In the SN1 mechanism, the carbocation intermediate is sp2
hybridized and planar, A nucleophile can attack on the carbocation from either face, if reactant is chiral
then attack of nucleophile from both faces gives enantiomers as the product, which is called
racemisation.
Mechanism of racemisation (SN1

Reagents for alkyl halide are : H2O , RCOOH , ROH & RSH
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Organic Reaction Mechanisms-III

H Oacetone
Ex-1. 
2
 + HBr (3° alkyl halide hence no SN2 reaction)

CH OH/Ag
Ex-2. 
3
(carbocation rearrangement)

H O
Ex-3. 
2
 + (Racemic product)
AgNO3

(2) SN1 Reaction of Alcohols

(i) 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 into 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 (OH) into 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
nucleophilic Br and I ions.
(iii) Concentrated hydrobromic acid rapidly converts t-Butyl alcohol to t-Butyl bromide. The strong acid
protonates the hydroxyl group, converting it into 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 SN1 mechanism.
(iv) 1-Butanol reacts with sodium bromide in concentrated sulfuric acid to give 1-Bromobutane by an
SN2 displacement.
NaBr, H2SO4
CH3 (CH2 )2  CH2OH   CH3 (CH2 )2  CH2Br
1  bu tanol 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 S N2 displacement.
(v) Secondary alcohols also react with HBr to form alkyl bromides usually by the S N1 mechanism.

HBr
e.g.  

(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.

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 
RDS
Mechanism : R–OH R  OH2  R R–X
H2O

Reactivity of HX : HI > HBr > HCl

Reactivity of ROH : 3° > 2° > 1°

e.g. CH3 CHCH 3 CH3 CHCH 3

| |
OH Br
Isopropyl alcohol Isopropyl bromide
CH3 CH3
| |
e.g. CH3  C  CH2 – OH CH3  C  CH2 – CH3
| |
CH3 Br

Lucas Reagent
(i) A mixture of concentrated hydrochloric acid and anhydrous zinc chloride is called the Lucas reagent.
(ii) Whether an alcohol is primary, secondary or tertiary is identified by the Lucas test, which is based
upon the difference in reactivity of the three classes of alcohol towards hydrogen halides.
(iii) Alcohol (of not more than six carbons in their molecule) are soluble in the Lucas reagent. The
corresponding alkyl chlorides are insoluble.
(iv) Formation of a chloride from an alcohol is indicated by the cloudiness that appears when the
chloride separates from the solution hence, the time required for cloudiness to appear is a measure of
the reactivity of the alcohol.
(v) A tertiary alcohol reacts immediately with the Lucas reagent, a secondary alcohol reacts within five
minutes and a primary alcohol does not react appreciably at room temperature.
anhy. ZnCl2 /HCl
e.g. CH3  CH2  CH  CH2  CH3   CH3  CH2  CH  CH2  CH3
| |
OH Cl
3  Chloropentane

Section (B) : Bimolecular nucleophilic substitution reaction (SN2)

Nucleophilic substitution in which incoming group replaces leaving group in one step only.

(1) SN2 Reaction of Alkyl halide :

Mechanism : 
 + X– (Leaving group)

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.

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Organic Reaction Mechanisms-III
4. Energetics of the reaction :

Figure : A free energy diagrams for SN2 reaction

5. No intermediates are formed in the SN2 reaction, the reaction proceed through the formation of an
unstable arrangment of atoms or groups called transition state.
6. The stereochemistry of SN2 reaction : 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
 

7. Factor's affecting the rate of SN2 reaction Number of factors affect the relative rate of SN2
reaction, the most important factors are
(i) Effect of the structure of the substrate 
SN2 reactivity CH3 > 1° > 2° >> 3° (unreactive)
The important reason behind this order of reactivity is a steric effect. Very large and bulky groups can
often hinder the formation of the required transition state and crowding raises the energy of the
transition state and slow down the rate of reaction.
Table : Relative rate of reaction of alkyl halides by SN2 mechanism.
Substituent Compound Relative rate
Methyl CH3X 30
1° CH3CH2X 1
2° (CH3)2CHX 0.02
Neopentyl (CH3)3CCH2X 0.00001
3° (CH3)3CX ~0
(ii) Concentration and reactivity of the nucleophile :
– As nucleophilicity of nucleophile increases rate of SN2 increases.
– Anionic nucleophiles mostly give SN2 reaction
– A stronger nucleophile attacks upon -carbon with faster rate than the rate of departing of leaving
group.
(iii) The effect of the solvent : Polar aprotic solvent have crowded positive centre, so they do not
solvate the anion appreciably therefore the rate of SN2 reactions increased when they are carried out in
polar aprotic solvent.
(iv) The nature of the leaving group  Weaker bases are good leaving groups. A good leaving group
always stabilise the transition state and lowers its free energy of activation and there by increases the
rate of the reaction. Order of leaving ability of halide ion F¯ < Cl¯ < Br¯ < I¯
Reagents for alkyl halide are : OH¯ , SH¯ , I¯ ,CN¯, NH3 ....... (strong anionic nucleophiles)

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Organic Reaction Mechanisms-III
aq.KOH
Ex-1. CH3–Cl  CH3–OH + Cl–

(:OH )strong nucleophile

NaOHDMF
Ex-2. CH3–CH2–CH2–Br  CH3–CH2–CH2–OH + Br–

KOHDMSO
Ex-3. 
 (inversion)

(2) SN2 Reaction of Alcohol :

(i) Reaction with HX : The protonated  unbranched primary alcohol is well suited for the SN2 reaction.

X
Mechanism : R–OH R  OH2  R–X + H2O

(ii) Reaction with phosphorus trihalides

Several phosphorus halides are useful for converting alcohols to alkyl halides. PBr 3, 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 HOPX 2, a good leaving group due to the
electronegative atoms bonded to the phosphorus.
(iii) Reaction with PCl5
SN2
R–OH + PCl5 R–Cl + HCl + POCl3
(iv) 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
||
Pyridine
R–OH + Cl  S  Cl   R–Cl + SO2 + HCl
Heat

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Mechanism :
..
.. .. O:
  – H
 R–O
.. – S + HCl
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.
Ex-1. CH3CH2CH2CH2CH2OH CH3CH2CH2CH2CH2Cl
n  Penty l alcohol n  Penty l chloride

CH3 CH3
| |
PCl3
CH3 – CH2 – CH – CH2 – OH 
Ex-2.  CH3 – CH2 – CH – CH2 – Cl

PCl
Ex-3. 
5


SOCl
Ex-4. 
2

Py

(3) SNi Reaction :

In SNi 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
ROH + SOCl2   RCl + SO2 + HCl
Mechanism :
..
 .. .. O:

 
– H
 R–O
.. – S + HCl
Cl
Chlorosulphite ester


 R – Cl + SO2

Ex-1.

SOCl
Ex-2. 
2


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Section (C) : Bimolecular aromatic nucleophilic substitution reaction

(SN2 Ar)
This is the characteristic reaction of arylhalides with ortho or para electron withdrawing substituent. The
reaction mechanism can be visualised as :

Step I  X (fast)
+ Nu 
 
RDS Step II

Intermediate ion is stabilized by resonance.

EWG  Rate of reaction 

F Cl Br I

Reactivity order towards SN2Ar : > > >

NO2 NO2 NO2 NO2

Cl OH
KOH
Ex-1. + KCl

NO2 NO2
Br OCH3
NO2 –
NO2
CH3O –
Ex-2. + Br

NO2 NO2

Section (D) : Nucleophilic substitution reaction of Ethers & Epoxides

(1) SN1 Reaction of Ethers
(i) 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 3º then mechanism will be SN1 otherwise SN2 .

X
Mechanism : R–O–R`   R`–X
– ROH


HCl
Ex. (CH3)3COC(CH3)3   (CH3 )3 C O C(CH3 )3
|
H

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 (CH3 )3 C + (CH3)3COH



 (CH3)3CCl

(ii) Reaction with H2O/H+ :

+ +
H+ + H2O
R–O–R R–O–R –ROH
R R–OH2 –H+ R–OH
H
CH3 CH3
H2O/H+
Ex. CH3–C–O–CH2–CH3 CH3–C–OH + CH3–CH2–OH
CH3 CH3
(2) SN2 Reaction of Ethers
(i) 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 3º then mechanism will be S N1
otherwise SN2.
Mechanism :

HX
+ 
 X R +   X – R + X – R
alkyl halide

H 
Ex. CH3CH2–O–CH3 

excess HBr
Ex. 


Ex.

(ii) Reaction with H2O/H+ :

H+ + H2O +
R–O–R R–O–R R–OH + R–OH2 –H+ R–OH
H
(Steric crowding R > R)

+ +
H+ H2O
Ex. CH3–CH–O–CH2–CH3 CH3–CH–O–CH2–CH3 CH3–CH–OH + CH3–CH2–OH2
CH3 CH3 H CH3 –H+

CH3–CH2–OH

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(3) Nucleophilic substitution 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.

Nu Nu
| H |
Mechanism : R — CH — CH2   R — CH — CH2
| |
O OH

Ex.

RMgX
CH3–CH–CH2 CH3–CH–CH2–CH2–R
H2O
O CH2 OH

In acidic medium mechanism is SN1 type. Nucleophile attacks on more substituted carbon.

Nu
H |
Mechanism : 
 R — CH — CH2
|
OH

H O
Ex. 
2

H

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PART - I : SUBJECTIVE QUESTIONS

Section (A) : Unimolecular nucleophilic substitution reaction (SN1)
A-1. Which compound in the following couples will react faster in SN1 reaction and why ?
(a) 1-Bromopentane or 2-Bromopentane
(b) 1-Bromo-2-methylbutane or 2-Bromo-2 methylbutane.
A-2. 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.
A-3. Why 3-Chlorocyclopropene is solvolyzed in methanol at much higher rate than 5-Chlorocyclopenta-1,3-
diene ?
A-4. For each of the following solvolysis reaction give the products (major as well as minor)

CH OH, aq.ethanol
(a) 
3
 (b) 

aq. AgNO3
(c) (d)  

A-5. Write the mechanism of the following reaction and mention the rate determining step.

(a)

(b)

Section (B) : Bimolecular nucleophilic substitution reaction (SN2 & SNi)

B-1.^ Arrange the compounds of each set in order of decreasing reactivity towards SN2 displacement.
(a) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
(b) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 2-Bromo-3-methylbutane
B-2.^ Which reacts faster
(a) PhCH2Br or PhCMe2Br (H2O / C2H5OH)
(b) PhCH2CH2Br or PhCMe2Br (Na/ Acetone)
B-3. Work out the stereochemistry of following reaction

B-4. What will be the major product of the following reaction ?

CH3 HC H
3
PCl5 NaOH
(a) CH3–CH–CH–CH3 
 (b)  
DMSO

OH H I

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B-5. Write the product of the following reaction with proper stereochemistry.

CH3 OH SOCl
(a)   (b) 
2

Ether

Section (C) : Bimolecular aromatic nucleophilic substitution reaction (SN2 Ar)

C-1. Write the correct reactivity order with NaOH for the following compounds.

C-2. Write the mechanism of following reaction :

NaOH
 


C-3. Give the products in following reactions :

Cl
O2N NO2
NH3 / Cu2O /  NaOH
(a)   (b)  


NO2

C6H5  CH2  SNa NH2  NH2

(c)   (d)  
 

Section (D) : Nucleophilic substitution reaction of Ethers & Epoxides

D-1. Predict the product of the following reactions using one equivalent of HI.

(a) (b)

D-2. Few dialkyl ethers & cyclic ethers were allowed to react with excess of HBr with the following results.
Identify the ether in each case.

HBr HBr
(P) 
 + CH3–CH2–CH2–CH2–Br ; (Q) 

excess excess

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Organic Reaction Mechanisms-III
D-3. Give the products of the following reactions

(i) X (ii) Y

PART - II : ONLY ONE OPTION CORRECT TYPE

Section (A) : Unimolecular nucleophilic substitution reaction (SN1)
A-1.^ SN1 reaction occurs through the formation of intermediate :
(A) Carbocation (B) Carbanion (C) Free radical (D) Carbene
A-2. In an SN1 reaction, the configuration of the product undergoes :
(A) inversion (B) racemization (C) retention (D) difficult to predict
A-3. When the concentration of alkyl halide is doubled and the amount of H2O taken as solvent is reduced to
half, the rate of SN1 reaction increases by:
(A) 3 times (B) 2 times (C) 1.5 times (D) 6 times
A-4. Which of the following is not expected to be intermediate of the following reaction ?

H2 O
 

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

A-5. Which of the following compound can show SN1 reaction :

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

A-6. Ph–CH2–CH–CH3 X (Major product)

OH
X is :
Cl
(A) Ph–CH2–CH–CH3 (B) Ph–CH–CH 2–CH3 (C) Ph–CH2–CH2–CH2 (D) Ph–C–CH3
Cl Cl Cl CH3

A-7. Which one of the following compound will give (d) and () form in SN1 reaction (as major product)

(A) (B)

(C) (D)

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Organic Reaction Mechanisms-III

A-8. Which describes the best stereochemical aspects of the following reaction ?

HBr
  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.
Section (B) : Bimolecular nucleophilic substitution reaction (SN2 & SNi)
B-1. SN2 mechanism proceeds through intervention of :
(A) Carbonium ion (B) Transition state (C) Free radical (D) Carbanion
B-2. In SN2 reaction if we doubled the concentration of reactant and nucleophile the rate of SN2 reaction
increases by :
(A) 2 times (B) 4 times (C) 8 times (D) No change
B-3. What is the major product obtained in the following reaction ?

NH
3
  product

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

B-4. Identify the reactants (X) and (Y) for the following reaction, respectively.
NaNH
(X) + (Y)  2
 4-Decyne
Alkyl halide Alkyne
(A) CH3(CH2)4CH2–Cl + CH3–CCH (B) CH3(CH2)2CH2–Cl + CH3–(CH2)2–CCH
(C) CH3(CH2)2CH2–Cl + CH3(CH2)3–CCH (D) CH3–CH2–CH2–Cl + CH3(CH2)4–CCH

B-5. Product, Product is :

CH3 CH3 CH3 CH3

H OH HO H H Br H D
(A) H D (B) H D (C) H OH (D) H OH
CH3 CH3 CH3 CH3

B-6. CH3 (CH2 )2 CH2OH  HBr X,

1  butanol
Identify X and the type of mechanism of the reaction?
(A) CH3–CH2–CH2–CH2–Br & SN1 (B) CH3–CH2–CH2–CH2–Br & SN2
(C) CH 3  CH  CH2  CH3 & SN1 (D) CH3  CH  CH2  CH3 & SN2
| |
Br Br
CH3
PCl
5
B-7. H OH  X ; (X) is

C2H5
(D-2-Butanol)
(A) S-2-Chlorobutane (B) R-2-Chlorobutane
(C) Mixture of R and S, 2-Chlorobutane (D) 1-Chlorobutane
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Organic Reaction Mechanisms-III
NaNH2
B-8. 6-Chlorohexan-2-ol major product is
OH
O
(A) H2N (B) Cl (C) (D)

NH2
NH2

SOCl 2
B-9.   Product
pyridine, 

Product of the above reaction is :

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

B-10. Consider the following reaction.

SOCl2 

ether
In the above reaction which phenomenon will take place :
(A) Inversion (B) Retention (C) Racemisation (D) Isomerisation
Section (C) : Bimolecular aromatic nucleophilic substitution reaction (SN2 Ar)
C-1. Which of the following reaction is SN2Ar reaction ?
CH3 CH3
NO2
   
(A) + Br +H (B) + NO2 +H

 
Br + OH OH+ Br
(C) (D)

C-2. Which of the following compound gives fastest SN2 Ar reaction ?

Cl Cl Cl
NO2
(A) (B) (C) (D)

NO2 NO2

RONa / 
C-3.  

Above reaction has maximum rate when :

(A) Y = – I (B) Y = – Br (C) Y = – Cl (D) Y = – F

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Organic Reaction Mechanisms-III

(CH3 )2 NH
C-4.   The product is :
Cu2 O, 

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

Section (D) : Nucleophilic substitution reaction of Ethers & Epoxides

HCl / 
D-1. In the given reaction, CH3–CH2–CH2–O–CH2–CH3   [X] + [Y]
[X] and [Y] respectively will be :
(A) CH3–CH2 –CH2OH & CH3–CH2 –Cl (B) CH3–CH2–CH2–Cl & CH3–CH2–OH
(C) CH3–CH2–CH2–Cl & CH2=CH2 (D) CH3–CH=CH2 & CH2=CH2

H3O
D-2.  X+Y

The products X and Y are

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

HBr
D-3.  (P) + (Q)
Alcohol Alkyl halide

(P) & (Q) respectively is :

(A) , CH3–Br (B) Ph–CH2–OH, CH3–CH2–Br

(C) CH3–OH, (D) CH3–OH, Ph–CH3–CH2–Br

Et2O (i)
D-4. + (CH3)2CHMgBr  
(ii) H2 O

What will be the product :

(A) CH3–(CH2)4–CH2–OH (B) CH3  CH  CH  CH  CH3
|
CH3

(C) (D) CH3  CH  CH2  CH3

|
CH(CH3 )2
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PART - III : MATCH THE COLUMN

1. Match List-I (Alkyl chloride) with List-II (Rates of solvolysis) and select the correct answer using the
code given below the lists :
List-I List-II
(P) Cl (1) 1

(Q) (2) 0.07

Cl
(R) Cl (3) 7700
(S) Ph Cl (4) 91
Codes :
(A) P–2 ; Q–1 ; R–4 ; S–3 (B) P–2 ; Q–1 ; R–3 ; S–4
(C) P–1 ; Q–2 ; R–3 ; S–4 (D) P–1 ; Q–2 ; R–4 ; S–3
2. Match the column-I with column-II :
Column-I Column-II
Substrate Stereochemistry of product
Ph

(A) C + H2O  (p) Retention

H Cl
CH3
CH3

(B) C + SH–  (q) Racemisation

D Br
H
Ph

(C) C Ether
+ SOCl2  (r) Inversion
H OH
CH3
Ph
C + PCl3 
(D) (s) Intermediate is carbocation
H OH
CH3

PART - I : ONLY ONE OPTION CORRECT TYPE

1. Arrange the following compounds in order of decreasing reactivity towards SN1 reaction.
I I I

(i) (ii) (iii)

O
(A) ii > iii > i (B) i > ii > iii (C) iii < ii < i (D) i > iii > ii
2. The decreasing order of rate of SN2 reaction for given compounds is :
(I) CH3–Cl (II) CH3  C  CH2  Cl (III) (IV) CH3–CH2–Cl
||
O
(A) IV > III > II > I (B) II > III > I > IV (C) II > I > IV > III (D) none

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3. In an SN1 reaction of alkyl halide on chiral centres there is :
(A) 100 % racemization
(B) inversion more than retention leading to partial racemization
(C) 100 % retention
(D) 100 % inversion
4.^ Following are the curves for nucleophilic substitution reaction.

(I) (II)

(III)

The correct statement is :

(A) ‘I’ is potential energy diagram for SN2 reaction that takes place with a negative potential energy
change.
(B) ‘II’ is potential energy diagram for SN2 reaction with a positive potential energy change
(C) ‘III’ shows potential energy diagram for SN1 reaction with large energy of activation for first
(slowest) step
(D) All of the above
5. Aryl halides are less reactive towards nucleophilic substitution reactions as compared to alkyl halides
due to
(A) The formation of less stable carbanion (B) Longer carbon halogen bond
2
(C) The inductive effect (D) sp –hybridized carbon attached to the halogen

HBr HBr
6.  (A) ,
  (B)

 

The product (A) and (B) are respectively :

(A) & (B) &

(C) & (D) &

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Organic Reaction Mechanisms-III
7. SN1 reaction underoges through a carbocation intermediate as follows :

[R = t-Bu, iso-Pr, Et, Me] (X = Cl, Br, I)

The correct statements are
I. The decreasing order of rate of SN1 reaction is t-BuX > iso-PrX > EtX > MeX
II. The decreasing order of ionisation energy is MeX > EtX > iso-PrX > t-BuX
III. The decreasing order of energy of activation is t-BuX > iso-PrX >EtX > MeX
(A) I & II are correct (B) I & III are correct (C) II and III are correct (D) I, II & III are correct
Cl
H2O +
8.
OH OH
(R)
optically active
What is correct for the above reaction :
(A) Total three products are formed.
(B) Products mixture is optically active.
(C) Total two products are chiral.
(D) Intermediate carbocation is not formed in the reaction.
9. In the following reaction the most probable product will be :

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

EtONa
(1 mol)
10.   The product is :


NO2

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

EtO Cl
Cl

2 Br / Fe Conc. HBr
11.  product is -
 



(A) CH2Br + HO Br (B) CH2+ Br Br

OH
(C) (D)

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Organic Reaction Mechanisms-III
Ph
18
12. C CH2 H2O , The major product is
CH3 O H+
Ph Ph
| |
(A) CH3 – C – CH2 with retention, optically active (B) CH3 – C – CH2 with racemisation
| | | |
18
OH OH OH OH
18
18
Ph OH OH
| | |
(C) CH3 – C – CH2 with inversion, optically active (D) CH3 – C – CH2 with racemisation
| | |
18
OH OH Ph

PART - II : SINGLE AND DOUBLE VALUE INTEGER TYPE

1. The most reactive chlorine towards H2O is :

2. When the concentration of alkyl halide is tripled and the concentration of ion is reduced to half, the
rate of SN2 reaction increases by X times. Report your answer as 10 X.

PCl5 NaSH OH ( X)
3. CH2–OH   (X)      CH2–S–CH2

The number of times where SN2 reaction taken place in above reaction sequence is
4. Among the 6, how many cyclic isomers of molecular formula C7H13Br can form 1-methylcyclohexane-1-
ol on reaction with H2O/acetone/Ag+.

(i) (ii) (iii)

(iv) (v) (vi)

5. How many of the following compounds will give white precipitate with aqueous AgNO3.

(i) (ii) (iii)

Ph Ph
| |
(iv) (v) (vi) Ph — C — C — Ph
| |
OH Cl

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6. Find the total number of isomeric products obtained in these reactions. Report your answer as X Y :

H O/ AgNO HCl/ ZnCl

2 3
 X ; 2
  Y

7. In the following reaction the nucleophile (MeO) will displace which of the halogen atom most readily.

8.  Number of possible isomeric products including stereoisomers



will be :

PART - III : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. Which of the following order is/are correct for the solvolysis in 50% aqueous ethanol at 44.6°C.
(A) < <

(B) < <

(C) < <

(D) < <

2. Observe the following reaction I and II k1k1, k2k2 are rate constants. Select the correct option(s).

(I) CH3 – I

(II) CH3  CH  CH3

|
I
(A) k1 > k1 (B) k1 > k2 (C) k2 > k2 (D) k2 > k1

3. +  A (Major)

major product of this reaction is.

F
(A) NC (B)
H
H

(C) (D)

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Organic Reaction Mechanisms-III

TsCl NaBr
4.    X   Y. X and Y are :
Pyridine

(A) X = (B) Y = (C) X = (D) Y =

5.* Which of the following conditions are favour for SN2 mechanism in alkyl halides ?
(A) Strong nucleophile (B) High conc. of nucleophile
(C) 3º alkyl halide (D) Polar protic solvent
6. Which of the following reactions are nucleophilic substitution reaction ?

PCl5 C H  CH  SNa
(A) CH3 – CH2 – CH – Ph   (B) 6 5 2
 
| 
OH

SOCl HI
(C) 2
  (D) 

7. Identify correct steps representing SN1 mechanism for the cleavage of ether with HI
R–O–R + HI 


slow slow
(A)  RI + HOR (R is 1°)
 (B) 
 (R is 3°) + ROH
(rds) (rds)
fast slow
(C)   RI (D)  R–I

(rds)

O O
(1) KOH (2) R-X
8. NH 1 eq N—R

O O
In which option correct rate for step-2 is given for the different R–X
(A) CH3–CH2–Br < CH 3—CH—CH3 (B) Ph–Cl > CH3–CI
Br
(C) Ph–CH2–Br > (D) CH2=CH–CH2–CI > CH3–CH2–CH2– Cl

9. X+Y
In the above reaction which of the following are correct.
(A) step-1 is an acid-base reaction (B) step-2 is an SN2 reaction
nd
(C) X = n-Butane; Y = aromatic compound (D) the nucleophile in 2 reaction is
10.^ CH3Br + NH3  
 [(CH3)4] N Br
excess salt
About the salt obtained which is true ?
(A) by SN2 mechanism. (B) NH3 is nucleophile.
(C) by SN1 mechanism (D) 4 equivalent of NH3 is used during reaction.
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PART - IV : COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension # 1
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 the chiral 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 reactions, the reaction mechanism respectively is :

() 
 () 
 +

() 
 (V) 


(A) SN2, SN1, SN2, SNi (B) SN2, SN1, SNi, SN2 (C) SN1, SN2, SNi, SN1 (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) 

D
C2H5 CH3
Na
(C) CH3 Br + HOH 
 (D) H OTs  
C3H7 C2 H5
Comprehension # 2
An organic compound ‘A’ has molecular formula C5H9Br decolorises brown colour of bromine water but
does not rotate plane polarised light. ‘A’ on treatment with HBr/ROOR forms C5H10Br2 which on further

treatment with NaOH(aq) gives the cyclic ether

O
4. The starting compound ‘A’ most likely to be.
(A) (B) Br
Br
Br
(C) (D)
Br

5. Compound ‘A’ on treatment with HBr will produce

(A) An achiral dibromide (B) A racemic mixture
(C) A single pure enantiomer (D) A meso dibromide

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Organic Reaction Mechanisms-III
Comprehension # 3
Answer Q.6, Q.7 and Q.8 by appropriately matching the information given in the three columns
of the following table.

Columns 1,2 and 3 contain reactants, reagents & products respectively.

Column-1 Column-2 Column-3
*
Ph–CH–CH3
(I) Ph–CH2–CH2–Br (i) NaOH/H2O (P)
OH
(±)

CH3 Me
(II) H Br (ii) HI, H2O/acetone (Q) HO H
Ph Ph
CH3
(III) H OH (iii) NaOH/DMSO (R) Ph–CH2–CH2–OH
Ph
Me
(IV) Ph–CH2–CH2–OH (iv) SOCl2/Pyridine, (NaOH/DMF) (S) H OH
Ph
6._ SN1 + SN2 mixed mechanism is oleserved in the reaction :
(A) (I), (iii) (P) (B) (II) (i) (P) (C) (III) (iv) (Q) (D) (IV) (ii) (S)
7._ Only SN1 mechanism is observed in :
(A) (I), (i) (R) (B) (II) (iii) (P) (C) (IV) (ii) (S) (D) (III) (ii) (P)
8._ SN2 mechanism is observed in :
(A) (I), (iii) (R) (B) (IV) (iv) (R) (C) (II) (iii) (Q) (D) all

PART - I : JEE (ADVANCED) / IIT-JEE PROBLEMS (PREVIOUS YEARS)

* Marked questions may have more than one correct option.
1. An SN2 reaction at an asymmetric carbon of a compound always gives : [IIT-JEE-2001(S), 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. The compound that will react most readily with NaOH to form methanol is : [IIT-JEE-2001(S), 1/135]
+ – + –
(A) (CH3)4N I (B) CH3OCH3 (C) (CH3)3S I (D) (CH3)3C–Cl
3. Cyclobutyl bromide on treatment with magnesium in dry ether forms an organometallic (A). The
organometallic (A) reacts with ethanal to give an alcohol (B) after mild acidification. Prolonged
treatment of alcohol (B) with an equivalent amount of HBr gives1-bromo-1-methyl cyclopentane (C).
Write the structures of (A), (B) and explain how (C) is obtained from (B). [IIT-JEE-2001(S), 5/135]
4. Identify X, Y and Z in the following synthetic scheme and write their structures.
(i) NaNH
2 2 4 H / Pd . BaSO alkaline KMnO
CH3CH2CC–H   X 
(ii) CH CH Br
 Y 
4
 Z
3 2

Is the compound Z optically active ? Justify your answer. [IIT-JEE-2002(M), 5/150]

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–
O C2H5 (excess)
5. + C2H5I   product, major product is [JEE-2003(S), 3/144]
Anhydrous(C2H5 OH)

(A) C6H5OC2H5 (B) C2H5OC2H5 (C) C6H5OC6H5 (D) C6H5I

6. 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(S), 4/144]

7. Compound (X) is reacted with aqueous acetone it gives following

products. [JEE(S)2005, 3/144]

(A) K, L (B) K, M (C) L only (D) M only

8. Explain the following observations : [JEE 2005(M), 4/144]

(A) Acidic solution

Neutral solution

(B) + F¯

No release of F¯

(C) but not

(D) +

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9. The major product of the following reaction is [JEE-2008, 3/162]

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

HBr
10. In the reaction OCH3   the products are : [JEE-2010, 3/160]

(A) Br OCH3 and H2 (B) Br and CH3Br

(C) Br and CH3OH (D) OHand CH3Br

11. The synthesis of 3-octyne is achieved by adding a bromoalkane into a mixture of sodium amide and an
alkyne. The bromoalkane and alkyne respectively are : [JEE-2010, 3/160]
(A) BrCH2CH2CH2CH2CH3 and CH3CH2CCH (B) BrCH2CH2CH3 and CH3CH2CH2CCH
(C) BrCH2CH2CH2CH2CH3 and CH3CCH (D) BrCH2CH2CH2CH3 and CH3CH2CCH
12. The major product of the following reaction is : [JEE-2011, 3/163]

(A) (B)

(C) (D)

13. KI in acetone, undergoes SN2 reaction with each P, Q, R and S. The rates of the reaction vary as

H3C–Cl [JEE-2013, 2/126]

P Q R S
(A) P > Q > R > S (B) S > P > R > Q (C) P > R > Q > S (D) R > P > S > Q

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14. The major product in the following reaction is : [JEE(Advanced)-2014, 3/120]

OH

(A) (B)

(C) (D)

15. The acidic hydrolysis of ether (X) shown below is fastest when : [JEE(Advanced)-2014, 3/120]

(A) one phenyl group is replaced by a methyl group.

(B) one phenyl group is replaced by a para-methoxyphenyl group.
(C) two phenyl groups are replaced by two para-methoxyphenyl groups.
(D) no structural change is made to X.
Paragraph for questions 16 and 17
Schemes 1 and 2 describe sequential transformation of alkynes M and N. Consider only the major
products formed in each step for both the schemes.
1. NaNH2 (excess)
H 2. CH3CH2I (1 equivalent)
HO X Scheme-1
M 3. CH3I (1 equivalent)
4. H2, Lindlar's catalyst

Y Scheme-2

16. The product X is : [JEE(Advanced)-2014, 3/120]

H3CO

(A) (B)
H H
CH3CH2O H

(C) (D) H
H H CH3CH2O
17. The correct statement with respect to product Y is [JEE(Advanced)-2014, 3/120]
(A) It gives a positive Tollens test and is a functional isomer of X.
(B) It gives a positive Tollens test and is a geometrical isomer of X.
(C) It gives a positive iodoform test and is a functional isomer of X.
(D) It gives a positive iodoform test and is a geometrical isomer of X.

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18. The major product of the reaction is [JEE(Advanced)-2015, 4/120]
H3C CO2H
NaNO2, aqueous HCl
CH3 NH2 0ºC
H3C NH2 H3C CO2H
(A) (B)
CH3 OH CH3 OH
H3C CO2H H3C NH2
(C) (D)
CH3 OH CH3 OH

19.* For the following compounds, the correct statement(s) with respect to nucleophilic substitution reaction
is (are) [JEE(Advanced)-2017, 4/122]
CH3 CH3
Br Br H3C—C—Br Br

CH3
I II III IV
(A) Compound IV undergoes inversion of configuration
(B) The order of reactivity for I, III and IV is : IV > I >III
(C) I and III follow SN1 mechanism
(D) I and II follow SN2 mechanism

PART - II : JEE (MAIN) / AIEEE PROBLEMS (PREVIOUS YEARS)

1. SN1 reaction is feasible in : [AIEEE-2002, 3/225]

(1) (CH3)3C–Cl + KOH 

 (2) + KOH 


(3) (4)

H2O
2. The reaction : (CH3)3C–Br   (CH3)3C–OH is an example of - [AIEEE-2002, 3/225]
(1) elimination reaction. (2) substitution reaction.
(3) free radical reaction. (4) rearrangement reaction.

3. Bottles containing C6H5I and C6H5CH2I lost their original labels. They were labelled A and B for testing.
A and B were separately taken in a test tube and boiled with NaOH solution. The end solution in each
tube was made acidic with dilute HNO3 and then some AgNO3 solution was added. Substance B gave a
yellow precipitate. Which one of the following statements is true for this experiment ?
[AIEEE-2003, 3/225]
(1) A was C6H5I (2) A was C6H5CH2I
(3) B was C6H5I (4) Addition of HNO3 was unnecessary

4. Tertiary alkyl halides are practically inert to substitution by SN2 mechanism because of:
[AIEEE-2005, 3/225]
(1) steric hinderance (2) inductive effect (3) instability (4) insolubility

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5. The structure of the major product formed in the following reaction is : [AIEEE-2006, 3/165]

NaCN

DMF

CH2Cl CH2Cl CH2CN CH2CN

(1) (2) (3) (4)
CN
 CN  CN

6. 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, 3/165]
(1) D > C > A > B (2) D > C > B > A (3) A > B > C > D (4) B > D > C > A
7. 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
8. 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
9. Which of the following on heating with aqueous KOH, produces acetaldehyde ? [AIEEE-2009, 4/144]
(1) CH3CH2Cl (2) CH2ClCH2Cl (3) CH3CHCl2 (4) CH3COCl
10. 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
11. Consider the following bromides : [AIEEE-2010, 4/144]

The correct order of SN1 reactivity is :

(1) B > C > A (2) B > A > C (3) C > B > A (4) A > B > C
12. A solution of (–)-1-chloro-1-phenylethane in toluene racemises slowly in the presence of a small
amount of SbCl5, due to the formation of : [JEE(Main) 2013, 4/120]
(1) carbanion (2) carbene (3) carbocation (4) free radical
13. An unknown alochol 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(Main) 2013, 4/120]
(1) secondary alcohol by SN1 (2) tertiary alcohol by SN1
(3) secondary alcohol by SN2 (4) tertiary alcohol by SN2
14. In SN2 reactions, the correct order of reactivity for the following compounds: CH3Cl, CH3CH2Cl,
(CH3)2CHCl and (CH3)3CCl is : [JEE(Main) 2014, 4/120]
(1) CH3Cl > (CH3)2CHCl > CH3CH2Cl > (CH3)3CCl
(2) CH3Cl > CH3CH2Cl > (CH3)2CHCl > (CH3)3CCl
(3) CH3CH2Cl > CH3Cl > (CH3)2CHCl > (CH3)3CCl
(4) (CH3)2CHCl > CH3CH2Cl > CH3Cl > (CH3)3CCl
15. The synthesis of alkyl fluorides is best accomplished by : [JEE(Main) 2015, 4/120]
(1) Free radical fluorination (2) Sandmeyer's reaction
(3) Finkelstein reaction (4) Swarts reaction

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16. The product of the reaction give below is : [JEE(Main) 2016, 4/120]
1. NBS/h
X
2. H2O/K2CO3

OH O CO2H
(1) (2) (3) (4)

17. The increasing order of the reactivity of the following halides for the SN1 reaction is :
[JEE(Main) 2017, 4/120]
CH3CHCH2CH3 CH3CH2CH2Cl p–H3CO–C6H4–CH2Cl

Cl
(I) (II) (III)
(1) (II) < (I) < (III) (2) (I) < (III) < (II) (3) (II) < (III) < (I) (4) (III) < (II) < (I)

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EXERCISE - 1
PART – I
A-1. (a) 2-Bromopentane (b) 2-Bromo-2-methylbutane
A-2. (a) Rate - doubled (b) Rate – tripled
A-3. 3-Chlorocyclopropene form aromatic carbocation while 5-Chlorocyclopenta-1,3-diene form antiaromatic
carbocation.

CH3 OH, 
A-4. (a)   +
SN 1 alcoholysis

aq .ethanol
(b)   +
SN 1

(c) +

aq . AgNO3
(d)   +
SN 1

CH3
|
CH3  CH  CH  CH3 Slow
A-5. (a)  
| rds
OH
3  Methyl  2  butanol

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H O
(b) 2
 
rds

B-1. (a) > >

(b) > >

B-2. (a) PhCMe2Br (b) PhCH2CH2Br

B-3. X= Y=

CH3
H 3C OH
B-4. (a) CH3–CH–CH–CH3 (b)
Cl H H

B-5. (a) + (b)

C-1. II > III > I

C-2. Mechanism 
Cl Cl OH Cl OH Cl OH OH
OH Cl

NO2 NO2 NO2 NO2 NO2

OH

O2N NO2
C-3. (a) (b) (c) (d)

NO2

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D-1. (a) + CH3I (b)

D-2. P= Q= CH2OCH2

D-3. (i) X = CH3CH(OH)CH2OH (ii) Y = CH3CH(OH)CH2OMe

PART – II
A-1. (A) A-2. (B) A-3. (B) A-4. (A) A-5. (D)
A-6. (B) A-7. (B) A-8. (C) B-1. (B) B-2. (B)
B-3. (A) B-4. (D) B-5. (B) B-6. (B) B-7. (B)
B-8. (D) B-9. (A) B-10. (B) C-1. (C) C-2. (C)
C-3. (D) C-4. (B) D-1. (A) D-2. (B) D-3. (C)
D-4. (C)

PART – III
1. (A) 2. (A)  q,s ; (B)  r ; (C)  p ; (D)  r

EXERCISE – 2

PART – I
1. (B) 2. (C) 3. (B) 4. (D) 5. (D)
6. (A) 7. (A) 8. (C) 9. (B) 10. (A)
11. (A) 12. (C)

PART – II
1. 3 2. 15 3. 3 4. 5 (Except (ii))
5. 4 (Except (i, iv)) 6. 22 7. 2 8. 4
PART – III
1. (BC) 2. (AB) 3. (AC) 4. (AB) 5. (AB)
6. (ABCD) 7. (BC) 8. (CD) 9. (ABC) 10. (AB)

PART – IV
1. (B) 2. (C) 3. (B) 4. (C) 5. (B)
6. (B) 7. (D) 8. (D)

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EXERCISE – 3
PART – I
1. (D) 2. (C)

3. (A) = ; (B) = ; (C) =

(i) NaNH
4. CH3–CH2–CCH 
(  NH3 )
2
 CH3–CH2–CCNa


CH3  CH2  C  C  CH2  CH3 CH3–CH2–C C . CH2  CH3 

| | (Compound ' X )
H H
y  cis  Hex  3  ene
OH OH
| |
CH3  CH2  C  C  CH2  CH3
| |
H H
(Compound ' Z' )

5. (B)

6. 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)

7. (A)
1 1
8. (A) In 1st SN reaction is possible so by-product is HBr in 2nd SN reaction is not possible.
2
(B) 1st can give SN Ar but 2nd can not give because –m of –NO2 is not opperating.
(C) 2nd product has two antiaromatic rings but 1st does not have antiaromatic system.
(D) –NO2 is metadirecting but –N=O group is ortho-para directing due to +m of –N=O.
9. (A) 10. (D) 11. (D) 12. (A) 13. (B)
14. (D) 15. (C) 16. (A) 17. (C) 18. (C)
19. (ACD)

PART – II
1. (1) 2. (2) 3. (1) 4. (1) 5. (3)
6. (1) 7. (2) 8. (3) 9. (3) 10. (2)
11. (1) 12. (3) 13. (2) 14. (2) 15. (4)
16. (1) 17. (1)

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This Section is not meant for classroom discussion. It is being given to promote self-study
and self testing amongst the Resonance students.

PART - I : PRACTICE TEST-1 (IIT-JEE (MAIN Pattern))

Max. Time : 1 Hr. Max. Marks : 120
Important Instructions
1. The test is of 1 hour duration.
2. The Test Booklet consists of 30 questions. The maximum marks are 120.
3. Each question is allotted 4 (four) marks for correct response.
4. Candidates will be awarded marks as stated above in Instructions No. 3 for correct response of each
question. ¼ (one fourth) marks will be deducted for indicating incorrect response of each question. No
deduction from the total score will be made if no response is indicated for an item in the answer sheet.
5. There is only one correct response for each question. Filling up more than one response in any
question will be treated as wrong response and marks for wrong response will be deducted accordingly
as per instructions 4 above.
1. The reaction most likely occurs by which of the following mechanism ?

CH O
3


 (1) Addition-elimination (2) addition only (3) Elimination-addition (4) Neither of these
2. The product 'P' is
F

OH
NaOH / 
I P (major)
NO2
OH F

(1) OH (2)
OH O
NO2 NO2
O OH

(3) (4) OH
I OH
NO2 OH
HO OH
SOCl2
3. Product is :
Pyridine
Cl Cl HO Cl
(1) (2)

Cl
Cl Cl
HO
(3) (4)

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CH2–Cl
H2O
4. Product is :

Cl
CH2–Cl CH2–OH CH2–OH
(1) (2) (3) (4)

OH OH Cl

acetone
5. + KOH  Product

(1R, 3S)–Cis–1–Bromo–3–methylcyclohexane.
The product formed in the reaction is
(1) (1R, 3S)-Cis-3-methyl cyclohexanol (2) (1S, 3S)-Cis-3- methyl cyclohexanol
(3) (1S, 3S)-Trans-3-methyl cyclohexanol (4) (1R, 3R)-Trans-3-methyl cyclohexanol
6. Which configuation will be adopted by the poduct at cabon atoms marked (1) and (2) respectively in the
given reaction.
CH3
|
* Ether 
CH – SNa + CH3 CH2  C H  CH3 
* |
(R) (R ) Br
(1) R, R (2) R, S (3) S, S (4) S, R
7. What is the correct order of reactivity of alcohols in the following reaction?
R–OH + HCl + ZnCl2  R–Cl + H2O
(1) Ethanol > Propan-1-ol > Butan-2-ol (2) Butan-1-ol > Propan-1-ol > Butan-2-ol
(3) Neopentyl alcohol > t-Butyl alcohol > Methanol (4) t-Butyl alcohol > Butan-2-ol > Propan-1-ol
8. The increasing order of reactivity of the following isomeric halides with AgNO3 (H2O + alcohol) is :
(I) C6H5–CH=CH–CH2–CH2–Cl (II) C 6H5  CH  CH  CH  CH3
|
Cl
C 6H5
|
(III) C 6H5  C  CH  CH2  CH3 (IV) C 6H5  C  CH  CH2
| |
Cl Cl

(1) III < IV < II < I (2) I < III < IV < II (3) III < I < II < IV (4) I < II < IV < III

H2O H2O
9. (1)  (2) 
r1 r2

H2O
(3) 
r3
the rates r1, r2 and r3 are in the order :
(1) r1 > r2 > r3 (2) r3 > r1 > r2 (3) r1 > r3 > r2 (4) r2 > r1 > r3

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H2O
10.  ‘Y’ Product :
AgNO3

(1) (2) (3) (4)

11. What will be the major product of the following reaction

Product

(1) (2) (3) (4)

HCl / ZnCl
12. 2
  [X]

Identify product X and the mechanism of the reaction.

(1) CH3–CH2–CH2–CH2–Cl & SN1 (2) CH3–CH2–CH2–CH2–Cl & SN2
(3) CH3  CH  CH2  CH3 & SN1 (4) CH3  CH  CH2  CH3 & SN2
| |
Cl Cl

13. Which of the following curve correctly represents SN1 vs SN2

(1) (2)

(3) (4)

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14. The final product of the following reaction is :

DMSO
+ 

NO2
(1) O2N (2)

(3) (4)

15. Product

Product and mechanism of the reaction respectively is :

(1) , SN1 (2) , SN2 (3) , SN2 (4) , SN1

16. Consider the following reactions, which are carried out at the same temperature.
EtOH
CH3–Br + OH   CH3–OH + Br

....(i)
 DMSO 
CH3–Br + OH   CH3–OH + Br ....(ii)
Which of the following statement is correct about these reactions.
(1) Both the reactions take place at the same rate
(2) The first reaction takes place faster than second reaction.
(3) The second reaction takes place faster than first reaction.
(4) Both the reactions take place by SN1 mechanism

2SOCl
17.   Product, Identify the product

(1) (2) (3) (4)

NaOH(aq.)
18. Cl–CH2CH2CH2CH2OH   A, the product A is

(1) HO–CH2CH2CH2CH2OH (2)

(3) (4) ClCH2CH2CH2CH2ONa

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19. Which of the following reactions is the best choice for preparing methyl cyclohexyl ether ?

(1) + CH3I  (2) + CH3ONa 

(3) + CH3I  (4) + CH3OH 

20. Which product would be expected to predominate in the given reaction ?

CH OH
3



(1) (2) (3) (4)

21. Select correct statement

(1) Solvolysis of (CH3)2C=CH–CH2–Cl in ethanol is faster than primary alkyl chloride (25°C)
(2) CH3–CH=CH–CH2–OH when reacts with HBr give a mixture of 1-bromo-2-butene and 3-bromo 1-
butene.
(3) When solution of 3-buten-2-ol in aqueous sulphuric acid is allowed to stand for one week, it was
found to contain both 3-buten-2-ol and 2-buten-1-ol
(4) All of these

22. (CH3)3C–O–CH2–C6H5 can be prepared from Williamsons synthesis, using :

(1) (CH3)3C–Cl and C6H5CH2ONa (2) C6H5CH2Cl and (CH3)3C–ONa
(3) (CH3)3C–O–CH2–Cl and C6H5ONa (4) All of these

23. Consider the following reactions carried out at the same temperature.

(I) (II)

Which of the following statement is correct about these reaction.

(1) Both the reactions take place at the same rate
(2) The first reaction takes place faster than second reaction.
(3) The second reaction takes place faster than first reaction.
(4) Both the reactions take place by SN1 mechanism

24. Product,
Identify the major product :

(1) (2) (3) (4)

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EtO–K 
25.  A
EtOH

The product A is :

(1) (2)

(3) (4)

26. Which of the following statement is not true ?

(1) Nucleophiles possess unshared pairs of electron which are utillized in forming bonds with
electrophilic substrate.
(2) The cyanide ion is an ambident nucleophile and causes nucleophilic substitution of alkyl halide by
either of its carbon atom or nitrogen atom.
(3) The nitrite ion is an ambident nucleophile and causes nucleophilic substitution of alkyl halide by
either of its oxygen atom or nitrogen atom.
(4) Strength of nucleophile generally decreases on going down a group in the periodic table.
27. Which of the following statements are correct for the given alcohol ?

X
R – OH 
 R – X + OH
  
(1) Reaction will not take place because OH is poor leaving group; X is weak base and OH is strong
base
  
(2) Reaction will not take place because OH is poor leaving group; X is strong base and OH is weak
base.
  
(3) Reaction will not take place because OH is strong leaving group; X is strong base and OH is
weak base.
  
(4) Reaction will not take place because OH is good leaving group; X is weak base OH and is strong
base.
28. Identify the product in the following reaction ?
Cl
NO2
C6H5CH2SK, 

Br (1 eq)
CH3
SCH2C6H5 Cl
NO2
(1) (2)
Br NO2 C6H5CH2S
CH3 CH3
SCH2C6H5 Cl
NO2 C6H5CH2S NO2
(3) (4)
Br Br
CH3 CH3

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Reaction (I)
Me aq.H (1 eq.)
—O—Me (B+C)
29. Me
Me (A) Anhyd.HI (1 eq.)
(D+E)
Reaction (II)
Which of the following statements is correct ?
(i) The compounds (B) and (C) are Me3C—I and MeOH and reaction (I) proceeds by SN1 mechanism.
(ii) The compound (B) and (C) are Me3C–OH and Me and reaction (I) proceeds by SN2 mechanism.
(iii) The compound (E) and (D) are Me3C—I and MeOH and reaction (II) proceeds by SN1 mechanism.
(iv) The compound (E) and (D) are Me3C—OH and Me and reaction (II) proceeds by SN2 mechanism.
(1) (i) and (iii) (2) (ii) and (iii) (3) (i) and (iv) (4) (ii) and (iv)
30. Which of the following compound is least reactive in the nucleophilic aromatic substitution reaction with
NaOH?
(1) p-nitrofluorobenzene (2) p-nitrochlorobenzene
(3) p-nitrobromobenzene (4) p-nitroiodobenzene

Practice Test-1 (IIT-JEE (Main Pattern))

OBJECTIVE RESPONSE SHEET (ORS)

Que. 1 2 3 4 5 6 7 8 9 10

Ans.

Que. 11 12 13 14 15 16 17 18 19 20

Ans.

Que. 21 22 23 24 25 26 27 28 29 30

Ans.

PART - II : NATIONAL STANDARD EXAMINATION IN CHEMISTRY (NSEC) STAGE-I

1. A compound A has the molecular formula C5H9CI. It does not react with bromine in carbon
tetrachloride. On treatment with a strong base it produces a single compound B. B has a molecular
formula C5H8 and reacts with bromine in carbon tetrachloride. Ozonolysis of B produces a compound C
which has a molecular formula C5H8O2. Which of the following structures is that of A ? [NSEC-2000]

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

2. Find the identity of compound B in the following reaction sequence [NSEC-2000]

CH  CNa + CH3CH2CH2CH2Br  A
A + CI2  B
1 mol 1 mol
(A) trans-1,2-dichloro-1-hexene (B) cis-1,2-dichloro-1-hexene
(C) cis-1,2-dichlorobutane (D) trans-2,3-dichloro-2-hexene

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3. What is the effect of doubling the concentration of HCl on the rate of reaction between t-butyl alcohol
and HCl ? [NSEC-2000]
(A) It has no effect on the rate of reaction
(B) It halves the rate of reaction
(C) It doubles the rate of reaction
(D) It is not possible to predict its effect on the reaction.
4. The compound which undergoes SN1 reaction most rapidly is [NSEC-2003]

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

5. The aprotic polar solvent is [NSEC-2003]

(A) isopropanol (B) 1,2-dichloroethane (C) nitrobenzene (D) chloroform.
6. The reagent wihch can react with 1-chlorobutane to give substitution reaction is [NSEC-2003]
(A) AICI3 (B) KOH-MeOH (C) NaCN (D) Mg-ether
7. Compound which undergoes nucleophilic substitution reactions most readily is [NSEC-2003]

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

8. The following sequence of reactions give [NSEC-2004]

O H3 O 
+ CH3MgBr  

(A) 1-butanol (B) 2-butanol (C) 3,4-hexanediol (D) 3-methyl-3-pentanol.

9. The reagent which can react with 2-bromopropane to give mainly a substitution product is:
[NSEC-2004]
(A) sodium sulphate (B) sodium cyanide (C) sodium chloride (D) sodium ethoxide.
10. Arrange in order of decrease in rates of SN2 reaction. [NSEC-2005]
Cl
I. II. CH3Cl III. Cl IV.
Cl
(A) I > II > lll >IV (B) VI > II > I > lll (C) ll > I > III > IV (D) lll > ll > IV >l.
11. In the reactions given below:
(i) KCN, (ii) LiAlH
4 (i) AgCN, (ii) LiAlH
4
RCl   product A ; RCl   product B
the compounds A and B are : [NSEC-2006]
(A) chain isomers (B) position isomers (C) functional isomers (D) metamers.

12.

Conversion of I to II : [NSEC-2006]
(A) takes place by SN1 (B) takes place by SN2 (C) takes place by E1 (D) does not take place.

13. In a nucleophilic substitution reaction, the least reactive compound is [NSEC-2006]

(A) CH3CH2CI (B) (CH3)3CCI (C) CH2 = CHCI (D) CH2 = CHCH2CI.

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14. In the following sequence:
NaCN
CH3CH2Cl 
 (i)
Ni/H
2
(i)   (ii)
acetic anhydride
(ii)   (iii)
Product (iii) is : [NSEC-2006]
(A) CH3CH2CH2NH2 (B) CH3CH2CH2CONHCH3
(C) CH3CH2CH2NHCOCH3 (D) CH3CH2CH2CONHCOCH3
15. The product obtained on reaction of alkyl halide with AgNO3 is [NSEC-2006]
(A) alkyl nitrate (B) nitroalkane (C) alkyl nitrite (D) nitrosoalkane.
16. The reaction of cyclohexane epoxide with NaN3 in aqueous dioxane would give [NSEC-2006]
OH OH OH OH
(A) (B) (C) (D)
N3 N3 NH2 OH
17. The order of the rate of formation of carbocations from the following iodo compounds is : [NSEC-2007]

(A) I > II > III (B) I > III > II (C) III > II > I (D) III > I > II
18. Indicate the order of reactivity of the following compounds in nucleophilic substitution (unimolecular)
reaction [NSEC-2007]

(A) I > II > III (B) II > III > I (C) III > II > I (D) II > I > III
19. Which one of the following carbocations will not rearrange ? [NSEC-2008]

CH2 CH3 CH3


(A) (B) (C) (D)

20. The major product in the following reaction is : [NSEC-2008]

PhSNa
?

Br

(A) (B) PhS

SPh

(C) (D)

PhS

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21. SN1 reactivity of the following halides, [NSEC-2009]
(i) (CH3)3CBr (ii) (C6H5)2CHBr (iii) (C6H5)2C(CH3)Br (iv) (CH3)2CHBr
(A) iv > i > ii > iii (B) ii > i > iii > iv (C) i > iii > ii > iv (D) iii > ii > i > iv
22. The substances used for the preparation of ether by Williamson's synthesis are : [NSEC-2009]
(A) (CH3)3CBr and CH3ONa (B) (CH3)3CBr and CH3OH
(C) CH3Br and (CH3)3CONa (D) CH3Br and (CH3)3COH
23. The compound A in the reaction is :

dry ether
2 + 2Na   A + 2NaBr is : [NSEC-2009]

(A) (B) (C) 2 (D)

24. Among the following isomeric chloro compounds, the compound which will undergo SN2 reaction readily
is : [NSEC-2009]
(A) 4-chloro-1-butene (B) 1-chloro-1-butene (C) 1-chloro-2-butene (D) 2-chloro-1-butene
25. The intermediate formed in the following reaction is : [NSEC-2010]
Cl OH
| |
CH3 – CH2 – C – CH3 + NaOH  CH3 – CH2 – C – CH3 + NaCl
| |
CH3 CH3

(A) (B)

(C) (D)

26. The compound which would undergo SN2 reaction fastest is : [NSEC-2010]
Br
(A) (B) (C) (D)

27. The major product of the following reaction is [NSEC-2010]

(i) NaNH2 , (ii) CH3CH2Br
CH3–CH2–CCH  
(A) CH3–CH2–CC–CH2–CH3 (B)
CH2CH3
(C) CH 3 – CH 2 – CH – CH 3 (D) CH3–CH2–CC–NH2
NH2
28. The number of transition state/s and intermediate/s in a unimolecular nucleophilic substitution reaction
are respectively- [NSEC-2010]
(A) 3, 1 (B) 2, 2 (C) 2, 1 (D) 1, 1
29. Ethyl phenyl ether is treated with conc. HI at 0°C and the rnixture of products is treated with thionyl
chloride. The products formed are- [NSEC-2010]
(A) Ethanol + Chlorobenzene (B) Phenol + lodoethane
(C) lodoethane + Chlorobenzene (D) Chloroethane + Phenol

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30. The product (C) of the following sequence of reactions is : [NSEC-2011]
Cl (limited )
+ CH2=CH2 
(i) AlCl3
 A 
2
 B 
aq. NaOH
 C
(ii) H2O h

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

31. The order of reactivity of ammonia with the following compound is : [NSEC-2011]
(I) CH2=CHBr (II) CH3–CH2–COCl (III) CH3–CH2–CH2–Cl (IV) C(CH3)3C-Br
(A) IV > II > I > III (B) II > IV > III > I (C) III > IV > II > I (D) I > IV > II > III
32. The number of transition states in a unimolecular nucleophilic substitution (S N1) reaction is
[NSEC-2012]
(A) 0 (B) 1 (C) 2 (D) 3
33. The sequence of steps involved in aromatic nucleophilic substitution involving a benzyne intermediate
is :
(A) Addition-elimination (B) Elimination-addition [NSEC-2012]
(C) Addition-rearrangement (D) Elimination-rearrangement
34. Select the most correct statement among the following : [NSEC-2013]
(A) SN1 mechanism takes place in non-polar solvents
(B) SN2 mechanism in chiral substrates gives racemic mixtures as products
(C) SN1 mechanism is encouraged by polar solvents
(D) The solvent never influences the mechanism
35. In the reaction given below :

the product obtained will contain : [NSEC-2013]

(A) Only Compound I (B) Only Compound II

(C) Both compound I and II (D) this substitution cannot take place
36. The compound which undergoes hydrolysis on just warming with water and forms the corresponding
hydroxyl derivative is [NSEC-2014]
(A) 2,4,6-trinitrochlorobenzene (B) 2-chloro-1-butene
(C) 2-chloro-2-methylbutane (D) 2, 4-dimethoxychlorobenzene
37. The best sequence of reactions to prepare 2-heptanone is [NSEC-2014]
NaNH2 n C4H9Br4 H2O, Hg 2 
(A) Propyne 
 X 
Y 
H2SO4

NaNH n C H Br H O, Hg 2 
(B) Ethyne 
2
 X 
5 11
Y 
2
H SO

2 4
2
NaNH CH Br H O, Hg
(C) 1-hexyne 
2
 X 
3
Y 
2
H SO

2 4

NaNH C H Br H O, Hg 2 
(D) 1-pentyne 
2
 X 
2 5
Y 
2
H SO

2 4

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38. 1-Phenoxypropane is treated with excess of conc. H at 0°C and the mixture of products is treated with
thionyl chloride. The products formed are [NSEC-2014]
(A) n-propanol + Chlorobenzene (B) Phenol + n-propyl chloride
(C) n-propyl chloride + Chlorobenzene (D) n-propyl chloride + Phenol
39. (i) chlorobenzene is mono-nitrated to M (ii) nitrobenzene is mono-chlorinated to N
(iii) anisole is mono-nitrated to P (iv) 2-nitrochlorobenzene is mono-nitrated to Q
Out of M, N, P and Q the compound that undergoes reaction with aq. NaOH fastest is: [NSEC-2014]
(A) M (B) N (C) P (D) Q
40. Desosamine has the following structure

The number of functional groups which react with hydroiodic acid, the number of chiral centers, and the
number of stereoisomer’s possible respectively are [NSEC-2015]
(A) 4, 5, 8 (B) 3, 4, 16 (C) 3, 4, 8 (D) 4, 4, 16
41. Compound “X” reacts with diborane followed by alkaline hydrogen peroxide to form compound “Y”. “Y”
on reaction with a mixture of sodium bromide in sulphuric acid followed by bromobenzene and sodium
in ether gives n-pentylbenzene. Compound “X” is : [NSEC-2015]

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

42. The compound that undergoes solvolysis in aq. ethanol most easily is [NSEC-2015]

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

43. The best reaction sequence to convert 2-methyl-1-bromopropane into 4-methyl-2-bromopentane is

(A) (i) Mg in ether (ii) acetaldehyde (iii) H+, H2O (iv)  (v) HBr, H2O2 [NSEC-2015]
(B) (i) NaCCH in ether (ii) H2, Lindlar catalyst (iii) HBr, no peroxide
(C) (i) alcoholic KOH (ii) CH3COOOH (iii) H2/Pt (iv) HBr, heat
(D) (i) NaCCH in ether (ii) H3O+ + HgSO4 (iii) HBr, heat
44. The compound that will NOT react with hot concentrated aqueous alkali at atmospheric pressure is
[NSEC-2015]

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

45. The appropriate sequence of reactions for obtaining 2-phenylbutanoic acid from benzene is
(A) (i) 1-chlorobutane/AICI3 (ii) limited Cl2, light (iii) aq NaCN (iv) H+, H2O, heat [NSEC-2015]
(B) (i) 2-chlorobutane/AICI3 (ii) K2Cr2O7/H2SO4
(C) (i) propanoyl chloride/AlCl3 (ii) Zn-Hg/HCl (iii) limited Cl2(g), light (iv) aq. NaCN (v) H+, H2O, heat
+
(D) (i) butanoyl chloride/AICI3 (ii) NaBH4 (iii) CuCN (iv) H , H2O, heat
46. The compound that reacts fastest with methylamine is [NCSE-2016]
CH2 Br Br Br
Br
(A) (B) (C) (D)
Br
Br Br

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47. One mode of 4-nitrocatechol (4-nitro-1,2-dhydroxybenzene) on treatment with an excess of NaH
followed by one mole of methyl iodide gives- [NCSE-2017]
(A) 4-nitro-1, 2-diamethox ybenzene (B) 4-nitro-5methy-1, 2-dimethox ybenzene
(C) 2-methox y-5 nitrophenol (D) 2-methoxy-4nitrophenol
48. Which of the following ethers cannot be prepared by Williamson Synthesis ? [NCSE-2017]
OC(CH3)3 OCH3
OCH3
(A) (B) (C) (D)
O
49. Coniferyl alcohol is isolated from pine trees. The following observations were made about this alcohol.
[NCSE-2017]
I. It forms methylated product with Mel in presence of base
II. One equivalent of coniferyl alcohol reacts with two equivalents of benzoyl chloride
III. Upon ozonolysis, coniferyl alcohol gives a product 'Y' (M.F C2H4O2).
OH
OH OH OH OH

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

OMe OMe OH OMe
OMe OH OH OH
50. Terpinen-4-ol is an active ingredient in tea tree oil has the following structure

HO
The correct observations for terpinen-4-ol is/are [NCSE-2017]
I. It rotates the plane of plane polarized light.
II. It reacts with Baeyer's reagent to form form a triol
III. On reaction with NaBr and H2SO4, it gives form a diobromo compound
IV. On ozonolysis it gives a compound with molecular formula C10H18O3
(A) I, II, III and IV (B) I, III and IV (C) II and III (D) III and IV
51. The increasing reactivity of the sites (a-d) in the following compound is SN1 reaction is
Cl
d
Cl
c

b
a CHClCH 3

Cl [NCSE-2017]
(A) d > b > c > a (B) d > c > a > b (C) d > c > b > a (D) c > d > b > a

PART - III : PRACTICE TEST-2 (IIT-JEE (ADVANCED Pattern))

Max. Time : 1 Hr. Max. Marks : 66
Important Instructions
A. General %
1. The test is of 1 hour duration.
2. The Test Booklet consists of 22 questions. The maximum marks are 66.
B. Question Paper Format
3. Each part consists of five sections.

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4. Section-1 contains 8 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out
of which ONE is correct.
5. Section-2 contains 6 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out
of which ONE OR MORE THAN ONE are correct.
6. Section 3 contains 4 questions. The answer to each of the questions is a single-digit integer, ranging
from 0 to 9 (both inclusive).
7. Section 4 contains 1 paragraphs each describing theory, experiment and data etc. 3 questions relate to
paragraph. Each question pertaining to a partcular passage should have only one correct answer
among the four given choices (A), (B), (C) and (D).
8. Section 5 contains 1 multiple choice questions. Question has two lists (list-1 : P, Q, R and S; List-2 : 1,
2, 3 and 4). The options for the correct match are provided as (A), (B), (C) and (D) out of which ONLY
ONE is correct.
C. Marking Scheme
9. For each question in Section-1, 4 and 5 you will be awarded 3 marks if you darken the bubble
corresponding to the correct answer and zero mark if no bubble is darkened. In all other cases, minus
one (– 1) mark will be awarded.
10. For each question in Section-2, you will be awarded 3 marks. If you darken all the bubble(s)
corresponding to the correct answer(s) and zero mark. If no bubbles are darkened. No negative marks
will be answered for incorrect answer in this section.
11. For each question in Section-3, you will be awarded 3 marks if you darken only the bubble
corresponding to the correct answer and zero mark if no bubble is darkened. No negative marks will be
awarded for incorrect answer in this section.

SECTION-1 : (Only One option correct Type)

This section contains 8 multiple choice questions. Each questions has four choices (A), (B), (C)
and (D) out of which Only ONE option is correct.

1. 
SOCl2
Product

In the above reaction which phenomenon will take place :

(A) Retention (B) Inversion (C) Racemisation (D) Partial racemisation

2. A, Product (A) is

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

Na C H Br
3. 
 
2 5
 (A)

Product (A) in above reaction is

(A) , (inversion) (B) , (retention)

(C) , (racemic) (D) Ph–CH=CH–CH3

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4. An optically active, pure, four carbon containing saturated alcohol X when reacted with NaH followed by
CH3–I gives a compound M. Same alcohol (X) when treated with TsCl followed by sodium methoxide
gives M. M and M are
(A) Identical (B) Enantiomer (C) Diastereomer (D) Geometrical isomers
5. Replacement of chlorine from chlorobenzene to give phenol requires drastic conditions but chlorine of
2, 4-dinitrochlorobenzene is readily replaced because
(A) NO2 makes the ring electron rich at ortho- and para-positions.
(B) NO2 withdraws electrons at meta position.
(C) NO2 donates electrons at meta position.
(D) NO2 withdraws electrons from ortho and para positions.
6. Which of the following statement is correct.
(A) Nucleophiles have an unshared electron pair and can make use of this to react with an electron rich
species.
(B) AgNO3 increases the rate of solvolysis in SN1 reaction of alkyl halide.
(C) Inversion of configuration occurs at the carbon undergoing SN1 reaction.
(D) Aryl halides are more reactive towards nucleophilc substitution reaction as compared to alkyl halide.
H Br
Ag
7.  Rearranged Carbocation + AgBr

Rearranged carbocation is :
+
CH3
(A) (B) (C) (D) +

8.

The product X and Y are respectively :

(A) &

(B) &

(C) &

(D) &

Section-2 : (One or More than one options correct Type)

This section contains 6 multipole choice questions. Each questions has four choices (A), (B),
(C) and (D) out of which ONE or MORE THAN ONE are correct.

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9. When Cis-3-Methyl- 2,3-epoxypentane treated with aqueous acid.

Cis-3-Methyl-2,3-epoxypentane
CH3
(A) Ring opeing takes palce. (B) The product is chiral.
(C) The product is achiral. (D) Protonation takes place initially.
10. Which reaction results in the formation of a pair of enantiomers ?

I H O
(A) 
 (B) 2

Acetone

CH OH HBr
(C) 3
 (D) 


11. Which of the following reaction is/are not feasible ?

 
(A) ONa + CH3Br  OCH3

(B) + RO– 

(C) + ROH 

 
(D) Br + RONa  OR

12. Which of the following reactions take place by SN2 mechanism :

(A) CH3–CH2–ONa + CH3–CH2–Cl   (B) + NaOH 

(C) (CH3)3–C–CH2–CH2–Br + excess NH3  (D) CH3–CH2–OH + HBr 

13. The relative rates of nucleophilic substitution for the given substrates are as follows
Compoud Approx. Relative rate
CH3CH2Br 1.0
CH3CH2CH2Br 0.28
(CH3)2CHCH2Br 0.030
(CH3)3 CCH2Br 0.00000042
The correct statement (s) is/are :
(A) Each of the above reactions is likely to be SN2
(B) Each of the above reactions is likely to be SN1
(C) First two reactions follow SN2 and next two reactions follow SN1 pathway
(D) The important factor behind this order of reactivity is “steric effect”
14. Which of the following is/are correct regarding the given reaction ?

CH3MgI
 

(A) Nucleophilic substitution (B) Intramolecular nucleophilic attack

(C) Dehydration (D) Nucleophilic addition
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Section-3 : (One Integer Value Correct Type.)

This section contains 4 questions. Each question, when worked out will result in one integer
from 0 to 9 (both inclusive)
15. Number of compounds which slowly racemises on addition of SbCl5.

(i) (ii) (iii) (iv)

(v) (vi) CH2=CH–Cl (vii) (viii)

H O / Acetone
16. C2H5 — C  CH — CH2 — Br 
2

|
CH3
(E)
How many total substitution products are formed including stereoisomers in the above reaction ?
17. In the given reaction, the percentage of (-) enantiomer formed is :
* CH  I
CH3–HI–CH2– C 3  CH3– C* HI –CH2CH3

()obs = –15.90° ()obs = –15.26°
18. For the reaction: R–X + OH  R–OH + X–; the rate expression is given as rate = 6.0×10–5[R–X][OH–
–

] + 2 × 10–7 [R–X]. What percentage of R–X react by the SN2 mechanism when [OH–] = 0.01 molar.

SECTION-4 : Comprehension Type (Only One options correct)

This section contains 1 paragraphs, each describing theory, experiments, data etc. 3 questions
relate to the paragraph. Each question has only one correct answer among the four given
options (A), (B), (C) and (D)

Paragraph for Questions 19 to 21

A kinetic distinction between the operation of SN1 and SN 2 modes can be made by observing the effect
on the overall reaction rate by adding a competing nucleophile. The total nucleophilic concentration is
thus increased, so this will result in an increased reaction rate in SN2 route. By contrast for SN1 mode,
the [Nu:] will not appear in the rate equation, the addition of competing nucleophile will fails significant
effect on the observed reaction rate, though it will naturally influcence the composition of the products.
19. In which of the following reactions the overall reaction rate may increase by addition of NaN3.
(i) CH3Cl + NaOH     (ii) (CH3)3CCl + H2O 
 (iii)  (iv) (CH3)2CH–OH + NaBr + H2SO4 

(A) (ii) and (iv) (B) (i) and (iii) (C) (i), (ii) and (iii) (D) (iv) only
20. What is true about the following reaction

(A) If –H is displaced by –CD3 group walden inversion will be observed in the product.
(B) If NaN3 is added the rate of decrease in concentration of reactant will slow down.
(C) On addition of KI the molecularity of reaction will be three.
(D) If K is added rate of reaction will increase.
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21. On addition of NaN3 in the following reaction, the correct observation will be

(A) The rate of formation of alcohol will increase

(B) The rate of disappearance of alkyl halide will increase
(C) The product alkyl azide will have optical rotation zero.
(D) The product mixture will have optical rotation –xº.
SECTION-5 : Matching List Type (Only One options correct)
This section contains 1 questions, each having two matching lists. Choices for the correct
combination of elements from List-I and List-II are given as options (A), (B), (C) and (D) out of
which one is correct
22. Match List I (Reaction) with List II (Mechanism) and select the correct answer using the code given
below the lists :
List I List II

(P) (1) SN1

3 CH O 


NaOH
(Q)   (2) SN2

HBr
(R)   (3) SNi

SOCl2
(S)   (4) SN2 Ar

Codes :
(A) P–4 ; Q–1 ; R–2 ; S–3 (B) P–2 ; Q–1 ; R–3 ; S–4
(C) P–2 ; Q–4 ; R–1 ; S–3 (D) P–4 ; Q–2 ; R–1 ; S–3

Practice Test-2 ((IIT-JEE (ADVANCED Pattern))

OBJECTIVE RESPONSE SHEET (ORS)
Que. 1 2 3 4 5 6 7 8 9 10

Ans.

Que. 11 12 13 14 15 16 17 18 19 20

Ans.

Que. 21 22

Ans.
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PART - I
1. (1) 2. (3) 3. (2) 4. (3) 5. (3)
6. (2) 7. (4) 8. (3) 9. (3) 10. (3)
11. (3) 12. (3) 13. (2) 14. (4) 15. (3)
16. (3) 17. (1) 18. (2) 19. (1) 20. (1)
21. (4) 22. (2) 23. (2) 24. (1) 25. (1)
26. (4) 27. (1) 28. (3) 29. (3) 30. (4)

PART - II
1. (B) 2. (A) 3. (A) 4. (D) 5. (C)
6. (C) 7. (B) 8. (B) 9. (B) 10. (C)
11. (C) 12. (D) 13. (C) 14. (C) 15. (A)
16. (A) 17. (C) 18. (B) 19. (D) 20. (B)
21. (D) 22. (C) 23. (D) 24. (C) 25. (C)
26. (C) 27. (A) 28. (C) 29. (D) 30. (D)
31. (B) 32. (C) 33. (B) 34. (C) 35. (C)
36. (A) 37. (B) 38. (B) 39. (D) 40. (D)
41. (D) 42. (B) 43. (B) 44. (D) 45. (C)
46. (A) 47. (D) 48. (B) 49. (D) 50. (A)
51. (C)

PART - III
1. (A) 2. (B) 3. (B) 4. (B) 5. (D)
6. (B) 7. (B) 8. (A) 9. (ABD) 10. (BD)
11. (BD) 12. (ABCD) 13. (AD) 14. (A) (B) (D)
15. 3 (iii, iv, vii) 16. 4 17. 98% 18. 75% 19. (B)
20. (D) 21. (B) 22. (C)

PART - I

1.

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-
FO O
2
SN Ar
2.
I I
NO2 NO2
3. It is a SN2 reaction, so inversion takes place at sp3 carbon .

5.

6.

7. Rate of reaction  stability of carbocation intermediate

8. On the basis of carbocation stability.

9. Carbocation Stability >

Leaving group ability is Br > CI

Over all reaction order r1 > r3 > r2

H2O
10. 
AgNO3

11. 

13. 1º R-X gives SN2 reaction fastest and 3º R-X gives SN1 reaction fastest.
14. It is a nucleophillc aromatic substitution reaction.
15. Strong anionic Nucleophile so mechanism is SN2.
16. Polar aprotic solvent favours SN2 mechanism.

SOCl
2
17.  

This reaction follows SNi mechanism, so retention of configuration takes place.

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18. 

19. + CH3I 

strong anionic nucleophile and 1º alkyl halide favours SN2 mechansim.


20. – O SO2CF3. is better Leaving group and CH3OH give SN1 product as a major product.

21. (1)

SN
R—X   No stable carbocation
(1º R–X)

(2)

(3)

22.

23. Bridge head carbocation is not formed.

I–
24.     

EtOH
25. EtO–CH2– CH –CH3 
 EtO–CH2– CH –CH3
| |
O OH

26. Strength of Nucleophile generally increases on going down a group in the periodic table, so (4) is not
true.

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27. Nucleophilic substitution of alcohol is acid catalysed reaction.
Cl SCH2C6H5
NO2 NO2
C6H5 CH2SK
28. 

Br Br
CH3 CH3
29. Product (B + C) by SN1 Mech.
Product (D + E) by SN2 Mech.
30. Because rate of SN2 Ar is Ar–F > Ar–Cl > Ar–Br > Ar–I.

PART - III

SOCl2
1.  Product (Retention)
SNi

SNi Reaction condition follow retention of configuration.

2.

Aromatic halides do not give SN reaction in normal condition.

3.

(Retention)

4. Retention of product.

+ TsCI Inverstion take place.

M = Retention product and M = inversion product, so they are enantiomers.
H Br H
+

Ag
1, 2Bond shift
7.  
 (Rearranged carbocation)

8.

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H 
9. (i) 
CH3



I
10. 
 [Only one product]
Acetone

H O
2
 + [Enantiomeric pair]
SN 1

CH OH
3
 [Only one product]
SN 1

HBr

 + [Enantiomeric pair]

11. Correct product for (B) option.

+ RO– 

Option (D) is also not feasible because aromatic halide do not give SN reaction in normal condition.

SN2
12.   CH3–CH2–O–CH2–CH3

– H2O
+ OH  
acid base
Reaction

CH3–CH2–OH + HBr CH3–CH2–Br + H2O

13. Due to steric effect.

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14.

OH
H2 O / Acetone |
16. C 2H5 — C  CH — CH2 — Br  C 2H5 — C  CH — CH2 — OH + C 2H5 — C — CH  CH2
| | |
CH3
CH3 CH3 (R/S)
(E) (E/Z)

17.

[]obs = – 15.90º []obs =– 15.26º

–15.26
% of (–) enantiomers = × 100 = 96 %
15.96
Racemic mixture = (100 – 96) = 4%
Racemic mixture = 2% (+) + 2% (–)
(+) enantiomer = 2%
Total (–) enantiomer = 96 + 2 = 98 %
18. The rate is made up of two parts SN1 and SN2 rate
= 6.0 × 10–5 [RX][OH–] + 2 × 10–7 [RX]
 SN 2   6.0  10 –5 [RX][OH ] 
Thus % SN2 =   × 100 =  –5 – –7  × 100 = 75%
 SN 2  SN1  6.0  10 [RX][OH ]  2  10 [RX] 

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