CHAPTER 3:

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ALKENES AND ALKYNES
MPB
SY 2014-2015 2ND SEM
OUTLINE
1.) Definition: Alkene and Alkyne
2.) Structure of Alkenes and Alkynes
3.) Cis-Trans Stereoisomerism
4.) Naming: a.) Alkenes and Alkynes
b.) Cycloalkenes
c.) Polyenes
5.) Physical properties of alkenes and Alkynes
6.) Terpenes
7.) Characteristic Rxns of Alkenes:
a.) Hydrohalogenation
b.) Acid-catalyzed hydration
c.) Halogenation
d.) Reduction
8.) Polymerization
a.) Structure of Polyethylene
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b.) LDPE
c.) HDPE
WHAT ARE ALKENES & ALKYNES?
 unsaturated hydrocarbons that contain one or
more carbon–carbon double bonds, triple bonds,
or benzene-like rings.

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ALKENES
 Compounds containing carbon–carbon
double bonds are especially widespread
in nature.

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ALKYNES
 Alkynes are unsaturated hydrocarbons
that contain one or more carbon–carbon
triple bonds.
 The simplest alkyne is acetylene. Known
to be a natural ripening agent for fruits.

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PREPARATION OF ETHENE:

 Thermal cracking of natural gas:

-saturated hydrocarbon is converted to an
unsaturated hydrocarbon plus H2 by heating it in
a furnace to 800–900°C for a fraction of a second.

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WHAT ARE THE STRUCTURES OF
ALKENES & ALKYNES?

 The geometry around each carbon is called trigonal

planar
 All atoms directly connected to each carbon are in a
plane
 The bonds point towards the corners of a regular
triangle 7
 The bond angle are approximately 120
o
CIS & TRANS CONFIGURATION OF ALKENES
 Because of restricted rotation around double
bonds, two configurations can arise due to
different bonding positions of the groups.
 This is a type of Stereoisomerism

- cis-isomer – two groups on the same side

- trans-isomer – two groups on the opposite side

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CIS & TRANS CONFIGURATION OF ALKENES

 The orientation of the carbon atoms of the parent

chain determines whether an alkene is cis or
trans.
 If the carbons of the parent chain are on the same
side of the double bond, the alkene is cis; if they
are on opposite sides, it is a trans alkene.

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NAMING ALKENES AND ALKYNES
Alkenes and alkynes are named using the IUPAC
system of nomenclature
 The key to the IUPAC system of naming alkenes is
the ending –ene. To name an alkene:
1.) Find the longest carbon chain that includes the
double bond.
2.) Number the chain from the end that gives the
lower set of numbers to the carbon atoms of the
double bond.
3.) Branched alkenes are named in a manner similar
to alkanes; substituent groups are located and
named.

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NAMING ALKENES AND ALKYNES

 The key to the IUPAC system of naming alkynes is the

ending –yne. To name an alkyne, the same steps in
naming alkenes are followed.

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PRACTICE: IUPAC NAMING

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COMMON NAMES OF ALKENES & ALKYNES

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NAMING CYCLOALKENES

 Number the carbon atoms of the ring double bond

1 and 2 in the direction that gives the substituent
encountered first the lower number.

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NAMING CYCLOALKENES

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 DIENES, TRIENES, POLYENES
 We name alkenes that contain more than one double
bond as alkadienes, alkatrienes, and so on.

For an alkene with one carbon–carbon double bond

that can show cis-trans isomerism, two stereoisomers are
possible.
For an alkene with n carbon–carbon double bonds, each of 17
which can show cis-trans isomerism, 2n stereoisomers are
possible.
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 same

 21 = 2 stereoisomers (one cis-trans pair) are

possible. The trans isomer of this alcohol, named
geraniol, is a major component of the oils of rose,
citronella, and lemon grass.

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 therefore, 24= 16 stereoisomers possible for this
structural formula. Vitamin A, the stereoisomer
shown here, is the all trans isomer.

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WHAT ARE PHYSICAL PROPERTIES OF
ALKENES & ALKYNES?

 Alkenes and alkynes are nonpolar compounds, and

the only attractive forces between their molecules are
very weak London dispersion forces.
 Their physical properties, therefore, are similar to
those of alkanes with the same carbon skeletons.
 Alkenes and alkynes that are liquid at room
temperature have densities less than 1.0 g/mL (they
float on water).
 They are insoluble in water but soluble in one
another and in other nonpolar organic liquids. 21
 WHAT ARE TERPENES?
 Among the compounds found in the essential oils
of plants are a group of substances called
terpenes.
 Terpenes – have a five-carbon skeleton isoprene.

Carbon 1 of an isoprene unit is called the head, and

carbon 4 is called the tail.
A terpene is a compound in which the tail of one
isoprene unit becomes bonded to the head of another 22

isoprene unit.
WHAT ARE TERPENES?

 Probably the terpenes most familiar to you—at

least by odor—are components of the so-called
essential oils extracted from various parts of
plants.
 Essential oils contain the relatively low-
molecular-weight substances that are largely
responsible for characteristic plant fragrances.

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EXAMPLES OF TERPENES
FOUND IN ESSENTIAL OILS:

 FIGURE 3.1 Four terpenes, each derived from two isoprene units
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bonded from the tail of the first unit to the head of the second unit. In
limonene and menthol, formation of an additional carbon–carbon bond
creates a six-membered ring.
EXAMPLES OF TERPENES FOUND IN
ESSENTIAL OILS:
Farnesol, a terpene with a
molecular formula of C15H26O,
includes three isoprene units.
Derivatives of both farnesol and
geraniol are intermediates in
the biosynthesis of cholesterol
(Section 21.3).

 Vitamin A (Section 3.3E), a

terpene with a molecular
formula of C20H30O,
 consists of four isoprene
units bonded head-to-tail
and cross-linked at one
point to create a six- 25
membered ring.
CHARACTERISTIC REACTIONS OF ALKENES

 The most characteristic reaction of alkenes is

addition to the carbon–carbon double bond: The
double bond is broken and in its place single
bonds form to two new atoms or groups of atoms.
 Table 3.1 shows several examples of alkene
addition reactions along with the descriptive
name(s) associated with each reaction.

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A. ADDITION OF HYDROGEN HALIDES
(HYDROHALOGENATION)

 The hydrogen halides HCl, HBr, and HI add to

alkenes to give haloalkanes (alkyl halides).
 Addition of HCl to ethylene, for example, gives
chloroethane (ethyl chloride):

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REGIOSELECTIVITY OF ADDITION REACTION

 Addition of HCl to propene gives 2-chloropropane

(isopropyl chloride); hydrogen adds to carbon 1 of
propene and chlorine adds to carbon 2. The observed
result is that almost no 1-chloropropane forms.
 Because 2-chloropropane is the observed product, we
say that addition of HCl to propene is regioselective.
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  Regioselective reaction - A reaction in which
one direction of bond forming or bond breaking
occurs in preference to all other directions

This regioselectivity was noted by Vladimir

Markovnikov (1838–1904), who made the
following generalization:
Markovnikov’s rule: In the addition of HX (where
x = halogen) to an alkene, hydrogen adds to the
doubly bonded carbon that has the greater number
of hydrogens bonded to it; halogen adds to the
other carbon.

“The rich gets richer, the poor gets poorer”. 30

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 Reaction mechanism - A step by-step
description of how a chemical reaction occurs.
 We use a curved arrow that shows the
repositioning of an electron pair from its origin
(the tail of the arrow) to its new location (the
head of the arrow).
 A species containing a positively charged carbon
atom with only three bonds to it and bearing a
positive charge is called a carbocation
 (carbon + cation).

 Carbocations are classified as primary (1°),

secondary (2°), or tertiary (3°), depending on
the number of carbon groups bonded to the
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carbon bearing the positive charge.
MECHANISM: ADDITION OF HCL TO 2-BUTENE
-rate-determining step
-Endergonic process
 STEP 1: FORMATION OF CARBOCATION -Slow reaction

 STEP 2: BONDFORMATION OF CARBOCATION & HALIDE ION

-Exergonic process
-rapid reaction

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REASON FOR REGIOSELECTIVITY:
MARKOVNIKOV’S RULE
 The H attaches to the carbon with more H atoms
attached to it because the positive charge in the
resulting carbocation is more stabilized due to
hyperconjugation.
( Stability: 3o > 2o > 1o carbocation)

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B. ADDITION OF WATER: ACID-CATALYZED
HYDRATION (HYDRATION)

 In the presence of an acid catalyst, most

commonly concentrated sulfuric acid, water adds
to the carbon–carbon double bond of an alkene to
give an alcohol. Addition of water is called
hydration.

Most industrial ethanol is made by the 35

acid-catalyzed hydration of ethylene.

B. ADDITION OF WATER: ACID-
CATALYZED HYDRATION
(HYDRATION)
 In the case of simple alkenes, hydration follows
Markovnikov’s rule: H of H2O adds to the carbon
of the double bond with the greater number of
hydrogens and OH of H2O adds to the carbon
with the smaller number of hydrogens.

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MECHANISM: HYDRATION (ACID CATALYZED)

Step 1

Step 2

Step 3
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ANSWER 3.9

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C. ADDITION OF BROMINE AND
CHLORINE (HALOGENATION)
 Chlorine, Cl2, and bromine, Br2, react with
alkenes at room temperature by addition of
halogen atoms to the carbon atoms of the double
bond.
 This reaction is generally carried out either by
using the pure reagents or by mixing them in an
inert solvent, such as dichloromethane, CH2Cl2.

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C. ADDITION OF BROMINE AND
CHLORINE (HALOGENATION)

 Addition of bromine is a useful qualitative test for

the presence of an alkene.

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D. ADDITION OF HYDROGEN:
REDUCTION (HYDROGENATION)
 Virtually all alkenes react quantitatively with
molecular hydrogen, H2, in the presence of a transition
metal catalyst to give alkanes.
 Because the conversion of an alkene to an alkane
involves reduction by hydrogen in the presence of a
catalyst, the process is called catalytic reduction or,
alternatively, catalytic hydrogenation.

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 MECHANISM: HYDROGENATION

ACTIVE FIGURE 3.2

The addition of hydrogen to an alkene involving a transition
metal catalyst.
(a ) Hydrogen and the alkene are adsorbed on the metal
surface and
(b ) one hydrogen atom is transferred to the alkene, forming
one new C-H bond. The other carbon remains adsorbed on
the metal surface. 46

(c ) A second CH bond is formed and the alkene is desorbed.

 HYDROHALOGENATION

 HALOGENATION

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POLYMERS

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 WHAT ARE THE IMPORTANT POLYMERIZATION
REACTIONS OF ETHYLENE & SUBSTITUTED
ETHYLENES?

A. Structure of Polyethylenes

 Polymer - any long chain molecule synthesized by

bonding together many single parts called
monomers

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 WHAT ARE THE IMPORTANT POLYMERIZATION
REACTIONS OF ETHYLENE & SUBSTITUTED
ETHYLENES?

A. Structure of Polyethylenes
 In the presence of certain compounds called
initiators, many alkenes form polymers made by
the stepwise addition of monomers to a growing
polymer chain, as illustrated by the formation of
polyethylene from ethylene.
 In alkene polymers of industrial and commercial
importance, n is a large number, typically several
thousand.

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WHAT ARE THE IMPORTANT POLYMERIZATION
REACTIONS OF ETHYLENE & SUBSTITUTED
ETHYLENES?

 To show the structure of a polymer, we place

parentheses around the repeating monomer
unit.
 A subscript n is placed outside the parentheses
to indicate that this unit is repeated n times

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WHAT ARE THE IMPORTANT POLYMERIZATION
REACTIONS OF ETHYLENE & SUBSTITUTED
ETHYLENES?

 The most common method of naming a polymer is

to attach the prefix poly- to the name of the
monomer from which the polymer is
synthesized— for example, polyethylene and
polystyrene.
 When the name of the monomer consists of two
words (for example, the monomer vinyl chloride),
its name is enclosed in parentheses. 52
Poly(vinyl chloride)
WHAT ARE THE IMPORTANT POLYMERIZATION
REACTIONS OF ETHYLENE & SUBSTITUTED
ETHYLENES?

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TABLE 3.2 LISTS SEVERAL IMPORTANT POLYMERS
DERIVED FROM ETHYLENE AND SUBSTITUTED
ETHYLENE, ALONG WITH THEIR COMMON NAMES AND
MOST IMPORTANT USES.

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TABLE 3.2 LISTS SEVERAL IMPORTANT POLYMERS
DERIVED FROM ETHYLENE AND SUBSTITUTED
ETHYLENE, ALONG WITH THEIR COMMON NAMES AND
MOST IMPORTANT USES.

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B. LOW-DENSITY POLYETHYLENE
(LDPE)
 The first commercial process for ethylene
polymerization used peroxide initiators at 500°C
and 1000 atm and yielded a tough, transparent
polymer known as low-density polyethylene
(LDPE).
 At the molecular level, LDPE chains are highly
branched, with the result that they do not pack well
together and the London dispersion forces between
them are weak.

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LDPE FABRICATION

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C. HIGH-DENSITY POLYETHYLENE (HDPE)
 In the 1950s, Karl Ziegler of Germany and Giulio
Natta of Italy developed an alternative method for
the polymerization of alkenes, which does not rely
on peroxide initiators.
 Polyethylene from Ziegler-Natta systems, termed
high-density polyethylene (HDPE), has little
chain branching.
 Consequently, its chains pack together more closely
than those of LDPE, with the result that the London
dispersion forces between chains of HDPE are
stronger than those in LDPE.
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HDPE

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HDPE PREPARATION

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END OF CHAPTER 3

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