Reaction of Alkenes

Reaction of Alkenes

- Two reactions will be considered:

- addition reaction (double bond breaking)

- elimination reaction (double bond forming)

 Reaction of Alkenes

- Two reactions will be considered:

- addition reaction (double bond breaking)

- elimination reaction (double bond forming)

- Organic reactions are studied by focusing on why the

reaction occurs, how it occurs and what products are

formed.
 Reaction of Alkenes

- Two reactions will be considered:

- addition reaction (double bond breaking)

- elimination reaction (double bond forming)

- Organic reactions are studied by focusing on why the

reaction occurs, how it occurs and what products are

formed.
Key to understand reaction:
Why, How & What (WHW)
 Addition reactions of Alkenes

How to understand the addition reaction of alkenes

C C + A—B C C
A B
s bond broken
Pi bond broken
2 s bonds formed
 Hydrohalogenation
Addition of Hydrogen Halides to alkenes

C C + H—X H C C X
X: F, Cl, Br, I

CH3 CH3
HBr CH3CH2CHCH3
C C
Br
H H
2-bromobutane
What will be the mechanism?
 Mechanism

-Mechanism is a full description of how a reaction occurs

-it describes what takes place at each stage of a chemical

transformation.

-Reactions occur in defined steps that lead from reactant

to product

- Mechanism describes these steps:

- Types of bonds that are formed and broken
- The order in which bonds are formed and broken
 Steps in Mechanism
The types of steps in a sequence are classified
- A step involves either the breaking or formation of a
covalent bond
- Steps can occur individually or in combination with
other steps

When several steps occur at the same time they are said
to be concerted
 Steps in Mechanism

Curved arrows are used to describe steps indicating the

motion of electrons (which bond forming and breaking)

electron rich electron poor

site site
 Mechanism

-Any reaction involves two types of reactants

Nucleophile

Electrophile
 Mechanism

-Any reaction involves two types of reactants

. Nucleophile (nucleus seeker): electron rich
species: pi bond, negative charge, unshared pair electron

. Electrophile (electron seeker): electron poor

species: positive charge and partial positive charge (dipole)
 Mechanism

- -Identify nucleophile and electrophile

HO CH3 I HC C

Br NH3 H2O H2C CH2

 Mechanism

- -Identify nucleophile and electrophile

HO CH3 I HC C

Br NH3 H2O H2C CH2

 Mechanism

Nucleophile will attack electrophile forming a covalent bond

Curved arrow moves from nucleophilic site to electrophilic site

_
Nu E+ Nu E
Arrow pulling

_
_
A B Nu A + B
Nu
Bond forming and bond breaking occur simultaneously
Arrow pushing
Use arrow pushing to explain the reaction

..– ..
(CH3)2CHCH2 O: + CH3CH2 Br
.. .. :

.. –
(CH3)2CHCH2OCH2CH3 + : Br
.. :

Bond forming:
Bond breaking:
Use arrow pushing to explain the reaction

..– ..
(CH3)2CHCH2 O: + CH3CH2 Br
.. .. :

.. –
(CH3)2CHCH2OCH2CH3 + : Br
.. :

Bond forming: O-C

Bond breaking: C-Br
Use arrow pushing to explain the reaction

..– d+ d-
..
(CH3)2CHCH2 O: + CH3CH2 Br
.. .. :

nucleophile
Carbone electrophilic site

.. –
(CH3)2CHCH2OCH2CH3 + : Br
.. :
Use arrow pushing to explain the reaction

Bond forming Bond breaking

..– ..
(CH3)2CHCH2 O: + CH3CH2 Br
.. .. :

.. –
(CH3)2CHCH2OCH2CH3 + : Br
.. :
 Predict the products from the mechanism
.. –
H O :
..
H CH3
CH3
C C
CH3
CH3 : X:
. .

Identify bond breaking and bond forming

 Predict the products from the mechanism

bond forming (O-H) bond breaking (C-H)

.. – and bond forming (pi
H O :
.. bond)
H CH3
CH3
C C
CH3
CH3 bond breaking (C-X)
: X:
.
.
 Predict the products from the mechanism
.. –
H O :
..
H CH3
CH3
C C
CH3
CH3 : X:
. .

CH3 CH3
.. .. –
H O
.. H C C :X :
..
CH3 CH3
Predict the products from the mechanism
 Predict the products from the mechanism

Oxygen nucleopile
Carbone electrophilic site
Predict the products from the mechanism

-
+ Cl
Predict the products from the mechanism
Predict the products from the mechanism
Predict the products from the mechanism
Predict the products from the mechanism

.. –
: Br
.. : + +
 Writing Mechanism
1- Inspect the reactants and products and assess what
happened in the reaction (what bond forming, bond breaking
or has anything been added or removed

2- Identify the nucleophilic centers in all reactant molecules

and decide which is the most nucleophilic
3- Identify the electrophiles present and decide which is
the most electrophilic
4- Draw a curly arrow from nucleophile to electrophile.
It must start on a pi bond, lone pair or negative charge and
finish on electron deficient site.
5- Make sure that overall charge is conserved in each step
Mechanism of hydrohalogenation

C C + H—X H C C X

Nucleophilic site

Electrophilic site
 Mechanism of hydrohalogenation

d+ d-
C C + H—X H C C X

Nucleophilic site

Electrophilic site
Mechanism

d+ d-
..
H X:
..

C C
Mechanism

d+ d-
..
H X:
..

C C
Mechanism

d+ d-
..
H X:
..

C C
Mechanism

+C C H

carbocation .. –
:X
.. :

d+ d-
..
H X:
..

C C
Mechanism

+C C H

.. –
:X
.. :

d+ d-
..
H X:
..

..
C C :X
.. C C H
 Unsymmetrical alkene

Two products can be obtained with unsymmetrical alkene

H3C H

C C + H—X
2 1
H H
To which carbon to add H,
C1 or C2?
H3C H H3C H

C C or C C
H H H H
H X X H
 Unsymmetrical alkene

H3C H H H
H Br
C C CH3 C C H or CH3 C C H
H H H H H H

Br Br

H Br Br H

CH3 C C H CH3 C C H

H H H H

Two constitutional isomers can be formed

 Unsymmetrical alkene

H3C H H H
H Br
C C CH3 C C H or CH3 C C H
H H H H H H

Br Br

H Br Br H

CH3 C C H CH3 C C H

H H H H

Only one product is formed among

the two constitutional isomers.
 Unsymmetrical alkene

H3C H H H
H Br
C C CH3 C C H or CH3 C C H
H H H H H H

Br Br
How to decide which product is formed
H Br Br H

CH3 C C H CH3 C C H

H H H H

Only one product is formed among

the two constitutional isomers.
 Unsymmetrical alkene

H3C H H H
H Br
C C CH3 C C H or CH3 C C H
H H H H H H

How to decide which product is formed

On the basis of carbocation stability
 Unsymmetrical alkene

H3C H H H
H Br
C C CH3 C C H or CH3 C C H
H H H H H H

How to decide which product is formed

On the basis of carbocation stability

The most stable carbocation, the fastest will form

 Mechanistic Basis

Protonation of double bond occurs in direction that gives

the most stable of two possible carbocations.

Stability of carbocation (inductive effect):

H3C + CH3 H3C + CH3 H3C + H

C C C

CH3 H H
Tertiary carbocation Secondary primary
Most stable Less stable
 Unsymmetrical alkene

H3C H H H
H Br
C C CH3 C C H or CH3 C C H
H H H H H H

primary secondary
carbocation carbocation

How to decide which product is formed

On the basis of carbocation stability

The most stable carbocation, the fastest will form

 Unsymmetrical alkene

H3C H H H
H Br
C C CH3 C C H or CH3 C C H
H H H H H H

primary secondary
carbocation carbocation
will not form will form
 Unsymmetrical alkene

H3C H H H
H Br
C C CH3 C C H or CH3 C C H
H H H H H H

Br

Br H
CH3 C C H
H H
 Unsymmetrical alkene

H3C H H H
H Br
C C CH3 C C H or CH3 C C H
H H H H H H

Br

Br H
CH3 C C H

Reaction is said to be regiospecific H H

(formation of only one constitutional isomer)
 Unsymmetrical alkene
H H
Ph H Br
C C Ph C C or Ph C C

Both carbocations are tertiary

 Unsymmetrical alkene

Ph H Br
C C

H H
or Ph C C
Ph C C

Tertiary carbocation stabilized

Tertiary carbocation
by resonance through the
stabilized by inductive effect
presence of phenyl group &
Less Stable (not formed)
inductive effect
Most Stable (fastest to form)
 Unsymmetrical alkene

Ph H Br
C C

Tertiary carbocation stabilized

by resonance
 Unsymmetrical alkene
H H
Ph H Br
C C Ph C C or Ph C C

Tertiary carbocation stabilized by

Tertiary carbocation stabilized resonance through the presence of
by inductive effect phenyl group & inductive effect
Less Stable (not formed) Most Stable (fastest to form)

Reaction is regiospecific: Br
only one possible isomer is
formed

Br H
Ph C C
 6.5 Regioselectivity

Regioselective :Term describing a reaction that can

produce two (or more) constitutional isomers but
gives one of them in greater amounts than the other.

A reaction that is 100% regioselective is termed

regiospecific (only one constitutional isomer is
formed).
 Aplication

CH3 H HBr
C C acetic acid
CH3 H
 Aplications

CH3 H
CH3 H HBr
CH3 C CH2
C C acetic acid 2 1
2 1 Br
CH3 H
 Markovnikov's Rule

When an unsymmetrically substituted alkene reacts with HX

-the hydrogen of HX adds to the carbon of double bond that
has the greater number of hydrogen substituents
-the halogen of HX adds to the carbon that has the fewer
hydrogen substituents.

CH3 H
CH3 H HBr
CH3 C CH2
C C acetic acid 2 1
2 1 Br
CH3 H
Carbon 1 has the greatest nb of hydrogens, therefore H
will be added to C1 and Br to C2
 Markovnikov's Rule

HCl
CH3
0°C
 Markovnikov's Rule

CH3
HCl
CH3
0°C Cl

1-chloro-1-methylcyclohexane
 Markovnikov's Rule

CH3
HCl
CH3
0°C Cl

1-chloro-1-methylcyclohexane

H H H
H
+
+ CH3 Cl –
CH3
Tertiary carbocation
secondary carbocation
Most stable
less stable: not formed