REACTIONS

OF ALKENES

6-1
 REACTIVITY OF DOUBLE BOND (ALKENE)
C=C more reactive than C-C

It can be explained by electron configuration

2px 2py 2pz p

sp2

2s C=C has both and bonds,

while C-C has only bond.
6-2
 ADDITION REACTIONS
1. For alkenes and alkynes, the most characteristic reaction is
the addition of groups of atoms to the carbons of the
double or triple bond.
2. Many different kinds of reactants can be added to double and triple bonds to form more
stable products.

3. Some addition reactions require a catalyst but others do not.

C C + X Y C C
X Y

The general equation for the addition reaction

6-3
SEVERAL ADDITION REACTION AND ITS OTHER NAME

React ion D escrip tive N ame(s )

H
C C + HCl C C Hydrochlorin ation
( HX) Cl (X) (hydrohalogen ation )
H
C C + H2 O C C Hydration
OH
(X) Br
C C + Br2 C C Bromin ation
( X2 ) Br (X) (h alogenation)

HO
H2 O
C C + Br2 C C Bromo(halo)hydrin
( X2 ) Br (X) formation

6-4
ADDITION REACTION

H2 O HgOAc
C C + Hg(OAc) 2 C C Oxymercuration
HO

C C + BH3 C C Hydrob oration

H BH2

C C + OsO4 C C D iol formation

HO OH (oxidation)

C C + H2 C C Hydrogenation
H H (reduction )

6-5
Example : Prediction of product

What is the product of this reaction?

a. cyclohexane
b. cyclohexyne
c. hexane
d. hexene

Answer: a. This is a hydrogenation reaction. The

double bond is converted to a single bond.

6-6
What is the product of this reaction?

a.

b.

Answer: b. Markovnikov's rule

c.
says that the carbon with the most
hydrogens gets the hydrogen in
addition reactions.
d.

6-7
Question
What is the product of this reaction?

a.

b.

c.

d.

Answer: a. Hydration reactions add a hydrogen atom and an -OH group

to the double bond.
6-8
Question

What is the equation for the hydrogenation of 2-methyl-2-butene?

a.

b.

c.

d.

Answer: b.

6-9
 The Influence of cis/trans,
substituent structure
on the reactivity of Alkenes

based on their enthalpy of hydrogenation

6-10
 Heats of Hydrogenation - cis & trans

Are the entaphy these two reaction same ?

H3C CH3 H H H H
C C H C C
+ H2 C C H H
H H H
H H

H3C H H H H H
H C C
C C + H2 C C H H
H H H
H CH3

6-11
 H0 COMPARISON OF CIS & TRANS

Reduction of an alkene to an alkane is exothermic

there is net conversion of one pi bond to one sigma bond

H0 for a trans alkene is lower than

that of an isomeric cis alkene
E H3C CH3
a trans alkene is more stable than a
C C + H2 cis alkene
H H
-120

H3C H
-115

C C + H2

H CH3

H H H H
H C C
C C H H
H H H

Reaction Coordinate
6-12
 STABILITY/REACTIVITY OF SUSTITUTED ALKENE

R H
mono C C

H H

E R H R H
di C C C C

H R R H

R H
tri C C The more subtituents that are present,
R R
the more opportunities exist for
R
hyperconjugation, and the more stable
R
the alkene.
tetra C C

R R (less energy, less reactivity)

6-13
 H0 of Hydrogenation
S tru ctural H
N ame Formu la [k J (k cal)/m ol]
Eth yle ne CH 2 =CH 2 -137 (-32.8)
Prop en e CH 3 CH=CH2 -126 (-30.1)
1-Bu te ne -127 (-30.3)

cis -2- Bu ten e -120 (-28.6)

t rans -2-Bu te ne -115 (-27.6)

2-M eth yl-2-b uten e -113 (-26.9)

2,3-D ime th yl-2-b ute n e -111 (-26.6)

H0 depends on the degree of substitution

the greater the substitution, the lower the value of H
6-14
 Hydrogenation for Manufacturing of margarine

commonly used catalysts are transition metals (Pt, Pd, Ru, and Ni)

the process is called catalytic reduction or, alternatively, catalytic

hydrogenation
6-15
 STEREO SELECTIVITY OF HYDROGENATION

Compositon (cis and trans )

even though addition syn stereoselectivity, some
product may appear to result from trans addition

CH3 CH3 CH3

H2 / Pt
+
CH3 CH3 CH3
70% to 85% 30% to15%
1,2-D imethyl- cis-1,2-D imethyl- t rans -1,2-D imethyl-
cyclohexene cyclohexan e cyclohexane
(racemic)

6-16
 Syn SELECTIVITY OF Hydrogenation

Hydrogenation is sensitive to steric hindrance

explaining the selectivity for reaction

hydrogen addition occurs with "syn addition", with

hydrogen entering from the least hindered side.[

6-17
HALOGENATION

6-18
 HALOGENATION

In the halogenation reactions of alkenes or alkynes, halogen atoms such as

chlorine or bromine are added to the double or triple bonds.
The reaction occurs readily, without the use of any catalyst, and adds halogen
atoms to yield a di- or tretahaloalkane product.
In the general equation for halogenation, the symbol XX or X2 is used for
Cl2 or Br2.

X X
C==C + XX CC

6-19
 BROMINATION

(a) When bromine is added to an alkane in the first test tube, the
red color of bromine remains because the alkane does not react
or react slowly. (b) when bromine is added to an alkene in the
second test tube, the red color immediately disappears as
bromine atoms add to the double bond. 6-20
Addition of Cl2 and Br2
carried out with either the pure reagents or in an inert
solvent such as CH2Cl2 Br Br
CH3 CH=CHCH3 + Br2 CH3 CH-CHCH3
CH2 Cl2
2-Buten e 2,3-Dib romob utane
addition of bromine or chlorine to a cycloalkene gives
a trans-dihalocycloalkane
Br Br
+ Br2 +
CH2 Cl2
Br Br
Cyclohexen e
trans-1,2-D ibromocyclohexane
(a racemic mixture)

addition occurs with anti stereoselectivity; halogen

atoms add from the opposite face of the double bond
we will discuss this selectivity in detail in Section 6.7
6-21
Addition of Cl2 and Br2
Step 1: formation of a bridged bromonium ion
intermediate
Br
Br
Br Br Br
-
C C C C C C C C + Br

Thes e carbocation s are major The bridged bromoniu m

contribu ting s tru ctures ion retains the geometry

6-22
Addition of Cl2 and Br2
Step 2: attack of halide ion (a nucleophile) from the
opposite side of the bromonium ion (an electrophile)
opens the three-membered ring to give the product
Br Br
Br
C C C C
Br
Br - Br
A nti (cop lan ar) orie ntation N ew man p roje ction
of ad ded b romine atoms of the p rodu ct
Br
Br Br

C C C C
Br
- Br
Br A nti (cop lan ar) orie ntation N ew man projection
of ad ded b romine atoms of th e p rod uct
6-23
Addition of Cl2 and Br2
for a cyclohexene, anti coplanar addition corresponds
to trans diaxial addition
the initial trans diaxial conformation is in equilibrium
with the more stable trans diequatorial conformation
because the bromonium ion can form on either face of
the alkene with equal probability, both trans
enantiomers are formed as a racemic mixture
Br
Br
Br
(1S,2S)-1,2-D ibromo-
Br cyclohexan e
+ Br 2
Br

Br
Br
Br (1R,2R)-1,2-D ibromo-
cyclohexane 6-24
HYDROHALOGENATION
Electrophilic Addition
Mechanism

6-25
HBr + 2-Butene
A two-step mechanism

Step 1:
proton transfer from HBr to the alkene gives a carbocation
intermediate

slow , rate
determining H
CH3 CH=CHCH3 + H Br CH3 CH-CHCH3 + Br
s ec-Butyl cation
(a 2 carbocation
intermediate)

Carbocations
6-26
HBr + 2-Butene

Step 2:
reaction of the sec-butyl cation (an electrophile) with
bromide ion (a nucleophile) completes the reaction

Br
+ CH3 CHCH2 CH3 fast
Br CH3 CHCH2 CH3
Bromide ion sec-Butyl cation 2-Bromobu tane
(a nu cleophile) (an electrophile)

6-27
Electrophilic Addition Carbocation formation

H3C CH3
H
+ 2o carbocation
H3C CH3
H H
+ H Br or Br-
H H H3C CH3
nucleophile electrophile + 2o carbocation
(Lewis base) (Lewis acid) H H
H

symetric

6-28
Electrophilic Addition symmetric

Br
nucleophile
H3C CH3 (Lewis base)
H 3C CH3
H H
+
H H H Br H
electrophile
(Lewis acid) only one product !!!!

6-29
HBr + 2-Butene
An energy diagram for the two-step addition of HBr to 2-butene
the reaction is exergonic

6-30
 regioselectivity in asymetric alkenes
one of two or more possible products is formed IN
PREFERENCE TO all others that might be formed

H adds to the carbon of the double bond having

the greater number of hydrogens

Br H H Br
CH3 CH=CH2 + HBr CH3 CH-CH2 + CH3 CH-CH2
Propene 2-Bromopropane 1-Bromopropane
(not obs erved)

Why to follow Markovnikovs rule ?

6-31
regioselectivity in Addition of asymetric alkenes

H 3C CH3
H 3o carbocation
H3C CH3 +
H 3C H
+ H Br or Br-
H3C H H 3C CH3
nucleophile electrophile +
(Lewis base) (Lewis acid) 2o carbocation
H 3C H H
H3C CH3 H3C CH3
H electrophile H
+ (Lewis acid) Br
H3C H H3C H
+ Br-
(Major) Markonikovs
nucleophile
H3C CH3
Rule
H3C CH3
(Lewis base) Br
+
regiospecific
H3C H H H3C H H
electrophile (Minor)
(Lewis acid) 6-32
 Look at
Stability Carbocations
that formed 1st step of
electrofili c addition

6-33
 Carbocations
has only six electrons in its valence shell and bears
positive charge (electrophiles);
that is, they are electron-loving (Lewis acids)

are classified as 1, 2, or 3 depending on the

number of carbons bonded to the carbon
bearing the positive charge

6-34
Stereo of Carbocations

bond angles about a positively charged carbon are approximately 120

carbon uses sp2 hybrid orbitals to form sigma bonds to the three
attached groups
the unhybridized 2p orbital lies perpendicular to the sigma bond
framework and contains no electrons
6-35
Carbocation Stability
relative stability
H H CH3 CH3
H C+ CH3 C+ CH3 C+ CH3 C+
H H H CH3
Methyl Ethyl Isopropyl t ert-Bu tyl
cation cation cation cation
(meth yl) (1) (2) (3)
Increasin g carbocation s tability

a 3 carbocation is more stable than a 2 carbocation, and

requires a lower activation energy for its formation
a 2 carbocation is, in turn, more stable than a 1 carbocation,
methyl and 1 carbocations are so unstable that they are never
observed in solution

6-36
Carbocation Stability
we can account for the relative stability of
carbocations if we assume that alkyl groups bonded to
the positively charged carbon are electron releasing
and thereby delocalize the positive charge of the
cation
we account for this electron-releasing ability of alkyl
groups by (1) the inductive effect, and (2)
hyperconjugation

6-37
The Inductive Effect
the positively charged carbon polarizes electrons of
adjacent sigma bonds toward it
the positive charge on the cation is thus localized over
nearby atoms
the larger the volume over which the positive charge is
delocalized, the greater the stability of the cation

6-38
Hyperconjugation
partial overlap of the -bonding orbital of an adjacent C-H or C-C
bond with the vacant 2p orbital of the cationic carbon
the result is delocalization of the positive charge

6-39
 Check with bonding energy

Bond D(kJ/mol)

(CH3)3CH 390

(CH3)2CHH 401 Ease of breaking:

CH3CH2H 420 3o > 2o > 1o

H H R H H R

R C+ R C+ R C + R C H R C H R C H

H R R H R R

Stability Reactivity

6-40
 CARBOCATION
Packing a mere six valence electrons,these electron-deficient
intermediates figure prominently in many reactions we meet in organic
chemistry, such as

nucleophilic substitution (SN1) and elimination (E1)

reactions

additions of electrophiles to double and triple bonds

electrophilic aromatic substitution

additions to carbonyl compounds and enolate chemistry

(albeit in masked form)

6-41
 Being electron-deficient (and therefore unstable),
formation of a carbocation is usually the rate-limiting step
in these reactions.
when the carbocation intermediate is more stable, the
energy of the transition state leading to its formation will be
lower.
Whats that going to do to the rate of the reaction? Its
going to speed it up.

3 main structural factors that help to stabilize carbocations.

Neighboring carbon atoms.
Neighboring carbon-carbon multiple bonds
Neighboring atoms with lone pairs.
6-42
 Since opposite charges attract, like charges repel,
you would be right in thinking that carbocations are
stabilized by nearby electron-donating groups.

1) Carbocations are stabilized by neighboring carbon atoms.

age-old explanation

electron-releasing groups through inductive effects.

6-43
Hyperconjugation stabilization through donation of the electrons in
C-H sigma bonds to the empty p orbital of the carbocation

6-44
2) Carbocations are stabilized by neighboring carbon-
carbon multiple bonds.

This effect, called delocalization is illustrated by

drawing resonance structures where the charge
moves from atom to atom

This is such a stabilizing influence that even primary

carbocations normally very unstable are remarkably
easy to form when adjacent to a double bond,
so much so that they will actually participate in SN1
reactions.

6-45
6-46
3) Carbocations are stabilized by adjacent lone pairs.

a neighboring atom that donates a pair of electrons to

the electron-poor carbocation, invariably results in
forming a double bond ( bond) and the charge will
move to the atom donating the electron pair.

Hence this often goes by the name of donation.

nitrogen and oxygen are the most powerful donors

The fact that atoms that we normally think of as
electron-wthdrawing (nitrogen, oxygen, chlorine)
can actually be electron-donor groups is probably
one of the most difficult factors to wrap your head
6-47
6-48
6-49
you can gain tremendous insight into many
different reactions, even though they may appear
vastly different.
Why is this important? Many reactions pass
through carbocation intermediates. What do you
think the effect of stabilizing the carbocation will be
on the reaction rates? Heres some specific
examples.

6-50
6-51
6-52
 Prediction of major product

Markonikovs Rule

CH3

CH3CH2CH CCH2CH3 + HCl

ether

6-53
Predict major product:

+ H Br
ether

6-54
Predict major product: Markonikovs Rule

regiospecific

CH3
H3PO4
CH3CH2C CHC(CH3)3
KI

6-55
Predict major product: Markonikovs Rule

regiospecific

CH2 CHCH2CH2CH2CH CH2 + HCl

ether

CH2 CHCH2CH2CH2CH CH2 + 2HCl

ether

6-56
Predict major product:
Markonikovs Rule

regiospecific

CH2
+ HBr
ether

6-57
Predict major product: Markonikovs Rule

regiospecific

+ HBr
ether

6-58
 CARBOCATION REARRANGEMENTS

Inelectrophilic addition to alkenes, there is the

possibility for rearrangement
Rearrangement: a change in connectivity of the
atoms in a product compared with the
connectivity of the same atoms in the starting
material

6-59
 Evidence of Carbocation

H H H H
H H
H H
H3C H H H
+ HCl H3C
+ H3C
Cl H
Cl H
CH3 H
CH3 CH3

minor major
H H
H
H H
H3C
+
CH3 H-shift

6-60
Carbocation Rearrangements
the driving force is rearrangement of a less stable
carbocation to a more stable one
CH3 slow, rate CH3
determining -

:
:
CH3 CCH= CH2 + H Cl : CH3 C- CHCH3 + : Cl :
+

:
H H
3-Methyl-1-butene A 2 carbocation
intermediate

the less stable 2 carbocation rearranges to a more

stable 3 one by 1,2-shift of a hydride ion

CH3 CH3
fast CH3 C- CHCH3
CH3 C- CHCH3
+ +
H H
A 3 carbocation
6-61
Carbocation Rearrangements
reaction of the more stable carbocation (an
electrophile) with chloride ion (a nucleophile)
completes the reaction
CH 3 CH 3
- fast

:
CH 3 C- CH 2 CH 3 + : Cl : CH 3 C- CH 2 CH 3
+

:
: Cl :

:
2-Chloro-2-methylbutane

6-62
Predict all products:

CH3
+ HBr

6-63
CH3 CH3 +H CH3
+
+ H Br +
CH3
+

CH3 Br CH3
+
E&Z

Br
+ CH3 CH3
Br- E&Z

Br
CH3 CH3
+

6-64
 Explain this Carbocation Rearrangements

Cl
+ HCl + Cl

3,3-Dimethyl- 2-Chloro-3,3-dimethylbutane 2-Chloro-2,3-dimethylbutane

1-butene (the expected product; 17%) (the major product; 83%)

6-65
 Explain this Carbocation Rearrangements
in acid-catalyzed hydration of an alkene

OH
H2 SO4
+ H2 O
3-Methyl-1-butene 2-Methyl-2-butanol

6-66
ANTI-MARKOVNIKOV PRODUCT

6-67
 anti-Markovnikov product

is formed when HBr is added in the presence of peroxides

Example:
ROOR
CH3 CH CH2 + H Br CH3 CH CH2

H Br
The reason for the change in regiochemistry is
that the reaction proceeds via a free radical
mechanism rather than a carbocation
mechanism. The production of free radicals is
initiated by the presence of the peroxide.

6-68
 Mechanism:

heat
RO OR R O + O R

R O + H Br R OH + Br

CH3 CH CH2 + Br CH3 CH CH2

Br

CH3 CH CH2 H Br CH3 CH CH2 + Br

Br H Br

Note that reaction proceeds to form the most stable

radical.
6-69
 ALKENES Oxidation with O3
Treatmentof an alkene with ozone followed by a
weak reducing agent cleaves the C=C and forms
two carbonyl groups in its place
CH3 O O
CH3 C= CHCH2 CH 3 1 . O3 CH3 CCH3 + HCCH 2 CH3
2 . ( CH3 ) 2 S
2-Methyl-2-pentene Propanone Propanal
(a ketone) (an aldehyde)

6-70
Oxidation with O3
the initial product is a molozonide which rearranges to
an isomeric ozonide
O OO
O3
CH 3 CH= CH CH 3 CH 3 CH- CHCH3
2-Butene A molozonide

H O H O
C C ( CH3 ) 2 S
H3 C CH 3 CH 3 CH
O O
An ozonide Acetaldehyde

6-71