1. ALKENES
NAMING HEXENE WITH DIFFERENT
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.
When we discuss the chemical reactions of alkenes,
we will see that the primary site of reaction is the
double bond and the most common type of reaction
is the addition of atoms to the double bond to make
a saturated molecule.
NOMENCLATURE
Alkenes are hydrocarbons that contain one or more
double bonds, while alkynes contain one or more
triple bonds. The naming conventions for these
compounds are similar to those for alkanes.
I. IDENTIFYING AND NUMBERING THE
LONGEST CHAIN
Alkene and alkyne compounds are named by
identifying the longest carbon chain that contains
both carbons of the double or triple bond. This
longest chain is named by the alkane series
convention: “eth-” for two carbons; “prop-” for three
carbons; “but-” for four carbons; etc. The carbon
backbone is numbered from the end that yields the
lowest positioning for the double or triple bond.
II. ADDING SUBSTITUENTS
Substituents are added to the name as prefixes to
the longest chain. Rotation is restricted around the
double bond, so prefixes can be added to
differentiate stereoisomers. Cis or trans is used to
indicate whether higher priority substituents are
located on the same or opposite sides of the bond.
If the compound is cyclic, this information is noted by
adding the “cyclo-” prefix.
III. CHANGING THE SUFFIX
Next, the position of the double or triple bond is
indicated using the position of the carbon in the bond
with the lower backbone number, and the suffix for
the compound is changed to “-ene” for an alkene and
“-yne” for an alkyne. For cycloalkenes, the carbons
in the double bond are numbered as positions 1 and
2.
IV.
SUBSTITUENTS
Examples of substituted hex-1-enes. Remember
that the 1 could go in front of the word hexene as
well. For example, the middle molecule could be
named as 4-methyl-1-hexene.
Alkenes with the same molecular formula and the
same connectivity of atoms can exist
as stereoisomers. These isomers differ because
groups bonded to the double bond have different
spatial arrangements with respect to each other. We
call these compounds geometric
isomers. Geometric isomers have
different configurations.
Consider an alkene whose formula is CXY═CXY.
We can draw the structural formula in two ways.
These two structures represent different molecules.
In the structure on the left, two X groups are on the
same “side” of the molecule. This is the cis isomer.
In the structure on the right, the X groups are on
opposite “sides” of the molecule. It is called
the trans isomer.
Cis and trans isomers are possible only if an alkene
has two different atoms or groups of atoms attached
to each double-bonded carbon atom. For example,
in 1,2-dichloroethene, each unsaturated carbon
atom has a chlorine atom and a hydrogen
atom attached to it. These groups are different, and
both cis and trans isomers are possible.
If one of the unsaturated carbon atoms is attached
to two identical groups, cis–trans isomerism is not
possible. For example,
neither chloroethene nor 1,1-dichloroethene can
exist as cis and trans geometric isomers.
Cycloalkenes in small- and medium-sized ring
compounds have cis configurations. There are not
enough carbon atoms within the ring to bridge the
two carbon atoms of the double bond in
the trans configuration without introducing
considerable strain energy. However, both cis-
and trans-cyclooctene are stable compounds at
room temperature. The cis isomer is more stable
than the trans isomer by approximately 40 kJ
mole− 1. With an increasing number of CH2 groups to
span the two carbon atoms of the double bond, the
strain of the trans isomer becomes less severe. For
example, the isomeric cyclododecenes are of
comparable stability.
TYPES OF UNSATURATED HYDROCARBONS
Unsaturated hydrocarbons, based on the types of
bonds they contain, can be classified into alkenes,
alkynes, and aromatic hydrocarbons. The different
types of organic compounds that can be classified
as unsaturated hydrocarbons are briefly discussed
below.
• The hydrocarbons that contain at least one
double bond between two adjacent carbon
atoms are called alkenes or olefins. The
simplest alkene is ethylene (or ethene), given
by the chemical formula C2H4.
• Alkenes containing only one double bond
and having no functional groups or
substituents attached to them can be
generalized to the chemical formula CnH2n.
• Hydrocarbons containing a minimum of one
triple bond between two carbon atoms that
are positioned adjacent to each other are
referred to as alkynes. The alkyne with the
simplest structure is acetylene (systematic
IUPAC name: ethyne) with the chemical
formula C2H2.
• The alkynes that have only one carbon-
carbon triple bond and have no functional or
substituent groups attached to them can be
generalized to the chemical formula CnH2n-2
• Cyclic hydrocarbons that contain at least one
double or triple bond between two carbon
atoms are also considered to be unsaturated
hydrocarbons, one such example being
cyclopentene (C5H8).
• Although Aromatic Hydrocarbons (ring-
shaped hydrocarbons that contain
delocalized pi electrons) can be considered
as unsaturated hydrocarbons, they are
generally referred to as aromatic compounds
because they are relatively stable and do not
share similar properties with other such
unsaturated compounds.
In order to check whether a given hydrocarbon is
unsaturated, bromine water can be added to it.
Should the bromine water become decolorized, the
hydrocarbon in question is unsaturated. If a white
precipitate is formed, the hydrocarbon sample is a
phenol or aniline. It can be noted that benzene does
not decolorize the bromine water.
USES OF UNSATURATED HYDROCARBONS
Some uses of compounds belonging to the
unsaturated hydrocarbon category are listed below.
• Many fruits can be artificially ripened with the
help of alkenes.
• Mustard gas, a poisonous gas used in
chemical warfare, can be created with the
help of alkenes.
• Unsaturated hydrocarbons are extremely
useful organic compounds in the
manufacturing of plastics.
• LDPE, which is a low-density variation of
polyethylene, is used in the manufacturing of
grocery bags
• Polystyrene is used in making egg cartons,
disposable cups, and other convenient
products.
• Industrial chemicals such as alcohols include
the usage of alkenes in their manufacturing
process.
• Some unsaturated hydrocarbons are used
as general anesthetics.
• Many organic compounds of high industrial
importance are manufactured with the help of
alkynes.
PHYSICAL PROPERTIES
ALKENES
The melting and boiling points of alkenes are
determined by the regularity of the packing, or the
closeness, of these molecules. Alkene isomers that
can achieve more regular packing have higher
melting and boiling points than molecules with the
same molecular formula but weaker dispersion
forces. Alkenes are non-polar, and they are both
immiscible in water and less dense than water. They
are generally soluble in organic solvents. In addition,
they do not conduct electricity.
CHEMICAL REACTIVITY
ADDITION REACTIONS
Most reactions that occur with alkenes are addition
reactions. As the name implies, during an addition
reaction a compound is added to the molecule
across the double bond. The result is loss of the
double bond (or alkene structure), and the formation
of the alkane structure. The reaction
mechanism of a reaction describes how the
electrons move between molecules to create the
chemical reaction. Note that in reaction mechanism
diagrams, as shown in Figure 8.15, curved arrows
are used to show where electrons are moving. The
reaction mechanism for a generic alkene addition
equation using the molecule X-Y is shown below:
REACTION MECHANISM OF A GENERIC
ADDITION REACTION.
In this reaction, an electron from the carbon-carbon
double bond of the alkene attacks an incoming
molecule (XY) causing the breakage of the carbon-
carbon double bond (lefthand diagram) and
formation of a new bond between one of the alkene
carbons and molecule X. The original electron from
X that was participating in the shared bond with Y, is
donated to Y causing the breakage of the X-Y
bond. In the intermediate state (middle diagram),
the alkene is carrying a positively charged
carbon ion, called a carbocation, and Y is in a
negatively charged anion state. The negative anion
is attracted to the positively charged carbocation and
donates the two electrons to form the C-Y bond and
complete the product of the addition reaction
(righthand diagram).
There are four major types of addition
reactions that can occur with alkenes, they include:
Hydogenation, Halogenation, Hydrohalogenation,
and Hydration.
1. HYDROGENATION
In a Hydrogenation reaction, hydrogen (H2) is
added across the double bond, converting an
unsaturated molecule into a saturated molecule.
Note that the word hydrogen is found in this reaction
name, making it easier to remember and
recognize: Hydrogen-ation. In a hydrogenation
reaction, the final product is the saturated alkane.
2. HALOGENATION
In a Halogenation reaction group 7A elements (the
halogens) are added across the double bond. The
most common halogens that are incorporated
include chlorine (Cl2), bromine (Br2), and Iodine
(I2). Notice that the term halogen is found in this
reaction name, making it easier to remember and
recognize: Halogen-ation. In halogenation
reactions the final product is haloalkane.
.
3. HYDROHALOGENATION
In Hydrohalogenation, alkenes react with
molecules that contain one hydrogen and one
halogen. Hence the name Hydro–Halogen-
ation. HCl and HBr are common hydrohalogens
seen in this reaction type. In hydrohalogenation, the
hydrohalogen is a polar molecule, unlike the
nonpolar molecules observed in the halogenation
and hydrogenation reactions. In the case of the
hydrohalogen, the end of the molecule containing
hydrogen is partially positive, while the end of the
molecule containing the halogen is partially
negative. Thus, when the negatively charged
electron from the alkene double bond attacks the
hydrohalogen, it will preferentially attack the
hydrogen side of the molecule, since the electron will
be attracted to the partial positive charge. The
halogen will then form the negatively charged anion
observed in the intermediate structure and attach
second during the addition reaction. The final
product is a haloalkane.
4. HYDRATION
Just like when your are feeling thirsty, the
terms hydration and dehydration refer to
water. Hydration means the addition of water to a
molecule, just like when you feel fully hydrated or full
of water, while dehydration means the removal or
elimination of water, just as when you are feeling
dehydrated and need some water to drink. Similar to
the hydrohalogenation reaction above, water is also
a polar molecule. In this case, the water is split into
two groups to be added across the double bond of
the alkene. It is split into the H- and the -
OH components. Similar to the hydrohalogenation
reaction, the hydrogen adds first, as it carries the
partial positive charge. the OH group forms the
negative anion intermediate and is then added to the
carbocation to form the final product, which is an
alcohol.
OXIDATION REACTIONS OF ALKENES
Alkenes undergo a number of reactions in which the
C=C double bond is oxidized. For organic
compounds, a conventional way to tell whether the
oxidation or reduction occur is to check the number
of C–O bonds or the C–H bonds. An oxidation
reaction increase the number of C–O bonds or
decrease the number of C–H bonds. On the other
side a reduction reaction increase the number of
C–H bonds or decrease the number of C–O bonds.
The relative oxidation state of some common
organic functional groups are listed here based on
the trend.
The relative oxidation state of some common
organic functional groups
CYCLOALKENE
Cycloalkenes are hydrocarbons containing a ring of
carbon atoms and one or more double bonds in the
cycle that do not form an aromatic ring (a cyclic
molecule is considered to be aromatic when it
follows Hückel’s rule, which requires that the number
of π electrons equals 4n+2 where n is an integer).
Cycloalkene ring systems with one or more double
bonds are found in many natural products. Some
industrial processes involve cycloalkene synthesis
such as that of cyclohexene, which is typically
obtained by catalytic hydrogenation of benzene.
Besides practical applications, pyrolysis of
cycloolefins has been studied in relation to the
formation of aromatic compounds, particularly those
with condensed cycles (polycyclic aromatic
hydrocarbons, PAHs) [1,2]. One of the typical
reactions of cycloalkenes with five or six carbon
atoms in the cycle is hydrogen elimination by a
reaction of the type:
This type of reaction easily forms cyclopentadiene
for a five-carbon ring parent compound and benzene
for a six-member ring parent compound.
Cyclopentadiene also leads to aromatic compounds
when further heated. Ring substitution does not
adversely affect the formation of aromatic
compounds.
1. ALKYNES
Alkynes are organic molecules made of the
functional group carbon-carbon triple bonds and are
written in the empirical formula of CnH2n−2. They are
unsaturated hydrocarbons. Like alkenes have the
suffix –ene, alkynes use the ending –yne; this suffix
is used when there is only one alkyne in the
molecule. If a molecule contains both a double and
a triple bond, the carbon chain is numbered so that
the first multiple bond gets a lower number. If both
bonds can be assigned the same number, the
double bond takes precedence. The molecule is
then named "n-en-n-yne", with the double bond root
name preceding the triple bond root name (e.g. 2-
hepten-4-yne).
NOMENCLATURE
I. IDENTIFY THE LONGEST CONTINUOUS CHAIN
OF CARBON ATOMS THAT CONTAINS THE
CARBON-CARBON TRIPLE BOND.
The parent name of the alkyne comes from the
IUPAC name for the alkane of the same number of
carbon atoms, except the - ane ending is changed
to - yne to signify the presence of a triple bond.
Thus, if the longest continuous chain of carbon
atoms containing a triple bond has five atoms, the
compound is pentyne.
II. NUMBER THE CARBON ATOMS OF THE
LONGEST CONTINUOUS CHAIN, STARTING AT
THE END CLOSEST TO THE TRIPLE BOND.
Thus, is numbered from right to left, placing the triple
bond between the second and third carbon atoms of
the chain. (Numbering the chain from left to right
incorrectly places the triple bond between the third
and fourth carbons of the chain.
III. THE POSITION OF THE TRIPLE BOND IS
INDICATED BY PLACING THE LOWER OF THE
PAIR OF NUMBERS ASSIGNED TO THE TRIPLE-
BONDED CARBON ATOMS IN FRONT OF THE
NAME OF THE ALKYNE.
Thus the compound shown in rule 2 is 2-pentyne.
IV. THE LOCATION AND NAME OF ANY
SUBSTITUENT ATOM OR GROUP IS INDICATED.
For example, the compound is 5-chloro-2-hexyne.
Note: Although alkynes possess restricted rotation
due to the triple bond, they do not have
stereoisomers like the alkenes because the bonding
in a carbon-carbon triple bond is sp hybridized.
In sp hybridization, the maximum separation
between the hybridized orbitals is 180°, so the
molecule is linear. Thus, the substituents on triple-
bonded carbons are positioned in a straight line, and
stereoisomers are impossible.
PHYSICAL PROPERTIES
Alkynes are nonpolar, unsaturated hydrocarbons
with physical properties similar to alkanes and
alkenes. Alkynes dissolve in organic solvents, have
slight solubility in polar solvents, and are insoluble in
water. Compared
to alkanes and alkenes, alkynes have slightly higher
boiling points. For example, ethane has a boiling
point of -88.6 C, while ethene is -103.7 C and
ethyne has a higher boiling point of -84.0 ?C.
CHEMICAL REACTIVITY
ALKYNES: ADDITION REACTIONS
The principal reaction of the alkynes is addition
across the triple bond to form alkanes. These
addition reactions are analogous to those of the
alkenes.
HYDROGENATION.
Alkynes undergo catalytic hydrogenation with the
same catalysts used in alkene hydrogenation:
platinum, palladium, nickel, and rhodium.
Hydrogenation proceeds in a stepwise fashion,
forming an alkene first, which undergoes further
hydrogenation to an alkane.
This reaction proceeds so smoothly that it is difficult,
if not impossible, to stop the reaction at the alkene
stage, although by using palladium or nickel for the
catalyst, the reaction can be used to isolate some
alkenes. Greater yields of alkenes are possible with
the use of poisoned catalysts. One such catalyst,
the Lindlar catalyst, is composed of finely divided
palladium coated with quinoline and absorbed on
calcium carbonate. This treatment makes the
palladium less receptive to hydrogen, so fewer
hydrogen atoms are available to react. When a
catalyst is deactivated in such a manner, it is
referred to as being poisoned.
The mechanism of alkyne hydrogenation is identical
to that of the alkenes. Because the hydrogen is
absorbed on the catalyst surface, it is supplied to the
triple bond in a syn manner.
Alkynes can also be hydrogenated with sodium in
liquid ammonia at low temperatures. This reaction is
a chemical reduction rather than a catalytic reaction,
so the hydrogen atoms are not attached to a surface,
and they may approach an alkene from different
directions, leading to the formation of trans alkenes.
HALOGENATION.

The addition of halogens to an alkyne proceeds in

the same manner as halogen addition to alkenes.
The halogen atoms add to an alkyne molecule in a
stepwise fashion, leading to the formation of the
corresponding alkene, which undergoes further
reaction to a tetrahaloalkane.

POLYMERIZATION.

Alkynes can be polymerized by both cationic and

free-radical methods. The reactions and
mechanisms are identical with those of the alkenes.

Unlike most hydrogenation reactions, it is possible to

stop this reaction at the alkene stage by running it at
temperatures slightly below 0°C.

HYDROHALOGENATION.

Hydrogen halides react with alkynes in the same

manner as they do with alkenes.

Both steps in the above addition follow the

Markovnikov rule. Thus, the addition of hydrogen
bromide to 1-butyne gives 2-bromo-1-butene as the
major product of the first step.

The reaction of 2-bromo-1-butene in the second step

gives 2,2-dibromobutane as the major product.

OXIDATION.

Alkynes are oxidized by the same reagents that

oxidize alkenes. Disubstituted alkynes react with
potassium permanganate to yield vicinal diketones
(Vic-diketones or 1,2-diketones) or, under more
vigorous conditions, carboxylic acids.