CLASS 12th -

Term -1 CBSE -2022

Haloalkanes &
Haloarenes
HANDWRITTEN NOTES

with ¥*¥¥#
Bharat Panchal Sir
By
• •*¥_⇐→¥⇐•÷B•¥ot•¥BzOEDÉOB¥O÷B¥É Bshhaaraatt Bannen at Sir
00088 Bharat Panchal -

Chemistry Guruji a. o
 Haloalkanes and Haloarenes
INTRODUCTION : -

The derivatives of aliphatic

halogen
and aromatic hydrocarbons are called alkyl
halide ( Halo alkahest and aryl halide ( Halo . aren.es )

Halo alkanes contain

halogen atom attached to
the spshyboidised c- atom
of an alkyl grouts :

whereas Haloarenes
contain halogen atom attached to spa hybridised
c- atom of an
aryl grouts .

CLASSIFICATION OF HALO ALKANES & HALO ARENE

(A) On the basis of no .

(A) On the basis of
hybridisation state
of halogen atoms
.

µ
it 4115 ✗
&
-

'

( mono halo alkanes ) R -

-
✗

it ( 1° Primary )
41 ✗ H -
-

( Dimaio alkanes)
p
'

( Ha -

X
"
C- ✗ Secondary)
'

I R C2
41
" -

'" ✗
-
-

fprihaeoaikqnesy te
CH -
✗ '

EH, ✗ ,R
Fenian
-

f- ✗ (
'

R'
✗
cmonohaloarenes )
,
-

R
'"
Haloalkane)

( Dihaloarenes )
✗ = f, Cl, Br I ,

ctsihaloarenes )
 ALLYLIC HALIDES : -

the halogen is bonded to an

Sps c- atom next to the c=c .

§i- Allylic
e-
9 .
R -
CH - CH -
CH -
✗
,

Allylic # carbon .

carbon

BENZYLIC HALIDE : -

the halogen atom is bonded

to ]
c- atom to
sing
an sp next an aromatic

g ith ✗
-

e.
-

¥1
PROPAGYL HALIDE ! -

the halogen atom is bonded to

]
an sp c- atom next to a CEC bond
, .

e.g R -
CE C -
CH
,
-
✗

Vinyltlaide :
Aryltlalidei .

halogen atom is bonded is

the the halogen atom
to an spa c- atom bonded to sb'
✗ ✗
e. c- atom of an
G R CH -

,
__ en -
✗ ,
I
ring
'
aromatic .

NOMENCLATURE OF HALO ALKANES

common Name IUPAC Name

•
CH -4
, Methyl chloride chloro methane

• CH, CH CH Br n -
Propyl Bromide Bromo propane
, ,

U isobath chloride 1- chloro

cYµjCH
• CH
]
-
- -

2- methyl
,
propane
CH
] 1- chloro -2,2

&µ,- neobentyl chloride

•
CH CH -6
]
-

,
-
dimethyl
propane
-
.
a) When both halogen atoms b) when two halogen
are attached to the same atoms are present
c- atom , these are called at adjacent c-

gem - di halides then they are

also called albylidene called vicinal
dihalide .

di halide
called alkylene
CHILL
✗ also
*(✗ e.g CH -

] dihalide
✗ ✗
etheelidene
gem dihalide
-4¢ CHA CHA
-
-

dichloride -

'
ce Le
ethylene dichloride
NOMENCLATURE OF HALOARENES
a

! * ce il
"
a tu
chlorobenzene 1,2 -
Pichon benzene
1,3 -

Rich / on 14 Pichon
-

co Pichon
-
benzene benzene
benzene ) ( M Pichon
-

( b- Dickon
benzene ) benzene)
6 ortho
ortho -
a

melee 5¥ 's meta stingy

O Mgb
para ,
Nature of C- ✗ Bond
the c- ✗ bond is covalent
but the
electronegativity of halogen atom
is more than C, due to which C- ✗ bond is bolar

§ & "-✗s Polar Bond

-

-
-

✗ → -

•
Molecular structure of ctfu
the c- ✗ bond is formed

hybrid orbital
by overlaying of
]
the Sp
of

④
c- atom and b- orbital of U - atom

C
METHODS OF PREPARATION b. orbital
☐ go .

OF HALO ALKANES : -
②
④
I. from Alcohol

a) By the action of halogen acid

R -
OH + HX → R -

X +
H2O
1. & 2° alcohols form chloro alkanes when
,
hydrochloric acid
gas is passed
through
alcohol in the presence of anhydrous 2nd
,

This is known as
"
Groove 's

poocessu@oB88oBhasatPancha1-ChemistryGurujia.o
 2nA , help in the cleavage of C- 0 bond .

→ 3
'
alcohols are very reactive , they react with
conc .
tell at room tenets . without 2nA
,

CH OH + HU K CH]
CHA U -1110
CHA
-
-
•
- -

,
2h6

die ? OH
,
"

ay
-

+ HU K CH
,
-
did?u + Hao
"%
fHz EH]
CH C- OH tell
+
-

CH
,
f U + Hao
- -

]
dig tents .

µ
,

Nole 2. & so bromides and iodides can not

be prepared from the respective alcohols

because 20 & 80 alcohols on
heating with conc
.

and
Has 04 Undergo dehydration form alkene

is least reactive
fluoro alkane is
→ Hf .
So not
formed .

of reactivity of alcohol → 3728in 10

Order
Reactivity of halogens → HI > HBR > tell
•

By the action of phosphorous Halides :

R OH -
+ Pus → R U -
+ Polls + HU

R -
OH + PU, → R U -
+ typo]
Note PB.rs & PI are not stable , so they
}
are prepared on the site of reaction CSITU )

By the action of thionyl Chloride

R OH -
+ SOU
,
É R U -
-1
SIT + HUT

00888 Bharat Panchal -

Chemistry Guruji a. o
tea This method is preferred than other method
because both the side products C SO, & Hell
are
gaseous and can easily escape .

# from Hydrocarbons
a) from Alkanes
ce , & Bs reacts with alkanes in
,

the light to form halo alkanes

presence of Uv

free radical
"

This reaction is
"
substitution reaction

ex . CH, CH CH] CH, CH CHAU + CH ] CHCH ]

, ,
he
145 't ) ( 55 %)
Note -7 Thereactivity of different type of
hydrogen in halo compound are
{ Benzylic allylic > Alkyl > Vinyl aryig =
-
-

→
Allylic and benzylic halides can be easily
prepared
•

CH = CH -

CH 1- Cl, A- CH
,
= CH - C Hall + HU
,
,
ICH] fHzU
, + U
,
→
€4 + HU

→ Both are highly reactive and this can be explained

in terms of stabilisation by resonance
CH Its ← ÉH -

CH = CH
,
,

000880 Bharat Panchal -

Chemistry Guruji a. o
 É÷ ]
1912
I →
,

From Alkenes
i i
Jc=cf + tix →
- -
-

' '
n ✗
•
It is possible in symmetrical alkenes C- CH -
-
CH -7

Markovnikov 's Rule : -

In unsymmetrical alkenes ,
the - ve
part of addendum goes to that
the
carbon
having lower no of Hydrogen .

otcetr Negative 4)
cH=cH + HX → CH, " CH
(µ T
-
-

did
-
]
lower , ,

Edd# Hydrogen ✗

ANTI MARKONIKOV 'S RULE

- : -

E- É o o -1%1
↳ Applicable to
ga
- -

H Br

↳ takes place in the presence of organic peroxide

In unsymmetrical alkenes ,
the negative part of
the additive goes to that carbon having
higher no -

of hydrogen
CHz-ctt-CHg-HBr-wide.CH
-
CH - CH
] , ,
'
Br
Anti Markovnikov 's Rule is also known as

peroxide effect or kharasch effect .

other Negative ← )
EI Higher BOBBIO Bharat Panchal Chemistry Guruji a. o
#
-

Ed Hydrogen •
 Addition of Halogen : when Brz & U
,
is added to
alkenes the addition occur at the double bond

forming vicinal di halide

Po Po
> c=cf + Br, YC -

CC
( vicinal di halides )

NÑewB This test is used to check unsaturation

because reddish brown colour of Bra
disappeared when reacts with alkene

By Halogen Exchange : -

Acetone NAX
R ✗
-

+ NAI > R I + U ,Br)

(✗
-

=
Heat
Finkelstein Reaction

•
fluoro alkanes are difficult to poetsare directly
these chloride
are prepared by treating alkyl
and bromide with
inorganic fluoride such as
and this reaction is
( Hggnrzg Agf , Cofz , Sbfz )
termed as Swarts reaction

CH ] -
Br +
Agf → CH
]
-
f + Ag Br
•
From Silver salt of Acids : -

CH, COO Ag + Brats cHzBr -110L ICH COO

ASBY
, Ag -11-2
+
( tycoon, -1102+2 Agt
Boro dine
"

Hllnsdiecker "
Birnbaum Simonin
Reaction "

Reaction
"

00888 Bharat Panchal -

Chemistry Guruji 2. o
 Methods of Preparation of Halo arches
•

.
Electrophilic substitution of Arches or
Direct Halogenation of aromatic
ring :

+ ✗
a
Halogen carries + HX (✗ = U, Br )
310 -320K

{ Here Halogen carrier → red , / Fe Br , IAIU }

LEWIS ACID }
Mechanism: -

SHb-1_ Generation of electrophile

-1
U + fell ]
,
→ Felty + a

SHb-2_ formation of carbocation Intermediate

e+→i É¥ i¥÷,
"
+

SHp-3_ loss of booton from the Intermediate

a

+ Fella →
f + the + Feel
,

If excess of Halogen is used ,

the second
halogen attached to ortho & bara position

1¥ + a
:* .÷¥*•+É%
0008-8 Bharat Panchal -

Chemistry Guruji a. o
Note The reaction with fluorine is violent
→
or

vigorous and can not be controlled

→
The reaction with Ig is not possible because
when product is formed ,
HI reduce to back

+ Is + HI

→
So the reaction is carried out in the presence
of oxidising agent CHIO ] , Hgo ) to oxidise HI .

ra side chain Halogenation :

f Hall
ÉÑ -14
'

.
÷¥s + HU
"
→ in
"
is
"
"
If U excess than all H are replaced by U
,

when the side chain is larger than a methyl

group , halogenation occur at c- atom next to
benzene ring .

÷k %
Ctb
-

"ICH ] -

-16
,

v0 From Diazonium Salt :

•
piazotization Reaction
NANO + HU → Nall + HOMO
,
NIU
-

Nth + Homo + HU É
-

+ Hao

sand Meyer Reaction

4- Na cx=4Br )
Nice
¥1s
-
→ Gaiter Mann Reaction

ÉI ¥ + %

+ KI ← É☒ + ix. + KU

roo Balz Schliemann Reaction

-

[ ☒ Nini]
^5'4- HBF I +
BIG
-

,
,

→ from Silver salt of Aromatic Acid :

00^-8 + Bra c÷ - +
coat Ag Br

Note Haloarenes can't be prepared from phenol because

it is difficult to replace -
OH group This . is
due to resonance in phenol .

Physical Properties of Halo alkanes : -

→ In general halo alkanes are colourless 1 when bare)

sweet
smelling liquids .

→ They are
slightly soluble in water because of
low tendency to form Hydrogen Bond .

→
Density :
fall < Bo LI
more no .

of H -
atom ,
less is density
e-
G CH, Uz { CHU ]
→
Boilingpoint-B.pt ✗ Moi Mass .

B- Pt ✗ 1-
Branching
# Physical Properties of Haloarenes :

1. These are generally colourless liquid or crystalline

solid .

2. The aryl halides are heavy than water .

insoluble in water but soluble in organic solvents .

3. The m.pt & b.pt of aryl halides are nearly

the same of alkyl halide containing the same
no .

of carbon atoms .

B.pt → ortho > Para > meta

M.pt → Para > ortho > meta

Chemical Properties Of Halo alkanes

*1 Nucleophilic substitution Reaction : -

¥-1T
°
Nuo If
-

Nut ✗
ie ✗
-

-
→ + →

Reactivity order : - R I > R Br > R U > R F

- - -
-

Types Uni molecular Nucleophilic sub Rxn )

Sni (
.

*
SN ' ( Bimolecular Nucleophilic Sub .
Ran )

SNL R ✗ + Nuo → R Na- +✗

-

X]
rate ✗ TR
-

Mechanism fH ,
CH3

CH É £+0 + ✗
O

Steb -1 -

, f- ✗
l -
CH
Formation of et Ctf CH
,
,

CH,

§É
3 ,
step -2 + Nuo -19 C- Mu
Attack Of Nucleophile CH
,
CH
, CH ! t.CH
,
 ra Retention as well as inversion of configuration
takes place

CHIC (CHIH
'
order of SN reaction -
✗ > -
✗ > ( Hjctf X -

> CH, ✗-

Allylic and
benzylic halides show
higher reactivity
towards the SN reaction
'
.

The carbocation thus formed get stabilised

through resonance .

SNL ( Bimolecular Nucleophilic Substitution Rxnl

°
R ✗
-
+ Nuo → R Nu-
+ ✗

Rate ✗ ER X ] [ Nuo]
-

Mechanism
H H
th , H
,
•
no a → no . . . .
c.E.cl → no - C + 6-0
'
'
n h n

Order of SNZ reaction ÷ CHSX > 1° > 273°

roo inversion of configuration takes place

A beam of ordinary light consist of electsomag .

when
metic waves
vibrating in all planes
-

pass through Nicol prism ,

vibrates in one blane
called PPL ( Plane polarised light)
Dextrorotation -
which rotate PPL towards
right
Levu -
Rotatory - which rotate PPL towards left .

>
I
dextro
rotatory

BHF
_gIbk ally
inactive

i. I
laevo
Rae¥ Mt_¥ rotatory
equi molar mixture
of d and l , so that met rotation of
ppl is zero .

i.

÷
Nucleophilic Substitution Reaction

substitution by Amino Grout :

NH, R AH, + HX
R X-
+ → -

when halo alkanes in excess amount then

is
R)
all three of NH, is replaced by grouts (
R X -
+ NH, → BN + HX
( excess )
reaction
"
"

Hoffman Ammo no lysis

R ✗ + A-
KANG R O N -0 + KX
• -
- -
-

A-
A- ✗ + Agnos R -

NI ? + AGX ,

00888 Bharat Panchal -

Chemistry Guruji a. o
•
Substitution by -
OH
group . .

R X + KOH
☐
R OH
-

i -
+ KX or
or Agx
Agon
•
Substitution by alkoxy group
NE Max
A '

R ✗
-
+ -
OR > R O R
-
-
+

This reaction is known as Williamson synthesis

•
Substitution by cyano Group coni.HU
"
10^111

-
R ✗ + KCN
-
→ R CN -

+ KX
pil.HU or NaOH
CH, COOH
GHS I
-
+ KCN → gpg.cn,
É CH
, Ctf NH,
LIA /Hy ,
M
Mendius Reaction : The formation of 1° amines by reduction
with nascent
hydrogen obtained by
the action of sodium on alcohol .

Substitution by isocyanide group :

R ✗ -
+
Agent → R Ne +
-

Agx
activate N & K activate c- group
Note Ag
-

group

• Substitution by azide group :

R X + Nan,
- → R N,- + Nax

• Substitution by carboxyl group :

R
'
- did-0 Ag + X R - IÉR '
-
É - or + Agx
 Elimination Reaction (
Dehydrogenation )
•

when a halo alkane with B H atom- is

healed
with ale . KOH there is an elimination of H atom -

from p -
C and a halogen from ✗ -
C
,
result an
alkene is formed
H

? IT C. c- + BH -1×0
B → =
-
-

£
1
I

( here B- base ✗
leaving group)
-

If there is a
possibility of formation of more than one
alkene due to
availability of more than one § H usually -

alkene is formed product

one as
major .

→ (
Hs Ctf CH CH Ctf Cs , %,
- - -
-
-

CH ] Ctf Ctf gu Ctg

-
-
- - -

( 19%7
Ctf Ctf Ctf CH :(
Hz
-
- -

→
" "
•
Acc . to
Saytzeffis Rule the alkene with greater no of alkyl
,
-

group is preferred [ R, c- CR, > RI CHR > RICH, > RCH CH, ] -
-
-
-

Note → A primary alkyl halide prefer a SNL reaction .

→ A Sec . halide prefer SNL & SN

'
depending
upon the
strength of base / Nuo and alert .
halide
prefer SN '

Reactivity 37271° > CH, ✗ Cas carbocation

-

→ Alcoholic KOH causes elimination ,

while aqueous
leads to substitution
solution of base

GOBBO Bharat Panchal -

Chemistry Guruji a. o
Go Reaction with active metals -

-
Da Reaction with magnesium
¥ ( U Bo I]
R ✗
R ✗ +
Mg Mg
→
- - -

✗ , ,

ether
Grignard Reagent
→ These grignard reagents are very reactive
compounds .
react with any source of Proton
They
to form hydrocarbons So it is very necessary
.

avoid traces of moisture from grignard

to
reagent -

R Mgx
H{÷.oµ,→ Hydrocarbonmg
-
+ R H
-
+
-
a

→ Reaction with Nac work Rxn )

r-ii-ia-nia-ix.ir#esR-R+2NaX
•

. . - -

to prepare
-
- - - - - -
i

used
alkanes
symmetrical
.

* Reaction with 2n ( Frankland Reaction )

2 ↳ Hs -

Br + 22h → ↳ Hs -2h -

Cates + 2h Bra
diethyl zinc ( Frankland
Reagent I
→ Reduction Reaction :

R X
-
+ 9TH ) → R - H 1- HX

↳ Hs U + 2Gt ) → ↳ Hb 1- HU

Ga following reagents are used too reduction

2h / HU Na / ↳ Hs OH WAI Ha ,
Red NUI
, ,

00888 Bharat Panchal -

Chemistry Guruji a. o
 Reaction
Rearrangement
→

CH ] CH CH
, ,
Cl
←¥ks CH, -
CH - CH
,

É ? Cail
"

É ?cHz
"

Af¥s
CH,
CH
-

cty
-

'
]
em,
he
# Chemical Proberties of Haloarenes :

Haloarenes
are less reactive than Halo alkanes due to

1. Resonance Effect →

☐ elocalisation of it eo
⑦
iii. ⑦
iia :

←
← e ←
i
N
Eso
2. Difference in hybridisation of C- ✗ Bond
'

spa R -

cµF✗sb
more s -
character more
electronegative so ,

hold eo pair more tightly so less reactive

,

3. Polarity of C- ✗ Bond
In c- ✗ bond of aryl halide
polarity is less ,
so reactivity is less

tea Nucleophilic Substitution Reaction

;Pr
•
Dow
once

1¥
"

+ Noon
-1¥ ¥8s
↳ Effect of substituent in Haloarenes on Reactivity :

→ The presence of co
withdrawing groups such as -
NO
,,
-
CN , -
COOH cte . at ortho and para position to the

halogen atom
greatly activates the halogen towards
Nucleophilic substitution
,0H
.

e.g is NaOH 623k

F1
¥ "
I Pheno
iildil.HU 30091m

OH

(q
it / 5% NaOH 443k ,

¥ iildil.HU
>

Nod
it - NO
,
it Aef NaOH
.
,
368k
, " -
NO
,

'
iildil.HU ¥
NO OH
N°2

-4¥
,
NO -
Nk
9%4^14
'
321K ¥
no no,
,

NOTE → Nitro
group C- NO, ) meta to the chlorine has
no effect on
reactivity .

Explanations .
-
NO
,
at para positions .

É%÷÷lÉ¥¥
U On
U OH
OH U OH U

¥
*
]
0¥
" + N

-0*0^1-0
-
. +0N -
-

if -0-6
.

00888 Bharat Panchal -

Chemistry Guruji a. o
In case
of ortho and para structures , one of
the
resonating structures bears a negative charge
atom
on the c-
bearing the -
NO, grouts .

These Carbo anions are stabilized by the -

V02 group
well
as as it eo of benzene ring .

However in structure
case of m -

,
none
of
the
resonating SH .
bear the -
ve charge on carbon atom .

bearing the -
NO, group .

: .
The - NO groups does not stabilise
,
the Carbo anion and thus has no effect towards Reactivity .

Q Out of chlorobenzene and cyclo hexyl chloride , which

one is more reactive towards nucleophilic
substitution reaction and why ?
Ay cyclo chloride is more reactive towards
hexyl
'

nucleophilic substitution reaction because c- A

bond
strength is less in cyclo hexyl chloride than
chlorobenzene .

atom is bonded
to
In cyclo hexyl chloride ,
I -

Sps hybrid c- atom while in chlorobenzene

U is bonded to spa hybrid c- atom
a bond in
chlorobenzene and
c-
less
is more
reactive towards nucleophilic Suh
strong .

Q Identify the chiral molecule in the following pairs .

Ya and a
~

AÉ
Nq is chiral
asymmetric
an
molecule
c-
as
atom which
it contains

U
is denoted by *
.

00888 Bharat Panchal -

Chemistry Guruji a. o
 =
PH

④N
11 ÷÷wp "

N 02

KA NO at ortho position :
,

IH
-

É¥÷÷li¥¥¥¥÷
o
-

I
É% * ÷:
" ④I

[ * ÷
=

6-• NO at meta
,
position
U OH
H
#

*ii. ( É¥¥¥ ¥¥%÷ 111

no
"
o

%÷÷j
"

*
fast
-
no
.
sleep

00088 Bharat Panchal -

Chemistry Guruji a. o
↳ substitution of Amino Grout :

il MHz

2 + INH, + Ago s
60 Ahn .
2 ¥1 +
cuff -11120
Aniline
Qa substitution by Celano Group
for in
+ CUCN É + Cee
Br
475K
Cyano benzene
ICON Ha
É→ or Benzo nitrile
gn,
%É
alk H2O,
Benzamidec
.

Partial
" Hydrolysis )
Benzoic
( complete
Alan LIAIHU acid
eighty hydrolysis )
benzene > ,

Na / ↳ Hs OH
Benylami.ecReduction )
-

↳ Reaction with Metal : -

mg Br
Grignard
5¥ -1mg -1¥ enemy
Reagent
magnesium
bromide )
K• Reaction with sodium
,

Wurtz -

tiltigrxu filtig Reaction

U + 2Nd -1 U CH U -12N a + UKI

-

, -

¥g TECH, 1%4=7-4-7
Up Reaction With Copper Ullmann Reaction

-
I -12 Cut I-II ← E- + Cu, Ia
tea Reduction

EI-ian-n.io + me

Benzene

↳ Electrophilic Substitution Reaction

Note d) Haloarenes undergo electrophilic substitution

reaction Slowly as compared to benzene

(E) Halogen group is Otho and Dara directing

Halogenation :

¥9 + U
, É É +
1¥ "
+ Hu

te Cmajoo ) (minor )
Nitration :

¥1 + H Nosecone , ÷jgi -11¥ (minor

""

) Ino Cmajool
+110
,

sulpho nation :

+ Hasoy
→^- %%H +
É÷gµ -1110

Frieda craft Alkylation :

" + ctfu ¥s ¥1,41B -1T¥ + the

kHz
Frieda craft Acylation :
coats they
t.CH Coll # -
+

,
AIU,
LOCH ]

00088 Bharat Panchal -

Chemistry Guruji a. o