SUBSTITUTION ELIMINATION (Organic Chemistry)

Nucleophilic substitution reaction (𝐒𝐍 ): ionisation is strongly endothermic process, rate of SN 1

Replacement (displacement) of an atom or group by another reaction depends strongly on carbocation stability because
atom or group in a molecule is known as substitution carbocation is the intermediate of SN 1 reaction which
reaction. If substitution reaction is brought about by a determines the energy of activation of the reaction.
nucleophile then it is known as nucleophilic substitution Reactivity of SN 1 ∝ stability of carbocation.
reaction. Generally, substitution takes place at sp3 carbon. SN 1 reactivity: 3∘ > 2∘ > 1∘ > CH3 − X
R − ℓg + Nu− ⟶ R − Nu + g − (ii) Concentration and reactivity of the nucleophile: The
Types of nucleophilic substitution reaction: rate of SN 1 reaction is unaffected by the concentration and
(I) SN 1 (II) SN 2 (III) SN i nature of the nucleophile.
Section (A): Unimolecular nucleophilic substitution reaction Weak and neutral nucleophile favours SN 1 reaction.
(SN 1) Mostly solvents (protic) itself functions as nucleophiles in
Nucleophilic substitution which involves two step process SN 1 reaction, so SN 1 reaction is termed as solvolysis
(a) First step: Slow step which involves ionisation (to form reaction.
carbocation) R − ℓg ⟶ R+ + ℓg − water → hydrolysis
(b) Second step: Fast attack of nucleophile on carbocation CH3 COOH → acetolysis
results into product. C2 H5 OH → ethanolysis
R+ + Nu− ⟶ R − Nu (iii) Effect of the solvent: (lonising ability of the solvent)
(1) SN1 Reaction of Alkyl halide Mechanism: The use of a polar protic solvent will greatly increase the rate
of ionisation of an alkyl halide in any SN 1 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 ⇄ R + X (Solvolysis)

Characteristics of 𝐒𝐍 𝟏 reactions:
1. It is unimolecular, two step process.
2. Carbocation intermediate is formed, so rearrangement is
possible in SN 1 reaction.
3. It is first order reaction.
4. Kinetics of the reaction Rate ∝ [Alkyl halide]
Rate of SN 1 reaction is independent of concentration and
reactivity of nucleophile.
5. Energetics of the SN 1 reaction:

Table: Dielectric constants (ϵ) and ionisation rate of t-

Butylchloride in few common solvents
Solvent ϵ Relative rate
H2 O 80 8000
CH3 OH 33 1000

Figure: Free energy diagram for the SN 1 reaction. C2 H5 OH 24 200

6. Factors affecting the rate of 𝐒𝐍 𝟏 reaction: (CH3 )2 CO 21 1
(i) The structure of the substrate: The rds of the SN 1 reaction
is ionization step, a carbocation is formed in this step. This CH3 CO2 H 6 -

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(iv) The nature of the leaving group: In the SN 1 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 (vi) HCl (Hydrochloric acid) reacts with alcohols in much the
state and this lowers the free energy of activation and there same way that as the hydrobromic acid.
by increases the rate of reaction. Leaving ability of halogen is (vii) Chloride ion is a weaker nucleophlile than bromide ion
F − < Cl− < Br − < I − because it is smaller and less polarizable. Lewis acid, such as
Stereochemistry of 𝐒𝐍 𝟏 reactions: In the SN 1 mechanism, ZnCl2 , is sometimes necessary to promote the reaction of HCl
the carbocation intermediate is sp2 hybridized and planar, A with primary and secondary alcohols.
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 (SN 1) :

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
Reagents for alkyl halide are : H2 O, RCOOH, ROH & RSH identified by the Lucas test, which is based upon the
difference in reactivity of the three classes of alcohol towards
(2) 𝐒𝐍 𝟏 Reaction of Alcohols hydrogen halides.
(i) Reaction with hydrogen halides (iii) Alcohol (of not more than six carbons in their molecule)
A common method is to treat the alcohol with a hydrohalic are soluble in the Lucas reagent. The corresponding alkyl
acid, usually HI or HBr. These acids are used to convert chlorides are insoluble.
alcohols into the corresponding alkyl halides. (iv) Formation of a chloride from an alcohol is indicated by
(i) In acidic solution, an alcohol is in equilibrium with its the cloudiness that appears when the
protonated form. Protonation converts the hydroxy group chloride separates from the solution hence, the time
from a poor leaving group (OH)Θ into a good leaving group required for cloudiness to appear is a measure of the
(H2 O). If the alcohol is protonated all the usual substitution reactivity of the alcohol.
and elimination reactions are feasible, depending on the (v) A tertiary alcohol reacts immediately with the Lucas
structure (1∘ , 2∘ , 3∘ ) of the alcohol. reagent, a secondary alcohol reacts within five minutes and
(ii) Halides are anions of strong acids, so they are weak a primary alcohol does not react appreciably at room
bases. Solutions of HBr and HI contain nucleophilic Br ⊖ and temperature.
I ⊖ ions.
(iii) Concentrated hydrobromic acid rapidly converts t-Butyl Section (B): Bimolecular nucleophilic substitution reaction (SN 2)
alcohol to t-Butyl bromide. The strong acid protonates the Nucleophilic substitution in which incoming group replaces
hydroxyl group, converting it into a good leaving group. The leaving group in one step only.
hindered tertiary carbon atom cannot undergo SN 2 (1) SN2 Reaction of Alkyl halide:
displacement, but it can ionise to a tertiary carbocation.
Attack by bromide ion gives the alkyl bromide. The
mechanism is similar to SN 1 mechanism.
(iv) 1-Butanol reacts with sodium bromide in concentrated
sulfuric acid to give 1-Bromobutane by an SN2 displacement. Characteristic of SN 2
1. It is bimolecular, one step concerted process
2. It is second order reaction because in the rds both species
are involved
Protonation converts the hydroxy group to a good leaving 3. Kinetics of the reaction: rate ∝ [alkyl halide] [nucleophile]
group, but ionization to a primary carbocation is rate = k [alkyl halide] [nucleophile]
unfavourable. The protonated unbranched primary alcohol If the concentration of alkyl halide in the reaction mixture is
is well suited for the SN 2 displacement. doubled, the rate of the nucleophilic substitution reaction is
(v) Secondary alcohols also react with HBr to form alkyl double. If the concentration of nucleophile is doubled the
bromides usually by the SN 1 mechanism. rate of reaction is also double. If the concentration of both
are doubled then the rate of the reaction quadriples.

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4. Energetics of the reaction: (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 SN 2 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)
Figure: A free energy diagrams for SN 2 reaction Ex. 1
5. No intermediates are formed in the SN 2 reaction, the
reaction proceed through the formation of an unstable
arrangment of atoms or groups called transition state. (2) 𝐒𝐍 𝟐 Reaction of Alcohol:
6. The stereochemistry of SN 2 reaction: As we seen earlier, in (i) Reaction with HX : The protonated β unbranched primary
an SN 2 mechanism the nucleophile attacks from the back alcohol is well suited for the SN 2 reaction.
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 (ii) Reaction with phosphorus trihalides Several phosphorus
nucleophilic attack. This inversion is also known as Walden halides are useful for converting alcohols to alkyl halides.
inversion. 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.
7. Factor's affecting the rate of SN 2 reaction: Number of
factors affect the relative rate of SN 2 reaction, the most
important factors are
(i) Effect of the structure of the substrate:
SN 2 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 SN 2
mechanism.
Remarks
Substituent Compound Relative rate
The mechanism for the reaction involves attack of the alcohol
Methyl CH3 X 30 group on the phosphorus atom, displacing a halide ion and
forming a protonated alkyl dihalophosphite
1∘ CH3 CH2 X 1 In second step a halide ion acts as nucleophile to displace
HOPX 2 , a good leaving group due to the electronegative
2∘ (CH3 )2 CHX 0.02 atoms bonded to the phosphorus.
(iii) Reaction with PCl5
Neopentyl (CH3 )3 CCH ∘ X 0.00001

3∘ (CH3 )3 CX ∼0 (iv) Reaction with thionyl chloride in presence of pyridine

Thionyl chloride (SOCl2 ) is often the best reagent for
(ii) Concentration and reactivity of the nucleophile: converting an alcohol to an alkyl chloride. The by products
• As nucleophilicity of nucleophile increases rate of SN 2 (gaseous SO2 and HCl ) leave the reaction mixture and ensure
increases. that there can be no reverse reaction.
• Anionic nucleophiles mostly give SN 2 reaction C2 H5 OH + Cl − SO − Cl → C2 H5 Cl + SO2 ↑ +HCl
• A stronger nucleophile attacks upon α-carbon with
faster rate than the rate of departing of leaving group.

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(3) 𝐒𝐍 𝐢 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 ↑

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EXERCISE - I (A) II > III > IV > I (B) IV > III > II > I
1. Major product of following reaction is: (C) III > IV > II > I (D) I > II > III > I
6. Which one of the following compounds will give
enantiomeric pair on treatment with HOH?

(A) (B)

(A) (B)

(C) (D)

(C) (D)
7. Consider the SN 1 solvolysis of the following halides in
aqueous formic acid, decide decreasing order of
2. Which compound undergoes hydrolysis by the SN 1 reactivity of above alkyl halide?
mechanism at the fastest rate?

(I) (II)
(A) (B)

(III) (IV)
(C) (D)

(A) III > IV > II > I (B) II > IV > I > III
3. Arrange the following compounds in decreasing order (C) I > II > III > IV (D) III > I > II > IV
of their reactivity for hydrolysis reaction 8. For the given reaction, which substrate will give
(I) C6 H5 − CH2 − Br (II) maximum racemisation?

(III) (IV)

(A) I > II > III > IV (B) IV > II > I > III
(A) (B)
(C) III > IV > II > I (D) IV > III > II > I
4. Which of the following is most reactive toward SN1
reaction?
(C) (D)
(A) (B)

9. Major product of following reaction is:

(C) (D)

5. Which of the following is most reactive toward SN 1

reaction?
(I) (II) (A) (B)

(III)
(C) (D) None of these
(IV)

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10. If 96% racemisation takes place in given reaction then

find out the correct statement:
(C) (D)

(A) Among the products 48% S and 48%R 16. Which of the following is most reactive toward SN 2.
configuration containing molecules are present CH3 Br + OH − ⟶ CH3 OH + Br −
(B) Among the products 50% S and 50%R (A) Rate = k[CH3 Br]
configuration containing molecules are present (B) Rate = k[OH − ]
(C) Among the products 48% S and 52%R (C) Rate = k[CH3 Br][OH − ]
configuration containing molecules are present (D) Rate = k[CH3 Br]o [OH − ]o
(D) Among the products 52% S and 48%R
configuration containing molecules are present 17. Select suitable reason for non-occurrence of the
following reaction.
11. In the given reaction the product [P] can be: Br − + CH3 OH ⟶ BrCH3 + OH −
CH3 − CH = CH − CH2 − OH ⎯⎯ HBr
→ P
SN 1' (A) Attacking nucleophile is stronger one
(A) CH3 –CH=CH–CH2–Br (B) Leaving group is a stronger base than nucleophile
(C) Alcohols are not good substrate for SN reaction
(D) Hydroxide ions are weak bases
(B)
18. Major product of following reaction is:
(C) CH2=CH–CH=CH2

(D)

12. Which of the following cannot give SN 1 reaction easily? (A) (B)
(C) Both (D) None of these
(A) (B) 19. The reactivity of given compounds towards SN 2
displacement is:
(I) 2-bromo-2-methylbutane
(II) 1-bromopentane
(C) (D) (III)2-bromopentane
(A) I > II > III (B) I > III > II
13. Which of the following compound is most rapidly (C) II > III > I (D) II > I > III
hydrolysed by SN 1 mechanism? 20. For the given reaction, CORRECT option regarding
(A) C6 H5 Cl (B) Cl − CH2 − CH = CH2 mechanism involved is:
(C) (C6 H5 )3 CCl (D) C6 H5 CH2 Cl
14. Among the bromides I − III given below, the order of
reactivity in SN 1 reaction is:
(A) I can't be SN 1
(B) II can't be SN 2
(C) I can be SN 1& II can be SN 2
(D) I can be SN 2 II can be SN 1
21. In which of the following replacement of Cl− is most
(A) III > I > II (B) III > II > I difficult?
(C) II > III > I (D) II > I > III
15. Which of the following is most reactive toward SN 2. (A) (B)

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

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22. Arrange these compounds in order of increasing SN 2

reaction rate:
(A) (B)

(C) H2 C = CH2 (D)

(A) III < I < II < IV (B) III < II < I < IV 29. Which reaction conditions (reagents) is suitable for
the following reaction:
(C) IV < III < I < II (D) III < IV < I < II
23. Which reaction proceeds faster with NaI in DMSO?

(A) (B)
Br2
(A) (B) SOBr2
CCl4
(C) PBr3 (D) HBr/ conc H2 SO4
30. Major product of following reaction is:
(C) (D)

24. The major product in the given reaction is:

(A)

(B)

(A) (B)

(C)

(C) (D) All of these

(D)
25. The compound CH3 − O − CH2 − Br gives faster rate
of nucleophilic substitution reaction than:
(A) CH3 Br (B) CH3 CH2 Br 31. Assuming all the substrate convert into substitution
(C) PhCH2 Br (D) CH3 OCH2 Cl products containing 0.05 mole of Configuration,
26. Which will give white ppt. with AgNO3 ? calculate the percentage of SN 2 mechanism.

(A) (B)

(C) (D) Both (A) and (C)

(A) 90% (B) 80%
(C) 70% (D) 95%
27. When ethyl bromide is treated with moist Ag 2 O, the
main product is: 32. The reaction of SOCl2 on alkanols to form alkyl
(A) Ethyl ether (B) Ethanol chlorides gives good yields because
(C) Ethoxy ethane (D) All of these (A) Alkyl chlorides are immiscible with SOCl2
(B) The other products of the reaction are gaseous
28. Major product of following reaction is:
and escape out
(C) Alcohol and SOCl2 are soluble in water
(D) The reaction does not occur via intermediate
formation of an alkyl chlorosulfite

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33. Major product of following reaction is: (A) S > R > Q > P (B) P > Q > R > S
(C) S > R > P > Q (D) P > S > Q > R
38. If P & Q are the major products then P & Q are
respectively:

(A) (B)

(A)
(C) H2 C = CH2 (D)

34. In the given pairs, which pair represent correct order (B)
of rate dehydrohalogenation reaction.
(A)

(C)
(B)

(D)
(C)

(D) CH3 − CH2 − Cl < CD3 − CD2 − Cl 39. On heating glycerol with excess amount to HI, the
product formed is
35. Major product of following reaction is: (A) Allyl iodide (B) Isopropyl iodide
(C) Propylene (D) 1,2,3-tri-iodopropane
40. Major product of following reaction is:
(A)

(B)
(A)

(C)

(B)
(D)

36. Major product of following reaction is: (C)

(D)
(A) (B)

(C) (D)

37. CORRECT order of rate of reaction for following

compounds with Conc. HBr is:
CH3 OH CH3 CH2 OH (CH3 )2 CHOH (CH3 )3 COH
(P) (Q) (R) (S)
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EXERCISE – II 6. Which of following reaction(s) produce Saytzeff

1. Rate of SN 2 depends on: product as a major product:
(A) Conc of Nucleophile
(B) Conc of substrate (A) (B)
(C) Nature of leaving group
(D) Nature of solvent
2. In the given pair in which pair the first compound is (C) (D)
more reactive than second towards SN 2 reaction.
(A)
7. SN 1 & SN 2 is not favourable in
(A) H2 C = CH − Cl (B) Ph − CH2 − Cl
(B) (C) Ph − Cl (D) H2 C = CH − CH2 − Cl
8. Among the following, which statement is correct?
(A) Alkyl-aryl product can be obtained in wurtz
reaction.
(C)
(B) Dipole moment of cyclohexyl chloride is more
than that of chlorobenzene.
(C) Alcohols are insoluble in lucas reagent while their
halides are soluble.
(D) (D) Preparation of ether by acid dehydration of
secondary alcohol is not suitable.
3. Which of the following statements is(are) correct for 9. In which of the following reaction(s), configuration
the given reaction. about chiral carbon is retained in the major product

(A)

(A) Product formation takes place due to the

breaking of C − O bond (B)
(B) Hydrolysis of major product gives optically active
carboxylic acid
(C) Reaction involves bimolecular nucleophilic
substitution reaction (C)
(D) Absolute configuration of major product is " R "
4. Which of the following statements is / are true?
(A) CH3 − CH2 − CH2 − I will react more readily than (D)
(CH3 )2 CHI for SN 2 reactions.
(B) CH3 − CH2 − CH2 − Cl will react more readily
than CH3 − CH2 − CH2 − Br for SN 2 reaction.
(C) CH3 − CH2 − CH2 − CH2 − Br will react more 10. A gem dichloride is formed in the reaction:
readily than (CH3 )3 C − CH2 − Br for SN 2 reactions (A) CH3 CHO and PCl5 (B) CH3 COCH3 and PCl5
(D) CH3 − O − C6 H4 − CH2 Br will react more readily (C) CH2 = CH2 and Cl2 (D) CH2 = CHCl and HCl
than NO2 − C6 H5 − CH2 Br for SN 2 reaction 11. Assuming that all products are major & R is
5. Incorrect statement about alkyl halides is / are: hydrocarbon while T is also organic product then
(A) Tertiary alkyl halides undergo SN 2 substitutions choose the correct option(s)?
(B) Alkyl iodides on exposure to sunlight gradually
darken
(A) T is more acidic than P
(C) Photo iodination is irreversible in presence of
(B) R has more heat of combustion than propene
HIO3
(C) Both P & Q can show stereoisomerism
(D) A nucleophilic substitution is most difficult in
(D) S is not an organic product
alkyl iodides

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12. Which of following are correct for given reaction 17. How many monobromo derivatives are possible for
Hydrocarbon (R)?

(A) Major product of reaction is (A) 2 (B) 3

(C) 5 (D) 1
Paragraph for Q. No. 18 to 19
Groups like CN & [−O − N̈ = O] : possess two nucleophilic
(B) Major product is centre and are called ambident nucleophiles. Actually,
cyanide group is hybrid of two contributing structures and
therefore can act as nucleophile in two different ways
⊖
(C) Major product formation involve substitution [C ≡ N ⟷: C = N⊖ ]. Similarly, nitrite ion also represents
(D) The reaction is E2 reaction
an ambident nucleophile with two different points of linkage
13. Which of the following reactions is (are) incorrectly
[O−= O].
matched with their major product:
HI 18. Correct option among the following:
(A) Me3 C − O − CH3 ⟶ Me3 C − OH + CH3 I (A) R − X ⎯⎯ KCN
→ RNC
HI Haloalkane MajorProduct
(B) H3 C − O − CH2 − CH3 ⟶ CH3 OH + ICH2 CH3
(B) R − X ⎯⎯⎯
→R − CNAgCN
Major
(C)
(C) R − X ⎯⎯⎯
KNO2
→R − O − N = O
H3 O+ 18 Major
(D) CH3 − O − CH2 CH3 ⟶ CH3 OH + CH3 CH2 O H (D) R − X ⎯⎯⎯ AgNO2
→R − O − N = O
Major product
14. Correct statement among the following is/are:
(A) The rate of hydrolysis of tertiary butyl bromide 19. Incorrect statement
increases by addition of Ag 2 O
(B) Aqueous Ag 2 O produces nucleophilic OH −
(C) The addition of a small amount of oxygen slows
down the photochemical chlorination of methane. (A) KCN is predominentely ionic in nature
(D) CH3 CH2 Cl is more reactive than PhCH2 Cl for (B) AgCN is mainly covalent in nature
bimolecular nucleophilic substitution reaction (C) In AgCN, carbon is the donor atom
(D) In AgCN nitrogen is the donor atom
15. Incorrect statement among the following is/are:
(A) ROH with NaI in the presence of phosphoric acid 20. Match the List I with List II
gives RI, but not in the presence of H2 SO4 List-I List-II
alc.KOH/
(B) 2-methyl propane on chlorination (Cl2 , hv) gives (A) CF3 − CHCl2 ⎯⎯⎯⎯ →CF2 = CCl2
1-chloro-2-methyl propane while bromination
(P) Elimination Reaction
(Br2 , hv) gives 2-bromo-2-methyl propane
(C) Usually higher temperature prefers substitution
over elimination (B)
(D) Triphenyl chloromethane cannot be hydrolysed
16. From left to right, correct statements are:
(Q) Carbocation
(C) CH3 − CH2 − Br ⎯⎯⎯→CH2 = CH2
alc.KOH

(R) Carbanion

(A) Rate of SN 1 mechanism increases in polar protic (D)

solvent
(B) Rate of SN 2 mechanism increases in DMSO
(C) Rate of E2 mechanism increases
(S) Free radical
(D) Rate of E1 mechanism increases

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21. Match the List I with List II

List-I List-II
(Reactions) (Products)
⊖
(A) CH3 − O − SO2 CH3 + C2 H5 O (P) CH3 − CH2 − PH2
(B) CH3 − CH2 − I + PH3 (Q) CH3 − O − C2 H5
⊖⊕
(C) HC ≡ C Na + CH3 − CH2 − Br (R) CH3 − O − CH3
Θ
(D) CH3 − Cl + CH3 − O (S) CH ≡ C − CH2 − CH3

22. Match the List I with List II

⊖
Z − CH2 Br + CH3 O ⟶ Z − CH2 − OCH3 + Br Θ
List-I (Z-) List-II (Relative reactivity)
(A) H − (P) 0.1
(B) CH3 − (Q) 3
(C) C2 H5 − (R) 1
(D) (S) 100

23. Match the List I with List II

List-I List-II

(A) E1CB (P)

(B) Saytzeff alkene as major product (Q)

(C) E2 (R)
(D) Ei (S)

24. Column-I Column-II

(Reactions) (Characteristics)
(A) CH3CH2CH = CH2 ⎯⎯
HBr
→ (P) Bimolecular
(B) CH3CH2CH = CH2 ⎯⎯⎯⎯⎯
→ HBr,Peroxide
(Q) Carbocation intermediate
(C) PhCH ( CH3 ) OH ⎯⎯⎯
SOCl2
→ (R) Regioselective
(D) PhCH ( CH3 ) OH ⎯⎯→
HBr
(S) Racemic modification
(T) Stereospecific reaction
25. Column-I Column-II
(Statements) (Consistent path of reaction)
(A) Reactions are concerted (P) SN 1
(B) CH3 X cannot react (Q) SN 2
(C) 3∘ R − X > 2∘ R − X > 1∘ R − X (R) E1
(D) R − I reacts faster than R − Cl (S) E2

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26.

Identify A, C&E in the sequence of reaction.

27. CH3 − CH2 I reacts more rapidly with strong base in comparison to CD3 CH2 I.
28. Predict the product(s) and write the mechanism of the given reaction:

29. What are the products of the following reactions?

(A) (B)

30. A primary alkyl bromide (A), C4 H9 Br, reacted with alcoholic KOH to give compound (B). Compound (B) reacted with HBr
to give an isomer of (A). When (A) was reacted with sodium metal it gave compound (D), C8 H18 , which was different from
the compound produced when n butyl bromide was reacted with sodium. Draw the structure of (A) and write equations
for all the reactions.

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EXERCISE – III (JEE MAIN) The correct order of SN 1 reactivity is

1. Following reaction is an example of: [AIEEE 2002] (A) A > B > C (B) B > C > A
(CH3 )3 C − Br + H2 O ⟶ (CH3 )3 C − OH + HBr (C) B > A > C (D) C > B > A
(A) Elimination reaction
8. 2-chloro-2-methylpentane on reaction with sodium
(B) Free radical substitution
methoxide in methanol yields: [JEE MAIN 2016]
(C) Nucleophilic substitution
(D) Electrophilic substitution
2. SN 1 reaction is feasible in [AIEEE 2002]
(A) (B)

(C)
(A) (a) and (b) (B) All of these
(D)
(C) (a) and (c) (D) (c) only

3. Bottles containing C6 H5 I and C6 H5 − CH2 I lost their 9. The product of the reaction given below is:
original labels. They were labelled A and B for [JEE MAIN 2016]
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 (A) (B)
statements is true for this experiment. [AIEEE 2003]
(A) A was C6 H5 I (B) A was C6 H5 CH2 I
(C) B was C6 H5 I
(D) Addition of HNO3 was unnecessary (C) (D)
4. The compound formed on heating chlorobenzene
with chloral in the presence of concentrated sulphuric
acid is [AIEEE 2003] 10. The reaction of propene with HOCl(Cl2 + H2 O)
(A) Gammaxe (B) DDT proceeds through the intermediate: [JEE MAIN 2016]
(C) Freon (D) Hexa chloro ethane (A) CH3 − CHCl − CH2+
(B) CH3 − CH + − CH2 − OH
5. The structure of the major product formed in the (C) CH3 − CH + − CH2 − Cl
following reaction is: [AIEEE 2003] (D) CH3 − CH(OH) − CH2+
11. The increasing order of the reactivity of the following
halides for the SN 1 reaction is: [JEE MAIN 2017]

(A) (B)

(A) (III) < (II) < (I) (B) (II) < (I) < (III)
(C) (I) < (III) < (II) (D) (II) < (III) < (I)
(C) (D) 12. Which of the following, upon treatment with tert-
BuONa followed by addition of bromine water, fails to
decolourize the colour of bromine? [JEE MAIN 2017]
6. Which of the following on heating with aqueous KOH,
(A) (B)
produces acetaldehyde? [AIEEE 2003]
(A) CH2 ClCH2 Cl (B) CH3 CHCl2
(C) CH3 COCl (D) CH3 CH2 Cl
7. Consider the following bromides: [AIEEE 2010]
(C) (D)

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13. 3-Methyl-pent-2-ene on reaction with HBr in

presence of peroxide forms an addition product. The
number of possible stereoisomers for the product is :- (A) (B)
[JEE MAIN 2017]
(A) Six (B) Zero
(C) Two (D) Four
(C) (D)
14. The major product obtained in the following reaction
is: [JEE MAIN 2017]
18. The increasing order of nucleophilicity of the
following nucleophiles is. [JEE MAIN 2019]
(a) CH3 COΘ
2 (b) H2 O
⊖
(c) CH3 SOΘ3 (d) OH
(A) (±)C6 H5 CH(Ot Bu)CH2 C6 H5 (A) (b) < (c) < (d) < (a)
(B) C6 H5 CH = CHC6 H5 (B) (b) < (c) < (a) < (d)
(C) (+)C6 H5 CH(Ot Bu)CH2 C6 H5 (C) (a) < (d) < (c) < (b)
(D) (−)C6 H5 CH(Ot Bu)CH2 C6 H5 (D) (d) < (a) < (c) < (b)
15. The major product formed in the following reaction is 19. Increasing rate of SN l reaction in the following
[JEE MAIN 2018] compounds is: [JEE MAIN 2019]

(A) (B)

(C) (D) (A) (B) < (A) < (C) < (D)
(B) (A) < (B) < (C) < (D)
(C) (B) < (A) < (D) < (C)
16. The major product of the following reaction is: (D) (A) < (B) < (D) < (C)
[JEE MAINS 2018] 20. The major product 'Y' in the following reaction is:
[JEE MAIN 2019]

(A) (B)
(A) (B)

(C) (D) (C) (D)

21. The major product of the following addition reaction

17. The major product of the following reaction is: is: [JEE MAIN 2019]
Cl2 /H2O
[JEE MAIN 2019] H3C − CH = CH2 ⎯⎯⎯ →
(A) (B)

(C) (D)

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22. An 'Assertion' and a 'Reason' are given below. Choose

the correct answer form the following options:
[JEE MAIN 2019] (C) (D)
Assertion (A): Vinyl halides do not undergo
nucleophilic substitution easily.
27. Which one of the following alkenes when treated with
Reason (R): Even though the intermediate
HCl yields majorly an anti Markovnikov product?
carbocation is stabilized by loosely held π-electrons,
[JEE MAIN 2019]
the cleavage is difficult because of strong bonding.
(A) F3 C − CH = CH2 (B) H2 N − CH = CH2
(A) (A) is a correct statement but (R) is a wrong
(C) CH3 O − CH = CH2 (D) Cl − CH = CH2
statement.
(B) Both (A) and (R) are correct statements but (R) is 28. The major product of the following reaction is:
not the correct explanations of (A). [JEE MAIN 2019]
(C) Both (A) and (R) are wrong statements () ( )
i DCl 1equic.
CH3C  CH ⎯⎯⎯⎯⎯
( ii ) DI →
(D) Both (A) and (r) are correct statements and (R) is
(A) CH3 CD(I)CHD(Cl) (B) CH3 CD(Cl)CHD(I)
the correct explanation of (A).
(C) CH3 CD2 CH(Cl)(I) (D) CH3 C(I)(Cl)CHD2
23. Which one of the following is likely to give a
29. The major product of the following reaction is:
precipitate with AgNO3 solution? [JEE MAIN 2019]
[JEE MAIN 2019]
(A) (CH3 )3 CCl (B) CCl4
(C) CHCl3 (D) CH2 = CH − Cl
24. What will be the major product when m-cresol is
reacted with propargyl bromide (HC ≡ C − CH2 Br) in
presence of K 2 CO3 in acetone? [JEE MAIN 2019]
(A) (B)
(A) (B)

(C) (D)

(C) (D)
30. The major products A and B for the following
reactions are, respectively: [JEE MAIN 2019]
25. Heating of 2-chloro-1-phenylbutane with EtOK/EtOH
gives X as the major product. Reaction of X with
Hg(OAc)2 /H2 O followed by NaBH4 gives Y as the
major product. Y is: [JEE MAIN 2019]

(A) (B) (A)

(B)
(C) (D)

26. The major product of the following reaction is:

[JEE MAIN 2019]
(C)

(D)
(A) (B)

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31. Increasing order of reactivity of the following

compounds for SN 1 substitution is:
(C) (D)
[JEE MAIN-2019]

35. The major product the following reaction is:

[JEE MAIN-2019]

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

(C) B < C < D < A (D) A < B < D < C
32. The major product the following reaction is:
[JEE MAIN-2019]
(A) (B)

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

36. Which of the following compounds will produce a

(C) (D) precipitate with AgNO3 ? [JEE MAIN-2019]

33. The major product the following reaction is: (A) (B)
[JEE MAIN-2019]

(C) (D)

37. The major product obtained in the following

(A) (B) conversion is: [JEE MAIN-2019]

(C) (D)
34. The major product the following reaction is:
[JEE MAIN-2019]

(A) (B)

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

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38. The major product the following reaction is: 41. The major product the following conversion is:
[JEE MAIN 2019] [JEE MAIN 2019]

(A)

(A) (B)

(B)

(C) (D)
(C)
39. The major product the following reaction is:
[JEE MAIN 2019]
(D)

(A) CH3 CH = CHCH2 NH2 (B) CH3 CH = C = CH2

(C) (D) CH3 CH2 C ≡ CH 42.

40. The major product the following reaction is:

[JEE MAIN 2019]
[JEE MAIN 2020]
Compound X will be:

(A) (B)

(A) (C) (D)

43. The correct order of reactivity of the given chlorides

(B) with acetate in acetic acid is: [JEE MAIN 2021]

(A)

(C)
(B)

(C)
(D)

(D)

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47.

44.
[JEE MAIN 2022]
In the above reaction ‘A’ is

(A) (B)

[JEE MAIN 2021]

The product " A " and "B" formed in above reactions are
(C) (D)

48.

The stable carbocation formed in the above reaction

is: [JEE MAIN 2022]
(A) (B)

45. The product formed in the first step of the reaction of

[JEE MAIN 2021]
(C) (D)

49. Decreasing order towards SN 1 reaction for the

with excess Mg/Et 2 O(Et = C2 H5 ) is: following compounds is: [JEE MAIN 2023]
(A)

(B)

(A) a > c > d > b (B) a > b > c > d

(C) b > d > c > a (D) d > b > c > a
(C)
50. The correct order of melting point of dichlorobenzenes
is [JEE MAIN 2023]
(D)
(A)

46. The major product (P) in the reaction

[JEE MAIN 2022]
(B)
[Ph is −C6 H5 ] is

(A) (B)
(C)

(C) (D)

(D)

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51. Identify A and B in the following sequence of reaction 55. The final product A, formed in the following multistep
[JEE MAIN 2024] reaction sequence is: [JEE MAIN 2024]

(A)

(A) (B)
(B)

(C) (D)
(C)

56. Given below are two statements: [JEE MAIN 2024]

Statement - I: High concentration of strong nucleophilic
(D)
reagent with secondary alkyl halides which do not
have bulky substituents will follow SN 2 mechanism.
52. The correct statement regarding nucleophilic Statement - II: A secondary alkyl halide when treated
substitution reaction in a chiral alkyl halide is: with a large excess of ethanol follows SN 1 mechanism.
[JEE MAIN 2024] In the light of the above statements, choose the most
(A) Retention occurs in SN 1 reaction and inversion appropriate from the questions given below:
occurs in SN 2 reaction. (A) Statement I is true but Statement II is false.
(B) Racemisation occurs in SN l reaction and retention (B) Statement I is false but Statement II is true.
occurs in SN 2 reaction. (C) Both statement I and Statement II are false.
(C) Racemisation occurs in both SN 1 and SN 2 (D) Both statement I and Statement II are true.
reactions. 57. The correct order of reactivity in electrophilic
(D) Racemisation occurs in SN 1 reaction and inversion substitution reaction of the following compounds is:
occurs in SN 2 reaction. [JEE MAIN 2024]
53. Which among the following halide/s will not show
SN 1 reaction: [JEE MAIN 2024]
(I) H2 C = CH − CH2 Cl (II) CH3 − CH = CH − Cl

(III) (IV)
(A) B > C > A > D (B) D > C > B > A
Choose the most appropriate answer from the options (C) A > B > C > D (D) B > A > C > D
given below:
(A) (I), (II) and (IV) only (B) (I) and (II) only
(C) (II) and (III) only (D) (II) only
54. Given below are two statements: one is labelled as
Assertion A and the other is labelled as Reason R:
[JEE MAIN 2024]
Assertion A: Aryl halides cannot be prepared by
replacement of hydroxyl group of phenol by halogen
atom.
Reason R: Phenols react with halogen acids violently.
In the light of the above statements, choose the most
appropriate from the options given below:
(1) Both A and R are true but R is NOT the correct
explanation of A
(2) A is false but R is true
(3) A is true but R is false
(4) Both A and R are true and R is the correct
explanation of A
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EXERCISE – IV (JEE ADVANCE) 11. The compound that will react most readily with NaOH
1. Chlorination of toluene in the presence of light and to form methanol is [IIT 2001]
heat followed by treatment with aqueous NaOH gives: (A) (CH3 )4 N + I − (B) CH3 OCH3
[IIT 1990] (C) (CH3 )3 S + I − (D) (CH3 )3 Cl
(A) o-cresol (B) p-cresol 12. Identify the set of reagents / reaction conditions ' X '
(C) 2,4-dihydroxytoluene (D) Benzoic acid and ' Y ' in the following set of transformation:
2. Aryl halides are less reactive towards nucleophilic [IIT 2002]
substitution reaction as compared to alkyl halides
due to [IIT 1990]
(A) The formation of less stable carbonium ion
(A) X = dilute aqueous NaOH, 20∘ C; Y = HBr /acetic
(B) Resonance stabilization
acid, 20∘ C
(C) The inductive effect
(B) X = concentrated alcoholic NaOH, 80∘ C; Y = HBr/
(D) sp2 hybridised carbonattached to the halogen
acetic acid 20∘ C
3. 1-Chlorobutane on reaction with alcoholic potash (C) X = dilute aqueous NaOH, 20∘ C; Y = Br2 /
gives: [IIT 1990] CHCl3 , 0∘ C
(A) 1-butene (B) 1-butanol (D) X = concentrated alcoholic NaOH, 80∘ C;
(C) 2-butene (D) 2-butanol Y = Br2 /CHCl3 , 0∘ C
4. The products of reaction of alcoholic AgNO2 with ethyl 13. CH3 MgBr + Ethyl ester → which can be formed as
bromide are [IIT 1991] product. excess [IIT 2003]
(A) Ethane (B) Ethyl nitrite
(C) Nitroethane (D) Ethyl alcohol (A) (B)
5. Arrange the following compounds in order of
increasing dipole moment [IIT 1996]
I) Toluene
II) m-dichlorobenzene (C) (D)
III) o-dichlorobenzene
IV) p-dichlorobenzene
(A) I < IV < II < III (B) IV < I < II < III 14. The product of following reaction is [IIT 2003]
(C) IV < I < III < II (D) IV < II < I < III
6. (CH3 )3 CMgCl reaction with D2 O produces: [IIT 1997]
(A) (CH3 )3 CD (B) (CH3 )3 OD
(C) (CD3 )3 CD (D) (CH3 )3 OD
(A) C6 H5 OC2 H5 (B) C2 H5 OC2 H5
7. Benzyl chloride (C6 H5 CH2 Cl) can be prepared from
(C) C6 H5 OC6 H5 (D) C6 H5 I
toluene by chlorination with: [IIT 1998]
(A) SO2 Cl2 (B) SOCl2 15. The following compound on hydrolysis in aqueous
(C) Cl2 , (hv) (D) NaOCl acetone will give: [IIT 2005]
8. The order of reactivity of the following alkyl halides
for a SN 2 reaction is: [IIT 2000]
(A) R-F > R-C > R-Br > R-I
(B) R − F > R − Br > R − Cl > R − I
(C) R-Cl > R −Br > RF > RI
(D) R-I > RBr > R-Cl > R-F
9. Which of the following has the highest
nucleophilicity? [IIT 2000]
(A) F − (B) OH −
(C) CH3− (D) NH2−
10. AnSN 2 reaction at an asymmetric carbon of a
compound always gives. [IIT 2001]
(A) an enantiomer of the substance
(B) a product with opposite optical rotation
It mainly gives
(C) a mixture of diasteremoers
(A) K and L (B) Only K
(D) a single stereoisomer
(C) L and M (D) Only M
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16. Match the following: [IIT 2006] 19. KI in acetone, undergoes SN 2 reaction with each of
Column-I Column-II P, Q, R and S. The rates of the reaction vary as
(A) CH3–CHBr –CD3 on (A) E1 reaction [JEE ADVANCED 2013]
treatment with alc.
KOH gives
CH2 = CH–CD3 as a
major product.
(B) Ph–CHBr–CH3- (B) E2 reaction
reacts faster than (A) P > Q > R > S (B) S > P > R > Q
Ph–CHBr – CD3. (C) P > R > Q > S (D) R > P > S > Q
(C) Ph–CD2–CH2Br on (C) E1 CD
20. The reactivity of compound Z with different halogens
treatment with reaction
under appropriate conditions is given below
C2H5OD/C2H5O–
[JEE ADVANCED 2014]
gives
Ph – CD = CH2 as
the major product.
(D) PhCH2CH2Br and (D) First order
PhCD2CH2 Br react reaction
with same rate.
The observed pattern of electrophilic substitution can
17. The major product of the following reaction is be explained by [JEE ADVANCED 2014]
[IIT 2008] (A) The steric effect of the halogen
(B) The steric effect of the tert-butyl group
(C) The elctronic effect of the phenolic group
(D) The electronic effect of the turt-butyl group
21. In the following reaction, the major product is
[JEE ADVANCED 2015]

(A) (B)

(A) (B)

(C) (D)
(C) (D)

22. The correct statement(s) for the following addition

reactions is (are) [JEE ADVANCED 2017]

18. In the reaction the products are

[IIT 2010]
(A)
(A) (M and O) and ( N and P) are two pairs of
diastereomers
(B) (B) Bromination proceeds through trans-addition in
both the reactions
(C) O and P are identical molecules
(C)
(D) (M and O) and (N and P) are two pairs of
enantiomers
(D)

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23. For the following compounds, the correct statement(s) 25. In the following reactions, P, Q, R, and S are the major
with respect to nucleophilic substitution reactions is products. [JEE ADVANCED 2023]
(are) [JEE ADVANCED 2017]

(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 SN 1 mechanism
(D) I and II follow SN 2 mechanism
24. The major product formed in the following reaction of
[JEE ADVANCED 2021]

The correct statement about P, Q, R, and S is:

(A) P is a primary alcohol with four carbons.
(A) (B) Q undergoes Kolbe's electrolysis to give an eight-
carbon product.
(B) (C) R has six carbons and it undergoes Cannizzaro
reaction.
(D) S is a primary amine with six carbons.
(C)
(D)

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ANSWER KEY
EXERCISE – I
1. A 2. B 3. B 4. C 5. A 6. C 7. A
8. C 9. B 10. C 11. B 12. C 13. C 14. A
15. D 16. D 17. C 18. B 19. C 20. C 21. D
22. A 23. B 24. A 25. ABCD 26. D 27. B 28. B
29. C 30. C 31. A 32. B 33. B 34. A 35. D
36. D 37. C 38. C 39. B 40. B
EXERCISE – II
1. ABCD 2. BD 3. ABCD 4. AC 5. AD 6. B 7. AC
8. D 9. AC 10. ABD 11. ABCD 12. AD 13. ABCD 14. ABC
15. CD 16. ABCD 17. C 18. C 19. C
20. (A) → P, R; (B)→P, Q; (C)→P; (D)→P, Q 21. (A)→Q; (B)→P; (C)→S; (D)→R
22. (A)→S; (B)→Q; (C)→R; (D)→ P 23. (A)→S; (B)→R, S; (C)→R; (D)→P, Q
24. (A)→ P,Q,R,S; (B)→P,R; (C)→T; (D)→Q,S; 25. (A)→Q, S; (B)→P,R,S; (C)→P,R,S; (D)→P,Q,R,S
26.

27. The elimination of HI (or DI) in presence of strong base shows E2 elimination. The rate determining step involves breaking
up of C − H (or C − D ) bond. The C − D bond being stronger than C − H and thus elimination is faster in case of CH3 −
CH2 I.

28. 29. Not available.

30.

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EXERCISE – III (JEE MAIN)

1. C 2. A 3. A 4. B 5. D 6. B 7. B
8. B 9. C 10. C 11. B 12. A 13. D 14. B
15. A 16. C 17. B 18. D 19. A 20. D 21. B
22. A 23. A 24. D 25. D 26. B 27. A 28. D
29. B 30. A 31. A 32. D 33. C 34. A 35. B
36. D 37. D 38. B 39. D 40. D 41. D 42. D
43. A 44. C 45. C 46. C 47. C 48. C 49. C
50. D 51. B 52. D 53. D 54. C 55. B 56. D
57. D
EXERCISE – IV (JEE ADVANCED)
1. D 2. BD 3. A 4. C 5. B 6. A 7. AC
8. D 9. C 10. D 11. A 12. B 13. D 14. B
15. A 16. (A)−Q;(B)−Q; (C)−R, S; (D)−P, S 17. A 18. D 19. B
20. ABC 21. D 22. AB 23. (ACD) or (ABCD) 24. B 25. B

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