Halvalkany and Halvanomy

al Is merism -
-

*
x
xY x ,
C
3
C 3 -> -
< >
↳ 3
We
rvur W
v
Nicol Biprism
Ordinary light l
Plane Polarised
light

↓
I
- . . . . . -

O 7
- -
-

3 -
-

7 - -
-
C
k > -

-
~

-
-

I
L

sal"
of optically Active upd

Active Those which

Optically
-

-
-
-
d
. eds can

plane polcoisd
plane
of
rotate the vibrational

light
Optically Active God can exist in two

forms
isomeric

--
Dexterotatory Lavorotatory
(b
"d'(t) l (-)

Muckwier (Rotate
PPL in
( Rotates PPL in
dir Anticlockwier
dir")
 Dexte
Gave

Non-superimposable mirror
image
I other
each -> Enantiomas

specific retation (4)

-

-
It

0x &
Clindu)
o <
Consor sal (Yous in
gr/me)
0 & l . cons.

0 =

[] -cons

[] ,
=

Fre
rotation
specific
'' and
#
(specific rotation) is
independent of
Salt
of
cows

27
- C
depends on the nature
of optically Active

upd wavelength of light temp and nature

,
,
of
Solvent-
<7
the ''
=) O depends on all
factors including
and Sal"
of
cons
 cality -I
Chiral(hrekword) ->
Hand

molecule
It can be
defined
as the
property of a

to which its
object
due
image
or mirror

will not be superimposable

"
-
F
F ~

⑧ 11800
kn u
~

- C
~
a
H
~ a
Br ~ Ba
~

↓
-
Nun
superimposable
-

mirror
of 18 Rotate
each
images
=

oher

(Enantioners)

I
C
a -- H

Ear
Nate Molecules
always optically
All Chiral are

Active
(No Exup")
Molecules which donet have
place
any of symmetry
=>

are
optically Active
(pd(Chiral (pd) ·

Rival
-
Cabin . Carbon) Atom which is attached

four different gps

a

to
 01
I
C13-11-112-743
* Chiral Carson)
Nis Molecules
having only one chiral carbon

always optically
is Active .

having
=> Molecules more than one chiral Cambon

optically
not be Active
may may
or .

:
a0
=>
iOS (2) oft .

Inactive

a
⑯ =>
POSC2) Inactive
-

⑳ * Br POSC) Inactive
=C
a ↳
planar)
-> All the Planar molecules are
always optically
Inactive
 ->
d
POSSES strations

⑧
N
ell -
=>

POS(XS (Active)

Ille
8

H W
a
i

-
,
&
-
I

⑰ Posses strations

⑧
An =>
POSIX) (Active)

En

.........
-
⑫

R
I
C
-
=>
POSC2) (Inactive)

E
 Enantiomers['d '') have
ply
Nate and same ricch
-

-
!
chemical
propertis but have
different
may
properties .

Diastonoisoners Non-superimposable and not

-

I1
-
-

-> 180
- -

other
images of
mirror each Ba
Bu Be E
T
I
⑳ I -

1 W I 11
X
I E
-

-
-

T I
-
-
III
-

⑭T = Diastasisines
-

a
Gar -
11
V
L
F
I
,
=) Identical
(superimposable)
which have
My ed Those code more than

chiral but
one carbon
they are
optically
Inactive due to the presence P O
of
. .
S .
⑲ ,
Natachiral
Carbon

/
⑧
-
Be

11
1
Chival --
& I
->

1
Carbon
- ⑧
b - Me

X
I
Mesod(X)

Chiral Carbon
Mercpd(X)
sa
⑤
Captically Active)
②
------- posses
111 ...
H

e
Moso d (-]
capt Inactives
Racemic
-

-
ture Homogeneous and
quimalar

grantones of
is
of God
mixture a know a

Racemic Mixture .

I son)
l Raumic Mixture
st
I >
-
↓

↓
rot optically Inactive in nature

-
 It is
eptically Inactive due to external
=>

compensation .

C I
=> d +
R => Not a Raumic Mixtire .
This

754 2St
eptically
·

Mixture is active and

rotates PPL in clockwise direction

Racemisation Inversion and Retention

- -
,
- -
-I

Reagent Reagent
Et
Et
I E
Et
I
⑭
->
I

⑦-C C
-
n

II.
⑧
-A 12 I Retention
X
..

H n
Enversion A
R
-

Me M2
((r)

-e
Inversion idt Retention Pd

(4) [Raumisation) ⑬=> Reagent (d(e)

I **⑬
Et
I sC
H
- -
-

③
CSo -) e (0)
Retention pdt)
(Invers
Enantirmas => (Racemic Mixture)

R in Whichas a e
each)
Racemisation
-

isomer
Theproces
 of apd
mixtore another is known as Racemisation

Fischer irn
· extin
1 - Carbon

·
ON
-

I 3
2k Y
⑤ c - -

-
=>

x -s

H -
01

E
Et
<I
CH3

prog
I
Fischer fir =>
·

I deal e S

H on

342-(Is
Y

3 Y

⑨ <ry-EH-11-13 I
As
die
=> 2
H 8
0H

H ⑤
R
3

3
 Rcongigation
=>
Give
teriority
to the
''gps acc to the

CIP Rules

y
=>

If gp
is Oh the vertical line then

I 3 CI
dockwise =) R Anticlockwis = S

ye the horizontal line then

If gp
=> is on

arckrint's it

⑨
if
-83
⑫
a
② makin ③ (13

&
8
H

① Br
Br
④

al
⑰+ 3

It
⑧ ③
⑧ y
②

Pong" i Used to represent the orirantation

of -Oh and -N2

gl
in an

ideal Fischer
projection .
 &-
⑦

I
11 -
1C-

H ~
Right

I
~

~
left~

1 01 ~
-
↑O H
~
-

3[Hz -

017 -
~
n
CH2-811
D-Wyaraldehyde
~

L
⑧ ↳yaraldehyde
ic -

⑨ glos H -
2

H
note
H
-
Y ↳
H
-
S
O->
On
Right
-12-01
D-Glucose

Malvalkans 7 and Halwarenes

-

↓ ↓
- Allyhalid Anythalide
↓
R (12 -

X
Eurmatio
x
-
eg 113-1 R
10 1
. -

I shluse elhane -

CERyt Chloride)
 eg --U
101
-
20 denzene

0
--- 2

⑲ 101 -
Ins
X 101 -
4
halide x
Alkyl
[Aty Zalide)
83< 2B x B
⑨ c - -

4 ⑯ ( -

1 -

7
-

2 7

1
↓

ba
Alkyn Lalide

(2 :
BB R
⑥( - - -

7 -

) -

7 ⑯ I
P2-7-Ph
B
de
13 Alkyl Lalide]
(3 Arky1Calide)
*

Bu
I
⑧ P2-2 = (1s

I
(2 Alkyfzalik)
⑰
= x ) 7
c -1
-
- -
-

k ***

↓11 Argen Carbon

Allyliz vinylic Carbon

Carbon
*

③
, ne candon

⑫
< =

(2 -
4 ⑰ (12 =

(112
↓
Benzet Chloride
vinyl 12100ide

⑤ CT2 (1 (112
=

-
-

Ally cherride

⑫
u ①
vingl Chloride

wit
⑭ CHX =

Haloform
Chow
8 CHCz=> form
.

Bromo
CHB2z =

forn
CHIS= Indo
form
12 3 7 S
E
< =C -

- - -

i
I UPAC=S 1 , 5-Dicklow pent-I- ene

Nature
-
-
-
Ex-
bord
-
⑰ ⑤
R-C12 X
- More preference
falar bond ↑
ke (pipale moment) -> (St or /5/X B L
.

⑧ ⑤ ⑰
1
-
F
1 -
4
Hz)
-

Be
13( -
I

a
b C d

Dipale Moment -) b a) d

I
Excel" (B :
L is the more

dominating factor)
 B L
. =
ac<xd

B .

E =
a)b)c)d
[BE)
Extrachill >
They nature
are of
deficient in

↓ I and have
tendency
to t fair
diving accept a
election

*,
⑰
,
⑰
H a Br
of , NO2 AlUs
/ ,
O ⑮
BE / CV2 1 -
4-H SO
/ ⑮ / 3
⑰
PUs & As
⑰
( 0
=

0 =

NH
⑰
= and
130 cannot act as electrophile .

Lave
they
bi do not vacant orbital

Nucleophile
-
Electron wish spries which

↓ I have at least one of fair

Nucleous living and attacks at of
deficient
<Proton)
(AV0S Carbon .

O
11
⑦ Eg
.

CN8, sit
, on OR
⑰ -:
N
M R- x 1 . R-
I
I8
,

a
8 ,
,

, ets
 0

-> CNO I C2- -

Cs -> HCN +

I in ⑧
-

⑦ 11

212 <
(13
-
-

SN
acting base
-> as a

do11 po
CNE I
=> 91 c
(3 (H) -
x13
-
- - > -

Wo
3
⑰
div
N
Now
acting nucleophile
=>
as a .

-
- strength of
affiting Nuaf linity
= Factors hi
-
3

Nuckaphil
- -
-

Etivity (Along
① the period) -

=>

ENgtnY in
-
Nut (d2 -Parnating
*
tendencyf)
-
7 · n F (Nu)
:

· C3 > ... > :

12 : * (Nu
FO
ENg= < Neutral O'

② Size (Down the

- gp) is
 Size
of dowie
Atom' lip
donating tendoncyf
->
Nut
Palam apratic salvent
only
but in -

⑦
-> q > C
⑦
3 Br> I
(in Polar artic
salvent)
=> In Palace protic salvent-> Size NuY

Ad
=> =Ot
I n
*
HF-WeaK
0
⑦ ⑰ X
NF->
= I t H
=>
- string Avid

Avidic St-> HF < HU < HB5 < HI

③ Extronic effect
N < ERG +M ,
+1
, +I)

ah( -

M
,
-
4
,
-

I)
n :H
I
g - -
10 I -101 (Nu)
- Y

↓02 M)
↓ 1z( +

H)
⑦ Anionic species are better
Nucleophile
than Neutral

&
H20 : < : Oh (NY)
⑦
-
Ni 7 is (NU)
3
⑤ Nux -
I
Steric hindrance
-
⑦
Q: 0 H
↑

- [Nu)
CH3
3
<
-

⑰
⑰
Q ⑧
+I 0
+I Els
1
- O
CH3 x)
-

[13
-

-
>X

a
,
b

Nu- abd

Basic St => b) a

preparation
-
Mallkams ( *y haid)
-
i
-

① From Alohals
-

2
-
-
-

(a) Reach
-By With HX
-

I ⑦
H
113-12-01 -- C1-(12 -
x +

H20
alide
itnism
- -
(
It
fallows SN , Mechanism
Hx- n +x
- Electrophile
H ⑰
<Hz-(2- --

Gi
N
21z
-

<1
2 - -

0 -

H
protonations
Nucleophile ↓
Proton]
(Add"of Profinated Alsuhal

o
↓ ⑰
RDS (Stowest
Step)

X : H
CHz C2 x < CH-(12 I
-

-
-

in
-

ast
-
-
I
halide
Alkyl Carbocation
(Intermediate) (2 2)
-

=>
In this reas carbocation intermediate is

formed so

rearrangement
is
possible .

Rate
of Meas a
Stability of Candication
=>

⑲
⑰
C-
* ⑦ ⑰ ⑰
- (R 0-R)
14 >
-P ↳ H2 >
↳
- 01
.
-

2
2

38 10

⑪ Ph-
#

I
↑2

C
-
I
OH
2
-Is
P2-(12-01 (1z-c-
C01
ps
2
3 dis
R-0-R = 1737 2
 etCations

No ↳electrophile I &
(Nat K*
cannot act as
,
.
A)

Na X
CH3-12-011
↳
⑰
⑰ -> CHz-TH2 -x +
Na + on
/
-
LG
.

on
-

-> This reach is not possible dez is a

bad
leaving gp as
compared Au 120 .

-St =I ⑰

C-122
⑦
Cry-iz-OR #) + X

↓
(1 -

12 -
x +

128 :

LiG
-

having go ability <

Stability of Ch
afte
=

leaving
⑰
228
↳
-
I R -

L G -
R +

E
>
=>

having go ability-> 120 : 01

than
=> Neutral
leaving gps are better
charged
leaving gas
= >

H -
F < #U < H-Br C H-I (R .

O -

R)
 H-FCH-U
=>
Rin Acidic St= <#-BUCH-I
-

↓
↑
3 Cons [R]
then the *
It
first n
=

Step will
shift in
forward
direction .

-> In case
of
MF
,
the
yield of Pht(R-F)
is less -

catalyst (Anydrams)
HC
In
of
a
=> case ,

is
required ↓
.

-
2nCz->Chs-a
-

=> cy-cAn-R +

an 21
I
a Ds
-

142
21 -

42 -

R * Carbolation

+
So
10-2nU2

n-> 2n42
120 +

Catalyst Regenerate
Lucas
Reagent - sonC HC +
Anhydrous InG2
=
·

test.
gent This test is used to
-
 distinguish among 1920 and 30 Allhal.

2nd2
R-ON concre R
41 120
+

-
- +

white
turbidity
(PPA)
Lucas
38 Arsohal
- Reagent Forms
turbidity Immediately
20
after
S
-
-
's -

Minutes (Approx)
U
I
-" · 3 e
'I after in

Reason 3) 201
- -

-
- Stability of
Candication ->

ROR &
Stability of Carbocation

- InS
E C
=
& = 0 S
c- -
HB2
7-
->
-

c -

1
ab
E
↓
Br I
[ C- -- 2
- - -
⑰
- C

I
Ca
-

L
I
C- < C
128
- -

bu
② epz
-
--2H-2s S 6
⑰
HI
L
(H
---
L =

(Hy
-
If......
4 I

3 2

I
CH3
⑪ CH3
A ↳I

I
⑰
⑰ /-
1 I
2
6

↳
-

Es
[H3

xt
-

↓
Pdt
Myir

A
-

⑥
C
# or
- bi
x- HCX
S C
- ⑦
101 2nUz x-c -
-2
101k
-
-
2
⑰ -

↓
To
-
 SN
,
Mechanism
I Unimolecular nucleophilic sube")-

↳=-
W
-

Malcolarity = on

substitution Nucleophiliz (First order

Meach)

Nut R-Nu xt
R -
X -- +

Mism
-
-

⑰ ⑤ (Salvent) ⑰

in
*
CH3 (n
- (Hz-(H 213
=
X + x
-
-

RD S

e
<Slow step) Carbocation

start
CHz-CH-(113
in
=>

It is a two
step reah and Ist step
is the RDS (Rate determining step)
·

R O R depends the
only
=>
. .

on RDS step

R O R
.
-

<
[R-x]' [NuG]O
Order Ma 1
of
=>
>

Molecularity of RDS step is (Unimacular

=>
one

Meach)
 Carbocation
formed
=>
Intermediate is so

is
possible
rearrangement
Rate Carbocation
of
SN , Meas
Stability of
=> &

leaving gl ability of 'x'

a

⑰ ④ R

E
⑰I

⑨ R-12
in
<R-C1 -X < R-C
-x

↳ X
(R-0-R)
-

I
10 28 &
3

Ph
I
⑰ ④
⑮ PL-c -

Ph DTanz ↳ X -

PL-21-Ph
↓
7
②
3
*
①
⑰ ⑰s
PL-112-x C (13-2 -

113 [R O
.

④ I
↓ ⑤

0>8> >Y (R -

O-R)
⑰
- ⑰
⑰
⑰
[12 ↳ X 242 - ↳
E 212↳X
-

CH2- X
-

② I I I
I x -
/-
--
10(
10 I
-
10 I
Y
↳ -

Ebe ( + m) + +

m)
⑤
in -

( M)
1
⑮ -
+1

(1yd 3)
-

① ② ④
=

⑤
 ⑰ I ⑰
(12 ↳x -

212 ↳
-

x (12IX-

A I
--
I
-
10 I 10 I 10 I
- - X
No fM)
-Des
⑤
( H)
⑥
+

(x1yd =

2)
R 0 R 8 > 074707853870
.

- =

=> R -

FC R-U < R
-

BU < R E-

(R 8-RS
.

R -
LG ↳
-
- -
R I In
-

leaving gp ability
&
Stability of La
offer
leaving
O
I8> Br8> 48
stability => >

leaving gpability => IE7 Br

*
> GO > FO
T-SI

M
I
X
T-SI
Egy Dan
causation "
=>

CERE (a)
↑
V

p E
.

---- R-Nu

Reaction cu-ordinate
 Semistry
of Mash SN ,

"
=>
In SN
,
reas Racemisation occurs -

Me

** -

Bu
-
RDS
-

any↓ I
C
1 Polar I

-
⑰
Ph salvent PL

(dowe) Carbocation
strigonal
Planar)

!
Me
-Me I
No-C 11 IIIC- Nu
In ↑
...

Ph
Ph
Inversion P ↓ Retention Pdt
-
Enantiomas

Cdextro +

leavol
[Racemic
formed)
Mixtu is

for
ne SN
Meas ,

① Nucleophile should be weak .

 -
-
All the Neutral
Nucleophiles are weak

except IH ,
R-NY ,
R-NA-R
Rhy
,

.
#
Weak
N=>128 :, 12 S : R-n
-

,
O

R /
R
- -on
-
etc .

② Solvent should be polar protic .

-
↓
*
Which can
give (R )
Proton

.
# M20 , 1255-011
,
Chy-Y-OR ,

eAle
13POy

Helps in virnisation R-X bond

I
->

=> It also stabliss the cumbocation .

⑰
H
⑤ ⑤ - ⑰

↳
~
R-

X
non-dipal
↑

interaction
H H
R ↑
0
- ↓ -

H
.... ⑰
......
"ug -

R
⑰
⑰
8-H
5
- -

-
H
↓ is
0

-
 helps
-> It in
decreasing the
nucleophilicity
Nucleophile I biz
protic nature)
of of
.

0
⑰ ⑤
...... H R -

X
⑦
Nu----
⑧
-- O ⑰

E ⑰
Nu I H -> Nu-H

③ should
stable carbocation be
formed
A

Cat last (20) having Som

6 (Ryd)) -

Nate 211 =
(1 -

x , HEC -X A
10 I
-

halide
vinyl x
Y Halobenzene

* C3-X , Cli-CHa-X donat

=>

Nucleophilis Subs" Meach SN

give via
,

mechanism biz carbocation

formed is
very
unstable
sp2
⑰->

!
->

very
unetable due to
high
etrain
angle
.
 (erular Nucleophilic Reach)
SN Subst
8 Maniem
2

II
-

↳
-

Molecularity =
2

Subs
E

Nucleophiliz Red order real)

[one step)
elementary
=>
It is an Mearh

C
S I
⑮ ⑤ ⑤ ⑤
Nut
C R X
> Nu R X
-

-
-...... -.....

R D
. .

S
Transition State

↓ &
Nu-R + X

= No carbocation
formed ,
so no

reacangement
is possible
=> RO R
-

<[R-x]' [NaJ'
of
Order reac= 2

Molecularity=2
Egy Diagram -

T- S
 -

.
l
R-X
-

.
* DH
.
=
Na-R

Setry
of SN2 Meach

&
(
H I
I ⑤ I ⑤
- Br Nut > -- I32
Nu C
Et .
- -
.......

V Ef"" -
IC I

Transition State

Strigonal Bifyramidal)

↓
-n
Na-P↳ ......
Et

(Inversion Pd(
Nut attake
from the back side
of th
=>
 so inversion pat is
formed
:

SN2
of
inversion the
configuration
=> In teach
,

about the Chiral carbin occues

(R + 5
,
S-R)
provided privrity of 24 and Ne are sale

E
g
②
- Et

#
⑭ O
R
⑪ or ⑪
> ⑧
s
H Bu -> n & -

H
SNz

s ③ 13
(d es
or
(dar1)

=>
R .
O .

R te
Steric Lindance in R-X
-

X (1)
Charge on
Carbon-x)
Nut
a
Strength of
R
⑰
- Cry -x) R-CA2-x> R- >R

⑭
& > -x - -
x

R (R ORS
.

⑧
of SNz
⑬ R - > Ph-
⑰ ⑰
x
-x) (12
-

(1-112
-

= >

x
-

T
-
-
I
-
-
I
-
 <13 -

x
> R-C12 X <R-0-R)
R
& - * ~G
Nate
-

R
.

x (1 C X CHEC
=

X
-
-

↓ X
(b12 of
,
particl double bind

Y I
character bond driones
stringer 3
--

10, ,
cannot SN2 Meas
give
.

Ri
of SNe Meash is

① Nucleophile should be
etwing
.

⑦
018 si OCks
Strong
Nu
# =)
I , ,
-
cr
,
0
(12-(H,
S / Y R-
RgX
(R)
Way [18 Re Fits
,

, et
, -

② solvent should be polan apratic

Eg DMSO=)
Dinky Solfloxin) (ts--Cs
0

Autore => (ty -

-Cs
-
Dinally other CK -
<3
O

DMF A I
n -
2 N-1H3
<DiMetyt formamize) -
3
 It
Helps in tionisation R-X
of
=>
bond :

=> It days not decrease the

Nucleophilicity of
Nu .

Net !

3)
Nut
Alkyl Lalie >
Always SN
,
Mech
,
O -
C - -> "
SN2 /

20

kin
Alkyl

sergi Weak Nu

SN Mech
SN2 Ma12 ,

in
of preparation of Alkyl halide
>

is

(b) -wi herous Halide f

(1
, -112-01
+ Pus -
(13-12 -

4 +

POUs +
HUlg
C13-OH +PUs - >

<11-4 +
13POs
These reashs
always follow
=>

SN Meth -
 Ph Ph
# I
C -01
PBU3 I
C
-> ( ( 1 B2 113483
-
-

-
-
- +

↓ SN
2
in

⑨ ---
12-01
1 PCs -- 4

-
SN2 ↓ +

POUs
⑭ +
salvert Hu(g)
Melod
-
c - 01 Ether
I sick - 4
Si)
-

-
-
+

through (hovide
+
Mul
-> Better method
(among these) to prepare
halide b12 pats
alkyl side are
gaseous
so

leave the
automatically
reaction mixture and

zalide
pure alkyl formed
is .

fallow
=>
This reach SNi with .

↳ intramolecular

=>
In this reas Ne attacks
from the
retection Pdt
same side
of h so is

formed .
= -7- 01 +
SUWZ Pyridine
-
( -

7 x +

Sig
(SN2MeI]
[Enversion]
+
Hull
01
e
⑲ I us -
-
- -

1 ->
SN2 I I

L
Inversion Pdt
-

↳ SOCL I
C

I-
Ea

(SNi)
Retention Pd
C
SOCz =
--
Agridire 1
② From Mybin -

⑰ From Alkane
-
by reach with
X2
.
S

2)
(13-1112 2113
-

x2 -
> CH3-11-1113
o

(25) Yo -
↓ MajorPd)
I

CH-(2-12 -

MX
 hi)
Ciy + 02 -> (1 - x + Hu

Mozochloro PdA

Lis
(13 -
x +

02 - (1242 + Hu
Dichloss

C1202 his I H
+ Uz -> CHUs
Trichloss

(14s +42 hD COy +

nu
-
Tetra Cho

Lis
I CHy t 02 -> [Hz -
c + Hu
Excess Pdt
Magir
2) +
= CHy t 02 -> Cay nu
Excess
Major Pdt

subsn mich
Mechanism - -radical .
↓
-

Cabin radical
Intermediate-> free
(i) ↳itiain
Step
x x
A - I -
so -Grin
(ii)
pagatingstep
 x
C3-(- Hy +
(1) [H-4 1s HX
-
- +

i
⑤ RDS
More Stable]
3)
<Hyd
=

213 <2 112 Y

<-C-Tiz
-
-

NX
-

i
+

(x1yd 2) =

I
13-cH-Cy X-x->
crystY
+

[MayinP(t)

cy-emit
xax- (1) -

12 -

x7 -

+ Y
(iii) mination Step :

i + x + x
2

R +
R +

R2

:
(A) (H .........
-(1) -)
CHy-7-CH-113
-

dis dis di
,
di
C3-CH2-112 ..........

(12-(42- (z =( -

711- 77
 Rof x
2
=
FzL 42 Br2) #2
↓ I
explosive How and

reversible

Reason
- -

-
I
In RDS
Step ,
MX is
formed

Thermodynamic Stability -> H-F) H-U) H-Br >H-I

bx B. E => H-FL H-G7 H-Br> H-I

of
Iodination slow and reversible bi2
of
=>
is

RI this is carried
formation of
so reach
I

presence
of string oxidising agents
out in He

like HNO3 and

HIU, :

0
his ⑪
sky + F2 ->
2Hz -
I I HI

Wild
=

I
- Pdt

Reducing
agent
HIO HI
I
Fz +

120
+

3
0 .

Al R
. A
 Stable
fr generate
-> Most radical will

the pst
major
32°
Stability of
Carbon
free radical -

Q=
b b
02/2)
-

T - How choo
many
-> mour

a a
C Plt

-+ I

At -

-
a

C
I b
↓
22)
② C- -1 -

C
a
+

Br2 -> Two monobromi Pats

b

↓
a

C C
2
I I
I
2 -

) -

) -

) -

Br t --- 2
3
Y
↓ Br
C Magir Pdt

C E
C

02/2i)
an

③ -- -> ( -
- -

↓ I
a

entye
Nate
Electivity Power <42 <Br2<I2
-

-
=

Selectivity Power e

Reactivity
Ratio Chlorination
Selectivity for ->

30 : 20 :
1 =>
S :
3 8 . : I

slectivity Ratio
for bromination -

38 · 20
:

10 =)1600 : 80 ! /
a

C C

② - !- ,c -
-

x
-

a I
a
b E

Magicpdt(1a
-

x I
ikyd =
9 C-[- 7

1
↓
Hyd
3 =

Minor4dt

-V(37
C
%
y x = X 100 64 28 %
.

+yY #
=
100 35 7 %
.

x
=

10 ⑧
W

28 <- 1 -1

·
I -

) -

R
& C3 -> 12-CH2-Cs 02/2)
-> 'X'
b a
At
-

b
 /My d 6
2"Myd Y
=

( -1 7)
-

i
X =
6X1 =
6

4x3 0 15 2
Y
.
= .
=

Pdt
May
in

x(3)
-

② -- CH3
10 1
-
-

-
Talwene -
I
-

-C42 C3
101 + -

-
101
-
Fro medical subsh
of X2 is
only
=>

possible at sp3 carbon .

-s
b a

& 23
Ethi
-

-H ,
H
Major it

Nate Another that be

-is reagent can used

bromination NBS
for of Alkane =

CN-Bromo
Bur
Succinimide)

[**Y)
⑫ Pr--Y ->
NBS
Ph-CH-
B
-

Majorit
④ Allan (Add" reaction)
with MX
is
tion -

&
[11-21 =
CH2 +
Hx -

> (11-11-1g
↓
&
Major4
t

=> Markonikov Add" take place -

C3-1-112
I
I
H X
Minol Id

ma
-
Mechanism
- -I

④
(13-1 (12 nX
213-21-113
=

> +
RD S
Nucleophile (StrwS More Stable Carbolation

-
213-211 -

12
⑰ -
C1z-CH-C113 = Cy
-4
-
s
Fast

Ph
Major
=> carbocation is
formed so
rearrangement is

possible -
 Cambocation
R R
Stability of
->
.
O -

<

8 ( -

I
a
c
A
=

C ( -

②
In
A
(=

rI-
↓
⑧
3

n
CROY

*
-
c-1- 2
9

<Hyd =
6
- 2
⑰
-

C
-
<Hyd=) 9 11
-

<Hyd 7
=

②> > (R-0-R)

PL-CH
me Ha
⑫ =
(11-23 -> PL-21-112-11s

I
pa -

* -

12-1

(/e)
④ ↑
2113 A HB2
# ⑦
CH3
x
x2
=
-

- n 21
-

-
- 12-
ins
-

⑮
Mo
shift
↓
 443
Ph-c- CH-11
B 2113
PL-C
I

-
↳ (13
-

be kn
Migpdt
-

C13
Q!
↓aI 213

#F
-
- I I 2

We
----------
nu ...... - <1 8
I
-> 6 / ->

1
·

.
3 ,

S Y

↓ Shift

·
Bond

H
-
C113
I Els /- -
⑰
eCl3
M
- 2
--> 6

1
⑰
L
--

1 3
1
H
"Y

I,
-

-
a
↓
Q
&
-12
-
A- I
--

↓
HT
->
-

E CH3
1 I
-
↓
 ↑Tas
-

At
Note Alkine MBr Peroxide Antimarkonikov
↳
+

- ->
PL

(Magir PNA)
This is Khanasch Peroxide
known as
effect
=>

or

effect
.

HB2
⑧ 113-11 =
(12 - >
(13-4-(12
Proxide
↓ bu

-I
fre
...

(R-00-RS
-
-

[Major Ph

Cy
-

- nu/Peroxide
11
-PR
-
S

Major
Am
Khanach
effect.
-> dical Add"mechanism

⑪
i
X
R- -R -> R-

j + R -
j
 I
② R-0 + H-Br -> R-ON+ Bi

③
. %
By
I
Bi->
8

<13-211- -

<12 + R-CH -

>12
Carbon
free radical

[Move Stable
t

R-CH-912
Bu Clas Stable)
④ R-CK-12-B2

I
+
H-Br ->

R-
(12 -

(112- 32

Major
-
-
Pdt

Nate 'By will attack to that carbon

-

-
-I of
which
Alkone on
free radical is

less stable -

H Br

pac
HB2
· Ph -c =

7-( ,
->
Peroxide
e
in his
⑦

⑨
t

-
A ---e
MB
1 ->
I
- Peroxide
Hie
↓
 x-3
↓
Br

Rigir
Pdt

te Kharash
effect
is
only possible in case

of MB2
/ Peroxide ·

#2 the
In M B E is
high so
.

-
,

Romilytic fission possible

is not .

I
=> In KI
,
the
found is
very
unstable
,

I
immediately combine with other to
form
T
-

2.

n - >
- i +
I

I I
I2
+
-

A
of Alkene-
(ii) each X2 with
-
-> salvent
C1-CHEC12 X2
->
cuy <1-11-212
Add "Reach
↓
sin ↓ X
2/22) ou
X2/ligh tes
vicinal dihalide

-
C =

<12
 halide
Allyl

(3-CH=CH2 +Bre CHy-1H-TH2

↓Reddish Brown lig bu bu
confirmating
-> This reaction is used as a test

to detect the unsaturation

(For I in

will decolawise
My Alline
Alkyne
decarbon .
or

the Reddish Brown allows

of Br2 :

Mechanism
-
-
⑰
⑦
Nucbaphil
it a cuy
-> 1
:
Ele trophile
I : =>
-

-
⑰
Me
i ..... ..
12
"
"
B·
Y ...
·

&
1
-
· C ·
-
I
c
=

L -> C-C
↓

f
H
1
love fair Me
Me

Trans But-2-ene
containing Non-classical
electrophile Carbocation
(Nucleophile)
(Bridged carbocation)
ne Q
H
*
-

- 2
-
/ - R

Arti Add"

H
↓
Me
I
 ↓18 i
-POSCr)
!

Feel
I
C a
Me

- Gl -

->
H R
- ..........

I
Me H ·
Me
I Me

Med POSI
Mpd
-

=> Mankonikov Add" take place that means

Nutrophile attacks at that carbon where (tre)

charge is more Stable in second step

=>
In this reach non-classical
(bridged) carbocation

which
is
formed due to
rearrangement
is not

possible -

It
=> is a
starospecific reach .
El trophil
and Nucleophile are attached
from
the opposite
sides .

This is known as Anti Add"

[ I
SN
,
reach is
starosprific
now reach

SN2 Is
-starospecific reach
 ⑰
=> Alkine + R
- >

Carbocation

L*, 4): :
(a Br
*

- Non-Classical Carbocation
stone fair
containing
electrophile)

- reagents
that can also
perform similar

reach

Br-ucun Br-I/c ,
&

-
-
,

nox/cey etc .

,
⑰
Ci
Bric B:
=>

: :
~-

Electrophile Nucle ophile

n
⑰
=>

not Nalephile --
+:X -
:

Ebtrophile
(x =
4
,
Br
, I)

Nate
⑪ Profe trans Allan - Meso upd
Et Add
H
2
g (AntiA"
-
= C

n -Et

② Improper Trans
/
Proper M*
Y Racemic Mixtie
Cis
, Improper Lis
(d +
e)
 Suf Sof

③ Proper Trans
Br -c
-
Raumic Mixtur

↓ ROX

Racemic Mixture

⑨
a
-1
I Hie
&/->

all
t
I

⑭ ↑
/-
a
H + 1-

41
H
Major
-Br-4

3
⑰ Dr

&
th
<-
<
=

->
-

in
BrPh
in

--- -- Th
p
11
-CH-2 -

PL I
in be
↓
 ⑦ ⑰
③ Br I
C1, -21 (112
= -

C1-PR-C
->
X

Et Ph
I -
④ = C
C2
Myo upd
->
1
Ih Et Cy
Et

Proper Trans
Ph

-------------- :
Et
I
POSI
wh
I

213 3
⑤
y--
-

> Raumic Mixtran

,
CH3 C13

I , I
H Br Br H

H By
B2 H
-

C3 [13

Raumic Mixture

(d +

e)
 Mesocpd Arti Trans
#Rule -
--
Add (Praper)
ofx2
Proper -> Mer
Cis+
Syneas" upd
two l
of
·
③
-ide
By haligen Exchange rach
From

⑧
V Ir-

⑰ Finkelstein reach -

-
-I

--- ⑰

als-x24, x +
Na I
-
↳
-
Dry /

(15-12-It
A stone

(x 4
Br) ↓
=

, Nax ↓
falvert
&
PPA

(X =
4
, Br)
=>

Nall
,
NaBe are not saluble in Autor while

NaI is salukle in Autore

the 4Pt NaBe

BC2
of formation of of Nall or
=>

equilibrium shifts forward

in Actor in direction .

This
Mostly polar
fallow
=> reas
SN2 Mac $12

apratic edvent is
present (Alo
.

Ne is
strong)
-
③ ③
C13
2113
⑧
Y ⑤ ④ Na ⑰ ⑫ ⑭
- C
H ⑤
C
Actore I B
H

(SN2)
& (2-Cs (Walden Inversion)
② CH2-[13
Inversion Pdt

=> Inversion
of the
cougr(S->R) take place .

④
each
AgF
④ E

cis-ct * -
C1-72-F +
AgXt
(x =
4
,
Br
,
I) Salvent PPt

(X =
G Br
, , I)
=>

AgF is soluble in
120 but
(AgU AgBr AgI)
, ,

not soluble in
are
120
·

of formation of of Agx(x=>
=> BC PPA 4 Br
I)
, , <

oth will
shift in
forward
direction .

Other ert that be swart's

for
can used
reag
->

meas -
ligzFz ,
CoF I 36Fz
 Preparation of halide
---
Arge I
-
vom benzene
-
↑

(Haloareness
-
↑
,
ARQ3
+

2 -> + na
- ↓
Catalyst
-

- Electrophilic Aromatic Subs" reaction .

Mechanism
-
-
-
-I Ebtraphilic Aromatic Subs Mechanism
-

①
Electrophic
Generation
e
of i)

- Are I
I
->
*
- 0
↳All -

al
-

↳wis Base
Gwis Avid
↓
⑰
O I Ar
Electrophile

② -
A X ⑰ RD S ⑰
H

**
I ->
&
↑
I C r
How
Electrophil
-/ (
Nucleophil - Non-Aromatic
Carbocation
Aromatic3
(Avenium ion)
20 complex)
(Resonance Stablised)
 ⑦
C-> AlOn
③ ⑰ v: /
/
,a
-

14 Fast *

11 ->
↑ + nu I
X Y
(Non-Aromatic <Aromatics
C
ARU3
I ⑦
/Regenerate
S↓
⑰ u-
Ar-u
R

= Rate
of reach a
Stability of Amonium ion

density benzene
t
x
ring
on

~ ERG ( +M ,
+I
, +H)
al FM , I
1)
-
-

- >
,
EWL

Gi
NOZ
I
0
CH3
I
+ 1
⑧
" -

H
-

&
M

⑲ I

To
- --
-
10 I 10 I 10 /
- - - -
I 2
3 Y

R OR =
.

2>3) 471 C13 + 11

( +
M) I
(N( M) : + M) :-
an
-
-
⑪ 41
it
3 ,
I
-- - -
101
Yo -
②
X
10
a40/ Ryde
0 42-
↑ H
13 (1)(+ H)
-- I
--
10 I 10 I
⑤X ⑥X (1yd 3)
=

<My 1 =

2)
R .
O
.

R towards E -
S R -
.

&>>0>8>
④> ⑪

=>

Regent Used
for Halogenation of benzene/substituted
denzere ->
(X2 + Lewis
Acid)
eg
-
Unt ARUS ,
Br2tARDs , Br2+FeBrs
,

42t zaVa Brzt Fe Uz + Fe

, ,

=>
3 BU2 +2Fe ->
2FBU3
2 Male
So Mat Gwis Acid

47 Mal C 2 Mole
- =
-

E-S R
#ituted benzene
.

-I

=>

directing
gps
=
E R L .
.
like (+1 +H] are
orto-fara
,

directing that means

incoming electrophile will
attach at bes
otho and para position I
autho para position
density
· is more at and .

the feat para pat

henrally major
is
=>

lessen hinderance but

of
bi steric sometimes

Intramolecular
of
othe pdt be /22
major
can

hyd bonding
:

Wit
↳
:, C +M

I 1
⑭B = -->

&①

-
D i
0(13

/-
-
I
I
A-Set Cc +
~
41 I /⑰
-

-> E
er I

l ↳
↳/
-
&
02113 -0913
I
⑭-

** R
--

I *
-
- -
i
↑ E
[Note
-
is the Main reason is
always stability of
Aremism ion
I
Electron
#tinggps is
The
withdrawing gps
like -M
,
-1) are meta
directing
that means

at
incoming electrophile will attack meta
position .

A
CEN - )
_ x27 4)
-

a -

I I
/* - ⑰ -
⑰ /-
I
I
⑰ -

11
Y I11
C-
I
E/~
/
⑰

Nate the which show (I)

-

-
is gts can
only effect
not ooho-Para
are
directing.
which show
only effect
The
gl can
3-I)
=>

not
directing
are meta :

C
HI) > Not a
Ortho-Para directing gp
z

-
a - -

⑰ I Activating gp
I ~STE
- >

10
-

<Ryd
=

Activating gls = +M
,
+R
,
+ I (which increases
density in
benens
 practivating gps--M ,
-1
,
-I
(which deceases &

* 11 mensity on
benzone)
,
>
Deactivating gl
I (but not Meta
- directing)
101
Y
=> disubstituted dinzeme
.

Case position
3I both
I
(tm)
-) gps of
-

are
-
,
-

incoming electrophile divided

by More
stringue
( M)
94
+

I tee a
one

e e

then
Case #
I of both are (M)
gps
More
-

- -

stringen - M)
R
will devide

( + m) ⑥

⑲ CI
- -

N - -
N

A
101
- UL
-
AlUs 10 I
-
· u
↓
I
Pdt
Major
 O

o-
-

N1z

Fa
-
2+m]
:- - 1 ⑧
(Minor Pat)
(tm)
,

*
(1
⑳
NH-c-21s 0

10 1
~

o cy 0

But
Y 7
* NH-ECs
10 I
Br
-
Pdt
⑧

o - -C I
3 ↳
I
--N--ts
(-
) 11
⑧
Br
0
-
! -N2 C
11

③ it C-N2

⑰ Frfte
10 I ,
A
- 10 /
-
Br

th "
⑭ o *
Br2/F10 -
-

/
-

I
K

10 i -> ⑧
[ -
H Il
- H
- X
-

k m
Majis
-
 - Int
O

⑤ / -
NOz " -
H

101
-

e) -N2
I

- 10 I
*
I
By I
Major

of Alkyl/Anye
halide
improperties -

=g ( - -

R <-- - -

2 -

x(B(t)

Bet < MM

Vanderwall's
forces &MM

⑲
I
x- x)( 7
-
(- -
-

x ( u
-
-

↓
T
-

I
#

Bet
of
(In
+
-
case
Frowa)
Branching
Bet [In
<
Surface area
case
of Isowess
⑧ - FF<7 = u L 2 7 Brc
- -

2 =

I(B(t)

H
=>

Alkyl
halide are las soluble in
120 b12
they
donet
form Hyd bond with 120(87 -

which bond
Note is
Organic Hods can
form Myd
soluble
with 101) are in
120(1) .

⑱ - 2 -
R 7 -
---- -
-
R
Isolubility in

I 101)/
nin-polar

C-1 F <( 42 ( 7 Br < (- 1

(Density)
-

=>
-

Wit M.
⑰
⑬ Cy <
[AzC <1242 [Cy (density)
I al
*
↳

I Gre- I
R
44x
⑨ - -

TI -
-

- 1871200 101
- -
-
881ho Dic20r
benzene
(Metal -I Para
 Bet => Ortho] Panas Meta

Mpt eas
Egginny

Met Packing solid

crystal (Incase
Efficiency of
=> <

Isomas)
of

#to
I
Galaf
C

-mr tions
Alkyl halide Lalide
of Arye and

=> I
Arkyl
halide
mainly
stows Nucleophiliz
the via
subs" reach in
ference of
Na

SI mech
,
or
SN2

ready studied

-
is #Nis>
⑦
Ck3
S CH3-2-
a
<3-
-

s
↓ ⑰
n
(SN, )
it
I
,
...
120
3
Allyl Ag
⑰ +
D :

Lalita [Weak Nu)

 (1)
C13
I
(
73
ratination
C
(Ay-**C13
pib-n
-
-

n
· i I
I
L
n
~
-
I
2

⑪ -

-
, C1z- wi &
H

dis
I
-

⑰
->
Weak Nu CH3 21

-
C3
-

(SNS

-
↳ 213
-
⑰
<
[12 Ts
-
-
: -
C
,
di
I
(13 12-713
In
-

Major ↑ It

[13

pis I
②

&G
120 :
Et
-
-

⑰Ph
Et
Ph

30
Alkyl fro halide
:
 C13 C113
on"
Et

Ph
" Ph
Et

Retention Pat Inversion

Pd

Raamic Mixture

(d e)
_
-
+

⑨ - / -
C Na
⑰
i
IOCHs
1 I -> /-

-
-
13
Strong Nu)
1 I
20 Lalide
CSN2) -
-
1
,

Arkyl
-
Inversion Pdt

a
-

2113 ⑰ ⑦ C13

I
⑧ NaSH
->
"- u
(SN2) ast in

[12-C ,

(20 2112-73

RedP+4z
⑰ C- -
01 C-(- a
->
↓
PU3
⑧
%
*
NaBy ⑰
<--- 2 -> C-5-[
12 SUY
I
be
↓
*

I
2

&
enBr
< -

77

Br
⑰ ⑰ ** *
Nate
-
O
I R -

x
- k NaCN
R -

CEN

↑ I
-

Arkyl cyanide (Nitrile)

irnia led

k
·

=
i
↓
E
n

tambi dentate Nucleophil

⑰ ⑦
NEC

-
R,* -> R -

or R-NEC
-

↓ Alkyl is
oy
amide
covalent
upd
& R
↳ iaN
x
R 0-N 0
-

,
-
=

↑ -
↓
virnic upd
Ankyr
Nitrite

j
...
18
* -
N
k & a

[Ambidentate Nucleophile

ifC AgNOz R-N 0

=

->

%
↓
↓coval e nt ⑧
..
Nitru Alkane
-N 0
Ag-
=

* -

*
- -

-
-

⑧
-
-⑦
↑
e

-
-
⑳

qx 0
 ↳of Aryl halide substitution reach
I
X
Sp2
C il -
·

-
14 Nut
+ No Reach
->

-
=>
Anyt
Galide
(Halvarims) are

very
less

reactive towards
Nucleophilia Subs" reach

than
Alkyl
halide bez
of
the
fallowing Reasons-

① Bond
SAy (spc-X < Sic -x <S1 -x)

② :k Bi Rernance (C-X) bond

/ of
=>
-

1 I has partial double bond character

Y bi bond
strength
which
of increase .

③ The Carbocation
formed is unstable
after
:

x
the removal

F ⑰
-- -
10 I ->
10 I
- -
Unstable Carbocation
⑦ The
Nucleophile will be repelled
incoming
by the i of cloud
of denzevering (which
is also
a
Nucleophile) .
That is
why
benzere or substituted

give Electrophilic subs" reach

benzene .

⑦
Nat
&So
NaOH ,
G
01
I
/ H
-

-
I -> -
11- 101
Iu
350C 300 ath 0
,

- -

[01
⑦

Nat

I
I
/ - ⑰ & I
NaUl Acid --
I
101
->
-
B as
+

10
Meas

Acidic
-
Salt
a

-
A
OH
I
s
10 I Mark th, --
10 I
,

⑰
- (ii) H
-
= This is known as Dow's proces
.

C 01
A Cis Naon 178) A
10 / 101
,
-->
(ii) n

Fr
-

No +M
 Erron
01

Cis NaON 95° ANZ

101
,
--
- (ii) H
*
-
viz Miz
a

N
02 A
↳
-
NVz OH

10 I
NOZ
e --
Nau
a

NE
10 I
You
Fi