2

Chemical Properties-I
-

·
 CHEMICAL PROPERTIES Of Alkyl Halides:

1. Nucleophilic Substitution (SN)

2. Elimination Reaction (E) (OC 1)
-
V

3. Action of Heat alkene

4. Wurtz Reaction xith F

5. Reaction with Metals (formation of organo-metallic

6. Reduction RX
redn
RH

7. Isomerisation Skelton of substrate undergoes

rearrangement
1. Nucleophilic Substitution (SN)

solvent
RX + Nu- R-Nu t X-

substrate reagent SN leaving

Selectrophilic) (nucleophile) group

Protic Aprotic

nalysis of SN Reaction :

1
. w r
. . Substrate
t

2
. writ
leaving group
3 w u . . f solvent

Nucleophile
4
. w v t. .
 2
Understanding SN reaction in
ways 2
possible paths
substrate : + 5 -

Polar)
C X
electrophilic
T
-
=> an

+I
(I) Substrate

Path -
I

o
Slow ERDS
2t
-

t X
onisation
carbocation
of substrate
· a
Step-1
stability 33+> 2+ D1x
·
=
+
R Vn- 2 Nu
fast
=> Path is Unimolecular or order of Rxn = 1

Hence the product formed a

SN1
Path -
I product
&+ Slow I- &+
8- -
* -

Nut R- X Nu - ---R--- X . Nu-R + X

&
RDS

Nu-makes an attack at X-C to form a TS

.

RDS RXn is Bimolecular Sp

?
= a

3 or 0 . R = 2 product
 Cl
1
. w r .
t substrate : R-X ( + F)
Bu
.

Types F

Alky) (10 ; 20 30) cycloalkyl (20; 3)

%
&
; ;

* Basic ease of RXU allylic (10 ; 3) ,

2
; benzylic
RI > FBr > R-C1 D R =
F (10 ,
2
, 39
Path-I :
SN1 : Focus is on
stability of Carbocation
%
3
rX
> 22X1RX >) CH3 X

Benzylic >allylic .
> Tert
Path-I SNz : observe that
LRX( & CX) do not

follow Sir path (3) since 1+ (b)

are
poorly stable.
CRX > 2XD) 3RX
IMP : °
donot follow SN2 path
benzylic > allylic > 1 RX

(in SN2 Path) !1 .

.
2 W r
. . t
leaving group : ease
of reaction : RIXRBUYRUDRF

(a) w r
. . t B D E
. .

of C-X bond

Observe that :

C -
F > c -
C > C- Br > C
-
I

5 *
· B . D E :. highest B :
DE : Lowest
·

strongest bund !I · weakest bond !

Every small size ·

very large size

of Fatom) of I-atom

H II
Y
F- is a
poor leaving I is the best
it is difficult to
as
leaving group as

break for both

SNY/sx2 it is
very easy
Paths to break this bond

Clearly ease of via both SNYSN2

Paths
SNda SN2 : RI <RBr >RD DRF
No SN Rxus
(b) Focus
leaving (X halides)
on
stability of group : :

i+ 8
NU
-

RL R -
Nu + L
-
> I will be a
good leaving
group only it is able to

Stabilise
(itself) its electron cloud
(-recharge) !I How to
decide
Please consider Fion ?
(which we know is a
good leaving group)

it is a
large sized species !
being large in size
,
it stabilises its
negative by
polarising/dispensing it over a
large area
Recall it
·
that
property of
is a weak base a

Criteria of a
leaving group (Good) is that ?
"
A weak base is good leaving a
group
Sn
general; How to think of basic charader of an

anion ) obviously leaving group) ?

line CT Br, F F-
up : , ,

* Visualise their conjugate acids.

HI HE
HCl HBr

Audic
*
Arrange these as
per their
strengths .

Clearly ; HI > -Bu > HC > HF

↓
strong weakest and
acid
N
& weakest F- is strongest base
Base
Conjugate of tid
strong is Weaker & Vice-Versa
*
of base a
3
. w r . . t solvents :

* Protic Solvents :
Ot
Ho ; R-O-H
&+

; R-Pot
ItN-fot
solvents
· are
highly ionising
(polarising solvents)
=> Profic solvents will favor SNd Path /Carbocation

e 2oRX like both SN' & SN2 formation)

g
.

Nut looks
=> 3rX SN1 Path
Ho dominant
*
Aprotic Solvents :
St
O
Me
OSt
Acetone ; H- N-
Xi CH3-s-ci
-

+
St -Me
coCH] THE
DMSO DMF
·
these solvents are
Non-ionising ; Hence will
favour
Paths
SN2 mainly
. Nut
eg
. UhCHaBr SN1
As

DMSO SN2
4
. w v
. .
t
Nucleophiles : (Ni)
What is a
nucleophile ?

an electron rich
species ; looking to
approach/attack
Nu-
an electron deficient species/regions or it simply add

to a
free naked electrophile .

Proton
also has Basic character ie.
affinity
if love of a nuchophile 7. tendency to share

its electron cloud with a PROTON (ht) ; it

is
referred to as Basic Character
of a nucleophile
if it shares itse-cloud with an
-
A- substrate
electrophilic = Sv Reaction
e-rich species
>
-
if it removes a
proton = E reaction

* All Ni are bases & vice-versa

& Vice-versa
it All bases are abo
nucleophiles
=> So & E reactions will compelete against
each other .

Nut
RX SN

base
E

*
usually both Si &E products are formed with one

of them will be
major
)
%

*
if only SN is
Major Jusually at room T = 25

only Major Jusally at high C)

%
* if E is +3
,
100

· other factors controlling SNVs E are :

types of substrates ; types of nucleophiles

& temperature
Types of Nucleophiles :

C Nucleophiles which do ONLY SN reaction (whose

nucleophilic character is dominant over basic character)
irrespective of type of substrate.
· HS- (NHS) hydrogen sulphide
- t
· Rs (RSNa) alkyl sulphide (mercaptide)
& I- (NE) iodide

N (NaNz) azide

(Rcnta) Carboxylation
R--
·

All of above will do

only SN Reactions
 2- X : Substrate

(X + F)
NaNs 2-X -
2 - N3 (Alkylazida)
NHS 2 -
X- 2 -
SH (This alcohols)
NR /

2 -
X -
2 -
S R
-

(This-ethers)
NaF- 2 -
X 2 -
I
(todides)

R- 2 X 2 0
c (Esters)
-
-
-
-

· SN Product only
· NO E vxn here
Seven as Minor)
Te
I Nucleophiles which have
strong uncleophilic
character and also a
good basic character as well.

(though Ni character is dominant)

=> SN product will
usually be
major ! 1.
&
yel
Look for cases/Nu type where E'product
IN will be
·

(KCNal/NaCWald) cyanide major

· R-CE (RCEN) alkynide
- +
- R Rhi alkyl carbanian
E-

R2MgB
R2Culi
-

·
H 7
LiAH/ether Hydride ion

Ottag/Naolaq
-

·
OH hydroxide
MoistAgOE AgOH
KOH
conc?
Note that all of above
always do SN in %0 alkyl
1 halide

Whereas
many of them will do E in 30 alkyl halide

R-X : Alkyl halide (including 20

X #F
cycloalkyl halides)
EtoH
R-X R-CN Jalkyl cyanide)
+ KCNak
R-X + RICECNat >
- R-CEC-RI (a higher allynide)
RL (higher alkane)
!
R-X + R-R
I
+
RMgX
+ Raculi
R X
Can alkane)
-
-
H R -
H

+ -
LiA/ether
↓ Nat 2- H
 R-X + Kottag
does SN in % % 30
2 2

+
Agzo Calcohol)
moist R-OH
hydrolysis +
Ag ottaq
of ↓ Kott conc
alkyl halides
Observe : R #30 in all of above

If R = 30 CH3 KCN
'Only (Major cases

I E
CH3-c-Br al CH2 = C- CH3
+z - t ki (isobutene)
RCEC-NaE
.

99
Kott an E-product
Mez C-OH
Ho LiAIH4E 99 · No SA
laq) ether
product
Du) 10H

(av
Eee
Conc
Type & abo
Nucleophils which are
very strong bases

character is very
good nucleophiles but their base

Dominant & hence

they do
mainly E in all
1
, 2030 substrates
except a
special case

whereIn occurs
!
NH2 (NaNHa)kNH2) Amide ion
superstronga
·
: :

alcoholic koh EHa A

very good
·
:
Rot
base

Ro-(RON)
alkoxide on he A base
·
E :
good

& alKOH Note : ROH + KOH- > NORxy

RE
ROH +
Nay,
-
 RX + MNT E
only (No SN Product)
(r = 29 20
, , 39 an alkene

I'
only
Ho a
RX -
an alkene

(r = 29 20
, , 39 (No SN Product)

R -
X + Ro E occurs + SN Minor
R'Ot
2
% 30

RX + Ro SN occurs - E : Minor

1
o
ROt as
Major product
· When RX is 10 ; then ·
Ether R-O-R/
ether formation is
SN Product
known as
Williamson's Synthesis
Type-IV : ·
Neutral
nucleophiles
·

ep over i' i' &' atoms works as

,

nucleophilic centre

H R
* ; ;
R
*H ; R ; ReNH ; RsN Amine

*
ii Rit ; Ri ; Rep Phosphines
Weak bases &
Note : * All of these are Weak Nu
*
Usually they do SN reactions but at high
lamp (T-100 +1 70c) ; they will do E' as well
 SN Product
⑧ RX Nitz alc
R-NH
Nu
(substrate)
. as

Cfastery
R- + RX
RzNH SN Product
as Nu

Rit + RX
RzN SN Product

as Nu

RN : + RX RpX-4 (qual)
to tra alkyl
as Nu
a mm . Salt
𝓚𝓲𝓷𝓮𝓶𝓪𝓽𝓲𝓬𝓼

𝓜𝓸𝓽𝓲𝓸𝓷
𝓘𝓷
2𝓓

ℙ𝕒𝕘𝕖 ℕ𝕠. 𝕷𝖎𝖌𝖍𝖙 - 𝕽𝖊𝖋𝖑𝖊𝖈𝖙𝖎𝖔𝖓 & 𝕽𝖊𝖋𝖗𝖆𝖈𝖙𝖎𝖔𝖓