ALLYLIC HALIDES : -

Haloalkanes and Haloarenes the halogen is bonded to an

Sps c- atom next to the c=c .

INTRODUCTION :
§i- Allylic
e-
9
-

R CH CH
halogen derivatives of aliphatic CH
.

me
-
✗
- -
-

,
and aromatic hydrocarbons are called alkyl Allylic # carbon .

carbon
halide Chalo alkahest and aryl halide ( Halo aren.es )
BENZYLIC HALIDE
.

: -

Halo alkanes contain halogen atom attached to the halogen atom is bonded
to ]
c- atom to
the
sing
an sp
Sps hybridised c- atom aromatic
of an alkyl grouts :
next an

whereas Haloarenes
g ith ✗
-

e.
-

contain halogen atom attached to spa hybridised

c- atom of an
aryl grouts .
¥1
CLASSIFICATION OF HALO ALKANES & HALO ARENE PROPAGYL HALIDE ! -

the halogen atom is bonded to

( *) On the basis of no (A) On the basis of an sp
]
c- atom next to CEC bond
.

, a
hybridisation state
.

of halogen atoms
.

µ
e.g R -
CE C -
CH
,
-
✗

it 4115 ✗
& Vinyltlaide
-

Aryltlalidei
'
:
( Mono halo alkanes ) R ✗
.
-

halogen atom is bonded is

it ( 1° Primary )
the the halogen atom
44 ✗ H -

to spa c- atom
-

( Dimaio alkanes) an bonded to sb'

✗
,R
'
✗
( Ha ✗ e. c- atom of an
G R CH en ✗
-

-
- __
, ,
I
ring
'

R
"
C- ✗ C2 : secondary) aromatic .

"it
41 ✗
-
-

halo alkanes,
CH -
✗
te NOMENCLATURE OF HALO ALKANES
'

EH, ✗ ↑ common Name IUPAC Name

Fenian
-

f- ✗ (
"
R CH -4 chloride chloro methane
Methyl
- •

,
✗
cmonohaloarenes )
,
-

'"
Haloalkane) CH, CH CH Br n Propyl Bromide Bromo propane
R
• -

, ,

Dihaloarenes ) U isobath chloride 1- chloro

cYµjCH
( • CH
]
-
- -

2- methyl
✗ = f, U, Br I ,
propane
,

CH
( Trihaloarenes ) 1- chloro -2,2
]

&µ,- neobentyl chloride

•
CH CH -6
]
-

✗ ,
-
dimethyl
propane
-
.
a) When both halogen atoms b) when two halogen Nature of C- ✗ Bond
are attached to the same atoms are present the c- ✗ bond is covalent
c- atom , these are called at adjacent c-
but the
gem - di halides then they are
electronegativity of halogen atom

also called albylidene is more than C, due to which C- ✗ bond is bolar

called vicinal
dihalide .

di halide
& &E✗s polar Bond
-

✗ →
called alkylene
CHILL
✗
- -

also
-

*(✗ e.g CH -

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

dichloride -

'
ce Le
ethylene dichloride
NOMENCLATURE OF HALOARENES
a Molecular structure of ctfu
! il
•

* ce
the c- ✗ bond is formed
"
a tu by overlaying Sps hybrid orbital of
chlorobenzene
the
benzene of
1,2 Pichon 1,3 Rich / on
!
14 Pichon of U atom
- -

c- atom and b- orbital

- -

co Pichon
-
benzene benzene
benzene ) ( M -
Pichon ( b- Dickon C
benzene ) benzene)
METHODS OF PREPARATION b. orbital

ortho 6 -
a
ortho
OF HALO ALKANES : 000
②
.

5¥
-

's meta stingy ①

melee 1. from Alcohol
para
O
,
Mgb
a) By the action of halogen acid

R -
OH + HX → R -

✗ +
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
 2h42 help in the cleavage of C- 0 bond
ka This method is
.

preferred than other method

→ 3. alcohols are very reactive , they react with because both the side products C SO, & Hell
HU at
conc .

room tenets . without 2h42 are

gaseous and can easily escape .

K CH] U
CH
CHA OH + HU CHA -1110 # from Hydrocarbons
-
-
•
- -

]
2h6

die ? OH
,
"

die ?u
"
CH a) From Alkanes
}
-

+ Ha ah ctg -
+ Hao ce , & Bo reacts with alkanes in
,
2h42 form halo alkanes
ftlz PM]
the presence of Uv light to

CH C ¥ free radical
"
-

OH + tell CH This reaction is

"
substitution reaction
G U -1110
-

} - -

* Mb ]
↳
g CHACH
.

Cpg ex . CH, CH CH] CH, CH CHAU + CH ] ]

, ,

Note 2° & I
'
bromides and iodides can not 145%1 ( 55 %)
Note -7
be prepared from the respective alcohols Thereactivity of different type of
hydrogen in halo compound are
because 2° & so alcohols on
heating with cone .

Has 04 Undergo dehydration and form alkene { Benzylic allylic > Alkyl > Vinyl aoyig
=
-
_

→ Hf is least reactive .
So fluoro alkane is not →
Allylic and benzylic halides can be easily
formed .
prepared
of reactivity of alcohol → 3723in 1°
Order CH CH + Cl, A- CH CH -
CHAU + HU
Ctf
-
=
=
•

] ,

Reactivity of halogens → HI > Hbo > tell FH] fH2U

•

By the action of Phosphorous Halides : €4 + U

,
→
€4 + HU

R OH -
+ PUS → R U -
+ Polls + HU → Both are highly reactive and this can be explained
R -
OH + Pll] → R U -
+ Hypo] in terms of stabilisation by resonance

PI not stable , so they

CH ÉH EH -

CH =
Ctf
Note PBB & }
are , ,

prepared on the site of reaction CSITU )

help in
are
To our
•

By the action of thionyl Chloride

R OH-
+ SOU
,
É R I -
+ SO ↑ + HUT
, Journey , you
can donate
 ¥]
Addition of Halogen : when Brz & U is added to
÷ alkenes the addition
,

bond
at
.
occur the double

forming vicinal di halide Bo

Po
From Alkenes > c=cf + Br, > d- cc
i i c vicinal di halides )
> c=cf
N0Ñee%
+ tex →
- -
-

' '
This test is used to check unsaturation
n ✗
is possible in
It symmetrical alkenes C- CH CH -7 because reddish brown colour of Bra
• -
-

disappeared when reacts with alkene

Markovnikov 's Rule : -

unsymmetrical alkenes ,
the - ve
part of
In
addendum goes to that
the
•

By Halogen Exchange : -

Acetone
carbon
having lower no of Hydrogen . R ✗
-

+ NAI
Heat
> R I -
+ NAX
(✗ = a,Br)

otcet Negative ) Finkelstein Reaction

(H CHIH THX → CH] -
' _
'%
did
-

lower , ,

Edd* Fluoro alkanes are difficult to poebare directly

Hydrogen
•

these chloride
ANTI MARKONIKOV 'S RULE :
are prepared by treating alkyl
inorganic
-

and
-

bromide with fluoride such as

↳ Applicable to ☒ É - -
o -
o 'É.☐ and this reaction is
te Br ( Hgs Fa g Agf Cofz
, , Sbfz )
↳ takes place Ñn the presence of organic peroxide termed as Swarts reaction
In unsymmetrical alkenes the negative part of
,
CH ] -
Br +
Agf → CH
]
-
f + Ag Br
the additive goes to that carbon having
From Silver salt of Acids :
higher
•

hydrogen
-

no -

of
+ HB.ir#desCHz-CH Ag + By #
CH
CH, COO CHzBr -110, ICH

}
CHI CH COOAG -11-2
-

(
Hz
,
- , ,
, '
Br + A9Br
Anti Markovnikov 's Rule is also known as CH, COOCH, -119+2 Aest

peroxide effect effect Boro dine

"
or Kharasch Hllnsdiecker "
Birnbaum Simonin
.

Test ) Reaction "

Negative Reaction
"

EI Higher
Edd# Hydrogen .
 Methods of Preparation of Haloarenes Note
fluorine is
•
→
The reaction with violent or

vigorous and can not be controlled

.
Electrophilic substitution of Arches or
→
The reaction with Ign is not possible because
Direct Halogenation of aromatic
ring :
when product is formed ,
HI reduce to back

+ ✗
a
Halogen carrier
"
↑
+ HX (✗ = Cl, Br )
+ Ia É + HI

310 -320k is in
→
So the reaction carried out the presence
{ Here Halogen carrier → red ] / re Br ] IAIU } of oxidising agent CHIO ] , Hgo ) to oxidise HI .

LEWIS ACID }
r Side Chain Halogenation :
Mechanism :
f Hall
-

É+u
sHb-1_ Generation of electrophile
U + fell ] → fell i + Cl -1
.
3%4 ☒ + HU
"
☆ in
"
is
"
"
,
If U excess than all H are replaced by U
,
skkʰ_ formation of carbocation intermediate when the side chain is larger than a methyl
group , halogenation occur at c- atom to

¥Fie+→i¥+i÷↑ É¥
next
benzene ring .

¥k
CH
%
-

CHIH] - ]

-1cg
Slept loss of brown from the intermediate
6 To From Diazonium Salt :
+ Fedie →
1T¥ + tell + feel
]
◦
Diazotization Reaction
NANO + HU → Nall + HOMO
,
If excess of Halogen is used the second
NIU
-

,
Nᵗʰ + Homo + tell °
-

+11,0
halogen attached to ortho & bara position ☒

' +
9ex.is#Eii- ¥% Sand Meyer Reaction
✗ cx=4Br )
É
'
^5 "
- -

+ Na
→ Gaiter Mann Reaction # Physical Properties of Haloarenes :

crystalline
ÉI generally
1. These are colourless liquid or

¥ + % 2. The aryl halides are heavy than water .

solid .

water but soluble in

É☒ insoluble in solvents
+ KI ← + ix. + KU
organic .

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

roo Balz Schliemann Reaction
- the same of alkyl halide containing the same
no .

of carbon atoms .

[ ☒ Nini]
^5'4- HBF I +
BIG ortho > Para > meta
-

, B. Pt →

,
M.pt → Para > ortho > meta
→ from Silver salt of Aromatic Acid :

Chemical Properties Of Halo alkanes

00^-8 + Bra c÷ - +
coat Ag Br *) Nucleophilic substitution Reaction : -

¥-1T
°
Ni Ie
-

Haloarenes can't be prepared from phenol because Nu ✗

→ c- ✗
+
Note
-

→ + -

it is difficult to replace -
OH group This . is
due to resonance in phenol .
Reactivity order : - R I > R Br > R U > R F
- - -
-

Physical Properties of Halo alkanes :

Types
-

SN (
' Uni molecular Nucleophilic sub . Rxn )
In general halo alkanes are colourless 1 when bare)
{
→
-

SN ' ( Bimolecular Nucleophilic Sub Ran )

sweet
smelling liquids
.
.

→ They are
slightly soluble in water because of SNL NUO R NY +✗
_

R ✗ + →
X]
low
-

Rate ✗ TR
-

tendency to form Hydrogen Bond

-

→
Density :
fall < Bo LI Mechanism fH ]
CH}

atom less is É [⊕ + ✗
°
more no of H density Steb -1 Ctf f ×
-
. - -

,
/ -
CH
e-
G CH, Uz { CHU ] Formation of C+ CHS Ctf ]

CH,
Boilingpoint-B.pt
%!
→ 3 ,
✗ Moi Mass .
step -2 + Ny◦t C- Nu
B- Pt ✗ 1-
!
"
Attack Of Nucleophile CH CH CH
Branching , , CH
}
 ra Retention inversion of configuration Dextrorotation -
which rotate PPL towards
right
as well as

takes place Levu -

Rotatory - which rotate PPL towards left .

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

> CH, ✗-
>
I
dextro
rotatory

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

The carbocation thus formed get stabilised _gIbk ally

inactive
through resonance .

SNL ( Bimolecular Nucleophilic Substitution Rxnl i. I

°
R ✗ Nuo R Nu + ✗ laevo
Rae¥ Mt_¥
-
+ → -

Rate ✗ ER X ] [ Nuo]
-

equi molar mixture rotatory

Mechanism l
of d and , so that met rotation of
H H
th , H
ppl is
, zero
c.E.cl
.

•
no a → no . . . . → no - C + 6-0
'
'
n h n

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

roo inversion of configuration takes place

i.
of ordinary light consist
electsomag
÷
A beam of .

when
metic waves
vibrating in all planes
-

pass through Nicol prism ,

vibrates in one blane
called PPL ( Plane polarised light)
 Substitution by
Nucleophilic Substitution Reaction
OH
group
• -

. .

R ✗ ^-
-
+ KOH : R OH
-
+ KX or
or Agx
Agon
•
Substitution by alkoxy group
Na⊕_ OR Max
A '

R ✗
-
+ > R O R
-
-
+

This reaction is known as Williamson synthesis

•
Substitution by cyano Group coni.HU
"
TONY

,
R ✗ + KCN
-
→ R CN -

+ KX
pil.HU or NaOH
CH, COOH
4145 I + KCN
-
→ qq.cn,
MEY CH CH
, Nha
M
,
LiAttlee ,

Mendius Reaction : The formation of 1° amines by reduction

with nascent
hydrogen obtained by
the action of sodium on alcohol .

substitution by Amino Group : Substitution by isocyanide group :

R AH, + HX R ✗ -
+
Agent → R NC +
-

Agx
R X -
+ NH, → -

activate N & K activate c- group

when halo alkanes in excess amount then
is Note Ag
-

group
R)
all three of NH] is replaced by group (
• Substitution by azide group :
R X
-
+ NH] → BN + HX
( excess ) R X + Nan, → R N,- + Wax
reaction
-

"
"

Holtman Ammo no lysis

R ✗ + KNO A- ◦ Substitution by carboxyl group :
•
R O N -0 + KX
-

É
- -
-

,
Agnos
A- di 0 Ag KER '
OR + Agx
f+Ag✗
'
R -
✗ + R -
N R -
- + x -

R - -

-
 Elimination Reaction (
Dehydrogenation ) Aa Reaction
•

with active metals -

when a halo alkane with B H atom - is

healed
with ale . KOH there is an elimination of H atom - -
A Reaction with magnesium
from p -
C and a halogen from ✗ -
C
,
result an
I]
Mg #
alkene is formed R ✗ + R ( ✗ U Bo
Mg
→
- - -

✗ , ,

H ether
? I 1 Grignard Reagent
top -1×0 These grignard reagents
¥
B
-

→ -
C. = c- + BH →
are very reactive
1
I compounds .

They react with any source of Proton

( here B- base ✗
leaving group] to form hydrocarbons So it is very necessary
-

, .

If there is a
possibility of formation of more than one to avoid traces of moisture from grignard
reagent -

alkene due to
availability of more than one § H usually -

R Mgx
Hg÷◦µ.,→
+ R H +
is mg
-

alkene formed
-

one as
major bro duct .

a
carbon
→ (
Hs Ctf CH CH CH ( 81%1
- - -
-

]
_

CH } Ctf Ctf gu Ctg Reaction with Nac work Rxnl

-

*
-
- - -

→ Ctf
-

Ctf Ctb
-
-

CH -
-
CH
}
( 19%7
r-i.i.IIn.iq?-iI.i-rDM-r-R+2Nax
ether to brebare used
alkanes
" "
•
Acc . to saytzeffis Rule ,
the alkene with greater no -

of alkyl Symmetrical
.

group is preferred [ Rac = CR > Rac = CHR > BECH > RCH :(Ha ]
, , * Reaction with 2h ( Frankland Reaction )
Note → A primary alkyl halide prefer a SNL he action .

2 GHS Br + 22h → GHS Zn ↳ Hs + 2h BK

-
- -

→ A Sec halide prefer SNL & SN

'
depending
diethyl zinc ( Frankland
.

upon the
strength of
°
base / Nu and tert halide
a
Reagent I
.

prefer SN '
→ Reduction Reaction :

Reactivity 37271° > CH, ✗ Cas carbocation

-

R X
-
+ 2M ) → R - H + HX

Alcoholic KOH causes elimination while aqueous

↳ Hs Ut 2Gt ) GHG 1- HU
,
→
→
leads to substitution
solution of base
Clan following reagents are used too reduction

2h / HU NA / ↳ Hs OH liA1H4 ,
Red P / HI
, ,
 Reaction ↳ Effect of
Rearrangement substituent in Haloarenes Reactivity
→ on :

CHactb.UA#sCHy-c&-CHzcHs-&?cHiAf-YcHs-&H?cHz-CHz
CH ] → The presence of co
withdrawing groups such as -
NO
,,
-
CN , -
COOH de . at ortho and para position to the

halogen atom
greatly activates the halogen towards
'
Nucleophilic substitution
he
↑
.

CH,
e.g is NaOH 623k 1-

% " Pheno
# Chemical Properties of Haloarenes : iildil.HU 300am

Haloarenes

¥1
OH
less reactive than Halo alkanes
1¥
are due to it 15% NaOH 443k ,

>
1. Resonance Effect → I iildil.HU '
pelocalisation of H e -0 Nk
"
% in
⑦
iii. ⑦
it :
ftp.NAOH 368k ^"
A-
:
NO it ,

, +

÷ iildil.HU ¥
RJ
Jo NO OH
N°2
--
,
NO
2. Difference in hybridisation of C- ✗ Bond
No,
9*7^192
¥
"
323k ¥
spa R -
cµ¥ˢb3 NO
,
Nda

more s -
character more
electronegative ,
so
NOTE → Nitro
group C- NO, ) meta to the chlorine has
no effect on
reactivity
hold e◦ pair more tightly so less reactive
.

Explanation : NO at para positions

Polarity of C- ✗ Bond
-

3.
.

,
In c- ✗ bond of aryl halide
polarity is reactivity

É% [É¥
less so is less •
OH U On
U OH
,
cl OH

tea Nucleophilic Substitution Reaction

¥ slowness
#
Yo ☒
]
Do%Pr
•

Mo
once "

° GT
"

-0-4*-0
" -
-

÷÷ ¥÷:
- -

o
+ Noon
In case
of ortho and Para structures , one of
4,011 pH
the
resonating structures bears a negative charge =
on the c- atom
bearing the -
NO, grouts .
÷
fast
stop
¥
"

These stabilized by the NO,

Carbo anions are -

group ④N N°2
well "
as as it eo of benzene ring .

is
in
However case of m -
structure ,
none
of E-A
the
NO at ortho position :

resonating SH .
bear the -
ve charge on carbon atom .
,

bearing
-

É¥::÷1i¥¥
the NO,

:-p
-

group .

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

9 Out of chlorobenzene and cyclo hexyl chloride , which

one is more reactive towards nucleophilic
substitution reaction and why ?
At cyclo hexyl chloride is more reactive towards
ÉÉ¥% * ÷:
'

↳I
nucleophilic substitution reaction because c- 4

[
bond
strength is less in cyclo hexyl chloride than
ñ
.
≤
chlorobenzene .

atom is bonded
to
In cyclo hexyl chloride ,
I -

Sps hybrid c- atom while in chlorobenzene

U is bonded to stir hybrid c- atom
6-• NO at meta
A bond in position
c- is more
strong ,

¥E: ¥¥÷¥i¥o
chlorobenzene and less reactive towards nucleophilic Suh "
%
.

ii. [
9 Identify the chiral molecule in the following pairs .

"

~ and a
~
⑦
to
o

ce 111
AE
is chiral molecule as it contains EH
asymmetric
an c- atom which
U
is denoted by *
fast N°2
Sth
.
Cea substitution of Amino Grout : Cea Reduction
il NHL it
2 + INH, + Ago 4751<-2
book .
¥1 +
cuff -1110 + an + no

Aniline Benzene

Cea substitution by cyano Group Qa Electrophilic Substitution Reaction

for in
É Br
Note d) Haloarenes Undergo electrophilic substitution
+ CUCN
475k
☒ + Cee
reaction slowly as compared to benzene

Cyano benzene ii ] is Otho and

f0Nᵗk
( Halogen group Dara directing
or Benzo nitrile
Halogenation
.¥É
:

pm alk His
%
Benzamidec a
.

Partial
Hydrolysis ) "

¥9 ¥j 1¥
"
> + + the
Benzoic +4
( complete
Alan acid te Cmajoo ) (Minor )
benzene
liAIHcey.CH ,
NH
,
hydrolysis ) Nitration :

¥Éi T¥
Na / ↳ Hs OH
BenlglaminecReduction ) ¥4
-

""
+ H Nosecone , -1 + Hao
Cea Reaction with Metal : -

mgbr (minor ] Into ,C major )

Grignard sulbho nation :

1¥ -1mg IE
%%H+,µ
Reagent
( phenyl magnesium
bromide )
É¥ + Hasoy
→^- -1110

↳ Reaction with sodium fried al craft Alkylation :

Wurtz -

tiltigrxu
,

filtig Reaction " + asu Et

Men , + ¥4 + tell

kHz
☒U + 2Nd -1 U -

Ctb -4+2 Na + UKI Frieda craft Acylation :

¥g 7-1-41 ¥er☒-47 "

+ CHIOU
↳
AIU,
"_ "" 1 +
the

Cea Reaction with Copper Ullmann Reaction { OCH ]

☒ -
I -124 + I -4¥ 4-7-17 + beats G@BGG-oBharatPanehal-ChemistryGuruji2.o
Poly halogen Derivatives
→ Chloroform C Trichloromethane ,
CHU} )
< the -1342 ÉÉ CHU} + 344
Controlled
oxidation
→ Iodoform ( tri iodoform CHI] ]
,

NaOH CHI ↓ -13 Nat + CH] Cooma

Ctf coats +
31-2-14 →
]
+3110
on carbon Tetrachloride [ Cela ]

is CH, +44 , sunlight Cap -14 HCl

>

%) CHU} -142 is CCH -12 HU

Cela b a colourless ,
non -
inflammable poisonous liquid
, ,

soluble in alcohol and ether .

☆ Uses
as solvent for oils , fats resins
•
a
,
in dry extinguisher
cleaning
•
◦
as fire

Dichlorodiphenyltrichloroethane )
'
DDT ( b b -

4- it
(1-0)%-8-4
-

"
a- u
? ,
-

te a-☒ he
a
-
%& -
bis 6- chloro
chloral
Chlorobenzene phenyl )
1,1 I -

Kichwa ethane
,

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