Universidad de La Sabana

Edisson Tello Camacho

2
 H H H H
C C CH3
H3C C C
H H H H

3
4
 The stability of alkenes depends
upon number of substituents

R H R H R H R R
< < <
H H H R R R R R

The more substituents, the more stable

Steric repulsion is responsible for energy
differences among the disubstituted alkenes

H3C H H H H3C H
> >
H3C H H3C CH3 H CH3
Trans butene genere 5 kJ less heat than
cis-buteno

7
 Electrons in the orbital stabilize the orbital
The alkyl groups are better than H

8
Typical for unsaturated systems
is the addition reaction: A+B C
CH2 CH3 CH2 CH3
HBr(aq)
H2C C H2C C Br
CH3 H CH3

CH3
CH3
C HBr(aq) C Br
C C
H H H
 A LOOK AT THE
REACTANTS

CH2 CH3 CH2 CH3

H2C C + HBr(aq) H2C Br
CH3 H CH3

WHAT IS THE NATURE

OF THIS REAGENT?
 electrophile

HBr + H2O Br + H3O

Hydrogen bromide is a strong acid and forms

hydronium ions, H3O+, and bromide, Br,
when dissolved in water.

H3O+ is positively charged,

thus it is electron deficient
it is electrophilic electron loving
In the presence of an electron-rich species
the hydronium ion reacts:

H3C H2C H H3C H2C

C CH2 + O H C CH2 + H2O
H3C H H3C H

electrophile

A new positively charged species is formed.

The newly formed species, a
carbocation, is again electron
deficient, thus it is electrophilic.

CH2 CH3
H2C C
H CH3
electrophile
The two species, electrophile and
nucleophile, combine and form a new
compound.

CH2 CH3 CH2 CH3

H2C C + Br H2C Br
H CH3 H CH3
electrophile nucleophile

HBr + H2O Br + H3O

H3C H2C H H3C H2C

C CH2 + O H C CH2 + H2O STEP 1

H3C H H3C H

CH2 CH3 CH2 CH3

STEP 2
H2C C + Br H2C Br
H CH3 H CH3

Intermediates are species with a very short

lifetime.
 ENERGY PROFILE 1st step

energy maximum

activation
energy
ENERGY PROFILE 2nd step

energy maximum
activation
energy
 TS 1

The chemical species that exists

at the transition state, with old
bonds in the process of breaking
and new bonds in the process of
forming: bond
bond breaking
H forming
TS 2

H3C O
CH2
H H
H2C C Br
H bond
CH3 forming
 electrophile
R R Z
R
+ Y ++ Z - R
R
R R Y R
nucleophile

Electrophilic addition to the double bond is a two-step process

First, the bond reacts with an electrophile.

Second, the resulting carbocation reacts with a nucleophile

Electrophilic reagents we can use are
hydrogen halides:
HF, HCl, HBr, HI
H
HCl

Cl
cyclopentene chloro-cyclopentane
H
HI

I
cyclopentene iodo-cyclopentane
In case the olefin has different, or different number
of substituents, two products are possible.

HBr
+
Br H
A B
H Br
1-bromo-1-meti l - 1-bromometi l -
ciclopentano ciclopentano

Is there a preference for one product?

Which is the preferred product?
 H H
CH 2 CH 2
HBr B
A +
slow

We could obtain two structurally

different Carbocations; however, A is
formed much faster.
H
CH2 Br-
fast
Br
H
 Comparing many reactions with different
alkenes leads to a classification of
carbocation intermediates.

R H H H

> > >

R R R R R H H H

The more substituents, the more stable the cation

 HI
I + H
H I
1-methylcycohexene 1-iodo-1-methyl- 2-iodo-1-methyl-
cyclohexane cyclohexane
Major product Minor product

regioselectivity
CONSTITUTIONALS ISOMERS
 Regioselectivity Markovnivkov XIX
He found that the hydrogen, which is the electrophile,
adds to the carbon that contains the larger number of
hydrogens.
CH CH
2 2
H C CH + H O X
3 2

1-butene
H
CH CH H C l, tra c e CH
2 2 2 CH
2
H C CH + H O H C
3 2 3 CH

1-butene 2-butanol OH
28
29
 H
CH 2 CH 2 slow CH 2 CH 2
+
+H H 3C CH
H 3C CH

1st step is electrophilic attack of H+

H H
CH2 CH2 + H2O CH2
fast CH2
H 3C CH H 3C CH
O
H H
addition of nucleophile protonated alcohol

2nd step is nucleophilic attack of H2O

 H H
CH2 H2C CH2
H2C
CH CH
H3C H3C +
O + H
O
H H H
protonated alcohol

3rd step is deprotonation to generate the

alcohol.
H+ is regenerated, so that only catalytic
amounts of acid are necessary.
Alcohols react the same way as water

H 3C H + H3C CH3
C CH2 + CH3CH2 OH CH3
O
H 3C
H2C CH3
2-methylpropene ethanol
tert -butyl-ethyl ether

Note: the reaction works only in the

presence of acid.
Initiating the reaction: generating a
carbocation

H
electrophilic attack of H +
H 3C H+ H 3C CH2
C CH2 + CH3CH2 OH
H 3C slow
CH3
2-methylpropene carbocation
The resulting carbocation is attacked by
the nucleophilic alcohol

nucleophilic attack of ethanol

H

H H3C CH2
H 3C CH2 CH3
+ CH3CH2 OH H O
fast
CH3 ethanol H2C CH3
 Completion of the reaction:
Deprotonation of the alkoxonium species

H3C CH3 H3C CH3

CH3 CH3
H O O + H+
H2C CH3 H2C CH3

alkoxonium species t-butyl-ethyl ether

 The alkenes can react with electrophiles to produce
several products by addition.

Alcohols (ad: H-OH)

Alkanes (ad: H-H)
Halohydrins (ad: HO-X)
Dihalides (ad: X-X)
Halides (ad: H-X)
Diols (ad: HO-OH)
Cyclepropane (ad: :CH2)

36
 Bromides and halides added over the double bonds to
produce 1,2-dihalides, a important industrial process
F2 is too reactive and the I2 do not add
Cl2 react like Cl+ Cl-
Br2 is similar

37
 The addition is trans exclusively

38
39
 Is the addition of HO-X to an alkene (with +OH like
electrophile) to give 1,2-halo alcohol, called
halohydrins
Br2 o Cl2 in water and organic solvents

40
 Br2 is added, then water is added
Orientation
Do not work in aromatic rings

41
 Is the addition of H-OH to give the alcohol
Acid Catalyst

Oxymercuration Desmercuration

Alkene Water Mercury (II)

Acetate

42
Mechanism

Regiospecific and
stereoselective
 Herbert Brown (HB) invented the hydroboration (HB)
Borane (BH3) is electro-poor and is a Lewis acid
Borane is added over the alkene to give an organoborane

44
 Water addition to alkenes :
Hydroboration
Addition of H-BH2 (BH3-THF) to three alkenes to produce a
trialkylborane

Then, the oxidation with hydrogen peroxide in water produce

the alcohol

Anti-markovnikov

45
Regioselective and
stereospecific
 More stable carbocation is also consistent with
steric preferences
 H2O2, OH- inserts OH in place of B
Retains syn orientation
 Addition of H-H over C=C
What is reduction?
Require Pt or Pd In powder and H2
Hydrogen is first absorbed in the catalist

49
 Selective for C=C. Do not react with C=O,
C=N
Polyunsaturated liquid oils are converted in
solids
If one side is blocked, react by the other side
 Heterogeneous Reaction between phases
Addition of H-H is syn

51
 CH CH
3 P t /C 3
H
+ H
2
H
The mechanism of the hydrogenation is as follows:
1. Absorption of hydrogen on the metal surface
2. Alkene approaches surface
3. bonds are replaced by C-H bonds, rehybridization
 Hydroxylation: add -OH over each C=C
Catalyzed by Osmium tetroxide
Addition is syn
The product is a 1,2-dialcohol or diol

53
 Hydroxylation convert to syn alcohols
Osmium Tetroxide, then sodium bisulfate
Via a cyclic intermediary Osmate diester

54
 Potassium Permanganate (KMnO4) can produce
carboxylic acids and carbon dioxide if Hs are presents
in the C=C

55
Me2S
 Used in determination of structure of an unknown
alkene

57
 The carbene functional group is half of an alkene
Carbenes are electrically neutral with six electrons in
the outer shell
They symmetrically across double bonds to form
cyclopropanes

58
 Addition of dichlorocarbene is stereospecific cis

59
 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.
Alkenes can be used as a monomeric unit
to form chain-growth polymers

styrene

polystyrene

n
Instead of the phenyl ring as shown with
polystyrene, many other substituents can be
placed on the alkene part.

H C CH H C CH H C CH
2 2 2 2
CH Cl
3 vinylchloride
ethylene propylene

F C CF H C CH H C CH
2 2 2 2 2 2
CN COOCH
3
tetrafluoroethylene acrylonitrile methyl acrylate

H C CH
2
OOCCH
3
vinylacetate
For the polymerization reaction we can use
electrophilic addition reactions.

BF
3
F B
3

In the initiation step an electrophile (BF3)

adds to the alkene to form a carbocation
intermediate.
Subsequent propagation steps grow the
polymer until all monomers are consumed.

+
F B F B
3 3
Termination can also be accomplished by
adding a nucleophile.

Nu
F B
3

n
Nu

F B
3

n
An alternative way to initiate polymerization
is starting with a radical initiator.
D
RO OR 2 RO
(h n)
radicals

The radical adds onto the alkene to form a

new radical. Propagation is accomplished via
subsequent radical additions.
R
R R
RO
RO
Termination takes place when the polymeric
chain comes across another radical and they
combine.
R R

RO R'
R

R R

RO R'
R