MODULE 4: UNSATURATED HC (REACTIONS) AND AROMATICS (PROPERTIES)

Unsaturated Hydrocarbons - A cyclic unsaturated hydrocarbon with one

Unsaturated hydrocarbon or more carbon–carbon double bonds within
- a hydrocarbon with one or more carbon– the ring system.
carbon multiple bonds (double bonds, triple • Cycloalkenes with only one double bond
bonds, or both). have the general molecular formula CnH2n-2.
• Physical properties similar to those of • The simplest cycloalkene: Cyclopropene
saturated hydrocarbons. (C3H4), a three-membered carbon ring
• Chemical properties are distinct. system with one double bond.
• Chemically more reactive than saturated • Cycloalkenes with more than one double
hydrocarbons. bond are possible but are not common.
• Reactivity of unsaturated hydrocarbons is
due carbon–carbon multiple bond(s).

Functional Group
- Part of an organic molecule responsible for
most of its chemical reactions.
• Unsaturated hydrocarbon functional group:
Carbon–carbon multiple bonds.
• Alkenes: Contain one or more carbon–
carbon double bonds
• Alkynes: contain one or more carbon–
carbon triple bonds IUPAC Nomenclature for Alkenes and
• Aromatic hydrocarbons: A special type of Cycloalkenes
“delocalized” bonding that involves a six IUPAC Rules
membered carbon ring Rule 1: Replace the alkane suffix -ane with the
suffix -ene
Characteristics of Alkenes and Cycloalkenes Rule 2: Select as the parent carbon chain the
Alkenes longest continuous chain of carbon
- An alkene is an acyclic unsaturated atoms that contains both carbon
hydrocarbon that contains one or more atoms of the double bond.
carbon – carbon double bonds. Rule 3: Number the parent carbon chain beginning
• Functional group: C=C group. at the end nearest to the double bond.
• Naming: Names end with an “-ene” versus If the double bond is equidistant from
• The -ene ending means a double bond is both ends of the parent chain, begin
present. numbering from the end closer to a
• General molecular formula: CnH2n substituent.
• Two simplest alkenes are ethene (C2H4) Rule 4: Give the position of the double bond in the
and propene (C3H6). chain as a single number, which is the
• The arrangement of bonds about the carbon lower-numbered carbon atom
atom in alkanes is tetrahedral. participating in the double bond.
• The arrangement of bonds about carbon Rule 5: Use the suffixes -diene, -triene, -tetrene,
atoms with double bonds in alkenes is and so on when more than one double
trigonal planar. bond is present in the molecule.
CH 2 CH 2 Rule 6: Do not use a number to locate the double
bond in unsubstituted cycloalkenes
Ethene with only one double bond because
that bond is assumed to be between
carbons 1 and 2.
Rule 7: In substituted cycloalkenes with only one
CH 2 CH CH 3 double bond, the double-bonded
carbon atoms are numbered 1 and 2
Propene in the direction (clockwise or
counterclockwise) that gives the first-
Cycloalkanes
 MODULE 4: UNSATURATED HC (REACTIONS) AND AROMATICS (PROPERTIES)

encountered substituent the lower Constitutional Isomerism in Alkenes

number. • Constitutional isomerism possible in alkenes
Rule 8: In cycloalkenes with more than one double as well
bond within the ring, assign one • There are more alkene isomers possible for
double with numbers 1 and 2 and the a given number of carbon atoms than there
other double bonds the lowest are alkane isomers
numbers possible. • Constitutional isomerism: Same molecular
formula but different structural formulas
Common Names (Non-IUPAC Names) • Positional isomers: Same number of carbon
• Common names exist for alkenes and hydrogen atoms but the position of the
• There is no scientific basis for assigning C=C is different
such names therefore one must have to • Skeletal isomers (Cis-Trans): Each C atom
memorize them in the double bond contains the same
• Two most common names for alkenes are: groups but their position is different
- CH2=CH2 - Ethylene (IUPAC name –
Ethene) Cis-Trans Isomerism in Alkenes
- CH2=CH2-CH3 – Propylene (IUPAC name – • Cis–Trans isomerism in alkenes results
propene) from the structural rigidity associated with
C=C double bonds.
Alkenes as Substituents • Rotation about C=C (or CΞC) is not possible
• Alkenes substituents are called alkenyl
groups Isomers
• Most Frequently encountered alkenyl - Have same molecular formula and have
groups: different structural formula.
- Methylidene (one- carbon)- Common name:
methylene Cis-Trans Isomers:
- Ethenyl (two- carbon) - Common name: - Conditions: Each carbon atom in the double
vinyl bond contain two different groups attached
- 2-propenyl (three-carbon) - Common name: to it.
allyl - Cis isomer: Two similar groups on same
side of double bond
Line-Angle Structural Formulas for Alkenes - Trans isomer: Similar groups on opposite
sides of the double bond

Naturally Occurring Alkenes

Pheromones
• A pheromone is a compound used by
insects (and some animals) to transmit a
message to other members of the same
species.
• Pheromones are often alkenes or alkene
derivatives.
• The biological activity of pheromones is
C=C bonds present in a cis or a trans
configuration.
 MODULE 4: UNSATURATED HC (REACTIONS) AND AROMATICS (PROPERTIES)

• Example: The sexual attractant of the Alkene Addition Reaction

female silkworm is a 16-carbon alkene
derivative containing an -OH group.

Terpenes
• Organic compounds whose carbon skeleton
is composed of two or more 5-carbon
isoprene structural units
• Isoprene (2-methyl-1,3-butadiene) is a five-
carbon diene
• Terpenes are widely distributed in nature
• >22,000 Terpenes are found in biological
systems and are responsible for the
characteristic odors of many trees and plant Symmetric Addition Reactions:
fragrances • Hydrogenation reaction: In alkene
hydrogenation a hydrogen atom is added to
Physical Properties of Alkenes and each carbon atom of a double bond.
Cycloalkenes o Catalyst (usually Ni or Pt)
• Physical properties are similar to alkanes • Halogenation reaction: In alkene
• The boiling and melting point of an alkene is halogenation a halogen atom is added to
usually lower than that of alkane with same each carbon atom of a double bond.
number of carbon atoms o No catalyst is needed
• Alkenes with 2 to 4 carbon atoms are gases
at room temperature Unsymmetrical Addition Reactions
• Unsubstituted alkenes with 5 to 17 carbon • Markovnikov’s Rule: When an
atoms are liquids unsymmetrical molecule HQ (e.g., H-Cl, H-
• Alkenes with >17 C atoms are solids OH, H-F) reacts with an unsymmetrical
alkene, the hydrogen atom from the HQ
A Physical-State Summary becomes attached to the unsaturated
carbon atom that already has the most
hydrogen atoms
• Two types of unsymetrical addition
reactions:
- Hydration: Addition of Water
o H2SO4 is a catalyst that is why
written on arrow.
o Catalysts speed-up reactions.
- Hydrohalogenation
o Addition of H-X (X = F, Cl, Br, I)

Polymerization of Alkenes: Addition Polymers

• Polymers are macromolecules in which
small units (monomers) are repeated again
and again.
• Examples: Polyethylene, polypropylene,
polyester etc.
Chemical Reactions of Alkenes
Chemical Properties • Polymers are huge molecules so their
molecular formulas are not written.
• Combustion: Alkenes are very flammable
and the combustion products are carbon • The simplest repeating unit in parenthesis
dioxide and water. with “n” as subscript to shows the number of
monomers.
• Addition Reactions: Atoms or group of
atoms are added to each a carbon atom of
a multiple bond.
 MODULE 4: UNSATURATED HC (REACTIONS) AND AROMATICS (PROPERTIES)

Alkynes
• Alkyne: An acyclic unsaturated hydrocarbon
that contains one or more carbon–carbon
triple bonds.
C C • Alkyne functional group: CΞC group
• Naming: Names end with a suffix -yne
• General formula: CnH2n-2
n • Simplest alkynes: C2H2, C3H4

IUPAC Nomenclature for Alkynes

• Alkenes and substituted alkenes form is an
addition polymer. • The rules for naming alkynes are identical to
those used to name alkenes except the
• An addition polymer is a polymer in which
the monomers simply “add together” with no ending -yne is used instead of -ene.
other products formed besides the polymer.
Isomerism and Alkynes
• Addition polymerization is similar to the
• cis–trans isomerism not possible because of
addition reactions described previously
the linearity (180º angles) about an alkyne’s
except that there is no reactant other than
the alkene or substituted alkene. triple bond
• Example: Formation of polyethylene • Constitutional isomers are possible—both
relative to the carbon chain (skeletal
Substituted-Ethene Addition Polymers isomers) and to the position of the triple
bond (positional isomers).

Physical Properties of Alkynes

• Physical properties: Similar to those of
alkenes and alkanes
• Insoluble in water but soluble in organic
solvents
• Densities less than that of water
• Boiling points increase with molecular mass
• Low-molecular-mass alkynes are gases at
room temperature
Butadiene-Based Addition Polymers
• Polymerization of 1,3-butadiene results in a Aromatic Hydrocarbons
butadiene polymer
• Contains benzene ring with alternate double
• These polymers contain double bonds and single bonds
(unsaturated polymers)
• Double bonds are different than alkenes
• The polymers are flexible
• These are called delocalized (=) bonds: All
C-C bonds are similar
Addition Copolymers
• Resonance structures (differ only in
• A copolymer is a polymer in which two
arrangement of electrons
different monomers are present.
Benzene Usually written as
• Examples:
o Saran Wrap: a polymer chloroethene
(vinyl chloride) and 1,1-
dichloroethene.
o Styrene–butadiene rubber: Leading
synthetic rubber - contains 1,3-
butadiene and styrene in a 3:1 ratio
(major ingredient in automobile tires)
 MODULE 4: UNSATURATED HC (REACTIONS) AND AROMATICS (PROPERTIES)

Names for Aromatic Hydrocarbons Fused-Ring Aromatic Hydrocarbons

• Name the substituent followed by the name • Fused-ring aromatic hydrocarbons:
benzene. Aromatic hydrocarbon whose structure
• When more than one substituent present, contains two or more rings fused together
indicate the position by number followed by and two carbon rings share a pair of carbon
name of the substituent and the name atoms
benzene • Examples:
o No need to indicate position if there
is only one substituent
o Positions 1,2 are also known as
Ortho positions
o Positions 1,3 are also known as
Meta positions
o Positions 1,4 are also known as
Para positions
-O Cl Cl
O-
F N+
Cl N+
O
O
fluorobenzene nitrobenzene
1,2-dichlo robenzene 1-chloro-2-nitrobenzene
Aromatic Compounds
Aromatic Hydrocarbons: Physical Properties Benzene Structure
and Sources • Benzene
• Has 6 electrons shared equally among the 6
• Insoluble in water C atoms.
• Soluble in non-polar solvents like • Is also represented as a hexagon with a
hydrocarbons etc. circle drawn inside.
• Less dense than water therefore floats on
water
• Benzene is colorless, flameless liquid, burns
with sooty flame
• Petroleum is the primary source of aromatic
hydrocarbons
o Gasoline has significant amount of
benzene in it
Aromatic Compounds in Nature and Health
Chemical Reactions of Aromatic Hydrocarbons
• Aromatic hydrocarbons do not readily
undergo the addition reactions because of
delocalized bonding system (resonance)
• Benzene undergoes substitution reactions
• Two important types of substitution
reactions for benzene and other aromatic
hydrocarbons are alkylation and
halogenation
o Alkylation
CH3
AlCl3 Naming Aromatic Compounds
+ CH3Cl + HCl
• Aromatic compounds are named
• With benzene as the parent chain.
o Halogenation
Br • With one side group named in front of
FeBr 3 benzene.
+ Br2 + HBr
 MODULE 4: UNSATURATED HC (REACTIONS) AND AROMATICS (PROPERTIES)

Substitution Reactions
• In a substitution reaction, a hydrogen atom
on a benzene ring is replaced by an atom or
group of atoms.

Some Common Names

• Some substituted benzene rings
• Have common names used for many years. Halogenation
• With a single substituent use a common • In a halogenation
name or are named as a benzene • An H atom of benzene is replaced by a
derivative. chlorine or bromine atom.
• A catalyst such as FeCl3 is needed in
chlorination.
• A catalyst such as FeBr3 is needed in
bromination.

Aromatic Compounds with Two Groups

• Two naming systems are used when two
groups are attached to a benzene ring.
Nitration
o Number the ring to give the lowest
numbers to the side groups. • In the nitration of benzene
o Use prefixes to show the • An H atom of benzene is replaced by a nitro
arrangement: (-NO2) group from HNO3.
ortho(o-) for 1,2- • An acid catalyst such as H2SO4 is needed.
meta(m-) for 1,3-
para(p-) for 1,4-

Sulfonation
• In a sulfonation
• An H atom on benzene is replaced by a —
SO3H group from SO3.
• An acid catalyst such as H2SO4 is needed.
H SO3H
H2SO4
+ SO3

Properties of Aromatic Compounds Benzene Benzenesulfonic acid

Aromatic compounds
• Have a stable aromatic bonding system.
• Are resistant to many reactions.
• Undergo substitution reactions, which retain
the stability of the aromatic bonding system.
 MODULE 4: UNSATURATED HC (REACTIONS) AND AROMATICS (PROPERTIES)

Addition Reactions Trans Fats

• In addition reactions, • In vegetable oils, the unsaturated fats
• Reactants add to the carbon atoms in usually contain cis double bonds.
double or triple bonds. • During hydrogenation, some cis double
• A double or triple bond is easily broken, bonds are converted to trans double bonds
which makes them very reactive. (more stable) causing a change in the fatty
acid structure
• If a label states “partially” or “fully
hydrogenated”, the fats contain trans fatty
acids.

Halogenation
• In halogenation, halogen atoms add to the
carbon atoms of a double bond or triple
bond.

Testing for Unsaturation

• When bromine (Br2) is added to an alkane,
Hydrogenation the red color of bromine persists.
• In hydrogenation, • When bromine (Br2) is added to an alkene
or alkyne, the red color of bromine
• Hydrogen atoms add to the carbon atoms of
disappears immediately.
a double bond or triple bond.
• A catalyst such as Pt or Ni is used to speed Br2 Br2
up the reaction.
H H
Pt
H2C CH2 + H2 H2C CH2

H H
Ni
HC CH + 2H2 HC CH
H H
Hydrohalogenation
Hydrogenation of Oils • In hydrohalogenation, the atoms of a
• Adding H2 to double bonds in vegetable oils hydrogen halide add to the carbon atoms of
produces a double bond or triple bond.
o Compounds with higher melting H Cl
points. CH3 CH CH CH3 + HCl CH3 CH CH CH3
o Solids at room temperature such as
margarine, soft margarine, and H
+ HBr
shortening.
Br

Markovnikov’s Rule
• When an unsymmetrical alkene undergoes
hydrohalogenation, the H in HX adds to the
carbon in the double bond that has the
greater number of H atoms.
H Cl
CH3 CH CH2 Does not form

CH3 CH CH2 + HCl

C with the most H
Cl H
CH3 CH CH2 Product that forms
 MODULE 4: UNSATURATED HC (REACTIONS) AND AROMATICS (PROPERTIES)

Hydration Common Synthetic Polymers

• In the addition reaction called hydration
• An acid H+ catalyst is required.
• Water (HOH) adds to a double bond.
• An H atom bonds to one C in the double
bond.
• An OH bonds to the other C.

• When hydration occurs with a double bond

that has an unequal number of H atoms,
• The H atom bonds to the C in the double
bond with the most H. Polymers from Addition Reactions
• The OH bonds to the C in the double bond
with the fewest H atoms.

Polymers
• Polymers are
• Large, long-chain molecules.
• Found in nature, including cellulose in
plants, starches in food, proteins and DNA
in the body.
• Also, synthetic such as polyethylene and
polystyrene, Teflon, and nylon.
• Made up of small repeating units called
monomers. More Monomers and Polymers
• Made by reaction of small alkenes.

Polymerization
In polymerization, small repeating units called
monomers join to form a long chain polymer.
Monomer unit repeats.
H H H H H H
C C + C C + C C
H H H H H H
Ethylene monomers
H H H H H H
chain continues C C C C C C chain continues
H H H H H H

Polyethylene