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STRUCTURE, NOMENCLATURE,
PROPERTIES, AND REACTIONS OF
UNSATURATED HYDROCARBONS
(ALKENES, ALKYNES, AND AROMATIC COMPOUNDS)
Prof. Christian Paul P. de la Cruz, Ph.D. (cand.)

Outline
12.1 Nomenclature of alkenes
12.2 Geometry of alkenes
12.3 Properties of alkenes
12.4 Addition polymers
12.5 Alkynes
12.6 Aromatic compounds and benzene
12.7 Nomenclature of benzene derivatives
12.8 Properties and uses of aromatic compounds

Unsaturated hydrocarbons
Contain one or more double or triple bonds

between carbon atoms and belong to one of the

three classes:

Simplest unsaturated hydrocarbons

What can you say about the bonding patterns of

these unsaturated hydrocarbons?

Why considered unsaturated?

12.1 The nomenclature of alkenes (olefins)

General formula CnH2n (same as that of

cycloalkanes)
Number of structural isomers increases as the

number of carbon chain increases

IUPAC rules for naming alkenes,

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Solution to learning check 12.1

In each of these alkenes, the double-bonded

carbons occur at positions 1 and 2.

a. 3-bromo-1-propene
b. 2-ethyl-1-pentene
c. 3,4-dimethylcyclohexene

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For alkenes with more than one double bonds

Important components of natural and synthetic

rubber
Nomenclature is similar to alkenes with one double

bond, except that the endings indicate the number

of double bonds present in the molecule
E.g.,

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Solution to learning check 12.2

a. The chain is correctly numbered from the

right to give 2-methyl-1,3-butadiene

b. The chain is correctly numbered from the

left to give 2-methyl-1,3,6-octatriene

c. 7-bromo-1,3,5-cycloheptatriene

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12.2 The geometry of alkenes

Hybridization involves mixing a 2s orbital and two

2p orbitals to form three hybrid sp2 orbitals

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sp2 hybrid orbitals lie in the same

plane and are separated by

angles of 120
unhybridized 2p orbital of the

carbon atom is located

perpendicular to the plane of the
sp2 hybrid orbitals

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Geometry of ethylene (ethene) its planar!

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Geometric isomerism in alkenes

Presence of a double bond prevents the free

rotation of the atoms around the carbon (unlike in

alkanes)
Geometric isomers the cis- and the trans-

isomers

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cis-, trans- isomers are chemically distinct

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Conditions of cis-trans isomerism

cis-trans? YES! Why?

cis-trans? NO! Why?

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Consider again
cis-trans? NO! Why?

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Solution to learning check 12.3

a. This

structure does not exhibit geometric

isomerism because there are two Hs attached to
the carbon at position 1

b. Structural formulas

c. This

structure does not exhibit geometric

isomerism because there are two methyl groups
attached to the left double-bonded carbon

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12.3 Properties of alkenes

Physical properties non-polars, insoluble in water, soluble in

non-polar solvents, less dense than water, and more acidic than
alkanes
Physical state depends on molecular mass
Alkenes with 4 or fewer carbon chain gas (unpleasant, gasoline-like odor)
Alkenes with 5-17 carbon chain liquid
Alkenes with 18 or more solid (waxy)

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Chemical properties more reactive than

alkanes
Reactions of alkenes take place at the double bonds

Addition reactions substance is added to the double

bond; two reactants that combine to form one product

Common addition reactions involving alkenes,

Halogenation addition of halogens

2. Hydrogenation addition of hydrogen atoms
1.

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Halogenation
addition of halogens to an alkene and the resulting

product contains only carbon-carbon single bond called a

haloalkane or alkyl halide an alkane derivative

E.g., bromination of 1-butene

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Bromination of 1-hexene

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*Addition of halogens is used to quantitatively determine

the degree of unsaturation (e.g., vegetable oils,
margarines, etc.)

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Solution to learning check 12.4

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Hydrogenation
Addition of hydrogen atoms (within the double bond) in the

presence of a metal catalyst such as platinum, palladium,

nickel
Converts the alkene into the corresponding alkane

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Polyunsaturated high degree of unsaturation;

characteristics of vegetable oils such as soybeans and

cottonseed oil
Hydrogenation converts oils into low-melting point solids

such as margarine and shortenings

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Solution to learning check 12.5

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Halogenation coupled with hydrogenation

Addition of both a halogen and hydrogen (within

the double bond) acidic compounds such as

HF, HCl, HBr, and HI to form the alkyl halide

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Addition of H-X results in two products? How?

However, only one product is formed in significant

amounts?
Markovnikovs rule in the addition of HX to an alkene,

the hydrogen becomes attached to the carbon atom that is

already bonded to more hydrogens, e.g.,

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Solution to learning check 12.6

a. The major product will be the one where H

attaches to the CH carbon:

b. Position 1 on the ring has an attached hydrogen,

whereas position 2 does not have any attached

hydrogens. Thus, H attaches to position 1.

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Hydration
Water adds to carbon-carbon double bonds to give

alcohols in the presence of an acid catalyst such as

sulfuric acid
Water molecule is split and the H attaches to one carbon

of the double bond, and OH attaches to the other carbon

Follows the Markovnikovs rule

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hydration of alkenes provides a convenient

method for preparing alcohols on a large scale

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Alkene hydration in living system

Make use of an enzyme (e.g., fumarase) instead of sulfuric

acid

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Solution to learning check 12.7

a. Markovnikovs rule predicts that H will

attach at position 1 to give:

b. Structural formula,

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Reaction map for alkenes

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12.4 Addition polymers

In the presence of specific catalysts, alkenes undergo an

addition reaction (polymerization) with one another to form

addition polymers very large molecule made up of
repeating units (monomers)

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Other polymers

Copolymer

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Solution to learning check 12.8

The double bond becomes a single bond:

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12.5 Alkynes
Unsaturated hydrocarbons characterized by the

presence of a triple bond between carbon atoms

Rarely found in nature
Physical properties similar with alkanes and alkenes
Chemical reactivity similar with alkenes (addition reactions)
But, alkynes consume twice as many moles of addition reagents as

alkenes

Acetylene (ethyne) is the simplest and most

important

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Geometry of alkynes

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Alkyne nomenclature
Alkynes are named in exactly the same ways as

alkenes, except the ending -yne is used:

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Solution for learning check 12.9

Each chain is correctly numbered from the right.

a. 2-pentyne
b. 5-methyl-2-hexyne

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12.6 Aromatic compounds and the benzene

structure
Aromatic compounds - organic compounds containing the

characteristic benzene ring or its structural relatives

Research: discovery of benzene

Some are known for their aromas (not all have fragrance)
Aliphatic compounds any organic compound that is not

aromatic

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Nature of benzene cyclic structure

Benzene is clearly unsaturated but

does not show reactivity like alkenes

or alkynes do
Very few reactions, very slow to react

and requires heat and catalysts

Benzene must be a ring with

alternating single and double bonds

between carbon atoms

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Geometry of benzene
Each carbon atom has three sp2 hybrid orbitals and one unhybridized p

orbital
A single sigma bond between carbons of the benzene ring is formed by

the overlap of two sp2 orbitals, one from each of the double-bonded
carbons
The third sp2 hybrid orbital of each carbon forms a single sigma bond

with a hydrogen
The unhybridized p orbitals of each carbon overlap sideways above

and below the plane of the carbon ring to form two delocalized pi
lobes that run completely around the ring in the shape of a double
Conclusion:
torus

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Substituted benzene ring

only one hydrogen atom or group

can be attached to a particular

position on the benzene ring

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12.7 Nomenclature of benzene derivatives

The following guidelines are all based on the IUPAC aromatic

nomenclature system. THEY ARE NOT COMPLETE, and

YOU WILL NOT BE ABLE TO NAME ALL AROMATIC
COMPOUNDS BY USING THEM. However, you will be able
to name and recognize those used our class.

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Solution for learning check 12.10

Numbers or the term meta may be used:
a.

1,3-diethylbenzene or m-diethylbenzene

b.

The compound must be named as a derivative of

cyclopentane. The correct name is 1-chloro-3phenylcyclopentane

c.

Numbers must be used when there are three groups: the

name is 1,2,3-tribromobenzene

d.

If the compound is named as a derivative of benzoic acid,

then the methyl group is at position 2. The name is 2methylbenzoic acid

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12.8 Properties and uses of aromatic

compounds
Physical properties similar to alkanes and alkenes
Nonpolar and thus insoluble in water
Hydrophobic characteristic plays an important role in the

chemistry of some amino acids and proteins

Aromatic rings are relatively stable chemically

benzene often reacts in such a way that the aromatic ring remains

intact
benzene does not undergo the addition reactions
The predominant type of reaction of aromatic molecules is
substitution one of the ring hydrogens is replaced by some other
group

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Polycyclic aromatic compounds

A derivative of benzene in which carbon atoms are

shared between two or more benzene rings

Simplest polycyclic aromatic compound,

Original active ingredient in

mothballs

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complex polycyclic aromatic compounds are

known to be carcinogens chemicals that cause

cancer

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END OF CHAPTER.
THANK YOU FOR YOUR ATTENTION.
Prof. Christian Paul P. de la Cruz, Ph.D. (cand.)