chemistry

Haloalkanes Haloarenes
Sakshi Vora

IIT - Roorkee

10th, 12th CBSE State Topper

7+ Years of Teaching Experience

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Haloalkanes
Haloarenes
Alkyl Halide

⇒ Halogen derivative of alkanes

Ex :- R - X ( X = -F , -Cl , - Br, - I )

⇒ Alkyl halides are electrophilic in nature

Physical
Properties
Physical Properties

● C-X bond is polar in nature

● Alkyl halides are insoluble in H2O because they cannot form bond with
H2O.
● These are completely soluble in organic solvents.
● M.P & B.P. α molecular weight.
● For same alkyl group the order of B.P. is RI > RBr > RCl > RF
● Polarity order is RF > RCI > RBr > RI
● Reactivity order is RI > RBr > RCl > RF
Practice
Questions
Among the following compounds, which one has the shortest
C - Cl bond ?

A.

B. [Sep. 04, 2020 (II)]

C.

D.
Reactions
of
Alkyl halide
Reactions shown by alkyl halides

1. Substitution reaction
2. Elimination reaction
Substitution
Reactions
Nucleophilic Substitution Reaction (SN)
When a Nucleophile (Strong) substitutes another nucleophile (weak)
SN 2

Reactions
SN2 Mechanism
Substitution Nucleophilic bimolecular SN2
Important
points
Important points about SN2

1. One step mechanism

2. No carbocation intermediate is formed
3. No rearrangement is possible
4. A pentavalent transition state is involved
5. Bimolecular reaction
6. Backside attack of nucleophile takes place
7. Inversion takes place
SN 1

Reactions
Mechanism of SN1 Reaction
Substitution Nucleophilic Unimolecular Reaction
 Important points about SN1 reaction

1. Two step mechanism

2. Carbocation intermediate is formed
3. Rearrangement is possible
4. First order reaction
5. Nucleophile can attack from both sides
Factors
affecting SN
reactions
Factors for SN mechn : -

1. Structure of Substrate
2. Nature of leaving group
3. Nature of Nucleophile
4. Nature of solvent.
More the ease of dissociation,
more would be SN1
More stable carbocation, more will be SN1
Structure of
Substrate
Structure of substrate SN1

A.

B.

C.

D.
More the stability of TS by
EWG, more will be SN2
More the steric hindrance, lower SN2
Structure of substrate SN2
Structure of substrate SN2
Structure of substrate SN2
Important
points
3o ⟶ always SN1
1O, CH3 X⟶ always SN2
2o ⟶ can show both SN1 & SN2
Nature of
Leaving group
Nature of leaving group

In both SN1 and SN2,

RDS includes breaking of C-Leaving group,
Thus
better the leaving group, faster will be the rate
Nature of
Nucleophile
Nature of nucleophile

SN1: Nucleophile is not involved in RDS, no effect of concentration,

size or nucleophilicity of nucleophile

SN2: SN2 increases by

❏ Higher concentration of nucleophile

❏ Small size of nucleophile
❏ Higher ability of nucleophile to give electrons (nucleophilicity)
Nature of
solvent
Nature of Solvent
For SN1
Polar Protic Solvent - favors dissociation of bond along with
stabilization of ions hence SN1 increases in PPS
Nature of solvent

SN2: Polar protic solvent will solvate the nucleophile thereby

decreasing its nucleophilicity,

Thus a polar aprotic solvent will be required

Important
Points
 SN2 SN1

1o > 2o > 3o 3o > 2o > 1o

R - I > R - Br > R - Cl R - I > R - Br > R - Cl

Strong/small/ high Poor Nucleophile

concentration of (H2O, ROH, RCOOH etc)
Nucleophile

PAS PPS
(Acetone, DMF, DMSO, (H2O, ROH) etc
TMF)
Important
Points
Important point

➔ In most of the SN1 reactions nucleophile is not taken

SOLVENT itself behaves like a Nucleophile.

➔ Bridge head halides, aryl halides and vinyl halides never show SN1
and SN2
➔ Neopentyl halide never shows SN2 due to crowding
Practice
Questions
Predict the rate of SN1 and SN2
Predict the rate of SN1 and SN2
Predict the rate of SN1 and SN2
Predict the rate of SN1 and SN2
The mechanism of SN1 reaction is given as :

A student writes general characteristics based on the given

mechanism as :
[Sep. 03, 2020 (I)]
1. The reaction is favoured by weak nucleophiles.
2. R would be easily formed if the substituents are bulky.
3. The reaction is accompanied by racemization.
4. The reaction is favoured by non-polar solvents.
Which observations are correct ?

A. (1) and (2)

B. (1) and (3)
C. (1) , (2) and (3)
D. (2) and (4)
KI in acetone, undergoes SN2 reaction with each of P, Q, R and S.
The rates of the reaction vary as

[Adv. 2013]

A. P>Q>R>S
B. S>P>R>Q
C. P>R>Q>S
D. R>P>S>Q
An ‘Assertion’ and a ‘Reason’ are given below. Choose the correct
answer from the following options :

Assertion (A) : Vinyl halides do not undergo nucleophilic

substitution easily. [April. 12, 2019 (II)]
Reason (R) : Even though the intermediate carbocation is
stabilized by loosely held p - electrons, the cleavage is difficult
because of strong bonding.

A. Both (A) and (R) are wrong statements.

B. Both (A) and ® are correct statements and (R) is the correct
explanation of (A)
C. Both (A) and ® are correct statements but (R) is not the correct
explanation of (A).
D. (A) is a correct statement but (R) is a wrong statement.
The decreasing order of reactivity of the following compounds
towards nucleophilic substitution (SN2) is :

[Sep. 03, 2020 (II)]

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

B. (II) > (III) > (IV) > (I)
C. (III) > (II) > (IV) > (I)
D. (IV) > (II) > (III) > (I)
Stereochemistry
of
SN1 reactions
Stereochemistry of SN1 reactions

In SN1 reaction partial racemisation takes place, slightly invented product

dominates.
Stereochemistry of SN2

Configuration of bonds at a chiral centre may or may not change

Methods of
preparation
of
Haloalkanes
Preparation
from alkanes
 By Halogenation of Alkanes
Halogenation of alkanes takes place by free radical mechanism.

h𝝂
R-H+X-X R-X+H-X
 Reed’s Reaction

RH + SO2Cl2 ----------------> RCl + HCl + SO2

Notes

● Formation of Radical is r. d. S
● Chain Reaction
● Oxidation Reaction of (R - H)
Predict the product of the reaction

SO2Cl2

hv
Preparation from
alkenes by
Hydrohalogenation
From alkene: Hydrohalogenation
Practice Questions
The decreasing order of reactivity of the following organic
molecules towards AgNO3 solution is :

[Sep. 04, 2020 (I)]

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

B. (A) > (B) > (D) > (C)
C. (A) > (B) > (C) > (D)
D. (B) > (A) > (C) > (D)
Which of the following compounds will form the precipitate with
aq. AgNO3 solution most readily ?

A.

B. [Sep. 04, 2020 (II)]

C.

D.
Preparation from
alcohols
From Alcohol :-

(i) Using dry H - X :-

Anhydrous ZnCl2
R - OH + H - X R - X + H2O
Δ, 300oC
Mechanism
Important points
Important points:

● Mechanism is SN1
● CARBOCATION INTERMEDIATE IS FORMED
● The reactivity order of HX is - HI > HBr > HCl
● Rearrangement is possible
● Order of rate of reaction for ROH

3o > 2o > 1o < CH3 - OH

SN1 SN1 SN2 SN2

Use of Catalyst :

HI - Usually no catalyst required

HBr - H2SO4 as catalyst
HCl - LUCAS REAGENT Conc HCl - Anhyd ZnCl2
Important points:

3o Alcohol ⟶ Immediate turbidity

2o Alcohol ⟶ 5 to 7 min far turbidity
1o Alcohol ⟶ No turbidity until heating is not done
Predict the products on reaction with Lucas reagent
Reaction of SOCl2 (Darzen Reaction)

(a) R - OH + SOCl2 ⟶ R - Cl + SO2 (g) + HCl (g)

Thionyl
Chloride
SNi Reactions
Mechanism of Darzen reaction
Note

(a) Reaction of ROH & SOCl2 is SNi mechn

(b) Retained product is obtained
(c) In presence of weak base (like pyridine mechanism is SN2 &
inversion takes place
predict the products of darzen reaction
Finkelstein Reaction
Finkelstein Reaction

R - Br or R - Cl + Kl Acetone R - I + KCl

In this reaction only exchange takes place and the reaction is called
as Halogen exchange reaction
Important Points

1. Reaction occurs due to formation of ppt because NaCl is

insoluble in acetone
2. The mechanism involves SN2
3. Inversion product is formed
Predict the products of the reaction
Swarts Reaction
Swarts reaction

1. AgF is taken in polar aprotic solvent DMF

2. SN2 mechanism is followed

R - Br or R - Cl Ag F/ Δ R-F

or Hg2F2 / Δ
predict the product of the reaction
Grove’s Reaction
Grove’s Process
Reaction of alcohol with PCl3 or red P/Cl2

(a) Using PCl3 :- 3ROH + PCl3 ⟶ 3R - Cl + H3PO3

(b) Using PCl5 : - ROH + PCl5 ⟶ R - Cl + HCl + POCl3
Mechanism
Important points

It follows SN2 mechanism

Inverted product is formed

Practice Questions
Predict the products of the reaction

o
||
R - C - OH + PCl5

+ PCl5
O
Predict the products of the reaction

+ PCl5

o
||
R - C - Cl + PCl5
Ambidentate
Nucleophiles
Ambidentate Nucleophile :-

Nucleophiles having more than one electron donating sites.

Reaction with KCN :

R - X + KCN ⟶ R - C ≡ N + KX
Alkane nitrile
Reaction with AgCN :

R - X + AgCN ⟶ R - N ≡ C + AgX
Reaction with KNO2 :
SN NGP
Neighbouring
group
participation
SN - NGP in SN reactions

(i) Anchimeric assistance

(ii) Compound must have leaving group along with internal nucleophilic site

(iii) Both leaving group and the interval Nucleophilic site must be anti
SN - NGP in SN reactions

(iv) NGP increases rate of reaction

(v) For NGP concentration of external nucleophile must be low

(vi) Tendery of NGP decreases if leaving tendency is usually high.

Group showing NGP

(viii) Atoms/ group which show NGP are:

- Cl, - NR2 - OR - COOR

- Br - NHR -O- -C=C

-I - NH2 - COO - SR
Predict the product of the reaction

aq.
NaOH
(2. eq.)
Elimination
Reactions
1,2 Elimination Reactions
When both eliminating atoms / groups eliminate from vicinal sites (1,2)
E2
Elimination
Reaction
Mechanism of E2 elimination
Important points of E2 elimination
Important points of E2 elimination
NOTE
❖ No carbocation Intermediate
❖ One step reaction
❖ No rearrangement possible
❖ A pentavalent C - TS is involved
❖ Anti elimination
E1
Elimination
Reaction
Mechanism of E1 Elimination
Notes of E1 Elimination
NOTE

Two step mechanism

Carbocation Intermediate
Rearrangement possible

Formation of cation is r.d.s

E1cb
Elimination
Reaction
Mechanism of E1cb Elimination
Important points about E1cb elimination

NOTE

Two step mechanism

Carbanion intermediate
No rearrangement possible

Step II is r.d.s due to lower conc of Conjugate base

Factors affecting
Elimination
Reaction
Factors affecting elimination mechn

(a) Structure of reactant

(b) Nature of leaving group
(c) Nature of base
(d) Nature of solvent
(e) Effect of temp
Structure of alkyl
halide
Structure of alkyl halide: E1 Elimination

Higher the ease of dissociation / higher the stability of carbocation

higher would be rate of E1 mechn
3o > 2o > 1o
More the ease of dissociation,
more would be E1
More stable carbocation, more will be E1
Structure of alkyl halide: E2 Elimination

Since TS contains alkene like character,

hence higher the stability of alkene, higher would be stability of T.S

hence higher would be the rate of E2
More the stability of TS (alkene
like character), more will be E2
Structure of alkyl halide: E1cb Elimination

For E1 - CB

H H

-C-C-

EWG X

⇒ 𝛃 - Anion stabilizing group (EWG) must be present for E1 cb in R - X

Nature of leaving
group
Nature of leaving group E1 and E2

Since r.d.s of both E1 & E2 involves breaking of bond,

hence on increasing leaving tendency rate of both

Mechn increases
Nature of leaving group E1cb

For E 1 - CB

Very Bad leaving group

(-F, -OH, -OR etc)
Nature of base
Nature of Base

(For E1 )
Since r.d.s of E1 does not involve Base

hence No effect on rate of conc / size / basic strength of base

Usually weak base is used

Nature of Base

For E2
Since Base is involved in rds of E2 hence rate increases at

⇒ higher conc. and small size

⇒ high Basic strength
Important Base

Alcoholic NaOH
Alcoholic KOH (Caustic potash)

NaNH2

RONa

ONa

N
Effect of solvent
Solvents

(For E1)
Polar Protic Solvent (H2O ROH, HCOOH etc)

(For E2)
PAS (DMSO, DMF)

(E1 cb)
PPS
Important
Reactions
Dehydrohalogenation
Reaction
Dehydrohalogenation Reaction

Follows E2 mechanism

The TS should have alkene like character

Practice Questions
Predict the product of following reactions
predict the product of reaction
Important points
Note : -

Use of Bulky Bases favor formation of Hofmann product as a

major product

Alc. KOH

t-BuOK

Cl
Note : -

1. A leaving group with strong I effect and poor leaving tendency on

elimination gives hoffmann alkene as a major product.
2. Reaction mechanism follows E2a mechn
3. Such leaving groups are
- F, - NR3, - SR2 etc
Substitution vs Elimination : -

1. CH3 - X always show SN2

2. Higher temp favors elimination
3. Aq. NaOH and Aq.KOH shows SN2 mechn
4. Alc. KOH and Alc. NaOH shows E2 mechn
5. Use of Bulkcier Base gives higher yield of elimination (E2) product
6. On increasing Branching elimination mechn gets favored.
 Factors for elimination Mechn

SN2 SN1 E1 E2

(i) 1o > 2o > 3o (i) 3o > 2o > 1o (i) 3o > 2o > 1o (i) 3o > 2o > 1o

(ii) R-I >R-Br> R-Cl (ii) R-I >R-Br> (ii) R-I >R-Br> R- (ii) R-I >R-Br> R-
R-Cl Cl Cl

Strong nucleophile Poor nucleophile Poor base Strong base

NaI, NaSR, NaBr, Water, alcohol Water, alcohol NaOH, NaOR,
NaCN, NaN3 NaNH2, t-BuO-K+

Polar Aprotic solvent Polar protic Polar protic solvent Polar aprotic
solvent HEAT solvent
HEAT
Practice Questions
The major product in the following reaction is :

A.

B. [Sep. 03, 2020 (II)]

C.

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

A.

B.
[Sep. 02, 2020 (II)]

C.

D.
Consider the reaction sequence given below :

[Sep. 02, 2020 (II)]

Which of the following statements is true ?

A. Changing the base from OH to OR will have no effect on
reaction (2).
B. Changing the concentration of base will have no effect on
reaction (1).
C. Doubling the concentration of base will double the rate of
both the reactions.
D. Changing the concentration of base will have no effect on
reaction (2)
The decreasing order of reactivity towards dehydrohalogenation
(E1) reaction of the following compounds is:

[Jan. 08, 2020 (I)]

A. D>B>C>A
B. B>D>A>C
C. B>D>C>A
D. B>A>D>C
The major product of the following reaction is :

[Jan. 12, 2019 (II)]

A.

B.

C.
D.
The major product of the following reaction is :

[2018]

A. C.

B. D.
The major product obtained in the following reaction is :

[2017]

A.
B.

C.

D.
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100 %ile 100 %ile
 11th / 9, 10

12th / Drop

SAKSHI SAKSHI