Organic Chemistry

Alkenes, Alkynes, and Aromatic Compounds

Dr. Dikdik Kurnia, M.Sc

Laboratorium Kimia Organik – Jurusan Kimia

Fakultas Matematikan dan Ilmu Pengetahuan Alam
Universitas Padjadjaran
2009
Organic Chemistry
Code of Lecture : D10B. 03E0318
The Unit of Semester credits (SKS) : 2 (2-0)
Semester : Fm/1
Day/Time : Thursday, 13.00 – 14.40 am

Laboratorium Kimia Organik – Jurusan Kimia

Fakultas Matematikan dan Ilmu Pengetahuan Alam
Universitas Padjadjaran
2009
 Alkenes, Alkynes, and Aromatic Compounds
1. What are alkenes, alkyunes, and aromatic compounds?
Be able to recognize the structure of members of these three families of
unsaturated organic compounds and give examples of each.
2. How are alkenes, alkyunes, and aromatic compounds named?
Be able to name an alkene, alkyune, or simple aromatic compound from its
structure or write the structure, given name.
3. What are cis-trans isomers?
Be able to identity cis-trans isomers and predict their occurrence.
4. What are the general properties of alkyunes, and aromatic compounds?
Be able to describe and compare such properties as polarity, water solubility,
flammability, bonding, and chemical reactivity.
5. What are the common chemical reactions of alkyunes, and aromatic compounds?
Be able to predict the products of reactions of alkyunes, and aromatic compounds.
6. How do organic reactions take place?
Be able to show how addition reaction occur and describe the difference between
additon and substitution reactions.
 Alkenes, Alkynes, and Aromatic Compounds

Compounds in three families described in this chapter all contain carbon-

carbon multiple bonds;
a. Alkenes (ethlene), contain a carbon-carbon double bond
b. Alkyunes (acetylene), contain a carbon-carbon triple bond
c. Aromatic compounds (benzene), contain a six-membered ring of carbon
atoms with three double bonds or other rings with similar arrangment of
alternating double bonds.
 Saturated and Unsaturated Hydrocarbons

CH3CH2CH3
The alkanes are often referred to as saturated hydrocarbons because each
carbon atom is fully “saturated” by bonds to the maximum number of
hydrogen atoms: No more hydrogen atoms can be added.

CH3CH=CH3 CH3CHCH3

Alkenes and Alkyunes contain carbon-carbon multiple bonds to which more

hydrogen atoms can be added and are therefore knows as unsaturated
hydrocarbons.

Alkenes are hydrocarbons that contain carbon-carbon doube bonds

Alkyunes are hydrocarbons that contain carbon-carbon triple bonds
 Alkenes
Simple Alkenes are made in huge quantities by thermal cracking of natural gas
and petroleum and are the basic building block of the vast petrochemical
industri, which produces organic chemicals from petroleum.
750-900C
CH3(CH2)nCH3 H2 + CH4 + CH2=CH2 + CH2=CH2 + CH3CH2CH=CH2

-Caroten (a
polyalkene)

cis-polyisoprene (Natural rubber)

 Naming Alkenes and Alkynes
1. Name the parent compound
Find the longest chain containing the double or triple bond and name the
parent compound by adding the suffix –ene or –yne to the root for main
chain.
 Naming Alkanes and Alkyunes

2. Number the carbon atoms in the main chain.

Beginning and the end nearer the multiple bond, number each carbon
atom in the chain.
If the multiple bond is an equal distance from the both ends, as in the
middle structure, begin numbering at the end nearer the first branch
point.
 Naming Alkanes and Alkyunes

2. Number the carbon atoms in the main chain.

For the cyclic alkenes, the-ane ending of the cycloalkane is replaced by –ene.
No numbers are needed for an unsubstituted cycloalkene.
In substituted cycloalkenes, the double-bond carbon atoms are numbered 1
and 2 so that the first substituent has the lower number:
 Naming Alkanes and Alkyunes
3. Write out the full name.
Identify and number branching substituents in the same way as for alkaes:
Assign number to the branching substituents on the chain and list them
alphabetically.
Use commas to separates numbers and use hyphens to separate words from
numbers.
 Naming Alkanes and Alkyunes
3. Write out the full name.
Indicate the position of multiple bond in the chain by giving the number of the
first multiple-bonded carbon.
If more than one double bond is present, identify the position of each and use
the name endings –diene, -triene, tetraene, and so forth, to give the exact
number of double bonds.
In naming cycloalkenes, it isn’t necessary to include the number 1 to locate the
double bond.
 The Structure of Alkenes: cis-trans Isomerism
Alkenes and Alkyunes differ from alkanes in shapes because of their differet kinds of
bonds

Two carbons and four attached atoms that make up the double-bond functional
group always lie in planar.

Unlike in alkannes where free rotation around the C-C single bond occurs, there is no
free rotation around double bonds a new kind of isomerism is possible for
alkenes
 The Structure of Alkenes: cis-trans Isomerism
1-butene and 2-butene are isomers because their double bonds occur at different
positions along the chain.

Because of the rotation can’t occur around carbon-

carbon double bonds, there are two different 2-
butenes.

1. The two methyl groups are close together on the

same side of the double bond.

2. The two methyl groups are far apart on opposite

sides of the double bond.
 The Structure of Alkenes: cis-trans Isomerism

1-butene and 2-butene are isomers because their double bonds occur at
different positions along the chain, while 2-methylpropene is isomeric with
both because it has a different connection of carbon atoms.

2-methylpropene

1-butene

2-butene
 The Structure of Alkenes: cis-trans Isomerism

Isomers, cis-trans: Alkenes that have the same formula and connections
between atoms but differ in having pairs of groups on opposite sides of the
double bonds.

cis- isomer: Isomer with a specific pairs of atoms or groups on the same side
of thedouble bond.

trans- isomer: Isomer with a specific pairs of atoms or groups on opposite side
of thedouble bond.
 The Structure of Alkenes: cis-trans Isomerism
cis-trans isomers occurs in an alkene whenever each double bond carbon is
bonded to two different substituents groups.
If either double-bond carbond is attached to two identical cis-trans
isomerism is not possible.

These compounds are

identical, because the left-
hand carbon of the double
bond has two –H’s attached,
cis-trans isomerism is
impossible

These compounds are not

identical, neither carbon of
the double bond has two
identical groups attached to
it
 Properties of Alkenes

 Nonpolar: insoluble in water; soluble in nonpolar organic

solvent; less dense than water.
 Alkaline-like in melting points, boiling points, and other
physical properties.
 Flammable; gaseous alkenes not toxic.
 Display cis-trans isomerism when each double-bond C atom
has different substituents.
 Chemically reactive at double bond, which undergous
addition reactions.
Properties of Alkenes
 Chemical Reactions of Alkenes and Alkyunes
Most of the reaction carbob-carbon multiple bonds can be grouped under the
category of addition reactions, addition of a reactant of the general form X-Y
to the multiple bond of an unsaturated compound to yield a saturated
poduct.

Alkenes and alkynes react similarity in many ways, but we’ll look at alkenes
because they’re more common and more important
 Chemical Reactions of Alkenes and Alkyunes
Addition of Hydrogen to Alkenes and Alkyunes (Hydrogenation)
Hydrogenation: The reaction of an alkene (or alkyne) with H2 to yiels an alkane
product.
Chemical Reactions of Alkenes and Alkyunes
Addition of Cl2 and Br2 to Alkenes (Halogenation)

Halogenation: The reaction of an alkene (or alkyne) with halogen (Cl 2 or Br2) to
yiels a 1,2-dihaloalkane product.

Halogenation: The reaction of an alkene (or alkyne) with halogen (Cl 2 or Br2) to
yiels a 1,2-dihaloalkane product.
Chemical Reactions of Alkenes and Alkyunes
Addition of Cl2 and Br2 to Alkenes (Halogenation)

Bromination provide a convenient test for the present in a molecul of a

carbon-carbon double or triple bound
A drop of reddish-brown solution of bromin in carbon tetrachloride (CCl4) is
added to a sample of an unknown compound.
Immediate disapperarance of the coloras the bromine react to form a
colorless dibromide reveals the presence of the multiple bond.
Chemical Reactions of Alkenes and Alkyunes
Addition of HBr and HCl to Alkenes

Hydrohalogenation: The reaction of an alkene with HCl or HBr to yiels an alkyl

haide product.

An alkyl bromide

An alkyl chloride
 Chemical Reactions of Alkenes and Alkyunes
Addition of HBr and HCl to Alkenes

 Only one of the two possible addition products is obtained.

 This is what usually happens when HBr and HCl add to alkenes with
unsymmetrically substituted double bonds, that is, double bonds in which
one carbon is bonded to more hydrogens than other
 Chemical Reactions of Alkenes and Alkyunes
Addition of HBr and HCl to Alkenes

Markovnikov’s rule: In the addition of HX to and alkene, the H becomes

attached to the carbon that already has the most H’s,
and the X becomes attached to the carbon that has
fewer H’s.
Chemical Reactions of Alkenes and Alkyunes
Addition of H2O to Alkenes (Hydration)

Hydration, alkene: The reaction of an alkene with water (H2O) to yiels an alcohol.
This reaction occurs on treatment of the alkene with water in the presence of
astrong acid catalyst such as H2SO4.
 Chemical Reactions of Alkenes and Alkyunes
Addition of H2O to Alkenes (Hydration)

As with the addition of HBr and HCl, Markovnikov’s rule can be used to predict
the product when water add to an unsymmetrically substituted alkene.

Markovnikov’s rule: In the addition of HX to and alkene, the H becomes

attached to the carbon that already has the most H’s,
and the X becomes attached to the carbon that has
fewer H’s.
 How An Alkene Addition Reaction Occurs

Step 1
Two electrons from the C-C double bonds are
used to form a new single bond between the
incoming hydrogen ion and one of the carbons.
The other carbon now has only six electrons in
its outer shell and has a positive charge
Carbocation:
A polyatomic ion with a
positively charged carbon
Step 2 atom.
The positively charged carbocation then reacts
with the negatively bromide ion, using an
electron pair from bromide to form a single
bond between carbon and bromine.
The second carbon thus regains an outer-shell
octet

Figure 13.2 A reaction mechanism of how the addition of HBr to an alkene occurs.
The reaction takes place in two steps and involves a carbocation intermediate.
 Alkene Polymers
Monomer:
A small molecule combined to form a polymer
Polymer:
A very large molecule composed of identical repeating units and formed by the
combination of small molecules.

Vinil Monomer:
A compound with the structure CH2=CHZ that undergoes polymerization to give
a polymer with the repeating unit —CH2—CHZ—
Polimerization:
A reaction in which monomers combine to form a polymer.
Chain-growth polymer:
A polymer formed by the addition of monomer molecules one by one to the
end of a growing chain.
Alkene Polymers
Alkynes
Aromatic Compounds and The Structure of Benzene

Aromatic compound:
A compound that contains a six-membered ring of carbon atoms with three
double bonds or a similarly stable ring.

Resonance:
The exixtance of a molecul in a single structure intermediate among two or
more correct possible double-bond-containing structure that can be drawn.

Benzene, The simplest aromatic compound, is a flat, symmetrical molecule

with the molecular formula C6H6 (cyclohexatriene)
Aromatic Compounds and The Structure of Benzene
 Naming Aromatic Compounds

Ortho: Indicates 1,2 substituents on a benzene ring

Ortho: Indicates 1,3 substituents on a benzene ring
Ortho: Indicates 1,4 substituents on a benzene ring

No number is needed for monosubstituted benzene because all the ring

positions are equivalent.
 Naming Aromatic Compounds

Number must be included in the name when a benzene ring three or more
substituents.
In the same manner as for alkane, the numbers are chosen so that substituents
have the lowest possible numbers and the substituents are named in
alphabetical order
Naming Aromatic Compounds
 Naming Aromatic Compounds

Phenyl group: The name of the C6H5- unit when a benzene ring is considered a
substituent group.
Aryl group: The general name for any substituent derived from an aromatic
compound
 Chemical Reactions of Aromatic Compounds
Aromatic Substitution Reactions

Substitution reaction Aromatic:

Substitution of an atom or group for one of the hydrogens on an aromatic ring.
 Chemical Reactions of Aromatic Compounds
Aromatic Substitution Reactions

Nitration
 Chemical Reactions of Aromatic Compounds
Aromatic Substitution Reactions

Halogenation
 Chemical Reactions of Aromatic Compounds
Aromatic Substitution Reactions

Sulfonation
 Polycyclic Aromatic Compounds and Cancer

Polycyclic aromatic compound:

A substance that has to or more benzene-like rings fused together along their
edges.
Polycyclic Aromatic Compounds and Cancer