Alkenes, Alkynes

&
EA Reaction
Department of
Biochemistry
Faculty of
Pharmacy
University of Santo Tomas

Alkenes

Physical Properties
Alkenes & alkynes are
nonpolar
Physical properties are
similar to those of alkanes
with same C skeletons
Those that are liquid at RT
have densities <1.0g/mL

Physical Property: Boiling point

Alkenes have diffuse e- cloud; alkanes have stronger

interaction; & alkynes e- cloud is tighter than alkenes

ISOMERISM

STRUCTURE OF
ALKENES

Alkenes: cis & trans isomerism

cis

trans

All substituents are

on one side
of bond

All substituents are

on different sides
of bond

Alkenes: cis & trans isomerism

Alkenes: cis & trans isomerism

Alkenes: cis & trans isomerism

Cis/trans Isomerism in Cycloalkenes

For cycloalkenes with 7 or fewer C
atoms, the cis configuration is preferred

Cis/trans Isomerism in Di-, Tri-, &

Polyenes
Total # of cis-trans isomers possible = 2n
n = # of double bond
Double bond

2,4-heptadiene

C2 C3

C4 C5

trans
trans
cis
cis

trans
cis
trans
cis

What is the correct systematic name for the following?

Br

1.
2.
3.
4.
5.

1-bromo-2-hexene
6-bromo-4-hexene
cis-1-bromo-2-hexene
trans-1-bromo-2-hexene
trans-6-bromo-4-hexene

Alkenes: E/Z System

For more than two substituents the cis/trans,
the E/Z system is used.

Alkenes: E/Z System

I

H3C
H

H3C

(E)-3-fluoro-2-iodo-2-propene

CH2 OH
CH2 CH3
path goes to O,
not H

C O
H
H

comparison
stops here

C C
H

path goes to C,
not H

Alkenes: E/Z System

C H

CH CH2

CH CH2

C C C
H H

H3C

H H

CH2 CH3
CH2 CH3

C C H
H H

Which is the correct structure for E-3-bromo-2-chloro-2-pentene?

CH3

1.

CH2CH 3
C

Cl

3.

2.

CH2CH 3
C

C
Cl

Br
C

Cl

Br

CH3
Br

CH3

CH2CH 3

CH3

4.

Cl
C

Br

C
CH2CH 3

Alkenes: Stability
The stability of alkenes depends upon
number of substituents

Stability of Disubstituted Alkenes

H3C

>

>
H3C

H3C

H3C

CH3

CH3

ELECTROPHILIC ADDITION & OXIDATION

REACTION OF
ALKENES

Reactive Sites of Alkenes & Alkynes

CH3
H3C C
H3C

CH

Alkenes: Electrophilic Addition

electrophile

R
R

R
R

R
+ Y + + Znucleophile

R
Y

Z
R

Electrophilic addition to the double bond is a

two-step process

Alkenes: Electrophilic Addition

Alkenes: Electrophilic Addition

Alkenes: AE - Hydrogenation
CH3
+ H2

Pt/C

CH3
H
H

With the help of metal catalysts, H2 adds to

the double bond.
(Catalytic Reduction)

Alkenes: AE - Hydrogenation

Alkenes: AE - Hydrogenation

Alkenes: AE - Halogenation

Alkenes: AE - Halogenation

Alkenes: AE - Hydrohalogenation

Electrophilic reagents we can use are hydrogen halides:

HF, HCl, HBr, HI

Alkenes: AE - Hydrohalogenation

Alkenes: AE - Hydration

H
HCl, tra c e
CH2
CH2
CH2
CH2
H3C
+ H2O
H3C
CH
CH
1-b u ten e

2-b u ta n o l

OH

Alkenes: AE - Hydration

AE Markovnikovs Rule
HI

1 -me th y lc y c o h ex e n e

I +

1 -io d o -1 -me th y lc y c lo h e x a n e

2 -io d o -1 -me th y lc y c lo h e x a n e

Major product

Minor product

We obtain both products; however, one is the

major product.
We have a regioselective reaction.

AE Markovnikovs Rule
In the addition of HX or H2O to an
alkene, H adds to the C of the double
bond having the greater number of
hydrogens.

AE Markovnikovs Rule

AE Markovnikovs Rule

Carbocation Stability

Carbocation Stability

AE Markovnikovs Rule

AE Markovnikovs Rule
HB r

Br
H

1 -b ro mo -1 -me th y lc y c lo p e n ta n e

Br

1 -b ro mo me th y lc y c lo p e n ta n e

AE Markovnikovs Rule

Alkenes: AE Addition of Alcohols

Alcohols react the same way as water
H3C
H3C

C CH2 + CH3CH2OH

2-m eth ylpro pen e

eth an o l

H3C CH3
CH3
O

H2C CH3
tert-bu ty l-eth y l eth er

Note: the reaction works only in the

presence of acid.

Alkenes: AE Addition of Alcohols

Alkenes: Oxidation
Cold, alkaline KMnO4

acidic KMnO4
BOND CLEAVAGE

the 2 carbons separate to

form 2 products

Alkenes: Oxidation
Ozonolysis

Dihydroxylation with OsO4

BOTH ARE ALDEHYDE

Alkenes: Oxidation
Hydroboration oxidation

Polymerization of Alkenes
Polymers are large molecules that
contain a large number of repeating
units of a small molecule (monomer).
Biopolymers are typically synthesized
by organisms.
Synthetic Polymers are made in organic
laboratories.

Polymerization of Alkenes
Alkenes can be used as a monomeric unit to
form chain-growth polymers

styrene

polystyrene

Polymerization of Alkenes

Polymerization of Alkenes
For the polymerization, electrophilic addition
reactions can be used.
BF3

F3B

In the initiation step an electrophile (BF3)

adds to the alkene to form a carbocation
intermediate.

Polymerization of Alkenes
Subsequent propagation steps grow the
polymer until all monomers are consumed.

F3B

F3B

Polymerization of Alkenes
Termination can also be accomplished by
adding a nucleophile.

Nu
F3B

n
Nu
F3B
n

Polymerization of Alkenes
An alternative way to initiate polymerization is
starting with a radical initiator.
RO OR

D
(hn)

2 RO
radicals

The radical adds onto the alkene to form a new

radical. Propagation is accomplished via subsequent
radical additions.
R

RO
RO

-ELIMINATION REACTION

PREPARATION OF
ALKENES

PRODUCT

Preparation of Alkenes
-Elimination Reactions
Dehydrogenation of alkanes
Dehydration of alcohols
Dehydrohalogenation of alkyl halides
removal of hydrogen

removal of water

REVERSAL OF THE REACTIONS OF ALKENES

Dehydrogenation of Alkanes
VERY HIGH TEMPERATURES

Dehydration of Alcohols
STRONG ACID AS REAGENT

Zaitsevs Rule

ALPHA CARBON = ATTACHED TO FUNCTIONAL GROUP

Dehydrohalogenation of RX

OH

OH

+h2so4

CH3CHCH2CH3 + H2SO4
+H2O

CH3

ADDITION, OXIDATION, & ACIDITY OF TERMINAL ALKYNES

REACTION OF
ALKYNES

Reactivity of Alkynes

Hydrohalogenation

Hydrohalogenation

Halogenation

Hydration

Hydration of Alkyne & Tautomerism

Draw the ENOL tautomers of the following ketones:

Catalytic Reduction

Oxidation

Acidity of Terminal Alkynes

HC CH

+ NH2

HC C

+ H3N

Acidity of Terminal Alkynes

-FIN-