Alkenes and Alkynes

Alkenes and Alkynes

• Organic compounds containing one or more

carbon–carbon multiple bonds have fewer
hydrogen atoms than structurally related
alkanes or cycloalkanes. These compounds are
unsaturated.
The alkene functional group is found
in sources as varied as citrus fruits (limonene),
steroids (cholesterol), and insect pheromones
(muscalure)
• Alkenes are molecules containing a C=C double bond. They
are also sometimes referred to as olefins or as unsaturated
compounds. They called unsaturated because the C atoms in a
C=C double bond don’t have as many hydrogens bonded to
them as an alkane does.

• Molecules with one double bond are called

monounsaturated. Molecules with multiple double bonds are
called polyunsaturated. In contrast, alkane molecules with no
double bonds are saturated.
• Some alkenes, called polyenes, contain two or more carbon–
carbon double bonds. Alkenes with two, three, and four
double bonds are called dienes, trienes, and tetraenes,
respectively. Multiple double bonds are present in
polyunsaturated compounds called oils.
• These substances are esters that contain several
carbon–carbon double bonds.
• Polyunsaturated compounds are common in nature.
– For example, linolenic acid is a triene that is present as an
ester in some polyunsaturated oils. Arachidonic acid, a
tetraene, is a precursor to physiologically active molecules
called prostaglandins.
• β-Carotene is converted to vitamin A
in mammals by an enzyme-catalyzed reaction
that oxidizes β-carotene into two molecules
of vitamin A, which is essential for night
vision.
• β-Carotene and vitamin A contain double
bonds separated from one another by one
single bond. that the single and double bonds
are “alternating.” The alternation of single
and double bonds is called conjugation.
Therefore, both β-carotene and vitamin A are
conjugated polyenes.
• Some industrial products are derived from conjugated
dienes. Natural rubber is a polymer of isoprene. The
synthetic rubbers called neoprenes are produced from
chloroprene.
• The simplest alkene is ethene , the compound
which has previously been called “ethylene”.

• Ethene is produced in large quantities because

it is one of the most important substances in
the production of a wide variety of organic
compounds and technological materials.
• The parent alkyne is ethyne which is marketed
under the trade name of “acetylene”. This
substance is also a very important industrial
product.
• Both ethene and ethyne are flammable;
ethyne mixed with oxygen produces a very hot
flame so acetylene is used for gas welding.
Ethyne can be easily prepared from calcium
carbide and water:
Definition and Classification
• Hydrocarbons that contain a carbon–carbon double bond are
called alkenes (acetylenes,); those with a carbon–carbon
triple bond are alkynes (An old but still used synonym for
alkenes is olefins). Their general formulas are;

• Alkanes can be obtained from alkenes or alkynes by adding 1

or 2 moles of hydrogen.
• Double bonds are said to be cumulated when they
are right next to one another. When multiple bonds
alternate with single bonds, they are called
conjugated. When more than one single bond comes
between multiple bonds, the latter are isolated or
nonconjugated.
Alkenes - Nomenclature
The IUPAC rules for naming alkenes and alkynes are similar to
those for alkanes, but a few rules must be added for naming and
locating the multiple bonds.
1. The ending -ene is used to designate a carbon–carbon double
bond. When more than one double bond is present, the ending
is -diene, -triene, and so on.
The ending -yne is used for a triple bond (-diyne for two
triple bonds and so on).
Compounds with a double and a triple bond are -enynes.
2. Select the longest chain that includes both carbons of the
double or triple bond.
For example,
3. Number the chain from the end nearest the multiple bond so
that the carbon atoms in that bond have the lowest possible
numbers.

If the multiple bond is equidistant from both ends of the chain,

number the chain from the end nearest the first branch point.
4. Indicate the position of the multiple bond using the lower
numbered carbon atom of that bond. For example,

5. If more than one multiple bond is present, number the chain from
the end nearest the first multiple bond.

If a double and a triple bond are equidistant from the end of the chain,
the double bond receives the lowest numbers. For example,
• The first two members of each series are

• The root of the name (eth- or prop-) tells us the number of

carbons, and the ending (-ane, -ene, or -yne) tells us whether
the bonds are single, double, or triple. No number is necessary
in these cases, because in each instance, only one structure is
possible. With four carbons, a number is necessary to locate
the double or triple bond.
• Branches are named in the usual way.

rules are applied in the following examples:

• With cyclic hydrocarbons, we start numbering the ring with
the carbons of the multiple bond.
The simplest members of the alkene and alkyne series are
frequently referred to by their older common names, ethylene,
acetylene, and propylene
Two important groups also have common names.
They are the vinyl and allyl groups (IUPAC names are in parentheses)
• Each carbon atom of a double bond is connected to only three
other atoms, the two carbon atoms of a double bond and the
four atoms that are attached to them lie in a single plane.
• Although rotation occurs freely around single bonds, rotation
around double bonds is restricted.
• Ethylene does not adopt any other conformation except the
planar one.
• carbon–carbon double bonds are shorter than carbon–carbon
single bonds.
Alkenes contain trigonal planar sp²-hybridized carbon atoms. Therefore,
the bond angles around the sp²-hybridized carbon atoms should ideally be 120°.
The bond angles of alkenes are typically within a few degrees of this value.
For example, the H—C=C bond angle in ethene is 121.7°. The C—C=C bond angle of propene
is 124.8°.
Cis–Trans Isomerism in Alkenes
The rotation at carbon–carbon double bonds is restricted

– cis–trans isomerism (geometric isomerism) is possible in appropriately

substituted alkenes.
– For example, 1,2-dichloroethene exists in two different forms

– they are configurational stereoisomers and can be separated from one

another by distillation, taking advantage of the difference in their boiling
points.
• Geometric isomers of alkenes can be interconverted if sufficient
energy is supplied to break the pi bond and allow rotation about
the remaining, somewhat stronger, sigma bond . The required
energy may take the form of light or heat.

This conversion does not occur under normal laboratory conditions.

The Chemistry of Vision
• β-carotene, a yellow-orange pigment found in carrots and
many other plants. This C40H56 hydrocarbon has 11 carbon–
carbon double bonds in conjugation.
• It is the biological precursor of the C20unsaturated alcohol
vitamin A (also called retinol), which in turn leads to the key
substance involved in vision,11-cis-retinal.
In the liver, β-carotene is converted into vitamin A first
and then into 11-cis-retinal.
Cis and Trans Configurations of Alkenes
• The orientation of the carbon atoms of the parent chain
determines whether an alkene is cis or trans. If the carbons of
the parent chain are on the same side of the double bond, the
alkene is cis; if they are on opposite sides, it is a trans alkene.
Naming Alkene Cis and Trans Isomers

a) The chain contains seven carbon atoms and is numbered from the
right to give the lower number to the first carbon of the double
bond. The carbon atoms of the parent chain are on opposite sides of
the double bond. This alkene is trans-3-heptene.
b) The longest chain contains seven carbon atoms and is numbered
from the right so that the first carbon of the double bond is carbon 3
of the chain. The carbon atoms of the parent chain are on the same
side of the double bond. This alkene is cis-4-methyl-3-heptene.
E,Z nomenclature of geometrical isomers

• the cis and trans notation does not describe isomeric

trisubstituted and tetrasubstituted alkenes
Sequence Rules

1. If two atoms with different atomic numbers are directly

bonded to a double bond, the atom with the higher atomic
number receives a higher priority.
• The priority order of some common elements is
Br > Cl > F > O > N > C> 2H > H
2. If the atoms directly attached to the carbon atom of the
double bond have the same atomic number, consider the
second, third, and farther atoms until a difference is found. Then
apply rule 1.
3. A multiple bond is considered equivalent to the same number
of single bonds to like atoms. Thus, a double bond is counted as
two single bonds for both of the atoms in the double bond.
The same principle is used for a triple bond.
Alkene Stability
Physical Properties of Alkenes
• Density of Alkenes
The physical properties of the homologous series of alkenes
(CnH2n) are similar to those of the homologous series of alkanes
(CnH2n+2).

Alkenes are either nonpolar or very slightly polar.

Thus, they are insoluble in water but soluble in nonpolar
solvents such as hexane. They are also soluble in diethyl ether
and halogenated solvents.
• Boiling Points of Alkenes
Alkenes that contain fewer than
five carbon atoms are gases at
room temperature. The boiling
points of the alkenes, like those
of alkanes, increase with an
increasing number of carbon
atoms because the London
forces increase. And, like
alkanes, alkenes with branched
alkyl groups have lower boiling
points. Branched alkenes have
more compact structures than
the unbranched isomers, and
thus less intermolecular
contact, which diminishes the
intermolecular London forces.
Characteristic Reactions of Alkenes
HYDROGENATION
• Unsaturated alkenes can be converted into saturated alkanes
by the addition of hydrogen atoms across the double bond.
This reaction is usually catalyzed by a nickel or platinum
catalyst, and the hydrogen is usually added in the form of
diatomic hydrogen gas:
Hydrogenation-Addition of Hydrogen (Reduction)
• Virtually all alkenes react quantitatively with molecular
hydrogen,H2, in the presence of a transition metal catalyst to
give alkanes. catalytic reduction or, alternatively, catalytic
hydrogenation
Addition of Water: Acid-Catalyzed Hydration
most commonly concentrated sulfuric acid, water adds to the
carbon–carbon double bond of an alkene to give an alcohol.
Addition of water is called hydration. In the case of simple
alkenes, hydration follows Markovnikov’s rule: H of H2O adds to
the carbon of the double bond with the greater number of
hydrogens, and OH of H2O adds to the carbon with the smaller
number of hydrogens. Most industrial ethanol is made by the
acid-catalyzed hydration of ethylene.
Addition of Hydrogen Halides (Hydrohalogenation)
Haloalkanes (alkyl halides) are formed when a hydrogen halide
(HCl, HBr, and HI) is added to an alkene. Addition of HCl to
ethylene, for example, gives chloroethane (ethyl chloride):
Addition of Bromine and Chlorine (Halogenation)
Chlorine, Cl2 and bromine, Br2 react with alkenes at room
temperature by addition of halogen atoms to the carbon atoms
of the double bond.