Chemistry

Haloalkane and
Haloarene

In One Shot Om Pandey, IIT Delhi

Topics
1 Nucleophile and base

2 Leaving group

3 SN1 , SN2 , SN2'

4 E1 , E2 , E1Cb

4 SN2 Ar

FOR NOTES & DPP CHECK DESCRIPTION

Class 12th : Boards
 Nucleophile and Base
Nucleophile Base

O

 CD3 + O – C – H3C
NH2 + CH3 – Cl
H

 O
OH + CH3 – Cl 
ND2 + O – C – CH3
H

Nucleophilicity is measured by relative Basicity is measured by position of equilibrium.

rates of reaction. It tells about bond strength in product side
Nucleophilicity Steric factor plays on important role in nucleophilicity

r1
CH3 – O + CH3 – Cl

r2
CH3 – CH – O + CH3 – Cl
CH3
H3C r3
C– O + CH3 – Cl
H3C
CH3
Base CH3 – O + H+

CH3

H3C O + H+

CH3
In a period nucleophilicity and basicity have same order .
  
Nucleophilicity/ CH3 NH2 OH F
Basicity

In a group nucleophilicity increases and basicity decreases on moving top to bottom .


Nucleophilicity HO SH

F– Cl– Br– I–

Basicity HO SH

F– Cl– Br– I–
If donor atom is same then nucleophilicity and basicity .

O
H3C – O H – O

O O O O
H3C – C – O CF3 – C – O CF3 – S – O
O

O O O

NO2 OCH3
Negatively charged nucleophile Neutral Nucleophile

(i) HO– H2O

(ii) CH3 – O– CH3 – O – H

(iii) H – S– H2S

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

Solubility in non-polar solvent : NaF NaCl NaBr NaI
{ Weakly polar solvent }

Nucleophilicity in non-polar solvent : F– Cl– Br– I–

Solubility in polar solvent : NaF NaCl NaBr NaI

Polar protic solvent : F– Cl– Br– I–

Polar aprotic solvent : F– Cl– Br– I–

 Leaving Group

DMF
Et – O Cl

DMF
Et – O Br

DMF
Et – O I


H
Nu + O
H


Nu + NN
Good L.G. ⟹ Less Basic Group.
⟹ Stable anion [ I > Br > Cl > F ]
⟹ Neutral [ H2O, NH3 ]
⟹ Gas [ N2, CO2, CO, H – Cl, SO2 ]
 O O
CH3 – O CH3 – C – O CF3 – C – O

O O
O
O=S=O
CH3 – C – O

CH3

Tosylate Ion [ O – Ts]
 SN2 Reaction

→
PE
HO
CH3 – I Acetone

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 :
CH3
Back side Attack
NaOH
↓ I Acetone
Walden Inversion D H
↓
Umbrella Inversion

Rate of Reaction
CH3 CH3 H
CH3 C I H3C C I H C I CH3 I
CH3 H CH3

CH3 I CH3 Br CH3 Cl CH3 F

 AgNO2

NaNO2

CH3 – CH2 – Br
AgCN

NaCN

NaN3
DMF
CH3MgBr LiAlH4
CH3 – CH2 – Br
JEE Main-13 April, 2023 Shift-II

Match List-I with List-II

1-Bromopropane is reacted with reagent in List-I to give product in List-II

List-I Reagent List-II – Product

(A) KOH (alc) (I) Nitrile
(B) KCN (alc) (II) Ester
(C) AgNO2 (III) Alkene
(D) H3CCOOAg (IV) Nitroalkane

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)

 JEE Main-29 July, 2022 Shift-I

Considering the below reactions, the compound ‘A’ and compound ‘B’, respectively are :
AgCN
‘A’ NaCN
‘B’
C2H5OH – H2O Cl
(Major Product) C2H5OH – H2O
(Major Product)

 ⊝  ⊝
A NC, NC

B CN, CN

 ⊝
C NC, CN
 ⊝
D CN, NC
 Reactivity Order

Reactant Rate (SN2)

(i) Cl 1

(ii) CH2 – Cl 79

CH2 – Cl
(iii) 200

(iv) R – O – CH2 – Cl 920

O
(v) Ph – C – CH2 – Cl 105
JEE Main-03 Sept, 2020 Shift-II

The decreasing order of reactivity of the following compounds towards nucleophilic

substitution (SN2) is :

CH2Cl CH2Cl CH2Cl CH2Cl

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

A (II) > (III) > (I) > (IV) B (III) > (II) > (IV) > (I)

C (II) > (III) > (IV) > (I) D (IV) > (II) > (III) > (I)
JEE Main-24 Jan, 2023 Shift-I

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

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

A (A) is false but (R) is true.

B (A) is true but (R) is false.

C Both (A) and (R) are true and (R) is the correct explanation of (A).

D Both (A) and (R) are true but (R) is NOT the correct explanation of (A).
 Unimolecular Nucleophilic substitution Reaction
[SN1]
H2O
R–X

Mechanism :

Kinetics :

Nature of solvent :
Intermediate :
Solvolysis : Weak nucleophile :

CH3
C2H5 – OH
CH3 – C – Cl
CH3
Rate of SN1 Reaction Alkyl Halide :

CH3 CH3 CH3

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

F Cl Br I
 Predict order of rate of reaction

H2O
(i) acetone
I OH

I H2O OH
(ii) acetone

H2O
(iii) I OH
acetone

I H2O
(iv) OH
acetone
JEE Main-30 Jan, 2023 Shift-II

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

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

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

C (b) > (d) > (c) > (a) D (d) > (b) > (c) > (a)
Catalysis (a) AgNO3

(b) Lewis acid [ AlCl3 / SbCl5 / BF3 ]

Following Alkyl halides do not participate in SN1 Reaction.

X
X
CH3 – X , CH3 – CH2 – X , CH2 = CH – X ,
Stereochemistry : ❖ Not, 100% Racemisation . Reason : Ion-Pair in solvent

% Inversion > % Retention

CD3
C2H5OH
H3C I

Ph

Ph

H2O
C acetone
H3C H
I
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
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.
(D) The reaction is favoured by non-polar solvents.
Which observations are correct?

A (B) And (D) B (A), (B) and (C)

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

Rearrangement :
H
H2O
Ph – C – CH2 – Br
CH3

Br

H2O
acetone

Me
Questions

Which of the following potential energy (PE) diagrams represents the SN1 reaction?

A B
PE PE

Progress of reaction→ Progress of reaction→

PE
C PE D
Progress of reaction→
Progress of reaction→
JEE Main-28 July, 2021 Shift-II

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

CH3
Cl Cl Cl CH3 CH2Cl

CH3
SN1 Vs SN2
H2O
NaI KCN
Acetone
CH3 – Br

NaI H2O
Acetone
CH3 – CH2 – Br
Acetone

C2H5OH

Br
C2H5 – OK
 C2H5OH – KOH
O
Br

C2H5OH

H2O

Br

NaCN
 Ph
H Cl MeOH
H Me +
AgNO3
Et

Cl
NaOH
DMSO

NO2

Cl
H2O

OCH3
JEE Main-08 April, 2023 Shift-I

Consider the following reaction that goes from A to B in three steps as shown below:

Choose the correct

Number of Rate
Number of Activated determining
intermediates complexes step
A 3 2 II

B 2 3 II

C 2 2 I

D 2 3 III
JEE Main-11 April, 2023 Shift-I

Cl Nu Nu
(I)
MeO OMe

Cl Nu Nu
(II)
O 2N O 2N
JEE Main-30 Jan, 2023 Shift-II

Decreasing order towards SN1 reaction for the following compounds is :

Cl Cl Cl Cl

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

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

C (b) > (d) > (c) > (a) D (d) > (b) > (c) > (a)
SN2’
CN-

Br

CN-

Br

Br

SH-
 SN2 Ar Nucleophilic Aromatic Substitution

OH

X
O2N
OH

Rate Stability of Carbanion

 F Cl Br I

Reactivity order towards SN2Ar :

NO2 NO2 NO2 NO2

F
Cl
Et – OK

NO2
 Cl
(1) NaOH / 443 K
(2) H+

NO2

Cl
NO2
(1) NaOH / 368 K
(2) H+

NO2

Cl
O2N NO2
Warm
H2O
NO2
JEE Main-25 Jan, 2023 Shift-I

The compound which will have the lowest rate towards nucleophilic aromatic
substitution on treatment with OH– is

Cl Cl
NO2
A B

NO2 NO2
Cl Cl
NO2
C D
NO2
JEE Main-08 April, 2023 Shift-II

The correct order of reactivity of following haloarenes towards nucleophilic

substitution with aqueous NaOH is :
NO2
Cl Cl Cl Cl

NO2 OMe O2N NO2

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

Choose the correct answer from the options given below:

A A>B>D>C B C>A>D>B

C D>C>B>A D D>B>A>C
JEE Main-27 June, 2022 Shift-I

Which one of the following product is correct ?

I
F ⊝ 
PhS Na
DMF

NO2

SPh I SPh SPh

F SPh F SPh
A B C D

NO2 NO2 NO2 NO2

 JEE Main-25 Jan, 2023 Shift-II
Identify the correct order of reactivity for the following pairs towards the
respectively mechanism.
Br Br
Br > Br
(A) SN2 (B) SN1 >

Br
Cl Cl Br
(C) Electrophilic (D) Nucleophilic substitution <
substitution >
NO2
NO2

A (A), (B) and (D) only B (A), (B), (C) and (D)

C (A), (C) and (D) only D (B), (C) and (D) only
JEE Main-24 Jan, 2023 Shift-I

Number of moles of AgCl formed in the following reaction is ___________.

Cl
Cl AgNO3
Cl (A) + X AgCl ↓
H

Cl
 Halogen Exchange Methods
Finkelstein Reaction CH3 — CH2 — Cl NaI
Acetone

CH3 — CH2 — Br NaI

Acetone

AgF / Hg F2
Swart’s Reaction CH3 — CH2 — Cl
[ H2O + EtOH ]

AgF
CH3 — CH2 — Br
H2O

AgF
CH3 — CH2 — I
H2O
JEE Main-25 Jan, 2023 Shift-II

For the reaction :

Acetone
RCH2 Br + I− RCH2 I + Br −
major
The correct statement is :

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.

 Elimination Rexn (i) E2 (ii) E1 (iii) E1Cb

Bimolecular Elimination Reaction [ E2 Reaction ]

H
Alc KOH 
CH3 – CH – CH – CH3
Br

H
Alc KOH 
CH3 – CH – CH – CH2
Br
 Solubility of Transition State
H
Alc KOH
(i) CH2 – CH2

Br

H
Alc KOH
(ii) H3C – CH – CH – CH3 
Br

H
Alc KOH
(iii) CH3 – C – CH – CH3 
CH3 Br
Rate of E2 Reaction

CH3 CH3 CH3

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

CH3 CH3
CH3 – C – Cl CH3 – C – I
CH3 CH3
Kinetics : H
C2H5OK+
H3C – CH – CH – CH3 CH3 – CH = CH – CH3
Heat
I

(i) No. of step =

(ii) Rate = K [substrate][base]

(iii) Molecularity = order ⟹

(iv) Base ⟹

(v) Heat ⟹

(vi) Anti-elimination
Stereochemistry :
Br
H3C CH3
Alc. KOH

I
NaNH2

D
H

H
H I NaNH2

H
CH3 H
 Ph
Me Br Alc. KOH

Me 
H
Ph

Ph
Br Me Alc. KOH / 

Me H
Ph
 NaI
Br Acetone

Br H
NaI
CH3 – C – C – CH3 Acetone
H Br

CH3
Ph Br NaI
Acetone
Ph Br
CH3
Hoffman Product :
Case – I : If base is bulky then Hoffman Product is a major product


NaNH2 O K


+ 
Li N 
O K+
Case – II : If leaving group is more electronegative then base abstract more
acidic hydrogen.

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

Ha
NaNH2
Hb 
Br

Cl
CH3 – O Na+

Ha Hb
JEE Main-02 Sept, 2020 Shift-II

The major product obtained from E2-elimination of 3-bromo-2-fluoropentane is

Br F

A CH3CH2 – CH – CH = CH2 B CH3 – CH = CH – CH – CH3

Br
C CH3CH2CH = C – F D CH3 – CH2 – C = CH – CH3

CH3
JEE Main-31 Aug, 2021 Shift-
II
The major product of the following reaction is

CH3
Cl NaOH
C2H5OH
Major Product

CH3
CH3
A B
OH
HO
CH3
OH CH3
C D
 E1 Reaction

Et OH
I
E

Reaction co-ordinate

Kinetics :
(i) No. of steps

(ii) Rate determining step

(iii) Rate 

(iv) Major Product

(v) Solvent
Rate : CH3 CH3
H3C I H I
CH3 CH3

I Br Cl F

CH3
H2O
Ph CH CH3
H Br
Br

H2O

JEE Main-03 Sept, 2020 Shift-II

The major product in the following reaction is:

I
t-BuOH
Heat

A B

O-But

C D
 E1Cb : Unimolecular Elimination Reaction via conjugate base

H
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 ]
 H
F
NaNH2
(i) Cl – C – C F 
F
Cl

Alc. KOH
(ii) 

O
NaNH2
(iii) Ph – C – CH2 – CH 
OCH3
E1 Reaction E2 Reaction E1Cb Reaction
H H H
CH3 – C – CH – CH3 CH3 – C – CH – CH3 O2N – C – CH – CH3
CH3 I CH3 I CH3 F

 C2H5OH  C2H5OK+  C2H5OK+

 H2O
H 
CH3
H–C – C
CH3 Br CH3 NaNH2


O
NaNH2

OH

Alc. KOH
NC

F
JEE Main-02 Sept, 2020 Shift-II

OH
Br OH + Br rate = k [ tBuBr ] …(1)
H2O

CH3
+ HOH + Br
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
Physical Properties
(i) Boiling Point  Molecular Mass  Inter molecular force of attraction

❑ Boiling Point : CH3Cl CH3Br CH2Br2 CHBr3

Chloromethane Bromomethane Dibromomethane Bromoform

Br Br
Br

❑ Boiling Point : Halogen derivative compound > Parent hydrocarbon

Cl
 Cl

❑ Boiling Point : Cl
Cl
1-Chlorobutane 1-Chloropropane Isopropyl chloride

I Br Cl F
❑ Boiling Point :

❑ For isomeric haloalkanes :

❑ Boiling Point : Br Br
Br
(ii) Melting Point
Due to symmetry of para isomer that fits in crystal lattice better than ortho
and meta isomer.

Cl Cl Cl
Cl
Melting Point :
Cl
Cl
Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl
Cl Cl Cl

Cl Cl Cl
Cl Cl Cl Cl
Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl
Cl Cl Cl

Cl Cl Cl
Cl Cl Cl Cl
 JEE Main-29 Jan, 2023 Shift-I

Choose the correct answer from the option given below :

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

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

(E) Boiling Point : Cl > Cl > Cl

A (B), (C) and (D) only B (A), (C) and (E) only

C (A), (C) and (D) only D (A), (B) and (E) only
JEE Main-25 July, 2021 Shift-II

The correct decreasing order of densities of the following compounds is:

Cl
(A) (B)

Cl Br

(C) (D)
Cl Cl

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

C (D) > (C) > (B) > (A) D (C) > (D) > (A) > (B)
Keep Hustling!