Iyoakanes ifheavenes

-
R -
H
+ X
X R
-

X Haloalkanes
- >

H
(Aerye Halide)
X
I I
H
Halo asenes
-

X ->

+X
SAryl Halide)
classification

was On theBasis of Halogen atom present:

of no

·
CH3-X-> Monohaloalkane X
I
·
CHy-CH-X-> Dibaloalkane
⑧ > Monohatoalene
↓ Gemdihalide X
I X
-
dinabalkane Dinaloarene
cits-2
-> ⑧

vicinal dihalide X
I X Tsiklocene
- ->
·
CHXy -> Thaloakane.
- X

Haloform

On the Basis
(b) of Hybridization:

sp3 hybridization:

R-C,-x-> 1°
(primary alkyl halide)
20
(secondary allege halide)
R-et-x
·
>
-

R
R X 30
(Textiary alkyl nalide)
4
· -
- -
 ·
R-CH= CH-C-X-> Alyl halide
-

spy hybridized carbon attached to c= c it is

If a

called
ally carbon.

CH2 -X

· Benzyl halide
->

If
a
spy hybridized carbon atom attached to a benzene
sing itis called
Benzyl carbon.

sphybridization:
·

U2 relide
c -X
vinyl
· =
->

Halogen attached to Carbon which forms a double band

willanother carbon ->
rings carbon
&
X

!- Anyl halide

Methods
of Preparation of Haloalkane:

(as From alkanes:

nV
CHy +
X2 >CH5x +
CH2x2
+

CHX +CX4
But in case
of higher alkanes a mixture
of Domenic producti
are
formed.
For chlorination
·
- relative
the attraction of 1,2,3 Hatom
chlorine are in the Ratio 1:3.8:5.2
by
·
For momination - relative
the attraction of 1,2,3 Hatom
bromine are in the Ratio 1: 82:1680
by
 iV
CH3-C2-CHy +Cy CCHICH-e+cytH-ens
(19 br (29
↓ ↓
IN Wn], [N4Wn]
6x1 4 2x3.8 7.6
=
=
=
=

(Minor Pat) (Major Pdt)

Biz
7 CHICH2-CHe-Bro CH4H -Cy
as
(i) De
(2)
↓ to
(Mar), (nnUn)20
6x1 4 2x 84 164
= =
= =

(minor Pat (Major Pdt)

·
Lodination of alkanes:

-
HI
CH4 + I CHg1 +

As I is a
very strong reducing agenttheReaction is
revessible in native. Thus to the reaction inmove
one direction
strong oxidising agentHIO or HM is
used in order HI
to oxidize the
formed.
2HI+ 2HNy -> I2 2N02
+
+
2420
54It H
IBG >312+ 3420

·
Fluorination of Haloalkanes:

is
The reaction
is
highly anothermic and explorive, there the
reaction done from suitible
alkyl chlorides reacting
nich
inorganic fluorides such as Site, AgF, Lot, Hg2R

C-CH2-el +
AgF-> CHHF+AgC
2
Cty-CH-21+ CoR ->
2C3CyF+ colla
This Reaction is called -
SWARTS REACTION
↳) From alkenes:

symmetrical
For alkene

CH2=CH2 HC->
+

CH-CH-4

Two isomeric possible.

assymetic
For alkenes: poll are

CHy-CH= CH2 Hec x CH

-CHy
+
CHCH2C2-Ch
+

el

[Major I Iminor]
HB
X CHy-CH-CH3 +
Leg Cty-CHy-Bro
in
[Major I Iminor]

This Rule is known as Markownikov's Rule:

while theunsymmetrical alkene, the

adding a haloacid to
negative partof theaddendom is attached to thecarbon containing
leastnumber of H-atom

Mechanism.

Ctg-- Hey +

e ->
cyacty + chych-i
[Ccerbocation [Pocarbocation

u-
CHg-PrCHY a

(Major Product)
If
thesame thing takes in
place presence of suitable organic
peronide [e:Benzoyl peroxide ⑥
mill
anti merkowniki's
takes This
place. occurs only in the addition
of HBs.

This i known as Peconide effect/Kharas effect

 ⑲
ph-c-0-0-c-Ph
-
CH3-C
=
CH2 + HBr
CH CH2-C2-Po
mechanism:
O 0 0
0 ↑

Ph-"-0-0-C-ph 7 in -" -0.+.0-2-ph

I

O ⑧
↑ I

Py-2-0.+ H -

Bus >py-"-oH+ i
I

My-CH= CH2
BCUn+CHG-i-4
-

[i tree Radical] [2" FreeRadical]

H- Be
Cz-CHz-CH2-Br L

This occurs
only withhis because homolyticdeavage of
Nice and HI are endothel mic in nature and requires ar

lotof
energy, thus not
favoured.

(2) From Alcohol:

By the action
of Halogen acid

Reachinnyorder
=>

of Halogen acid -> HI> HB>HC > HE

since the bond dissociation

case is themost
of HE
energy in
due to smalles size and more
tonne
dectronegativityof

R-OH + H-c
Anne R-X H20
+
Reactivityorder of Mohols >
Testiary) Secondary Primary
more
I alkyl
the
group more the + I
and therelease
of or
effect, so
-

becomes earive and after the

group
release of -OH group carbocation
the

formed is in the order

of 377210.

I Reagent
is For MCL: used
any Enck]
Mialive Reagent.
of
tee and
away Enck -> Lucas

This process is called - >

GROOVE'S PROCESS

CHy-CHz-OH t He anky, CHGCHC-21+H20

Enc
(10)
anhy
rec He
CHy-4-c CH-M-c+
X
Encez

129
CHeb
--- on that
any Inc is
not
X
cres-2 +

10
CH rege
CH3
his For HBer: [Reagentused H2SO4 I

Nar +
H-HSO4 ->
NaNSO4 +HBr

[Hpe is produced in sili

CHCH-OH + HB 3
CHBC-Br+H20

(s For HI: [Reagentused H3P04]

&I +

H-H2P04-> kHPOp+HI
CHy-CH2-OH + HI <
CH5C-I+H0
 action of 'X 2
·

By the PXs and PX5: =

X
- R- of
R-OH I P X >
H3P0y + 3R -
X

R-OH X

SO, 3ROH + PYB > 3R-X +

H3POg

- R -
0 -

H
Ch SRC+ POC + UCL

e - -e
--

a cl

So, ROH + P25 R-C POL

+ + Hect

the action Red P and Xe: [X=Br, I

by of
·

I P4 6P2 +

>4PBUs
3R-OH +
PBry->3Rr+ HyPOs
7 P4 +

6Iz >44I3

3R-OH +
PI3 > 3R -I H3PO
+

By action
the
of thionyl chloride
·

this is the
the
best
way for preparation of
the
in the
alkye chloride
as
by-producti formed escapes form of gases.

R H
0-
-

u
11

a
>R-a+ son"+Ha
-

S -

Best
yield
(d) Finkelstein Reaction:

todoalkanes prepared this metheard

can be best
in actone
by alcohol
E

the Nat are dissolved or

methyl
Nace and
Naper are little soluble in above
the bow
sweetthus
they from a precipitate. chloro aid
They
homo alkanes are not
prepared by this method.

Alone/
Chy-CH2-Cl + Nat x
CHBCH-I+ Nall
Methyl alcohol

Nat Areone/x CHBCH It Nau

Chy-CHz-Bro+
-

Methyl alcohol

Les Hundsdiecker Reaction:

Only momoalkanes are prepared in this process from

callsof
silvery acids.
fatty
0
I/
(C14
GHj-c-0-Ag + Br
I
> 2H5-Bro+ Agpr C02
+

Be

Methods
of Preparation of Haloarenes 8

as from aromatic
hydrocarbons:
es
I
Feel
Arly. -I
+C2
>
11
Dark
Bee

Bre
X -I
Arly Ferg
 Incacetimeanalogen is resent
second
of the hate in
·

C Ch
C I I
I el
Fed,
-

( I t
-I
11 +

(Majas
I
C

Be it is, it d
el+ el+ el

Since
recharge densityis in the who are
pala position
due
to +M
effect, thus 2
pali will be
formed.

· In case
of Toluene also same
thing will happen.

H CH
43 I I
Fecle - Ch
11
+

22 3
I I
-I

is
majors.
·
For iodination strong 0.A like HN or HIOs are used.
I

11 I2
HNO3 s
7 !,
HDOb

2 HY-
+ 2H
NOG X I2 +
2H20+2N
5HI + HIOG > 312+ 3 H20
 in from aniline:

NH2
I
NaNy+ rc
·ze
-I X -I
0-52

Ibenzene diazonium salt

I
I

-I
- es es -

RI/ -
- I I

Luch 7
I
C
N2
wei
+
+
N2
Gattern- He nee
Sandmayes
ann Reaction
Reaction -I
Cur
un Be
Be

HBU HB
L I
-I HBFG ⑥
--
V

Ne + Hell Ne + Hell
+

-
+

Balz. Schiemann Reaction

 chemical properties of Halo alkanes

solvent
Substrate Boduct-
+ Reagent >

SOLVENT

Non-Polar street Polarsolvent

- -

e 0
=

4+
0

cex, CS2, Benzene,

Cira, Petrot etc

V ~

Polar protic
solvent Polcy notic solvent

is bonded is notbonded
If it
fluorine,
to
If H to

Oxygen and
Nitrogen. fluorine, oxygen a
nitrogen
H-OH, H2N-H, CH50-H. Cty-0-1s, Aldine,
H - F etc.

CHy-S-Cymeltorient
etc.

REAGENT

Electrophik Neudeophile
(Election king species) (Nucleus loving species)
All charged species charged
All-ve
species.
the
· - ·

H+, RT, X, NO, Noxtete Hon X, IHT etc.

All free radical species All pair containing species

·
tone
-
·

Bi, ; n' etc. NH, H20, RON, R-NH2 etc

·
All vacantp ld orbital -

· Al a-bond conting species -

BHy, SDFs, Ally, Ply etc Aerene, Aryne, Bentene etc

 ROLE OF SOLVENT:

lay Non-Polar strent:

+ Nac > Bottication and Anion are

insoluble.

(b) Poler-Protic solvent.

t

120 + Naci > Bocrication and Anion are

soluble

H H
H -O
H
·or in
- 8:
- 0 < -

....
H
o

... H
..
i
-
I
H
-

0..Nat..O a
... ....
/

i ......H
H ..
O E
H
,- i
-

I H
0- H-
H O
H

(2) polar aprotic

solvent:

O
merc -
me + Naci >Only cation is soluble
But anion is not.

- S-
O
0 11 St
H

na.. 0 = 2 H
i 0
=
...

n -
-I
3 C -
H

-
I
I
H H
M

I -
(A) Nucleophilic Substitution Reaction:

· Sir Nucleophilic substitution unimolecular

Re R RI

Nu Nu
Re X X R2 Nu I R2
Polar Protic
solvent
R3 R3 R2

50% 50%
Retention Pat Inversion Pat
e

ENANTIOMERS Do

RACEMIC MIXTURE

Mechanism:

Ri R
⑦

R
H2o Nu
Racemic
slowtepa &
-X X 7
mixtive
-
RDS /
a
fast-
R3 R2 R3

Nut

protic solvent will dissolve

there
water
being polar
carbonation is
will discove
Halogen an a
produced.

[Rearrangement if possible]

in 2 steps.
-

lakes
place
⑧

18
·

step is the slow step ⑧

·
Intermediate isthe carbocation
·
Rate x I substrate -> unmolecular

Rate also depends on Carbocation -3'2']

stabilityof
·
 ·
3' alkyl halide is the moststable.
If alkyl group becomes same -
·

Rate depends on the leaving group.

F < Ct < pr< I
-

2.G -

of SN'- R-F
:Rate RI) RA > RC

Nucleophile needs to be
poor.
·

· Sa ->
Nucleophilic substitution bimolecular

H
H
Nu

Es
D C X X Ni
D
Polar
aprotic
E solvent-

-
1007 inversion
Walden inversion

Mechanism
H H
I
I Nut
-

-
Inverted
..........
E
X X Nu >
D stor Pdt
RDS
fast
DT

[Pentavalenttransition
State I

·
Takes place in 1 step.
·
No intermediate is formed
Rate
·

depends on substrate and nucleophile-thus bimolecular

Rate
·

of reaction invessly
proportional tostallic hindrance
of alleys helide, thus in alkyl halide SNI will occur
at a
faster rate.
 · Sit does not occur in alkyl halide
becomes same -
If alkyl group
·

Rate depends on the leaving group.

F < Ct < pr< I
-

2.G -

of SN'- R-F
:Rate RI) RA > RC

is needed.
strong nucleophile
·

aqueous
Non/KON R-OH Nax
+
Kx
X

H20 R
- OH + HX
X
+ -

NaOR
>R-0-R Nax'Williamson's
+

Na I
Synthesis
↑ R -
I + NaX

I
R -
X
Na-H, R-NH2 + HX

Hoffmann
R-NH-H R-NHR+HX
-

- amonolysis
R2N-H HX
X NRG +

R3
Ra i Bi
N
X

KCN
Y R -

CN
= + Itanenitle
Rx

AgCN >R NEC-+ -

Kx
[Acylisocyanide
KNO2 > R-O-N=0+Kx [Alkyl nitrile]
AgNoy, R-NOG +

Kx iritroacane

KCN ionic in nature dissociates to

is

kt and IC N. though
predominatly
thus give
there
are
attacking site, the
=
two

will
attack carbon C-C bond stable.
occur
through as is

+-
>
CH3 5Y I
4 CN > CH -

CN =
+ kX.
 ButAgCN is covalentin nature atom
0
and the
Nitrogen
I
only
free to donate the electron. Thus
bouganide in
formed.

⑭3
AgEicHz-w =
AgX
+

Similar is in case
the
of KNOG &
AgNOs:

·CHy-x +, N 0
>CH50 -N 0 + RX
=
-
=

is stronger nucleophile
there of a than
Nitrogen
O

-CHz-x AAg-g-i
+

0
=

>
CH5NY-+AgX

(B) Elimination Reaction

[Schydohalogenation Ray]:
this reaction in alcoholic Kot
occurs
presence of
or NaNHC/KN.

H Or
·Br
!* als. Note C-
C
4
=
-
-

I
~ X B-Elimination

H H

is--cz
I ald.
=CH-C3
·
X
ROH
B P
5 Boin the
p-carbon are in same]
Pat
Bel
I B all Major
<5-4= CH-cy+
CHy-4-4-c
·
X
KON
in CCHz-CH=CH2
IB-carbons are notthesame I
SYATZEFF RULE
of elimination
- >
 Rate of Dehydromalogenation ->

30 72"
Alkylnalide Alkylhalide> Alkyl halide

(C) Reaction willmetals:

↳s Reaction willMagnesium:

R dryelvier,
x
Mg R-Mg -x
- +

[Grignard Reagent
Ring -x kz0->R-H
+

+ Mg(OH) X
t of
;

In
Grighaldreagent, theCarbon-magnesium bond is covalent
highly polar. Gignard reagent
is
&

but highly reactive and I

react with
any type of proton togive hydrocarbons. Its
moistive avoid
necessary to remove any Thus
trace of from
to

it'scallied outin
the
Grignard reagent. dry ether.

↳s Reaction with sodium: [wartz Reaction

R-X+2Na+X-R yR-R+2NaX
 Chemical properties of Haloarenes

A. Nucleophilic Substitution Reaction:

halides are reactive towards

Anyl less nucleophillic
·

very
substitution Reaction due to
following
the reasons.

(a) Reconance effect >

· ..

:is: el: el: is: :is:

> I If If Alle I

1,53x,
V
-

15
as 11 -> I - -I
& -

3- Cl bond character due

bond aguises a
partial double
bond
to resonance butthe derage in haloalenes is difficult.

(b) difference in hybridization 7

:is:
&
13 sprhybridized carbon.

my midization this-cherecter is more they more

2
In
sp
electronegativity and itcan hold theelection pair of C-X
bond more
lightly.

2) Instability of Phenyl cation 7

:is:
-
is
=
i5(Phenylcation)
The formed is unitable there is
thenyt cation as no resonance

and it a non aromatic

compound.
chlorobenzene phenol in
converted to
by heating
*
can be aqueous
and
NaOH at
a
temperature of 623K pressure of 300 atm

> DOW's PROCESS

:is: OH
I I
asueous NaOH
13 - 13
T623k
=

P 300 atm
=

A presence of EWG (-NO2) can increase reactivityif

the
only C

In EWG is placed in and para

theonto
position notin
but
The meta position.
:is:
-

on ol
-
el od el on
esp
1 - OH
-
41
AI,
-

13 ->
I 3 = -- 1

I
stow
Pr &- I
Nt

- o- -
Nt

- -

pastathered me
(-Nonheigthecebonion
The
negative
ENG on
we charge is presenton this crator thatbear the NO group.
-

But in case meta, this

of is not
possible.

B.
Slectrophilic substitution Reaction:
..
:x: x X : x: :
> I If If ↓ Ha I
&11
V

·I
>

13 s -> I - -I
& -

As we
charges are presentin the onto a
pala position,
is
Thus Electrophile
which election
loving species mainly
attack orio?
the
Pala position forming two
pals out
which para is major pot due to less steric hindrance
of
and
symmetry.
 ::: is:
U2 I I
- el
arky Felly
7
13 + 13 ->
Halogenation
:is: is
I
:is: :is:
13 I
I
come. HNS Ne Nitration
> 13 I 1 - ->
come. He sou
wor
:is: :is:
I I SOH
come. HLSOG -

X I - I 13 -> sulphonation
bat
:is: :is:
I I
Hel CH3
Grafts
-

13 I 13 fridle
X ->
anhy Aec3 I alkylation
CH3
:is: :is:
I I
etboC Coct3
crafti
-
Isidle
7 I - ↑ 13 -

anhes All 3 I acylation

COCs

2. Reaction with metals:

Wustz Reaction
as
Fitig
R
4
Na
1
-
+ Nar + X Re dry, 2NaX +, Y
ether

LB Fittig Reaction

-X Na X
13 I Nar t
13 dry y 13 15
+
2Nax
other
Physical Properties of Halo alkanes and Haloarenes

·
Lower alkyl halides ear, Chych, 215 Br etc) are gases
at room
temperature.
·
Fisher ally halides are
mostly solids or liquids.
For alkyl groups the
same B.P
of alkyl halides follow
·

The orders RI>RBr > R-C> R-F

Due to theincrease in the

size and man
of Halogen atom
The magnitude of Vander wills' force increases.

isomericHaloalla deto the

des as with
the
ent
·

alsa

B.P are
nearly same
the in case
of Pomelic dihalobenzene
·

0-dihalobenzene
M.P
0f p-dihalobenzenes more than
·

and mdihalobenzene to and fitsin

due
symmetry the
-

crystal easily.
lattice