An unsaturated hydrocarbon is a hydrocarbon in which one or more carbon– carbon multiple bonds

(double bonds, triple bonds, or both) are present. Unsaturated hydrocarbons will have an increased
reactivity which is related to the presence of the carbon–carbon multiple bond(s) in such compounds.
Carbon– carbon multiple bonds are the functional group for an unsaturated hydrocarbon. A functional
group is the part of an organic molecule where most of its chemical reactions occur.

Alkenes

• is an acyclic unsaturated hydrocarbon that contains one or more carbon– carbon double bonds
(C=C)
• Functional group: double bond
• Unsaturated: element of unsaturation corresponds to two fewer H-atoms than in the saturated
formula
• General formula: CnH2n (for alkene containing one carbon–carbon double bond)
• Also known as OLEFINS (olefiant gas, meaning “oil-forming gas”) due to the oily appearance of
alkene derivatives
• Bond angle: 120O; trigonal arrangement
• Sp2 hybridized
• Bond energy of a carbon-carbon double bond is about 611 kJ/mol (~146 kcal/mol compared with
the single bond of about 347 kJ/mol )
• Hence, approximate energy of a pi bond is 611 kJ/mol – 347 kJ/mol = 264 kJ/mol
• Bond order: 2
• Double bond: composed of 1 pi bond and 1 sigma bond

Sigma Bond Framework

• Simplest member: Ethene

• Common name: Ethylene
• Alkenes are characterized by the reactions of their double bonds

• Each of the C-H σ bonds is formed by the overlap of an sp2 hybrid orbital

C – H bond length in ethylene (1.08 Å) is slightly shorter than C – H in ethane (1.09 Å), hence stronger
bond

Cycloalkene is a cyclic unsaturated hydrocarbon that contains one or more carbon– carbon double
bonds within the ring system.
General Formula: CnH2n−2 (for cycloalkene containing one carbon–carbon double bond)

Uses of Alkenes

• PHEROMONE - a chemical substance secreted or excreted by insects (and some animals and
plants) that triggers a response in other members of the same species
- alarm pheromones, aggregation pheromones, territorial pheromones, trail pheromones, and
sex pheromones
• ETHYLENE (or ethene) – the simplest alkene CH2 = CH2)
o A plant hormone used to ripen fruits
o Used in the manufacture of polyethylene
o Also converted to ethylene glycol, the major component of many formulations of antifreeze
used in automobile radiators.
• Lower alkenes are used as fuel and illuminant.
• For the manufacture of a wide variety of polymers, e.g., polyethene, polyvinylchloride (PVC) and
teflon etc.

•
• As a raw material for the manufacture of industrial Chemicals such as alcohols, aldehydes, etc.
• TERPENES – unsaturated compounds
-is an organic compound whose carbon skeleton is composed of two or more 5-carbon isoprene
structural units.
- responsible for the odors of cloves and peppermint, or perfumes from roses and lavender
(volatile oils synthesized by plants)
Nomenclature of Alkenes: IUPAC and Common Name Rules

Follows a similar process to that for alkanes

• The longest chain that contains the double bond is given the corresponding name of the alkane
modified by changing –ane ending to –ene.
• Longest continuous chain is numbered starting at the end closest to the double bond.

Alkenes: IUPAC Rules

• Use the smaller of the two numbers on the double-bonded carbons to indicate the double bond
position.

• Each branch is given its alkyl name and number location on the longest chain
• Prefixes (di-, tri-, tetra-, etc) are added to the alkyl name when there is more than one of the same
branch.
• Branches are listed in alphabetically before the parent name
Multiple Double Bonds
• A compound with two double bonds is a diene; a triene has 3 double bonds; tetraene has 4.
• Numbers are used to specify the locations of the double bonds

Alkenes as Substituents

• Alkenes named as substituents are called alkenyl groups.

• They can be named ethenyl, propenyl, etc or by common names.
• Common alkenyl substituents are vinyl, allyl, methylene, and phenyl (Ph) groups.
• Phenyl group is different because it is aromatic and does not undergo the typical reactions of alkenes.
• Most alkenes are conveniently named using IUPAC rules, but common names are sometimes used for
the simplest compounds.
• The sp2 carbons of an alkene are called vinylic carbons. An sp3 carbon that is adjacent to a vinylic
carbon is called an allylic carbon. a hydrogen bonded to a vinylic carbon is called a vinylic hydrogen, and
a hydrogen bonded to an allylic carbon is called an allylic hydrogen.
Cis-Trans Nomenclature

• Also called geometric isomerism

• Cis isomer – if 2 similar groups bonded to the carbons of the double bond are on the same side of the
bond
• Trans isomer – if the similar groups are on opposite sides of the bond
• If either carbon of the double bond holds 2 identical groups, the molecule cannot have cis and trans
forms.

• Trans cycloalkenes are unstable unless the ring is large enough (at least 8 C atoms)
• Hence, all cycloalkenes are assumes cis unless they are specifically named trans.
• The cis name is rarely used with cycloalkenes, except to distinguish a large cycloalkene from its trans
isomer.
E – Z Nomenclature

• Cis-trans isomers sometimes give ambiguous names.

• E-Z system is patterned after Cahn-Ingold-Prelog convention for asymmetric carbon atoms
• Cahn-Ingold-Prelog : ranking atoms based on ATOMIC NUMBERS: I > Br > Cl > S > P > F > O > N > C > H
• Z = if the 2 first-priority atoms are on the same side of the double bond; German word zusammen,
“together” (cis)
• E = if the 2 first-priority atoms are on the opposite side (trans) of the double bond; German word
entgegen, “opposite”
Cyclic Isomers and Multiple Double Bonds
Physical Properties of Alkenes and Cycloalkenes

• The general physical properties of alkenes and cycloalkenes include insolubility in water, solubility in
nonpolar solvents, and densities lower than that of water. Thus they have physical properties similar to
those of alkanes.

• The melting point of an alkene is usually lower than that of the alkane with the same number of carbon
atoms.

• Alkenes with 2 to 4 carbon atoms are gases at room temperature. Unsubstituted alkene with 5 to 17
carbon atoms and one double bond are liquids, and those with still more carbon atoms are solids.

Chemical Reactions of Alkene

• Combustion Reaction. Alkenes, like alkanes, are very flammable. The combustion products, as
with any hydrocarbon, are carbon dioxide and water.
o CnH2n + O2→ CO2 + H2O (complete combustion)
o CnH2n+ O2 → CO + C + H2O (incomplete combustion)
• An addition reaction is a reaction in which atoms or groups of atoms are added to each carbon
atom of a carbon–carbon multiple bond in a hydrocarbon or hydrocarbon derivative. A general
equation for an alkene addition reaction is

•
• Symmetrical addition reaction is an addition reaction in which identical atoms (or groups of
atoms) are added to each carbon of a carbon–carbon multiple bond.
• Unsymmetrical addition reaction is an addition reaction in which different atoms (or groups of
atoms) are added to the carbon atoms of a carbon– carbon multiple bond.
• Markovnikov’s rule states that when an unsymmetrical molecule of the form HQ adds to an
unsymmetrical alkene, the hydrogen atom from the HQ becomes attached to the unsaturated
carbon atom that already has the most hydrogen atoms. (Remember: The rich becomes richer)
• Markovnikov’s Rule (extended): In an electrophilic addition to an alkene, the electrophile adds
in such a way as to generate the most stable intermediate.
• The most substituted carbon is the carbon of the alkene that is attached to the most carbons.
• The less substituted carbon is the carbon of the alkene that is attached to the fewest carbons.
 Symmetrical addition reaction

a. Hydrogenation. A hydrogenation reaction is an addition reaction in which H2 is incorporated

into molecules of an organic compound.

b. Halogentaion. Halogenation reaction is an addition reaction in which two halogen atoms are
incorporated into molecules of an organic compound.

Unsymmetrical addition reaction

c. Hydrohalogenation reaction. Hydrohalogenation reaction is an addition reaction in which a

hydrogen halide (HCl, HBr, or HI) is incorporated into molecules of an organic compound.

d. Hydration. Hydration reaction is an addition reaction in which H2O is incorporated into

molecules of an organic compound. In alkene hydration, one carbon atom of a double bond
receives a hydrogen atom and the other carbon atom receives an -OH group.
When two isomeric products are possible, one product usually predominates. The dominant
product can be predicted by using Markovnikov’s rule.