CLASS - 6

ALKENES
• Chemical Properties-III
Properties Of Alkenes :

€€€
Physical Properties
Chemical Properties
CHEMICAL PROPERTIES:
(A) Addition Reactions
(B) Oxidation in Alkenes
(C) Substitution in Alkenes
(D) Polymerisation in Alkenes
(A) Addition Reactions:

1. Of Halogen Acids (HX) :X IF

+
2. Of Water in presence of Acid (H ions)
3. Of cold conc. Sulphuric Acid
4. Of Halogens in non-polar or weakly polar solvents ( Cola , ctlzclz )
5. Of Halogens in Water (Polar Solvent)
6. Oxy-mercuration & De-mercuration
7. Hydroboration & De-boration
8. Hydroxylation
9. Hydrogenation
Note : I (b) Addn .
of HBR in Peroxide
(only)
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
te .
. Reaction No .
1
, 2,3 : follow Markovnikov's Addr

(Don't think about syn & anti

'

addn in 1
, 2,43)

• Reaction No ,
445 :
follow ANTI Addis
Rxn . 5 also follow Markovnikov's addn (M -
addn )

Reaction follow Anti addis &

0,5¥
: 6 :
:
.

IN -
addn

follow Synaddn &

H☐B÷
• Reaction : 7 : :

Anti - M -
adds

• Reaction No . 8 & 9 :
follow only SYN -addn

•
Reaction : I (b) : follows Anti -
Markovnikov's
addition
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
Visualise the addn of Braley , in 2- Pantene @ symmetric)
n -

Me Me
H Me
' '

° anti Br H
H
-

Br
+ Brz 1-
H Br
ccl4 Br
-

H
c

Et Et
Et 4

Eis @ is + Anti -

→
Racemic : No Plane
ofsymm .

Me me
H Me
' '

C anti Br H
Br
-

H
+ Brz 1-
ccl4 Br H
-

H Br
c

4 Et Et Et

C-vans) Trans + Anti → Meso but here it is Racemic

mixture as there is
Noplaneofsymmety .

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 Br

cnz
-
ch = cn -

cuz +
Brz/µzO Cuz
-
In -
In -

cuz
*

Cis & Trans )

ton
• Observe I ' chiral centres
22=4 configurations
CH3
.

\ H
c- g- or
-1 Brz
11 1- HO -
Br CAR
H2O
f- a (Anti)
Cltz

Cis) Me me •
Enantiomers
* *
h OH no H .
Racemisation
* + *
Br 4 4 Br
( No plane
me
me of symm)
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
CH }

} -
H
s Ot Brz
Trans Anti Meso
+ ?
-

=
-

11 + HO -

Br
c
Anti -

-
on & -
Br are on same side
/
H ¥3 Me
• but a
Me
Racemic
Crans)
H OH 40 4
Mixture
+
Br H
H Br is
formed
why ?
Me me

* Observe that No PLANE of SYMMETRY is there hence

' '

2 enantiomers are
formed in equi -
molar proportion to

give Racemic Mixture .

* so in this case
,
4 configuration ( all optically active are there .

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

Reaction : 6 1

2.
.

oxymer curation
Derner curation :
:
Hg -@-É-cH3)z TAF
-71-20
NAB
1+4/420
( reduction
- .
Hg (OAC) , / THF -
Hao H

C - c
C -
C
2.
NaBh4/ Hao
04

The reaction is Anti addn .

* follow/s Markovnikov's reaction

* Products are
usually 20/30
* The reaction is
Regio -
selective

* H .
in product comes from NaBH4 ( )
Redn process
.

04 : in product comes from Hzo

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 H
Hg @ Ac)z / THE -
H2O
C C C C 1- CU
] COOH
I
oxymevcuration 0M
Hg - O - c
-93
to
420 H
NABHA De -
1-nercuration

( alcohol ) C
f H2o or On ( Reduction) DM

H
NABHA C- Hg ; -
c4zco0H )
(An anti addn)

1. HGCOAC) / THF ,
-

H2O 4 Me

2.
NaBH4/ V20 Me OH
Me Me
Anti addn Trans product

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 I. 014 it 2° ol
C4zC4 cuz cuz
cuz -44
= -
.

z . ☐ pg

04
TU }
I 0M
OH

cuz
- c =
cuz
.

3° ol
cuz f- cuz
-

2. DIY
cuz H

(Anti addn
)

Note : •
The reaction is Irreversible unlike acid catalysed
H+
hydration . Cuz =
cuz cuz CHZOH
H2O

The reaction does not Involve carbocation no

rearrangement
. so

is
possible .

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 t.H-ATHF-Dzoonz-cib-dn.CH
} / 2. NaBH4 H2O
I
•
City
-
d=CHz OD

" P
1. Hg( Otto)z / THF -
H2O
cuz
_§ >
-
cuz
2. NaBD4 / H2O toy

-1.1-19%2/141=-1320 ☐°

(Trans)
• e
2. NaBH4 / Hao

Antiaddn
Me ne n e

1. 059
N HO
•
2. DM ??
( anti ) & n me
Noa 's
/ trans ! !
Ye
(M addn)
-

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

• Reaction : 7 1.
Hydroboration : 1 .
BHS or 13211-6
/ THF

2 . Deb oration : 2 .
Hzoz
/ -0h (oxidation)

I. BH
,
or
BzH6/ THF
° ° E -
C
2 .
Hzoz/ On

40 H

synaddn .

• The reaction follows syn addn .

• The reaction follows Anti -

Markovnikov's addn .

•
-
H comes from BHS
from Hzoz /
-

-0h Comes OH

1° 2° alcohols formed
•

Usually or are

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 1. 1343 / THE
H H
2.
Hzoz / En syn addy

me me Me me ( Cis)
(syn )
adoin

1. 01^9 it
cuz ch cuz A
Addis
- - -

cnzcn = cuz 2. ☐ Til

4 20 alcohol
-

1. HBO
cuz CH CH .rs
( AM adidn
-

)
-
-

D -130
4
2. 1-
OH

⑤ alcohol)

043
fu ] in
cuz
-1C =
cuz
I .
0M
CHIC .
-

cuz €9 adding
-

2. ☐ in on

0435¥
1 "
V1 -130

qyz@t.MAddrD2.D
.

BO

n -1
_%- Enz ( M addis-

Hzo cuz
ₕydᵣₒcₐᵣbₒₙₛ ton C̲ i ̲r ̲c̲l ̲e̲
 1. OH ,

H
.
HO
2- D M .

H
Ye
r-ne.CM
)
ddn -

a.

•
( Anti)
add n
•
Syn
1 . HBO
OH H
•

2 . D- 0
(Trans)
Me Me
gq

• Anti Maddy

add n
Syw
-

n n
anti addn

Me
40

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

•

Hydroboration :
µ "
cnz =
cuz + H -
BL cuz -

cuz
-
B
/
-
, l H
H
Ethyl borane
/
" (Alkyl borane)
Cuz -

cuz B f- CUZ
-

CUZ
•
=
- µ
I µ
H cuz
'
-
CHIBI
n cuz cuz
'
n
Diethyl borane

( Dialled borane
)
H

Bf + cuz =C4z Check , n

-

cuz _c4z-
' B
#Cuz
n cuz cuz
↳ § cuz-012-4

Triethyl borane
-

( Tri alkyl borane

-

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 Chacha -
H
4202
}
-

B + BO
cuz Cuz C4z04
£42
-
-

on
C. 42-012-4 NaOH

13033
-

Etz B ( Rz B) oxidn Ron +

an alcohol
borate ion
.

Now observe that the reaction is

¥
Naz 1303
Anti -
Markovnikov's addn : -

It

cnzcn =
cuz + u -

Btn cus -

ga
-
cha
-

1342

H
Anti Maddin
-

(w.r.tt) Chzcn -_
cuz
-

"
cnzcn #2

¢43 -
ch -

cuz
)-zB
Ch
z
-
Ch -

cha
-

BT
I In Chz -
ch
'
-

cnz
" n

@ PV)zB
ₕydᵣₒcₐᵣbₒₙₛ
= -

C̲ i ̲r ̲c̲l ̲e̲
@ Propyl
"202
alcohol
nzcn cuz
)zB cnzcy-cuz.org n -
-

in on 4
Anti M addn ( Looe)
-
-

ch3
ft
3
1 opq
d d
.

cuz
-
- ch -

cuz
>
cnz -

'
-
ch -

cuz
2. ☐m
on
M-addn_

">
1. HBO
>
cuz _É -
ch -

cuz
2. DBO ' '
n on

A-M-addn_

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

Reaction -8 :
Hydroxylation : cold alkaline dit .kMn 04
t,
Baeyer 's reagent
C C
kMn0u Coil )
(purplish blue)
Cold , Alkaline
C C
T
purple - bluish .
vicinal diols
on oy

(Baeyer's Reagent) ( Glycols)

Test of Unsaturation : .
colourless

•
alkenes decolourises cold alk . dil kinnoq . side
product
solution or
Baeyer's reagent is dark brown ppt
• alkenes +
Baeyer's reagent → Mn0zµD of 14h02
( dark-brown)
.
It
follows Sywaddn .

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 alk . KMh04

H H

( obviously
cold & DID HO On

syn addn cis product

cis diol
cyclohexane -1,2
-
-

alk . KMNO 4
-

04 40
cis product
line Me
µ

addn
syn

alk - KMNO 4 *
cuz cn =
cuz cuz -
ch -

cuz
' '
on on
• Observe (A) : chiral centre

in the
product →
Racemic Mixture
(I de Mixture
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
cnzcn =
cncnz
alk '

cuz
- Fn -
Fn -

cuz
1
by
kmn 04
on
Csyn)
•
I' chiral centres
cis trans
• 22=4 configurations ??

Me n
C

syn
+ kMn04
alk
C
.

H Meso CSM
Me cis + syn
cis + Anti Racemic CAR

me Me

H OU no 4

H OH
Plane of Symmetry
HO H

Me me
Meso compound
ₕydᵣₒcₐᵣbₒₙₛ only 2
configuration
C̲ i ̲r ̲c̲l ̲e̲
The H
C

syn
+ kMn04
alk
C
.

Me
4
Trans Trans + syn Racemic TSR

ins + Anti Meso TAM

me the

H 04 4
no

HO H H 04

Me Me .

• No
plane of symmetry
-
Non -

Super imposable mirror

images
- Enantiomers in
equi molar
- mixture = Race misabion
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
Reaction : 9 Hydrogenation :
•
Hz
/ Ni 300°C

(reduction .
Hz / Pd - C
/ Eton or Meon

( 1- oatm ; 40 -60°C )
Hz/ Ni D
,
C C C C
or
Hz/ Pd -0
in Meon or
H
Eton
an alkene an alkane
add,
syn
Hz/ Ni 0
,

or
4 Cyclohexane
Hz/ Pd -0
in Meon
cyclohexane u n

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 Hz/ Ni D
,
H H
or
Hz/ Pd -0
Me Me in Meon the
me

Synaddn a cis
product
cis -1,2 -

dimethyl cyclohexane

Dz
D D or h 4
Ni
;
H 7- D D D
H H

cis isomer
synaddn
-

cis -1,2 -
dideut.ro
cyclohexane
Dz
D D
Ni
; cis -1,2 -
didentso -

Me Me
H D
me me 1,2 -
dimethyl cyclo
Synaddn ₕydᵣₒcₐᵣbₒₙₛ hexane
C̲ i ̲r ̲c̲l ̲e̲
 Dz
2- Butene ( Cis / trans) visualise the possible
my ,

products with their

the H
C Dz stereochemistry .

Nila
C
/ H
Me syn
cis

line Me

H D 4
D
Plane of Symmetry
H D -5 H

Me me
Meso compound
only 2
configuration

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

The H
C
Dz

C Nila
Me Trans + syn Racemic TSR
y
syn
Trans É Csm

me the

H D D -
H

D H n ☐

Me me .

• No
plane of symmetry
-
Non -

Super imposable mirror

images
in Racemisation
- Enantiomers equi molar
- mixture :

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

(C) Substitution Reactions in Alkenes :

vinylic H -
atom
-
c -
c - c -
H
Sp3 SPZ
spz

}
"
Allylic
^\
atom
BDE is
very high 1 .

n -

>
( sp s
) :
stronger bond
BDE relatively
-

is
lower
( sp3 ) : -
s
weaker bond

•
Vinylic
.

Allylic
Two
types of substitution

↳ & meaningful
is going to be
Important .

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

*
Vinylio Substitution :

Clz Clow con

c.)
Hzc =
CUZ HzC=C4
500°C
di
PVC (vinyl chloride )
@ polymer)
• Free radical substitution

•
Clz ZCP
A

.ci + H -
C =
cuz HCl + HÉ =
cuz
his vinyl FR
Clz
He =
cuz
① inyl chloride)
{,
-

Ci →
propagates
the reaction

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 substitution
Allylic :
350 -400°C

Cllzcn =
cuz + Clz Cnz -
Ch =
cuz
( low conch
) &,
•
Free radical Rxn Allyl chloride

•
zci ( Do not visualise
•
Clz substitution)
vinylic
CP Ch cuz
+
Hag g-
=
•

5h no + HZÉ -
CU =
cuz

•
Allyl FR

• is resonance

Recall - - . .
HzÉ~_ Cu =Ñz HzC=cn - En
,
stabilised

Resonance stabilisation

hzÉ Clz
ch =cnz 1- Clo
§,hz
-
ch =
cuz -
- - - - -

40
Hzc cn=CUz
-

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

di
Note :
By using Sozclz ( Sulphuryl chloride ,
the above

reaction i-
e
allylic chlorination can be carried

out at 40°C -
60°C .

SOZCIZ
cuz cuz ch cuz
CHZCU = =
-

⇐
Ct
50242
•

☐
CI

50242
•
cuz -
CECH cuz -
CECH

di
A
4
allylic
50202
c43 cuz
-4
=
cuz cuz
g-
-
•

cnz Chzcl

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

Allylic Bsomination :
Bvz
CU cuz
cuz
=

cuz -
Ch = cuz
'
NBS Br

Cola ; 60°C

NBS : N - Bromo succinimide lis cella ( Non-polar solvent)

0
↳ favour FR reaction
CHz-COOU cuz
-

0
NH
Luz -
Coon I
cuz
%
cuz
- -

'
Br
succinic acid 1
-

%
s=Éde -1% NBS

N -
bromosuccinimide
0

I'
0

N3r
cuz
-
"↳ II
Bro +
1 No
cuz
-8 homolylic cleavage 11
0

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 Bro +
{ Uz -
Ch -_ cure HBR + Énz -
ch = cuz
1h2 Allyl FR is
>
resonance stabilised
Bro
Enz -
ch = cuz {
" 2--04=042
( Termination)
Br
Br -
Br

GHz ch =
cuz + Bro
-

Br
(Propagation)
"'
4
Note: NBS sparingly
Non

(polar) polar
soluble → in the
form of FR( Bro +

Bsi FRS are low in concentration ;

NBSFR)

hence not attack bond

they do
-4=9
-

& allyl FR is more stable than alkyl FR

( with reference to
peroxide effect
•

~
1
.

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

Special cases :
NBS
Cms CU Cu
cuz (Br)
cc ,
#
Bro

842 ch =
circus allylic FR
⇐ HBD
- •

-
resonance stabilised

⇐, EÑcn cucnz
=
cuz = CU - EU -

cuz
u

Note : I & I are

different unlike in case
of allyl :
cnz=ChÉUz
(1) Enz -
ch = Cn
cuz B→ cuz -
CU =
circus P-
I
tsr
(E) cuz en En -

cuz P II
cnz
-_
ch ch
cuz __
- -
-

p
Br
Note : P I
-
will be
Major ( why ?)

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 NBS
(Br ) CHzÉÑcn=Ñz I

CU-gcttzcu-cnzc.gg
•
→

allyhz
,
Butene
1- , Bro -2°
Bro Pr * H
; I
I cUzcn=C4É4z cUzCU=cucnz
Meffect
PV
-
1° allylic (10-2) CU
,
-
ch -

ch =CUz
CP -

2)
NBS
cuz visualise -2 ' possible products
cqg
•
,
,

I Br° II
~ o

cuz cuz
✓ z°FR More stable
; IFR ; Bro
less stable
Bro

cuz cuz -
Br

P -
I Chaim ( minor
fz
,
ₕydᵣₒcₐᵣbₒₙₛ P I -

C̲ i ̲r ̲c̲l ̲e̲
 NBS
CH
} cclq ☐
Visualise É '

possible products
,

'
'
z
Allylic position 4 possible products
-

Bro 5° CHZ cH3

CHZ J 0

Bro Bro
P -1
Bro '

Bro Ctlz CHZ

3T
cH3 Br P-2
04
u Br
cH3p_z
MAJOR : P -1 .

Bro
CHZ CHZ
' P 4 -

o Br

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 NBS
Bro
CCI 4
,

4
Cally tic) Bro
C- HBV)

" 30
Gainor
p A

Br

Br

Bro

Chair

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 :

ethene

€€€ vinyl cyanide

(Alkenes
-
are
completed )