Organic Chemistry

Chapter 2
Alkenes
4.1Introduction
Molecules of the alkene (also called olefins) series of
hydrocarbons are characterized by having two adjacent carbon
atoms joined to one another by a double bond. The carbon-carbon
double bond is unsaturated and hence highly reactive toward a
wide variety of reagents.
The general formula of alkenes is CnH2n, where n is the
number of carbon atoms. The first nine members of this series are
listed in Table 4.1.

Table 4.1 The first nine member of the alkenes

General formula Structure Name
C2H4 CH2 = CH2 Ethene
C3H6 CH2 = CHCH3 Propene
C4H8 CH2 = CHCH2CH3 1-Butene
C5H10 CH2 = CH(CH2)2CH3 1-Pentene
C6H12 CH2 = CH(CH2)3CH3 1-Hexene
C7H14 CH2 = CH(CH2)4CH3 1-Heptene
C8H16 CH2 = CH(CH2)5CH3 1-Octene
C9H18 CH2 = CH(CH2)6CH3 1-Nonene
C10H20 CH2 = CH(CH2)7CH3 1-Decene

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4.2 Isomerism in Alkenes
Isomeric compounds are also possible in the alkenes. For the
molecular formula C4H8, there are three different ways of
organizing the four carbon atoms and the double bond:

4.3 Nomenclature
Common names are seldom used except for three simple
alkene; ethylene, propylene, and isobutylene. Most alkene are
named by IUPAC system.
1- The longest continuous chain of carbon atoms containing the
double bond serves as the parent compound.
2- The ending –ane of the corresponding alkane hydrocarbon
name is replaced by the ending –ene.
3- The position of the double bond is indicated by the lower
number of the numbers of the carbon atoms to which it is
attached. The number that represents this position is placed before
the parent compound name. Alkyl groups attached to the parent
compound are designated as is done for the alkane.

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4- If a geometric isomer is designated, the name begins with cis-
or trans-.

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4.4 Physical Properties of Alkenes
The alkenes possess physical properties that are essentially the
same as those of the alkanes. They are insoluble in water, but
quite soluble in non-polar solvents like benzene, ether, and
chloroform. They are less dense than water. The boiling point
rises with increasing carbon number; as with alkane, branching
lowers the boiling point.
Like alkanes, alkenes are at most only weakly polar. Since the
loosely held π electrons of the double bond are easily pulled or
pushed, dipole moments are larger than for alkanes.

4.5 Preparation of Alkenes

1- Dehydrohalogenation of alkyl halides

Dehydrohalogenation involves loss of the halogen atom and of
hydrogen atom from a carbon adjacent to the one losing the halogen (1,2-
elimination).

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 KOH, alcohol
CH3CH2CH2CH2Cl CH3CH2CH = CH2 + KCl + H2O
n-Butyl chloride 1-Butene

Mechanism :

The base :B can be neutral or negatively charged: for example, H2O or

OH-. The conjugate acid H:B will then be positively charged or neutral: for
example, H3O+ or H2O.
Halogen leaves the molecule as halide ion, and hence must take its
electron pair along. Hydrogen is abstracted by the base as a proton, and
hence must leave its electron pair behind; it is this electron pair that is
available to form the π bond between the carbon atoms.
2- Dehydration of alcohols
In the dehydration of alcohols, the H and OH are lost from adjacent
carbons (1,2-elimination). An acid catalyst is necessary and application of
heat.

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Mechanism :

For secondary and tertiary alcohols the above mechanism is generally

accepted. Step (1) is a fast acid-base reaction between the alcohol and the
catalyzing acid which gives the protonated alcohol and the conjugate base
of the acid. In step (2) the protonated alcohol undergoes heterolysis to form
the carbocation and water. In step (3) the carbocation losses a proton to the
base to yield alkene.

3- Dehalogenation of vicinal dihalides

Alkenes can be prepared by elimination of two halide atoms from a
vicinal (neighboring) dihalides.

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 Zn
CH3CHBrCHBrCH3 CH3CH = CHCH3 + ZnBr2
2,3-Dibromobutane 2-Butene

4- Reduction of alkynes
Trans alkene can be obtained by reduction of alkynes with sodium or
lithium in liquid ammonia. Cis alkene is obtained by hydrogenation of
alkynes with a specially prepared palladium called Lindlar catalyst.

4.6 Reactions of alkenes

The presence of the carbon-carbon double bond confers very
considerable chemical activity on the alkenes and consequently
they react with a much wider variety of reagents than do the
alkanes. The π-bond component of the double bond is weaker
than the σ-bond component and the π-electrons are more easily
accessible to attacking reagents.

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 (Addition Reactions)

1- Addition of hydrogen
When an alkene is mixed with hydrogen, there is no appreciable
reaction, but in the presence of certain metal catalysts such as nickel,
platinum or palladium, a fairly rapid reaction occurs leading to the uptake
of hydrogen.

H2, Ni
CH3CH = CH2 CH3CH2CH3

Propene Propane
(Propylene)

H2, Ni
CH2 = CH2 CH3CH3
Ethylene Ethane

2- Addition of halogen
Chlorine and bromine react readily with alkenes, in the liquid or vapour
states, to form dihalogeno addition products, the two halogen atoms are
attached to adjacent carbons. Iodine generally fails to react.

X2 = Cl2, Br2

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 Br2 in CCl4
CH3CH = CH2 CH3CHBrCH2Br
Propene 1,2-Dibromopropane
(Propylene) (Propylene bromide)

Mechanism:

In step (1) a halogen is transferred, without a pair of electrons, from a

halogen molecule to the carbon-carbon double bond; there is formed a
halide ion and organic cation. In step (2) this cation reacts with a halide ion
to yield the addition product.

3- Addition of hydrogen halides

Alkenes react, usually on heating, with hydrogen halides (either
gaseousor in concentrated solution) to form an addition product.

HX = HCl, HBr, HI

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 The hydrogen attaches itself to the carbon that already holds the greater
number of hydrogens. This statement is called Markovnikov's rule.

If the reaction takes place in the absence of peroxide, the addition of HBr,
to alkenes follows Markovnikov's rule. On the other hand, if the reaction
takes place in the presence of peroxide, HBr adds to alkenes in the reverse
direction.

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4- Addition of sulfuric acid
Alkenes are slowly absorbed when they are bubbled through, or shaken
with, cold concentrated sulphuric acid. The reaction involves the addition
of H and HSO4 groups across the double bond, to form alkyl hydrogen
sulfates, which is on dilution with water and heating yield alcohol.

5- Addition of water. Hydration

Alkenes are also reacting with water, and this reaction is carried out in
a dilute acid medium. The reaction follows Markovnikov's rule.

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6- Hydroxylation – glycol formation
Alkanes are highly resistant to chemical oxidizing agents under normal
conditions. In contrast, alkenes are quite sensitive to oxidation by several
oxidizing agent. If an alkene is shaken with a few drops of a dilute acidified
solution of KMnO4, the purple solution is rapidly decolorized. The alkene
is oxidized to an addition product, in which two hydroxyl groups have been
added across the carbon-carbon double bond; the product is a di-alcohol or
diol.

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7- Polymerization
In the presence of a certain catalyst, alkene molecule can add on to
each other in a head-to-tail fashion to form long-chain molecules of a very
high relative molecular mass.

O2, heat
n CH2 = CH2 - CH2 – CH2 - CH2 - CH2 - CH2 - CH2 –
pressure
or ( - CH2 – CH2 - )n
Ethylene Polyethylene

(Substitution Reactions)

Halogenation. Allylic substitution

Alkenes react with halogens, substitution reaction. The reaction carried
out as follow:

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 (Cleavage Reactions)

Ozonolysis
O3 (ozone) is produced by passage of an electric discharge through
oxygen O2. If the mixture of gases is bubbled through a solution of an
alkene at low temperature, an unstable product known as an ozonide is
formed. Ozonides are unstable and are readily hydrolysed to form
aldehydes or ketones.

Ozone Ozonide Aldehydes and ketones

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