Nucleophilicity Steric factor plays on important role in nucleophilicity

r1
CH3 – O + CH3 – Cl

r2
CH3 – CH – O + CH3 – Cl
CH3
Organic Chemistry H3C r3
C – O + CH3 – Cl
H3C
Haloalkane and CH3

Haloarene Base CH3 – O + H+

CH3

H3C O + H+
In One Shot Om Pandey, IIT Delhi
CH3

Nucleophile and Base In a period nucleophilicity and basicity have same order .
Nucleophile Base   
Nucleophilicity/ CH3 NH2 OH F
Basicity
O

 CD3 + O – C – H3C
NH2 + CH3 – Cl
H In a group nucleophilicity increases and basicity decreases on moving top to bottom .

 O Nucleophilicity HO SH
OH + CH3 – Cl 
ND2 + O – C – CH3
F– Cl– Br– I–
H

Basicity HO SH
Nucleophilicity is measured by relative Basicity is measured by position of equilibrium.
rates of reaction. It tells about bond strength in product side F– Cl– Br– I–
 If donor atom is same then nucleophilicity and basicity .
Solubility in non-polar solvent : NaF NaCl NaBr NaI
{ Weakly polar solvent }
O
H3C – O H– O Nucleophilicity in non-polar solvent : F– Cl– Br– I–

O O O O Solubility in polar solvent : NaF NaCl NaBr NaI

H3C – C – O CF3 – C – O CF3 – S – O
O
Polar protic solvent : F– Cl– Br– I–
O O O
Polar aprotic solvent : F– Cl– Br– I–

NO2 OCH3

Leaving Group
Negatively charged nucleophile Neutral Nucleophile
DMF
(i) HO– H2O Et – O Cl

(ii) CH3 – O– CH3 – O – H DMF

Et – O Br

(iii) H – S– H2S DMF

Et – O I

Lithium Di-isopropyl amide ( LDA ) is a non-nucleophilic base . H


Nu + O
H


Nu + NN
Good L.G. ⟹ Less Basic Group. SN2 Reaction

→
⟹ Stable anion [ I > Br > Cl > F ] PE
HO
CH3 – I
⟹ Neutral [ H2O, NH3 ] Acetone

⟹ Gas [ N2, CO2, CO, H – Cl, SO2 ] Mechanism →

Progress of reaction →

❖ No. of step →

❖ Kinetics → Molecularity = 2 Order = 2

❖ No , intermediate → ONLY Transition state

❖ Negatively charged Transition state → EWG will stabilise Transition state

❖ Nature of solvent →

Stereochemistry :
O O CH3
Back side Attack
NaOH
CH3 – O CH3 – C – O CF3 – C – O ↓ I Acetone
Walden Inversion D H

O ↓
O
O Umbrella Inversion
O=S=O
CH3 – C – O
Rate of Reaction
CH3 CH3 H
CH3

CH3 C I H3C C I H C I CH3 I
Tosylate Ion [ O – Ts] CH3 H CH3

CH3 I CH3 Br CH3 Cl CH3 F

 JEE Main-13 April, 2023 Shift-II
AgNO2
Match List-I with List-II
1-Bromopropane is reacted with reagent in List-I to give product in List-II
NaNO2
List-I Reagent List-II – Product
CH3 – CH2 – Br (A) KOH (alc) (I) Nitrile
(B) KCN (alc) (II) Ester
AgCN
(C) AgNO2 (III) Alkene
(D) H3CCOOAg (IV) Nitroalkane

NaCN A (A)-(IV), (B)-(III), (C)-(II), (D)-(I) B (A)-(III), (B)-(I), (C)-(IV), (D)-(II)

C (A)-(I), (B)-(II), (C)-(III), (D)-(IV) D (A)-(I), (B)-(III), (C)-(IV), (D)-(II)

NaN3
DMF

CH3MgBr LiAlH4
JEE Main-29 July, 2022 Shift-I
CH3 – CH2 – Br
Considering the below reactions, the compound ‘A’ and compound ‘B’, respectively are :
AgCN
‘A’ NaCN
‘B’
C2H5OH – H2O Cl C2H5OH – H2O
(Major Product) (Major Product)

 ⊝  ⊝
A NC, NC

B CN, CN

 ⊝
C NC, CN
 ⊝
D CN, NC
 JEE Main-24 Jan, 2023 Shift-I
Reactivity Order

Reactant Rate (SN2) Assertion (A) : Hydrolysis of an alkyl chloride is a slow reaction but in the presence of
NaI, the rate of the hydrolysis increases.

(i) Cl 1 Reason (R) : I– is a good nucleophile as well as a good leaving group.

(ii) CH2 – Cl 79
A (A) is false but (R) is true.
CH2 – Cl
(iii) 200
B (A) is true but (R) is false.

(iv) R – O – CH2 – Cl 920 C Both (A) and (R) are true and (R) is the correct explanation of (A).
O
(v) Ph – C – CH2 – Cl 105 D Both (A) and (R) are true but (R) is NOT the correct explanation of (A).

JEE Main-03 Sept, 2020 Shift-II Unimolecular Nucleophilic substitution Reaction

[SN1]
The decreasing order of reactivity of the following compounds towards nucleophilic H2O
R–X
substitution (SN2) is :

CH2Cl CH2Cl CH2Cl CH2Cl Mechanism :

NO2
(I) (II) (III) (IV)
NO2 NO2 O2N NO2
Br NO2

A (II) > (III) > (I) > (IV) B (III) > (II) > (IV) > (I)
Kinetics :
C (II) > (III) > (IV) > (I) D (IV) > (II) > (III) > (I)
Nature of solvent :
Intermediate :
Solvolysis : Weak nucleophile : Predict order of rate of reaction

CH3 H2O
(i) acetone
C2H5 – OH
CH3 – C – Cl I OH
CH3
I H2O OH
(ii) acetone

H2O
(iii) I OH
acetone

I H2O
(iv) OH
acetone

Rate of SN1 Reaction Alkyl Halide : JEE Main-30 Jan, 2023 Shift-II

CH3 CH3 CH3 Decreasing order towards SN1 reaction for the following compounds is:

CH3 – C – Cl H3C – C – Cl H – C – Cl CH3 – Cl Cl Cl Cl Cl

CH3 H H

NO2 OMe Cl
(a) (b) (c) (d)

F Cl Br I A (a) > (c) > (d) > (b) B (a) > (b) > (c) > (d)

C (b) > (d) > (c) > (a) D (d) > (b) > (c) > (a)
Catalysis (a) AgNO3 JEE Main-03 Sept, 2020 Shift-I

The mechanism of SN1 reaction is given as :

𝑌⊝
R – X → RX → R || X R – Y + X
(b) Lewis acid [ AlCl3 / SbCl5 / BF3 ]
Ion pair Solvent
separated ion pair
A student writes general characteristics based on the given mechanism as:
(A) The reaction is favoured by weak nucleophiles.
(B) R would be easily formed if the substituents are bulky.
(C) The reaction is accompanied by racemization.
Following Alkyl halides do not participate in SN1 Reaction.
X (D) The reaction is favoured by non-polar solvents.
Which observations are correct?
X
CH3 – X , CH3 – CH2 – X , CH2 = CH – X ,
A (B) And (D) B (A), (B) and (C)

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

Stereochemistry : ❖ Not, 100% Racemisation . Reason : Ion-Pair in solvent Rearrangement :

H
% Inversion > % Retention
H2O
Ph – C – CH2 – Br
CD3
CH3
C2H5OH
H3C I

Ph
Br
Ph H2O
acetone
H2O
C acetone
Me
H3C H
I
Questions SN1 Vs SN2
Which of the following potential energy (PE) diagrams represents the SN1 reaction? H2O
NaI KCN
Acetone
CH3 – Br

A B
PE PE

Progress of reaction→ Progress of reaction→

NaI H2O
Acetone
CH3 – CH2 – Br
Acetone

PE
C PE D
C2H5OH
Progress of reaction→
Progress of reaction→

Br
C2H5 – OK

JEE Main-28 July, 2021 Shift-II C2H5OH – KOH

O
The correct order of reactivity of the given chlorides with acetate in acetic acid is : Br

CH3
Cl Cl Cl CH3 CH2Cl C2H5OH

CH3
H2O

Br

NaCN
 Ph JEE Main-11 April, 2023 Shift-I
H Cl MeOH
H Me + Cl Nu Nu
AgNO3 (I)
Et
MeO OMe

Cl Cl Nu Nu
NaOH
(II)
DMSO O 2N O 2N

NO2

Cl
H2O

OCH3

JEE Main-08 April, 2023 Shift-I JEE Main-30 Jan, 2023 Shift-II

Consider the following reaction that goes from A to B in three steps as shown below: Decreasing order towards SN1 reaction for the following compounds is :
Cl Cl Cl Cl
Choose the correct
Number of Rate
Number of Activated determining
intermediates complexes step NO2 OMe Cl
A 3 2 II (a) (b) (c) (d)

B 2 3 II
A (a) > (c) > (d) > (b) B (a) > (b) > (c) > (d)

C 2 2 I
C (b) > (d) > (c) > (a) D (d) > (b) > (c) > (a)

D 2 3 III
 SN2’
F Cl Br I
CN-

Br Reactivity order towards SN2Ar :

NO2 NO2 NO2 NO2

CN-

Br

F
Br
Cl
SH- Et – OK

NO2

SN2 Ar Nucleophilic Aromatic Substitution Cl

(1) NaOH / 443 K
X
(2) H+
OH
NO2

Cl
X NO2
(1) NaOH / 368 K
O2N (2) H+
OH
NO2

Cl
O2N NO2
Warm
H2O
Rate Stability of Carbanion NO2
JEE Main-25 Jan, 2023 Shift-I JEE Main-27 June, 2022 Shift-I

The compound which will have the lowest rate towards nucleophilic aromatic Which one of the following product is correct ?
substitution on treatment with OH– is
I
Cl Cl ⊝ 
F PhS Na
NO2
A B DMF

NO2
NO2 NO2
Cl Cl SPh I SPh SPh
NO2 F SPh F SPh
C D A B C D
NO2
NO2 NO2 NO2 NO2

JEE Main-25 Jan, 2023 Shift-II

JEE Main-08 April, 2023 Shift-II
Identify the correct order of reactivity for the following pairs towards the
The correct order of reactivity of following haloarenes towards nucleophilic respectively mechanism.
substitution with aqueous NaOH is :
Br Br
NO2 Br > Br
(A) SN2 (B) SN1 >
Cl Cl Cl Cl
Br
Cl Cl Br
NO2 OMe O2N NO2
(C) Electrophilic (D) Nucleophilic substitution <
(A) (B) (C) (D) substitution >
Choose the correct answer from the options given below: NO2
NO2
A A>B>D>C B C>A>D>B
A (A), (B) and (D) only B (A), (B), (C) and (D)
C D>C>B>A D D>B>A>C
C (A), (C) and (D) only D (B), (C) and (D) only
JEE Main-24 Jan, 2023 Shift-I JEE Main-25 Jan, 2023 Shift-II

Number of moles of AgCl formed in the following reaction is ___________. For the reaction :
Acetone
Cl RCH2 Br + I − RCH2 I + Br −
Cl AgNO3 major
Cl (A) + X AgCl ↓
The correct statement is :
H

Cl A The transition state formed in the above reaction is less polar than the localized
anion.

B The reaction can occur in acetic acid also.

C The solvent used in the reaction solvates the ions formed in rate determining step.

D Br– can act as competing nucleophile.

Halogen Exchange Methods Elimination Rexn (i) E2 (ii) E1 (iii) E1Cb

Finkelstein Reaction CH3 — CH2 — Cl NaI
Acetone
Bimolecular Elimination Reaction [ E2 Reaction ]
H
CH3 — CH2 — Br NaI Alc KOH 
Acetone CH3 – CH – CH – CH3
Br
AgF / Hg F2
Swart’s Reaction CH3 — CH2 — Cl
[ H2O + EtOH ]

H
AgF Alc KOH 
CH3 — CH2 — Br CH3 – CH – CH – CH2
H2O
Br
AgF
CH3 — CH2 — I
H2O
 Solubility of Transition State Kinetics : H
C2H5OK+
H H3C – CH – CH – CH3 CH3 – CH = CH – CH3
Alc KOH Heat
(i) CH2 – CH2 I

Br
(i) No. of step =
H
Alc KOH (ii) Rate = K [substrate][base]
(ii) H3C – CH – CH – CH3 
Br (iii) Molecularity = order ⟹

H (iv) Base ⟹
Alc KOH
(iii) CH3 – C – CH – CH3  (v) Heat ⟹
CH3 Br
(vi) Anti-elimination

Stereochemistry :
Rate of E2 Reaction Br
H3C CH3
CH3 CH3 CH3 Alc. KOH

CH3 – C – Cl H3C – C – Cl H – C – Cl
CH3 H H I
NaNH2

D
H
CH3 CH3
H
CH3 – C – Cl CH3 – C – I H I NaNH2

CH3 CH3 H
CH3 H
 Ph Hoffman Product :
Me Br Alc. KOH
Case – I : If base is bulky then Hoffman Product is a major product
Me 
H
Ph 
NaNH2 O K


+ 
Ph Li N 
O K+
Br Me Alc. KOH / 

Me H
Ph

NaI
Case – II : If leaving group is more electronegative then base abstract more
Br Acetone
acidic hydrogen.

H H
Br H NaNH2
NaI
CH3 – CH – CH – CH2 
CH3 – C – C – CH3 Acetone F
H Br
Case – III : Steric Hindrance at  - carbon .

Ha
CH3 NaNH2
Hb 
Ph Br NaI
Acetone Br
Ph Br
CH3 Cl
CH3 – O Na+

Ha Hb
JEE Main-02 Sept, 2020 Shift-II E1 Reaction
The major product obtained from E2-elimination of 3-bromo-2-fluoropentane is
Et OH
I
E

Reaction co-ordinate

Br F Kinetics :
A CH3CH2 – CH – CH = CH2 B CH3 – CH = CH – CH – CH3 (i) No. of steps

(ii) Rate determining step

Br
C CH3CH2CH = C – F CH3 – CH2 – C = CH – CH3 (iii) Rate 
D
CH3 (iv) Major Product

(v) Solvent

JEE Main-31 Aug, 2021 Shift- Rate : CH3 CH3

II
The major product of the following reaction is H3C I H I
CH3 CH3
CH3
Cl NaOH
C2H5OH
Major Product
I Br Cl F

CH3
CH3
A B CH3
OH H2O
Ph CH CH3
HO
CH3 H Br
OH CH3
C D
 E1Cb : Unimolecular Elimination Reaction via conjugate base
Br
H
H2O
C2H5OK+
 O2N – C – CH – CH3
fast Slow
CH3 F

Rate = K [substrate][base]

Condition :
i. Electron withdrawing group at -carbon with a hydrogen (acidic)
ii. Strong Base/Heat
iii. Bad leaving group [ –OH / –OCH3 / –F / –OH2 ]

JEE Main-03 Sept, 2020 Shift-II H

F
NaNH2
The major product in the following reaction is: (i) Cl – C – C F 
F
I Cl
t-BuOH
Heat

Alc. KOH
(ii) 

A B F

O
O-But NaNH2
(iii) Ph – C – CH2 – CH 
C D OCH3
E1 Reaction E2 Reaction E1Cb Reaction JEE Main-02 Sept, 2020 Shift-II

H H H
OH
CH3 – C – CH – CH3 CH3 – C – CH – CH3 O2N – C – CH – CH3 Br OH + Br rate = k [ tBuBr ] …(1)
H2O

CH3 I CH3 I CH3 F CH3

+ HOH + Br
 C2H5OH  C2H5OK+  C2H5OK+ OH rate = k [ tBuBr ] [ OH ] …(2)
H2C CH3
C2H5OH

Which of the following statements is true?

A Changing the concentration of base will have no effect on reaction (2)

B Changing the concentration of base will have no effect on reaction (1)

C Changing the base from OH to OR will have no effect on reaction (2)

D Double the concentration of base will double the rate of both the reactions

H2O Physical Properties

H 
CH3
(i) Boiling Point  Molecular Mass  Inter molecular force of attraction
H–C – C
CH3 Br CH3 NaNH2
❑ Boiling Point : CH3Cl CH3Br CH2Br2 CHBr3

Chloromethane Bromomethane Dibromomethane Bromoform

O
NaNH2 Br Br
Br

OH

❑ Boiling Point : Halogen derivative compound > Parent hydrocarbon

Alc. KOH
NC

F Cl
 Cl JEE Main-29 Jan, 2023 Shift-I

❑ Boiling Point : Cl
Cl Choose the correct answer from the option given below :
1-Chlorobutane 1-Chloropropane Isopropyl chloride

(A) Boiling Point : Cl < Cl < Cl (B) Density: I< Cl < Br

Br Br
Br (D) Density : I Br Cl
I Br Cl F (C) Boiling Point : Br < Br < < <
❑ Boiling Point :
Br Br Br

(E) Boiling Point : Cl > Cl > Cl

❑ For isomeric haloalkanes :

❑ Boiling Point : A (B), (C) and (D) only B (A), (C) and (E) only
Br Br
Br (A), (C) and (D) only (A), (B) and (E) only
C D

(ii) Melting Point

JEE Main-25 July, 2021 Shift-II
Due to symmetry of para isomer that fits in crystal lattice better than ortho
and meta isomer. The correct decreasing order of densities of the following compounds is:

Cl Cl Cl Cl
Cl (A) (B)
Melting Point :
Cl Cl Br
Cl
Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl
Cl Cl Cl (C) (D)
Cl Cl
Cl Cl Cl
Cl Cl Cl Cl
A (C) > (B) > (A) > (D) B (A) > (B) > (C) > (D)
Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl
Cl Cl Cl
C (D) > (C) > (B) > (A) D (C) > (D) > (A) > (B)
Cl Cl Cl
Cl Cl Cl Cl