Physical Properties &

Chemical Properties of Alkyl Halides

-
Physical Properties: •

Physical state
Point
→
Boiling
•
Cs -

Ca : Gases .

Melting Point

• Cs -
Cs : liquid .

Solubility
•
Cq - - - -
: solids
Density
•
Dipole moment
(RF ; RCI ) : Gaseous
( RBV ; RI
) :
solids liquid

Boiling Point : ✗ strength of Intra - molecular

forces
G
R
Part functional group
Hydrocarbon
 8-1 5-

. Intermolecular ✗ charity : C -

G
'
Forces ✗ Vanderwaal F> a > Br > I

forces (Electronegativity)

Mo surface area ✗ 1-

* Observe :
branching
RH < RX < ROH ( increasing )
B. :P

(
No
polarity t, highly polar (H -

bonding)
( weakly
polar)
* observe :
cnzffcyzclgcnzB.rs CUZI (B.D)
increasing Mo ( overpowers polarity) ; increasing B. P

Note :
Among poly - halides - . .

<
Chzclz L Ch C) <
angel 3 cclq
increasing Mo 7 increasing B.PT
;
Recall B. P of Isomeric Pentanes :

> >
•

decreasing surface area ¢ lesser vanderwaal forced

•

decreasing boiling point

✗
> > -

Melting point : more or less ~~ Boiling point except

when
symmetry becomes the
key factor
* neo -

pentane (among the

pentane is most symmetric ;

hence its M.P is highest among pentane s - .

.

✗
-
< ✗
<
solubility (a) in Hzo (b) in organic
( polar protic) solvents .

Note : A solute is soluble in water ( polar) only if :

it to H water
is able break
existing bonding OR
-

• it is able to form new H -

bond with water

obs : RX must be less soluble in water (? ) .

. - . . .
.

' '

RX being less polar are unable to

form H - bonds

with water

* However alkyl halides are

highly soluble in
,

Non -

polar solvents such as : benzene, Celia ,

Toluene

petroleum products, xylene

¥t such as Acetone ;
ethers
(THF)
0
e.
g
Density : CRF & RCI
) are
lighter than Hao
& RI
(RBr ) are heavier than Hzo
because of high hot . masses of Br&I
Obs :
Increasing density : Cltzcl < check <
Chaz < Cci

↳ ✗ No .
of halogen atoms Mo
)

:@
9
d)
I

Dipole Moment =
qx or o -

↳ band length :
CIX
8-1 8- "

E- I
writ
Polarity : C -

F > c- Cl > C- Br >

Wirt bond length : C -

F < c- et 2C -

Br 2C I -

§ §
smallest
largest
Dipole moment (A) : Net in
'

will be decided by
'
'

optimisation of I
'
d'
q
order . - - . .

µ :
CHZCI > c4zF > cuz -
Br > cuz -
I

Bond Energy : ( B. D. E)
Observe : C -
F > c- a > c- Br > c- I
§ §
strongest ? weakest ?
because of
because of
very small size
atom
large size
off -

of I -
atom
 CHEMICAL PROPERTIES Of Alkyl Halides:

1. Nucleophilic Substitution ( SN )
2. Elimination Reaction ( E)

3. Action of Heat
4. Wurtz Reaction
5. Reaction with Metals (formation of organo - metallic)

6. Reduction
7. Isomerisation
1. Nucleophilic Substitution ( Sm )
solvent
RX 1- NUYHNU R Nu
-
+ ✗ THX
substrate
Reagent Snl Product

leaving group
ontic Aprotic
Analysis of SN Reaction :

1. w.at Substrate

2. w.r.li leaving group

3. W.r.li Solvent

4. w.r.li Nucleophile
Understanding SN in two
ways ( paths) : Path -
I / Path -
I

observe an alkyl halide :

> C- I ]
n E-
-
sort
c- ✗ •
observe polarity
⇐ I) ✗
I
electrophilicof
Observe
•→
Sps hybridise
-

nature
a- a
path -
I. :

\s+-
vu- + - c -
✗
←
Nu - d- + x
-

/ 1
electrophilic
substrate ( SN product
path I -

E-
=§+_ § ( )
-1 -
ionisation
-
+ ×

an intermediate ( carbocation)

-1g
-1

dy
+ Nu
-
-
Nu
1. W.r.li Substrate :

RX : ✗ f- FJ CI Br I
, ,

1° 2° 3° -3°
cyclo alkyl
alkyl ; 2° &
, ,

allylic & benzylic

•
Ease of SN Rxn : RI > RBR > RCI RF

( In general)
In Path Rxn 1° > 2°R× 3° RX
•
-
I
; ease
of ? RX

benzylic > allylic > L°R×

.su Path -
II ; ease of Rxn :

3°R× I benzylic 7- allylic > 2°R× L°R×

Note : Path -
I
depends upon stability of carbocation

( benzylic ~
allylic ~ 3.
{+ > 2%-1 1%+3
2 .
Wir .
t leaving group :

(a) Focus on B. D. E of C -
X bond

C- F > c- Cl > c- Br > C -

F
q pweakest
strongest

easy to break
difficult to break

F-
or a
good
or is poor leaving group
leaving group
Ease of Rxn :
RI > R Br > RCI R -
F

Isn )
Observe that F-
among halides ions
,
is strong base whearas
weak base
-

I is
1.1.1 .
(b) Focus on stability of leaving group :

R
LL Tearing
R -
L + Nui >
-
Nu 1-

:
group
Obs :
usually b- is a
good leaving grip only if it is

able to stabilise its ve

charge
-

How to decide ?
halide 1.1
-

consider ion I best

.
is
leaving group
-

• I
being large in size is able to stabilise

( disperse/ polarise / delocalise

) its -
ve
charge
( electron )
cloud
• this makes it stable
ie
intensely I becomes weak base
-

observe
-

more - - - - a

proton affinity decreases

Finally : criteria of a
good leaving group
is :

A WEAK BASE is a
good leaving group .
How to proceed .
? visualise the acidity of conjugate
acids of various leaving groups
? -

Fj
-

CT,
-

Br ,
I

Observe the decreasing acidity of HX .

HI > HBV > Act > HF

increasing basic character of conjugate bases ]

< CT F-
-

I S Br <
-

Is ; being weakest base is Best leaving Group &

F- i
being strongest base is Poorest leaving
group
RI > RBV > RCI RF

decreasing ease
of.SN reaction
Note : Some
Important leaving group [ Good ones
)

( CID O
- - -

* ✗ I > Bv >
; Hzo ; R -
c -

0
carboxylate ion

* sulfonates : R -
o - I -0 Alkyl sulphate
"
o
0

% 11
*
sulphonate s : -0 tolesylateion
-

R -
s ; cuz
-
s -
o

alkyl (Methyl sulfonate

sulphonate
; Cfz -505 Triflate :
0
11 ( super leaving group)
off
s -

me
-

Trifluoromethyl sulphonate

p -
Tolyl sulphonate ( Tos> late ion )
3. w.at Solvent : Aprotic & Photic

CH> COCU
} ; THF Hzo ,
ROH

DMSO j DMF B-Coon

( dimethyl (dimethyl NH3
suephoxide form amide

Aprotic solvents favour path -

I - ( why 2)
↳ Non -

ionising solvents

observe that path -

I does not required ionisation

path -
I :

hi +
IE ✗
o -

Nu - d- + x
-

/ 1
electrophilic
substrate ( SN product
 Photic solvents favour Path -
II .
Why ?

Path I-

E- § )
+
-
-
-1
+ ×
-
( ionisation

an intermediate ( carbocation)

-1g
-1

dy
+ Nu
-
-
Nu

observe that Path -

II
requires ionisation of substrate

for the formation of carbocation .

Protic solvents are

Ionising in nature .
4. iv. v. t Nucleophile :

solvent R Nu
-

Rx Nu X
-

+ + Leaving
-

← group
substrate SN product

Nu ? electron rich species ; looking to

-

: an

attack/ approach an
electrophilic substrate
or adds to a
free electrophile ( like Rt)

Nucleophilic character = SN reactions

Base character
= Elimination (E) reactions .
A nucleophile also shows

basic character & vice-versa

SN & E will always

compete with each other .
Nucleophilic character : Tendency of a
species to donate
share its electron cloud with others ?
or
give away or

(a) electrophilic substrate or (b) Free electrophiles

Basic character : If nucleophilic character is towards
this

Proton ( Ht) ; it is refers to as

a

Proton Affinity or Basic character .

Note : All Nucleophiles ( SW) are also bases (E)

RX + Nu -
SN Product
↳
as Base Alkene (E products)
-

Q ? •
Mixture of SN IE

•
only SN
•

only E
Types of Nucleophiles :

(I ) Nucleophiles which do ONLY SN reactions (whose

nucleophilic character is dominant over their

basic character ) irrespective of type of substrate .

( NÉH's) 5-
( Naas) sulphide
-

HS :
hydrogen sulphide :

Rs ( R5Ña) Alkyl sulphide ( liaercaptide)

-

( NII) ion
-

I : iodide

Nj ( N+aÑz) : Azide ion * All these

nucleophiles
R -5 (Rco5N+a) : carboxylate ion do SN only
§
-

_cu(co0Et)z : tnalonoate ion

Note : Malon oate : Eu Goo Et ,

Eto"
CHZCCOOH) > EH - (coottz : Diethyl malonoate
Ht
✗

cuz (COO Etz

d-
Methylene
-

.
22-4 : Acidic why ?
-

(COOETJ ,

( Active methylene B- = EWG

Base
>
T4(c°°Et)z : Malon oate ion

(A very good
nucleophile
R X : substrate
SNPwdud
-

⇐ F)
Na+H5 + R -

X > H -
S -
R Thio -
alcohol

R'-5 Nat + Rx > R' -

S -
R Thio -
ether

N+aÉ + RX > I -
R Alkyl iodide

(✗ * I)

Na+Nj + Rx > Nz -
R Alkyl azide

R'-co5N+a + R X R' -0 R Ester

§
-
- -

c-
4400ft ,
+ R -
X >

n R -
CH (COOEE)z
Base
higher diester
cHz(cooEt)z (alkylated)
Diester_
: Nucleophiles which have strong Nucleophilic character
and a
good base character ( where nucleophilic
character is dominant
such Nucleophiles give SN product mainly except
some cases where E
product is
major ( where ?)

IN ( Kavala ) : cyanide
R C _=E ( R ⇐ c- Nat ) : Alkynide ion
-
-

pi 12+5;
ÉM§
8-
✗ Alkyl carbanion

Rzculi
-

H LiAlHq :
Hydride ion

•
meta/ lies
organo
-
 -04 :
Kotlaq / Naotlaq
ion
: Moist
Agzo =
Agotlaq :
Hydroxide
-

. KOH conc

Note : All of above nucleophiles do SN reactions

halides ( alkyl
&
cyclo alkyls)
in 1° 2° &

whereas
they do E reaction in 30 halides

including cyclo alkyl .

RX

✗ IF RX 1- KCN RCN alkyl cyanide

ale

R -1-30 RX + Rt -c=ENa+ RLC _=c -

R

higher alkynes
Rx + R' LE
-

R - pi
( organo - metalics) higher alkanes

( unsymm alkane)
R' zculi
.

+
Corey -
House Sxn .
 RH
-

RX + H > : Alkanes
4
LiA1Hq
(reducing agent [ Redn . of alkyl halides]
Roy + OH
_aq R -04 : alcohols

IMP NOTE : RX t Nui E product is

major
(12--30) Base character is
dominant 3° halide
Type II
-

against
Gt3 CUZ
cÑa1c
e.
g. cuz -
d - Br cuz D=
-

cuz

12=30
£43 131-0=5 .
lsobutene
•
an alkene
E product
-

H -

on
-

Conc
type -
II : Nucleophiles strong bases
which are
very
( also good nucleophilic character giving
E
product as major except few cases ??

E- dominates product
product over SN ,

° Hz : Nanna : Amide ion ( strongest

or
KNHZ base)
alcoholic
-

ROH
OH
very good base
•
= : : A
ale
KOU you

• RE : Alkoxide ion : R5N+a : A

good base

or REIÉ

ale . KOH ,
• ROH 1- Na RENEE
ork
•

Ron + Kon → ak . KOH

•
2X + Na+NÑz E-product is
major
1° 2° 3°
, , (No SN product)

RX 1- KOUROU
major
•

E-product is
10,2° 3° date Kob
(No
,
product
.

SN
or Thala .

• RX + R' ONE
- R' -0 -
R an ether
go
alkoxide (SN product
-
RX + R' ONE E product ( an alkene
)
20/30 is
major however

Sao can be MINOR ,

 II Neutral Nucleophiles ( having ep ÉorN)
type : : : over

Hz RCO.0.tl
^

; R.0.tl ,

ivies ; Riruz ; Raisin ; Rzii

EH , ; Risks ; Rain ; R ]É ( Phosphines)

• All of these are weak Nucleophiles & weak bases
•
Usually they do SN reactions mainly except when
temperature is high they can also give G- products
, .

RX + Hzo Roy : an alcohol

+ R' 04 R -
O -
R
'
: an ether
 ' '
Rx + R R -012 ester
§
- c-on -
: an

RX t NHS 3- Nhz : a 1° amine

+ R' Nu ,
R -
Nn R -
'
: a 2° amine

+ RINN ,
R -

NRI : a 3° amine

Note :

RX 1- 133N R
] ,Ñ 15 : a 4° tetra alkyl

R ammonium halide

La salt
RX 1- Rzp R5§Ñ : a 4° tetraalkyl
R
phosfshoniom ion
Special case : Ambident Nucleophile
2' attack
species having nucleophilic sites to

Nu -
I
* IN :

Nu -
I

•
TSIN : + Rx RCN ( cyanide)
(ionic

Ñ=c
Ag CN : + Rx RNC = R -

( covalent) ( isocyanide) or R - N C
 -
Noz : -
O -
N = 0 : -
N=° I
- Ñ -10
→ o to -

KNOZ : K+ ENO
-

(ionic)
RX + ÑÉNO R -0^1=0 : Alkyl Nitrite
AgN0z :

covalent : Nito alkanes

RX +
Ag - Ñ=o R - µ+,=0
to
%
-

k+5cN RX R -

SCN alkyl thiocyanate

(ionic

Ag SCN : + RX R -
NCS alkyl isothiocyanate
covalent
Note : KNOZ / AgN0z : react only with 1%0 →
SN
 Alkyl Halides | Memory Map | Nucleophilic Substitution
KNO2/AgNO2 NaHS
R - ONO/R - NO2 -

R% - SH
(R # 3!)

R - OH Moist Ag2O NaSR

R -FT
X-R
R = 3! > 2! > 1!

(
R - OH Aqueous KOH (dilute) R% ' C & C ' Na R - C & C - R%
3! > 2! > 1! (R # 3!)

R - OH Conc. KOH LiAlH4 (H') R-H

(R # 3!) (R # 3!)

Alkene
3! > 2! > 1!
Alc. KOH _
R X
R_X NH3
Alc.
R ' NH2
RX
3 moles
R
R-N-R
R
N3
R - O - R% R%O '
R% = 1! or 2! R - N3
R = 1! only

RCN Alc. KCN R%OH R - O - R%

(R # 3!) (3! > 2! > 1!)

Alc. AgCN NaI

R - NC R-I
Acetone

R - O - C - R% R%COONa RMgX
R-R
O

3! > 2! > 1! " Means : Reactivity order is 3! > 2! > 1! Reactivity of Halides : RI > RBr > RCl >> RF
R # 3!$$$" Means : Reactivity order is 1! > 2! 3! If R = 3! elimination will occur instead of substitution
2 .
Elimination : ✗ -
Elimination ( 1,1 elimn)
( Dehydro halogenation
B- Elimination ( 1,2 -

Elimn
Reagent : ale . KOH

(KOU/ Ron) = Ohata : Does Elimination in

10,293° substrates

* d- Elimination :
-

Oh alc
Enact HCl + 8cm, : Carbene
ha 1<0%-1-04 I
• a FR acts

4- E- Jude reagent
" as

- Ha +
c , 8cal ,
d, Calc Kon )

(chloroform) ( dichlorocarbene)
FR acts as reagent
* B- Elimination : ( 1,2 -
elimn )
Hp
B-
B- + c- É , c c + Bn + X
-

B base
Base an alkene
×

•
B- : as base Cioemores P H & substrate
abstracts -

simple loses d- halogen simultaneously to give

an alkene ( E product

• Observe that B- elimination is an Anti -

elimination
ire ✗ -
X &
P -
H are removed from opposite
side

tole : ÑH
, / On
-ak = B- = E
product is 1%20/30
Note : observe the ease of B- elimination :

3°R× > 2°R× > 1° Rx

?
why
•
p -
elimination follows Saytzeff Rule ?
•
Stability of alkene ( E product) is the

key to
B- elimination .

"

Saytzeff 's Rule : A more alkylated alkene is more

"
stable
-
-

É
.

c-if.I.ci
Hz
C- -
Br stable
ovale
•

or
C
C

Ñhz
less stable
÷;
•
c-c-c
c-

BV
1 or
Onate

③ RBv > 2°RBr )

Use of Alkoxide ion ( R'0 Ña) :

! ONE
'
• Rx + R R -0 -

⇐ only)
* Alkoxide give SN ( ether product with 1° alkyl halide
'
R = 1° 2°
,

3° ( why ?)
Note : Above case is referred as Williamson 's
synthesis
( of ethers
( E- product is 1%0
but not 3°
formed ) ?
 20/302/1 1- R' Oita E
product ( Major)

Et5Ña
⇐
+ > Eto cuzcnz
cnzCUzBr
-
•

60°C

(5) Ethoxide Eton Diethyl ether

CSN)
60°C
9ezCHENa+
ezcyoymez.CH Cllzchz
-0 -

2°

Ethyl isopropyl
ether
( N)
+ the
>
C- 5M£ É '

occurs
!
Me> C-04
zo Why ?

C-ertbutoxide
 +II
But oxide
* Tert :
pre → electron rich
Me -
c
→
• I t
+I Mef + I
strongly basic

ineji::-O
-

'

-
.
. .

+I
(3%2) :
strong
&
* Tert butoxide is
sterically hindered bulky
base ; hence it fails to attack 1° d-C
g. 1.1
it able abstract B- 4 to
.

but is to

alkene
give an .

No SN Product
Importance of Saytzeff product (stability in
B- Elimination

Up
Eto Nat
•
I •
Br
+ ETOH
Eton A-
,

( cyclohexane) + Na Br

ch 3
Eto Nat Ch
]
•
cuz
-
Én^±d• dñ, -

Eton cuz cuz

- - d- cuz
130 ,

Br ( Anti Saytzeff)
-

less alkylated
cuz
( MINOR)
=D CU
cnzch
-

( say tuff product

More alkylated ( Major)
𝓚𝓲𝓷𝓮𝓶𝓪𝓽𝓲𝓬𝓼

𝓜𝓸𝓽𝓲𝓸𝓷
𝓘𝓷
2𝓓

ℙ𝕒𝕘𝕖 ℕ𝕠. 𝕷𝖎𝖌𝖍𝖙 - 𝕽𝖊𝖋𝖑𝖊𝖈𝖙𝖎𝖔𝖓 & 𝕽𝖊𝖋𝖗𝖆𝖈𝖙𝖎𝖔𝖓