Alkenes

Unsaturated hydrocarbon
Alkenes
(olefins)
Alkenes
general formula CnH2n
n = 2,3,4,5 …………
n= 2 C2H4
n= 3 C3H6
n= 4 C4H8
n= 5 C5H10
Structure and shape of alkenes
• unsaturated hydrocarbons (contain double bond)
• sp2 hybridization (3sp2 hybrid orbital + 1 p orbital)
• Bond angle - 120o
• Shape - trigonal planar
• Functional group = carbon-carbon double bond
• σ bond & π bond
C C
No rotation about double bond!

Pz orbital perpendicular to plane of paper
120 o Sp2 hybrid orbital
(a) Sp2 hybridization
(b) -bonds in ethylene
H H H H
(c) C C C C
H H H H
atomic p-orbitals molecular -orbital
Nomenclature of Alkenes
5 4 3 2 6 5 4 3 2 1
(a) CH3 CH2 CH2 C CH2 CH3 (b) CH3 CH2 CH2 C CH2 CH3
CH2
1 CH2
2-ethyl-1-pentene
2-etyhl-1-pentene
CH3
CH2 C CH CH3
1 2 3 4
2-methyl-1,3-butadiene Br
CH3CH2CH CHCH2CH3
Alkenes undergo Geometric isomerism
2 types – cis------- trans--------
H3C H3C Br
CH3 H3C H
H Br CH3
H H CH3
Cis - isomer trans- isomer Trans isomer
CH2 CH3
CH2 CH2
H3C C
H2 H3C CH3
The (E)-(Z) System for Designating Alkene
Diastereomers
The Cahn-Ingold-Prelog convention is used to assign the

groups of highest priority on each carbon
If the group of highest priority on one carbon is on the same
side as the group of highest priority on the other carbon the
double bond is Z (zusammen)
If the highest priority groups are on opposite sides the
alkene is E (entgegen)
Physical properties of alkenes:
The physical properties of alkenes are very similar to those

of alkanes, since the C=C double bond has no effect on
the van der Waal’s intermolecular forces and so does not
affect melting and boiling points significantly.
• Alkenes are nonpolar compounds
• insoluble in water.
• soluble in nonpolar solvents.
• They are less dense than water.
• Range of physical states:
– ≤ 4 C's — gases
– 5 - 17 C's — liquids
– ≥ 18 C's — solids
• The chemical properties of alkenes, however, are
completely different from those of alkanes.
Relative Stabilities of Alkenes
• Cis and trans isomers of alkenes do not have the same stability
● Strain caused by crowding of two alkyl groups on the same side

of a double bond makes cis isomers generally less stable than
trans isomers
Heat of Reaction
• Hydrogenation of alkenes is an exothermic reaction and the
enthalpy change is the heat of hydrogenation
• We can gain a quantitative measure of relative alkene stabilities

by comparing the heats of hydrogenation for a family of alkenes
that all become the same alkane product on hydrogenation
• The results of such an experiment involving platinum catalyzed

hydrogenation of three butene isomers are shown below
• All three isomers yield the same product—butane—but the heat
of reaction is different in each case
• On conversion to butane, 1-butene liberates the most heat (127

kJ mol-1), followed by cis-2-butene (120 kJ mol-1), with trans-2-
butene producing the least heat (115 kJ mol-1)
• Of course, alkenes that do not yield the same hydrogenation
products cannot be compared on the basis of their respective
heats of hydrogenation. In such cases it is necessary to
compare other thermochemical data, such as heats of
combustion,
Overall Relative Stabilities of Alkenes
● The greater the number of attached alkyl groups (i.e., the more
highly substituted the carbon atoms of the double bond), the
greater is the alkene’s stability
• Consider the two alkenes 2-methyl-1-pentene and 2-methyl-2-
pentene and decide which would be most stable
• First write the structures of the two alkenes, then decide
how many substituents the double bond of each has
• 2-Methyl-2-pentene has three substituents on its double

bond, whereas 2-methyl-1-pentene has two, and therefore
2-methyl-2-pentene is the more stable
CYCLOALKENES
• The rings of cycloalkenes containing five carbon atoms or fewer

exist only in the cis form
• The introduction of a trans double bond into rings this small
would, if it were possible, introduce greater strain than the
bonds of the ring atoms could accommodate
• trans-cyclohexene might resemble the structure shown below
• This molecule is apparently too strained to exist at room

temperature
• trans-cyclooctene has been isolated
• Here the ring is large enough to accommodate the geometry

required by a trans double bond and still be stable at room
temperature
•trans-cyclooctene is chiral and exists as a pair of enantiomers

Synthesis of alkenes via Elimination
Reactions
• dehydration of alcohols
• dehydrohalogenation of alkyl halides
• dehalogenation of vicinal dihalide e.g.
debromination
Dehydration of Alcohols
catalyzed by acid
• Typical acids used in dehydration are
H2SO4 and H3PO4
• The temperature and concentration of acid
required to dehydrate depends on the
structure of the alcohol
Primary alcohols are most difficult to
dehydrate, tertiary are the easiest
Rearrangements of the carbon skeleton can
occur
Mechanism of dehydration of alcohol
Carbocation Stability
• Recall the stability of carbocations is:
Tertiary alcohols react the fastest because
they have the most stable tertiary
carbocation-like transition state in the
second step
The relative stabilities of carbocations is 3° > 2°
> 1° > methyl
The carbon skeleton of while that of the products is
the reactant is
H H
H
Dehydrohalogenation
The reaction is favored by:
• Secondary or tertiary alkyl halides
• Alkoxide bases such as sodium ethoxide CH3CH2O-Na+
or potassium tert-butoxide
Mechanism
Zaitsev (Saytzeff, or Saytzev) rule:
an elimination occurs to give the most stable, more highly

substituted alkene
Russian chemist A. N. Zaitsev (1841-1910).

AN EXCEPTION TO ZAITSEV’S RULE
This happens when bulky base is used e.g. (CH3)3COH
+
• Formation of the Least Substituted
Alkene Using a Bulky Base
– Bulky bases such as potassium tert-butoxide
have difficulty removing sterically hindered
hydrogens and generally only react with more
accessible hydrogens (e.g. primary hydrogens)
DEBROMINATION OF VICINAL DIBROMIDES
Summary
• Alkenes –
– Structure
– Nomenclature
– Synthesis
– Chemical Properties/reaction
Chemical properties of alkenes
Reactions of alkenes :- alkenes undergo electrophilic
addition reaction - Reactivity of C=C
Electrons in -bond are loosely held.
Electrophiles are attracted to the - electrons.
Carbocation intermediate forms.
Nucleophile adds to the carbocation.
Net result is addition to the double bond

Electrophilic Addition
• Step 1: Pi electrons attack the electrophile.
E
+
C C + E C C +
• Step 2: Nucleophile attacks the carbocation.
E E Nuc
_
C C+ + Nuc: C C
Types of Addition reaction
type of addition reaction

C C product
H OH
H X
hydration hydrohalogenation
C C
H2O C C
HX
H H
H H
hydrogenation oxidative cleavage
C C C O
H2 O2 C O
H H
X X O
halogenation epoxidation
C C C C
X2 O
ADDITION OF HYDROGEN HALIDES TO ALKENE:
MARKOVNIKOV’S RULE
HI, HBr, HCl, and HF

The addition of HBr to propene: the main product is 2-
bromopropane.
The addition of HBr to 2-methylpropene: the main product

is tert-butyl bromide.
AN EXCEPTION TO MARKOVNIKOV’S RULE:
When alkenes are treated with HBr in the presence of

peroxides (i.e., compounds with the general formula
ROOR) the addition occurs in an anti-Markovnikov
manner in the sense that the hydrogen atom becomes
attached to the carbon atom with fewer hydrogen
atoms.
1) This anti-Markovnikov addition occurs only when HBr is used

in the presence of peroxides
HYDROGENATION OF
ALKENES
• Catalytic hydrogenation in the
presence of a metal catalyst eg. Pd, Pb,
Ni
ADDITION OF WATER TO ALKENES
Hydration
This reaction occur in the presence of acid catalyst. H2SO4, HCl, H3PO4
Mechanism
The hydration of an alkene is best carried out
using dilute acid so that the concentration of
water is high. It helps to use a lower temperature
Consider this reaction
•This reaction involves the formation of a carbocation

in the first step. the carbocation rearranges to a more
stable one if such a rearrangement is possible.
•This rearrangement can be prevent by using

Oxymercuration-demercuration methods
Oxymercuration-demercuration
• Oxymercuration-demercuration allows the
Markovnikov addition of H– and –OH
without rearrangements taking place.
Con’t
ADDITION OF BROMINE AND CHLORINE
• Alkanes do not react appreciably with bromine or
chlorine at room temperature and in the absence of
light.
room temperature
R-H + Br2 in the dark, CCl4 no appreciable reaction
Alkane Bromine
(colourless) (red brown)
Alkenes react rapidly with chlorine and bromine in

non-nucleophilic solvents to form vicinal dihalides.
Mechanism of bromination
A bromine molecule becomes polarized as it approaches the alkene. The

polarized bromine molecule transfers a positive bromine atom (with six
electrons in its valence shell) to the alkene resulting in the formation of a
bromonium ion.
Test for unsaturation
Oxidation of alkenes
• Oxidation of the double bond can be done
using cold potassium permanganate or
osmium tetroxide to form 1,2-diols
(glycols).
OXIDATIVE CLEAVAGE OF
ALKENES
Alkenes with monosubstituted carbon atoms are
oxidatively cleaved to salts of carboxylic acids by hot
basic permangnate solutions.
OZONOLYSIS OF ALKENES
• alkenes reacts vigorously with ozone to
form unstable ozonides
ozonolysis
3-Methyl-1-butene Isobutyraldehyde Formaldehyde

Alkenes

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Unsaturated hydrocarbon

general formula CnH2n

• σ bond & π bond

No rotation about double bond!

120 o Sp2 hybrid orbital

(a) Sp2 hybridization

(b) -bonds in ethylene

2 types – cis------- trans--------

The Cahn-Ingold-Prelog convention is used to assign the

The physical properties of alkenes are very similar to those

● Strain caused by crowding of two alkyl groups on the same side

• We can gain a quantitative measure of relative alkene stabilities

• The results of such an experiment involving platinum catalyzed

• On conversion to butane, 1-butene liberates the most heat (127

Overall Relative Stabilities of Alkenes

• 2-Methyl-2-pentene has three substituents on its double

• The rings of cycloalkenes containing five carbon atoms or fewer

• trans-cyclohexene might resemble the structure shown below

• This molecule is apparently too strained to exist at room

• Here the ring is large enough to accommodate the geometry

•trans-cyclooctene is chiral and exists as a pair of enantiomers

an elimination occurs to give the most stable, more highly

Russian chemist A. N. Zaitsev (1841-1910).

This happens when bulky base is used e.g. (CH3)3COH

Reactions of alkenes :- alkenes undergo electrophilic

addition reaction - Reactivity of C=C

Electrons in -bond are loosely held.

Electrophiles are attracted to the - electrons.

Carbocation intermediate forms.

Nucleophile adds to the carbocation.

Net result is addition to the double bond

• Step 2: Nucleophile attacks the carbocation.

type of addition reaction

HI, HBr, HCl, and HF

The addition of HBr to 2-methylpropene: the main product

When alkenes are treated with HBr in the presence of

1) This anti-Markovnikov addition occurs only when HBr is used

•This reaction involves the formation of a carbocation

•This rearrangement can be prevent by using

Alkenes react rapidly with chlorine and bromine in

A bromine molecule becomes polarized as it approaches the alkene. The

3-Methyl-1-butene Isobutyraldehyde Formaldehyde

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