Alkenes

Session objectives
1. Kolbes method
2. Dehydration of alcohol
3. Dehydrohalogenation
4. Miscellaneous method

General
characteristics of
alkene
Olefins
General molecular formula CnH2n
CC bond hybridization 1.34 A0
sp2 hybridization
Show chain, positional and geometrical isomerism

General characteristics
of
alkene
Chain isomerism
CH3 CH2 CH2 CH = CH2

H3C CH2 C CH3

CH2
2-methyl-1-butene

Positional isomerism
CH3 - CH2 - CH2 - CH CH2

1-pentene

CH3 - CH2 - CH CH- CH3

2-pentene

General characteristics of
alkene
Geometric isomerism

CH3
H

CH3
H

Cis 2 butene

CH3
H

H
CH3

Trans 2butene

Preparation of alkenes

The Kolbes electrolysis

- +

Anode

CH2COONa

Electric
current

- +

CH2COONa

2Na+

+2e
-2e

Dimerization

CH2
(Major)

CH2COO
CH2COO

sodium succinate

(Minor)
CH2

Cathode

2Na

.CH

CH2COO

. CH

-2CO2

CH2COO

H2O

2NaOH + H2

o
n
.1
c
H
S
O
2
4
C
6
0

Dehydration of
alcohols
(E1 - elimination)
CH3CH2CH2OH

CH3CH = CH2+ H2O

OH

Conc. H2SO4

CH3CH2CH2CH2OH

Al2O3
300 C

+ H2O

CH3CH2CH CH2
1-butene

-H
O
2
H

Mechanism
CH3 - CH2 - CH2 - OH

H+

CH3 - CH2 - CH2 - OH+

2

Oxonium ion

CH3 CH2 CH2

Carbocation

CH3 CH CH2
H

CH3 CH CH2
1 propene

Features of dehydration

A carbocation is formed as an
intermediate.

The ease of dehydration of alcohols

is 3 > 2 > 1
3 carbocation is most stable
H

R
R

OH >

H
OH >

30

20

10

OH

Features of dehydration

The stability of alkenes is

governed by Saytzeffs rule

R2C C R2

R2C CH R R2C CH2 ~ RCH CHR RCH CH2

loss of H2O

OH
H3C C

CH3
3

CH2

CH3

from 1, 2
position
loss of H2O
from 1, 3
position

CH3

CH

CH3

CH3
(major)
CH3

CH2

CH2
(Minor)

CH3

Features of dehydration

Dehydrohalogenation of alkyl halides:

(E2 or 1,2-elimination or -elimination)
H

2
CH2

1
CH2

Alc.KOH

CH2

+ H2O

CH2 + KBr

Br

Mechanism

OH

H H

C
Br

OH

Slow
C
H

C
H
Br

Transition state

+ Br- + H2O
H

Features of dehydration
Stereochemically, the best conformation
for elimination is the anti-coplanar
conformation, i.e. the three bonds HC,
CC and CBr are in one plane.
There is no formation of any intermediate in this reaction,
rather it proceeds through a transition state.
A trans- or anti- elimination in which the atoms leave
from the opposite sides is observed in most cases
The reaction is thus stereospecific, since a base pulls a
hydrogen, a strong base will accelerate E2 elimination.
predominant formation of a substituted alkene is formed
according to Saytzeffs rule

lc.K
O
H
A

Features of dehydration
CH3 - CH2 - CH2 - CH3
|
Br

CH3 - CH = CH- CH3 +CH3 - CH2 - CH = CH2

Major

Minor

H
atC
3

Hoffmans elimination
If the leaving group is very strong
electron-attracting, then elimination
takes place contrary to Saytzeffs
rule. The formation of a less
substituted alkene is observed.

The H at C1 is more acidic than

and is preferably pulled by the base.

Hoffmans elimination
CH3

CH2

CH2

CH CH3

C 2H5 O Na
C 2H5 OH

+N(CH )
3 3

CH3CH2CH2CH
Majo

CH2 + CH3CH2CH
Mino

CHCH3

Miscellaneous Methods
Debromination of vicinal dibromides
Zn/HOAC

Br

H
Na
acetone

Br

CH2
Br

Zn

+ ZnBr2

C
H

Br

CH

H
C

C
H

H
CH

+ I2 +2 NaBr

CH2

ZnBr2

Miscellaneous
Methods
Corey-House method
Cl

+ (CH2

CH)2CuLi

CH

CH2 + LiCl + CH3CH2Cu

Wittig reaction
O
(C6H5)3P

CH2

CH2 + (C6H5)3P
Methylene cyclohexane

Miscellaneous
Methods
Catalytic dehydrogenation

CH3CH2 CH2CH3

CrO3

CH3CH2CH CH2

Class exercise

C
H2C
C

C
H

C
H
C
H
C
H
2
3
2
2
H
3
C
H

C
H

C
H
2C
2
3
C
H3

Class
Exercise
1
Acetone reacts with
Ph3P+ CH CH3 gives
(a)

(c)

(b)

(d) None of these

Solution:

Wittig reaction.

CH2 C
CH3

Hence, the answer is (b).

CH2 CH3

Class Exercise 2
How many and bonds are present in
1,3-butadiene?
(a) 6
(c) 9

and 2

(b) 2

and 2

and 2

(d) 6

and 6

Solution:

9 and 2 bonds.

CH2 = CH CH = CH2

Hence, the answer is (c).

C
H

C
H

C
H

C
H
32
3
2
3
sp
a
n
d
sp

Class
Exercise
3
Which hybrid orbital/orbitals will form
the following compound?

(a)

(b) Only

(c) sp and

(d) sp and

Solution:

sp2, sp3 from the structure.

Hence, the answer is (a).

Class
Exercise
4
When an aqueous solution of sodium
acetate and sodium propionate is
electrolyzed, one gets
(a) ethane

(b) propane

(c) butane

(d) All of these

Solution:
Along with normal butane we get
unwanted product like ethane,
propane, etc.
Hence, the answer is (d).

Class
Exercise
5
Which has the least heat
of hydrogenation?

(a) 1, 3-butadiene

(b) 1-butene

(c) Trans-2-butene

(d) Cis-2-butene

Solution:
trans-2-butene is maximum stable.
Therefore, heat of hydrogenation
will be least.

Hence, the answer is (c).

C
H
3
H
C
H
C
H2 C
C
3
C
H3

Class
Exercise
6
The IUPAC name of
is

(a) 3, 3, 3-trimethyl-1-propene
(b) 3,3-dimethyl but-1-ene
(c) 1,1,1-trimethyl-2-propene
(d) 2,2-dimethyl-3-butene
Solution:
3,3-dimethyl but-1-ene
Hence, the answer is (b).

Class Exercise 7

Which of the following is a false

statement?

(a) There is sp3 hydridization in propane

(b) Ethyne has a linear structure
(c) There is sp2 hybridization in ethylene
(d) Alkynes show geometric isomerism
Solution:
Alkynes do not show geometrical
isomerism because it is a linear
structure.

Hence, the answer is (d).

Class Exercise - 8

Which of the following types of

isomerism is not exhibited by alkenes?
(a) Position isomerism
(b) Chain isomerism
(c) Geometric isomerism
(d) Metamerism
Solution:
Metamerism will not be
shown by alkenes.
Hence, the answer is (d).

H
3
H
C
H
C
H2 C
H
3 C
C
C
H
H
3C
3
C
H
3C
C
H
3
C
H2C
H2 C
H3
H
3C

Class
Exercise
9
Which of the following alkenes is least
stable?

(a)

(c)

(b)

(d)

Solution:

No hyperconjugation.
Hence, the answer is (c).

Class
Exercise

10
Convert the following reactant

C
H
O
H
H3
2 C
into product.

Solution
CH2 OH

CH2 OH2

H+ / H2O
CH+
2

H2O

CH3

CH3

H H +
H

3 stable carbocation

Properties of alkenes

Session
objectives
1. Chemical reactions of alkene
2. Addition of hydrogen, halogen, hydrogen halides
3. Markownikoffs rule
4. Anti-Markownikoffs rule
5. Hydroboration-oxidation
6. Oxymercuration-demercuration
7. Oxidation of alkene
8. Ozonolysis
9. Conjugated dienes

Addition of
Hydrogen
RCH= CH2

H2 /Ni

RCH2CH3

The ease of hydrogenation

CH2 CH2 RCH CH2 RCH CHR R2C CH2

Addition takes

predominantly cis manner.

Addition of Halogens
CH2 = CH2 + Br2

CCl4
Solvent

Brown
CH2 CH2 Br2

CH2 - CH2
|
|
Br
Br

Colourless
H2 O
Solvent

Test of unsaturation

Br CH2 CH2 OH HBr

Mechanism

Step I
C

Br

: ....... :

..

Br

..

: Br
:
..

Br

Bromonium ion

Step II
C

C
:

Br

Br
Br

Br

. .

B r o m o n iu m io n

A n t i a d d it io n

stereospecific reaction

Types of
reaction
Stereospecific reaction
R1

R3
C

R1

CH2

R4 (Singlet)

R2

R3

R2

C
R4

Stereoselective reaction
MeC

CEt

Ni / H2

Me

Et
C

C
H

Cis-isomer (major)

Addition of hydrogen halides

CH2 = CH2 + HCI CH3 CH2CI

CI
+

HCI

HI > HBr > HCI > HF

Markownikoffs
rule
Polar addition to an unsymmetrical
alkene takes place in such a manner
that the negative part of the addendum
attaches to that carbon atom which is
more highly substituted (or contains
the least number of H atoms)

r
B
Br

Markownikoffs rule
CH3
CH3
CH3

At Position
(1)

CH2

CH3

CH3

3
more stable cation

CH3

CH3

CH3

Br

Major Product

CH3
At Position
(2)

CH3

CH

CH2

1
less stable cation

CH3

CH3

CH

CH2 Br

Minor Product

Markownikoffs
rule
If HBr is added
to a symmetrical

alkene, only one product is obtained.

CH3CHCH2CH3
CH3

CH

CH

CH3

HBr

Br
CH3CH2CHCH3
Br

Markownikoffs addition product depends on the stability

of intermediate carbocation.

Markownikoffs rule
CH3

CH

CH

NO2 + HB
CH3

CH2

CH

NO2

Br
(Minor)

CH3

CH

CH2

Br
(Major)

NO2

Markownikoffs rule

Mechanism

CH3

CH

CH

NO2 + H+

CH3

CH
Major
I

CH3

CH2

+
+

CH

Minor
II

Q NO2 group at p position withdraws electron

cloud from benzene ring.

NO2

CH

NO2

Markownikoffs rule
CH3

CH

CH

NO2

Br

CH3

Major
I

CH3

CH2
Minor
II

CH

CH

NO2

CH

NO2

Br
Major

CH

NO2

Br

CH3

CH2

Br
Minor

Peroxide effect (Anti

Markownikoffs addition)
CH3

CH

HBr

CH2

Peroxide

CH3

CH2 CH2Br

Propyl bromide

Mechanism:
H2O2

2 OH
Hydroxide
free

OH + HBr

H2O + Br

Br + CH3 CH

CH2

CH3 CH CH2Br
2 stable free radical

CH3 CH CH2Br

CH3CH2CH2Br
Major product

Addition of water
Acid catalyzed addition
of water
(Hydration)
CH3

CH3
CH3

CH

H
O
/
2H

CH2

C CH2

H2O

65-70% H2SO4

CH3

CH

OH

CH3

CH3

C CH3

OH

CH3

B
H
H
O
/
H
3
2

Hydroborationoxidation

3CH2 = CH2

CH3CH2 3

Triethylborane

The addition is antiMarkownikoff

3CH3CH2OH
Ethyl alcohol

Hydroborationoxidation
CH3
CH3
CH3

CH

CH2

C
CH3

(i) BH3

(ii) H2O2/OH
CH3

CH3
CH3

(i) (BH3)2

(ii) H2O2/OH

CH CH2 OH

CH3

CH

CH

OH

CH3

CH3

In a substituted cyclic alkene, a trans alcohol is formed.

CH3

H3C

(i) BH3
(ii) H2O2/OH-

OH
H
trans - Methyl cyclo-pentanol

Oxymercuration
demercuration

H2C

H
g
O
(
A
C
)
2
T
H
FH
,O
2

CH2

CH2 CH2 Hg OAC

OH
NaBH4
OH

CH3CH2OH + Hg

Oxidation of
alkenes
Test for unsaturation
Baeyers test

+ 2KMnO4 + 4H2O

Cold

OH OH

This is also called Hydroxylation

cis-diol

+ 2 MnO2 + 2 KOH

Oxidation of alkenes

Cis- hydroxylation

CH3

CH

CH2

(i) OsO4
(ii) NaHSO3

CH3

CH

CH2

OH

OH

Oxidative cleavage of
alkenes
(i) Alk.KMnO4

CH3

CH

CH2
(ii) H+

CH CH
3

CH3 COOH + CO2 +

(i) Alk.KMnO4
CH CH3
(ii) H+

CH C
3

CH3

H2O

CH CH3

(i) Alk.KMnO4
(ii)

H+

CH3 COOH + CH3COOH

CH3
C
CH3

O + CH3COOH

Oxidation with peroxide

O
C

C6H5CO3H

CH2Cl2

Perbenzoic acid

OH

OH

H2O
trans-diol

OH

Ozonolysis of alkenes

CH3CH2CH

CCH3
CH3

O3

CH3

O
CH3CH2CH
O

Zn/H2O

O CH3

Ozonide

CH3CH2CH + CH3CCH3 + Zn(OH)2

Do you know

Write IUPAC name of alkene which on ozonolysis gives

one molecule of propanal and one molecule of propanone

Addition of methylenes
Cl

+ : CCl2
H

Cl

Dichlorocarbene

Cl
Cl

Base

Cl
- Cl
Chlorobenzene

Conjugated
dienes
(alkadienes)
H
C

C
H

CH2

CH

CH

CH2

Br2
CH2
Br

CH

CH

Br
1,2-addition

CH2 + CH2

CH

CH

CH2
Br

Br
1,4-addition

Conjugated
dienes
(alkadienes)
CH2

CH

CH

CH2

-80o
HBr

CH3 CH CH

CH2 + CH3 CH

Br
80 %

40o

CH3 CH CH
Br
20%

CH CH2Br

20%
CH2 + CH3 CH

CH CH2 Br
80 %

Class exercise

Class exercise 1

If singlet carbene is added to the

ethylene, the product formed will be
(a) propane

(b) butane

(c) cyclopropane

(d) cyclobutane

Solution:

Cyclopropane

Hence the answer is (c)

Class exercise 2

Hydroboration-oxidation of 1-methyl
cyclopentane will give
(a) trans-1-methyl cyclopentan-2-ol
(b) cis-1-methyl cyclopentan-2-ol
(c) Mixture of (a) and (b)
(d) 1-methylcyclopentan-1-ol
Solution:

cis-1-methyl cyclopentan-2-ol

Hence the answer is (b)

Class exercise 3

Anti-Markownikoffs addition of HBr

is not observed in
(a) But-2-ene

(b) Propene

(c) But-1-ene

(d) Pent-2-ene

Solution:
As but-2-ene is a symmetrical structure,
we get same product while antiMarkownikoffs rule applies.

Hence the answer is (a)


(d
c)C
H

C
H
B
r
i
o
n
2

Class exercise 4
Electrophilic addition of Br2 to
ethylene proceeds through
(a) a transition state

(b) a cyclic bromonium ion

Solution:

A three-centred cyclic bromonium ion is formed.

Hence the answer is (a)

Class exercise 5

Predict the major product of each of

the following reaction.
CH3

+ HBr

Solution:
CH3
Br

Peroxide

Class exercise 6

Predict the major product of each

of the following reaction.
CH=CH2

(i) BH3
(ii) H2O2/OH-

Solution:
CH2CH2OH

Class exercise 7
Predict the major product of each
of the following reaction.

CH3
(i) O3

(ii) Zn/H2O

Solution:

O
CHO

Class exercise 8

Write a mechanism for each of the

following reaction.
H
OH

Solution:
+
OH

+
O
H
+
H

CH3

Class exercise 9
A hydrocarbon (R) adds one mole of
hydrogen to form n-hexane . When R is
oxidized vigorously with hot alk. KMnO4
followed by acid treatment it yields a
single carboxylic acid containing
3 carbons. Give the structure of R
Solution:
R: CH3CH2CH = CHCH2CH3

Class exercise
10 (A) having
An organic compound

molecular formula decolourizes

bromine water.On hydrogenation (A)
yields 2-methylbutane and reductive
ozonolysis forms ethanal and propanone.
What is A ?
Solution:

A: