Unsaturated

Hydrocarbons
 Unsaturated Hydrocarbon

• it is a hydrocarbon in which one or more carbon-carbon multiple bonds double

bonds, triple bonds, or both) are present.
• Have physical properties to saturated hydrocarbon but not in their chemical
properties.
• Functional Group - is the part of an organic molecule where most of its
chemical reactions occur
• Unsaturated hydrocarbons are subdivided into three groups on the basis of the
type of multiple bonds present:
– Alkenes
• contain one or more carbon-carbon double bonds
– Alkynes
• contain one or more carbon-carbon triple bonds
– Aromatic Hydrocarbons
• exhibit a special type of “delocalized” bonding that involves a six-membered carbon ring.
 ALKENE
• an acyclic unsaturated hydrocarbon that contains one or more carbon-
carbon double bonds.
• -ene instead of -ane
• C=C instead of C-C

Ethene (instead of Ethane)

Propene (instead of propane)

 Cycloalkene
• a cycloalkene is a cyclic unsaturated hydrocarbon that contains one or more
carbon-carbon double bonds within the ring system.

Cyclopropane Cyclopropene
IUPAC nomenclature for
Alkenes and
Cycloalkenes
 Rule 1
• Replace the alkane suffix -ane with the suffix -ene, which is used
to indicate the presence of a carbon-carbon double bond.
 Rule 2
• Select as the parent carbon chain the longest continuous chain of carbon
atoms that contains both carbon atoms of the double bond
 RULE 3
• Number the parent carbon chain • If the double bond is equidistant from
beginning at the end nearest the both ends of the parent chain, begin
double bond numbering from the end closer to a
substitiuent.
4 3 2 1
1 2 3 4 5
 RULE 4
• Give the position of the 1 2 3 4
double bond in the chain as
a single number, which is
the lower-numbered carbon 2-Butene
atom participating in the 1 2 3 4
double bond. The number is
placed immediately before
the name of the parent
carbon chain
3-Methyl-1-butene
 RULE 5
• Use the suffixes -diene, -triene, - 1 2 3 4 5
tetrene and so on when more
than one double bond is present
in the molecule. A separate
number must be used to locate
each double bond

3-Methyl-1,4-pentadiene

1 2 3 4
1,3-Butadiene
 Rule 6

• Do not use a number to

locate the double bond in
substituted cycloalkenes
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 double bond, the Cyclohexene
double-bonded carbon atoms are
numbered 1 and 2 in the
direction (clockwise or
counterclockwise) that gives the
2
first-encountered substituent
1
the lower number. Again, no 3

number is used in the name to 4-Methylcyclohexene

locate the double bond 4

 Rule 8
• In cycloalkenes with more than one double bond within the ring, assign one
double bond the numbers 1 and 2 and the other double bonds the lowest numbers
possible. 3
2
4 2
1 3

5
1
6 4
6
5

5-Chloro-1,3-cyclohexadiene
1,4-Cyclohexadiene
 Common Names (Non-IUPAC Names)
• The simpler members of most families of organic compounds, including alkenes,
have common names in addition to IUPAC names. In many cases these common
(non-IUPAC) names are used almost exclusively for the compounds.

• Ethylene and Propylene

 Alkenes as Substituents
• Just as there are alkenes and alkyl groups,
there are alkenes and alkenyl groups. An
alkenyl group is a noncyclic hydcarbon
substituent in which a carbon-carbon
double bond is present. The three most
frequently encountered alkenyl groups are
the one-, two-, and three-carbon entities,
which may be named using IUPAC 1. Methylene group (IUPAC name:
nomenclature (methylidene, ethenyl, and 2- methylidene group)
propenyl) or with common name 2. Vinyl group (IUPAC name: ethenyl group)
(methylene, vinyl, and allyl). 3. Allyl group (IUPAC name: 2-propenyl group)
 • The use of these alkenyl group names
in actual compound nomenclature is
Methylene cyclopentane illustrated in the following examples:
(IUPAC name: methylidenecyclopentane)

Vinyl chloride
(IUPAC name: chloroethene)

Allyl bromide
(IUPAC name: 3-bromopropene)
 Line-Angle Structural Formulas For Alkenes
• Line-angle formulas for the three- to six-carbon acyclic 1-alkenes are as follows

Propene 1-Butene 1-Pentene 1-Hexene

• Representative line-angle structural formulas for substituent-bearing alks

include 5 3 1
6 4 2 4 2
5 3 1

3,5-Dimetyhl-1-hexene 2-Ethyl-3-methyl-1-pentene
2-Methyl-1,3-butadiene 1,4-Pentadiene
 Constitutional Isomerism in Alkenes

• Constitutional isomerism is possible for alkenes, just as it was for alkanes. In

general, there are more alkene isomers for a given number of carbon atoms that
there are alkane isomers.
 Four-Carbon Alkenes (three isomers)
Four-Carbon Alkanes (two isomers)

1-Butene

Butane

2-Butene

2-Methylpropane
2-Methylpropene
• Skeletal isomers are constitutional isomers that have different carbon-
chain arrangements as well as different hydrogen atom arrangements.
The C4 alkenes 1-butene and 2 -methylpropene are skeletal isomers.

• There are two concepts in the thinking pattern:

– The different carbon skeletons (branced or unbranched) that are possible
using five carbon atoms determined.
– For each of the carbon skeletons determined, different positions for
placement of the double bond are then considered.
 STEP 1
• There are three possible arrangements for five carbon atoms:

• C-C-C-C-C
C
• C-C-C-C
C
• C-C-C
C
 STEP 2
• For the first carbon skeleton (the unbranched chain), there are two possible
locations for the double bond; that is, there are two positional isomers:

• CH2=CH-CH2-CH2-CH3 (1-Pentene)

• CH3-CH=CH-CH2-CH3 (2-Pentene)
 Molecular Formula: C5H10

2-Methyl-1,2-butadiene
2-Methyl-1-butene 2-Methyl-2-butene

3-Methyl-1-butene
 Cis-Trans Isomerism in Alkenes
• Cis-trans isomerism is possible for some alkenes.Such isomerism results from
the structural rigidity associated with carbon-carbon double bonds: Unlike the
situations in alkanes, where free rotation about carbon-carbon single bonds is
possible. no rotation about carbon-carbon double bonds can occur.
• To determine whether an alkenes, like the ring of cycloalkanes, imposes
rotational restrictions.
• If each of the two carbons of the double bond has two different groups attached
to it, cis and trans isomers exist.

CH3 CH3 CH3 H

C = C C = C
H H H CH3

cis-2-butene trans-2-butene
 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 alkene-type
pheromones is usually highly dependent on whether the double bonds present
are in cis or a trans arrangement
• The sex attractant of the female silkworm is a 16-carbon ene derivative
containing an -OH group. Two double bonds are present, trans at carbon 10 and
cis at carbon 12.
 Naturally Occurring Alkenes
• Terpenes - a terpene is an organic compound 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

CH3

CH2 = C - CH = CH2
2-Methyl-1,3-butadiene
 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
 Chemical Reactions of Alkenes
• Alkenes, are like alkanes, they are very flammable. The combustion products, as
with hydrocarbon, are carbon dioxide and water.

• C2H4 + 3O2 2CO2 + 2H2O

• 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:

C = C + A-B C C
A B
 ADDITION REACTIONS
• Symmetrical Addition Reaction
– an addition reaction in which identical atoms (or group of atoms) are added to each
carbon of a carbon-carbon multiple bond.

• Unsymmetrical Addition Reaction

– an addition reaction in which different atoms (or groups of atoms) are added to the
carbon atoms of a carbon-carbon multiple bond.
 Symmetrical Addition Reactions
• The two most common examples of symmetrical addition reactions are hydrogenation and
halogenation.
• A hydrogenation reaction is an addition reaction in which H 2 is incorporated into molecules
of an organic compound..
• A halogenation reaction is an addition reaction in which a halogen is incorporated into
molecules of an organic compound. In alkene halogenation a halogen atom is added each
carbon atom of a double bond. Chlorination (Cl2) and bromination (Br2) are the two
halogenation processes most commonly encountered. No catalyst is needed.
Cl Cl
CH3 - CH = CH - CH3 + Cl2 CH3 - CH - CH - CH3
2-Butene 2,3-Dichlorobutane
 Unsymmetrical Addition Reactions
• Two important types of unsymmetrical addition reactions are hydrohalogenation
and hydration:
• A hydrohalogenation reaction is an addition reaction in which a hydrogen
halide (HCl, HBr, or HI) is incorporated into molecules of an organic compound
H Cl
CH2 = CH2 + H - Cl CH2 - CH2
• A hydration reaction is an addition reaction in which H2O is incorporated into
molecules of an organic compound
H OH
CH2 = CH2 + H - OH 2 H SO
4
CH2 - CH2
 Alkynes
• Alkynes represent the second class of unsaturated hydrocarbons. An alkyne is an
acyclic unsaturated hydrocarbon that contains one or more carbon-carbon triple
bonds. The alkyne functional group is, thus, a C C group.
• Ends with -yne

• CH CH CH C- CH3
Propyne
Ethyne
IUPAC Nomenclature for Alkynes
ALKYNES
IUPAC Nomenclature for Alkynes
• The rules for naming alkynes are
identical to those used to name
alkenes, except the ending -yne is
used instead of -ene. Consider the
following structures and their IUPAC
names.
Isomerism and Alkynes
 Physical and Chemical Properties of Alkynes

• The physical properties of alkynes are similar to those of alkenes and alkanes.
• In general, alkynes are:
– insoluble in water but soluble in organic solvents
– have densities less than water
– have boiling points that increase with molecular mass.
– Low-molecular-mass alkynes are gases at room temperature.
 Aromatic Hydrocarbons
• Aromatic hydrocarbons are the third
class of unsaturated hydrocarbons;
alkenes and alkynes are the two
classes.
• An aromatic hydrocarbon is an
unsaturated cyclic hydrocarbon that
does not readily undergo addition
reactions
• An alternative notation for denoting the bonding in benzene-a notation that
involves a single structure is:

• In this “circle-in-the-ring” structure for bezene, the circle denotes the electrons
associated with the double bonds that move “around” the ring.
• A delocalized bond is a covalent bond ich electrons are shared among more than
two atoms.
• This structure represented by the notation is called an aromatic ring system,
and it is the functional group present in aromatic compounds. An aromatic ring
system is a highly unsaturated carbon ring system in which both localized and
delocalized bonds are present
 Names for Aromatic Hydrocarbons
1. Benzene Derivatives with One Substituent
CH2CH3 Cl CH2
C(CH3)3 NO 2

t-Butylbenzene Ethylbenzene Nitrobenzene Chlorobenzene Benzyl group

2. Benzene Derivatives with Two Substituents

Br
Br
Br
Br

Br
Br
1,2-Dibromobenzene 1,3-Dibromobenzene 1,4-Dibromobenzene
o-Dibromobenzene m-Dibromobenzene p-Dibromobenzene

3. Benzene Derivatives with Three or More Substituents

 CH3 H3C
CH3 • The prefix system uses the prefixes
CH3
ortho-, meta-, and para- (abbreviated
CH3
CH3
o-, m-, and p-)
– Ortho- means 1,2 distribution
o-Xylene m-Xylene p-Xylene

– Meta- means 1, 3 distribution

– Para- means 1, 4 distribution
• When benzene ring is treated as a substituent-that is, as a phenyl group
• Toluene - one methyl group
• Xylene - Two methyl group
• When parent names such as toluene
and xylene are used, additional
substituents present cannot be the
same as those included in the parent
name. If such is the case, name the
compound as a substituted benzene.
The compound is named as a
trimethylbenzene and not as a
methylxylene or a dimethyltoluene
 Aromatic Hydrocarbons
• Physical Properties • Chemical Properties
– insoluble in water – alkylation
– good solvents for other nonpolar – halogenation
materials
– less dense in water
 Fused-Ring Aromatic Hydrocarbons
• A fused-ring aromatic hydrocarbon is
an aromatic hydrocarbon whose
structure contains two or more rings
fused together.