Topic 8 ALKENES

OVERVIEW
Organic compounds containing one or more carbon–carbon multiple bonds have fewer hydrogen
atoms than structurally related alkanes or cycloalkanes. For this reason, these compounds are said to be
unsaturated. In this chapter, we are going to focus our study about alkene.
Alkenes and their chemical cousins, the cycloalkenes, are very common in nature. Alkenes have
many biological functions. They occur in fats and oils, some vitamins, some are hormones, and others
act as pheromones. Ethene is the simplest hormone. It is produced in small amounts in many fruits and
stimulates ripening.
A more complex alkene, called muscalure, is a pheromone secreted by the common housefly
(Musca domestica). Muscalure, an unbranched alkene containing 23 carbon atoms, is released by the
female to attract males. Muscalure has been synthesized in the laboratory and can be used to lure male

flies to traps.
KEY CONCEPT:
 Alkenes are hydrocarbons in which there is at least one carbon-carbon double.
 To form IUPAC names for alkenes, change the -an- infix of the parent alkane to -en-.
 In naming cycloalkenes, the carbon atoms of the ring double bond are numbered 1 and 2 in the
direction that gives the substituent encountered first the smaller number.
 Cis, trans isomers - Isomers that have the same order of attachment of their atoms but a
different arrangement of their atoms in space owing to the presence of either a ring or a carbon-
carbon double bond.
 Cis - In cis, trans-alkene nomenclature, it refers to molecules in which the carbon atoms of the
main chain are on the same side of the double bond.
 Trans- In cis, trans-alkene nomenclature, it refers to molecules in which the carbon atoms of
the main chain are on opposite sides of the double bond.
 E-Z System - A system to specify the configuration of groups about a carbon-carbon double
bond.
 Z - From the German, zusammen, together. Specifies that groups of higher priority on the
carbons of a double bond are on the same side.
 E - From the German, entgegen, opposite. Specifies that groups of higher priority on the
carbons of a double bond are on opposite sides.
 Addition reaction A reaction in which two atoms or ions react with a double bond, forming a
compound with the two new groups bonded to the carbons of the original double bond.
 Regioselective reaction - An addition or substitution reaction in which one of two or more
possible products are formed in preference to all others that might be formed.
 Markovnikov’s rule - In the addition of HX, H2O, or ROH to an alkene, hydrogen adds to the
carbon of the double bond having the greater number of hydrogens.
LEARNING OBJECTIVES
 Write the name and structure of alkenes and cycloalkenes
 Describe the properties of alkenes
 Explain the preparations and reaction of alkenes

COURSE CONTENT:
An unsaturated hydrocarbon contains one or more carbon-carbon double or triple bonds. The
term “unsaturation” indicates that there are fewer hydrogens bonded to carbon than in an alkane. Alkenes
are hydrocarbons whose molecules contain a carbon–carbon double bond. An old name for this family
of compounds that is still often used is the name olefins. Ethene (ethylene), the simplest olefin (alkene),
was called olefiant gas (Latin: oleum, oil + facere, to make) because gaseous ethene (C2H4) reacts with
chlorine to form C2H4Cl2, a liquid (oil).

7.1 Structure of Alkenes

A. Shapes of Alkenes
Using valence-shell electron-pair repulsion for a carbon-carbon double bond, we
predict a value of 120° for the bond angles about each carbon.

B. Carbon-Carbon Double Bond Orbitals

A carbon-carbon double bond consists of one 𝜎bond and one 𝜎 bond (Figure 5.1). Each
carbon of the double bond uses its three sp2 hybrid orbitals to forms bonds to three atoms. The
unhybridized 2p atomic orbitals, which lie perpendicular to the plane created by the axes of the
three sp2 hybrid orbitals, combine to form two p molecular orbitals: one bonding and the other
antibonding. For the unhybridized 2p orbitals to be parallel, thus giving maximum overlap, the
two carbon atoms of the double bond and the four bonded atoms must lie in a plane.
Figure 7.1 Covalent bonding in ethylene. (a) Lewis structure and (b) orbital overlap model showing the 𝜎bond and one 𝜎

7.2 Nomenclature of Alkenes

Alkenes are named using the IUPAC system, but, as we shall see, some are usually referred to
by their common names.

A. IUPAC Names

To form IUPAC names for alkenes, change the -an- infi x of the parent alkane to -en-. Hence,
CH2=CH2 is named ethene, and CH3CH=CH2 is named propene. In higher alkenes, where isomers exist
that differ in location of the double bond, a numbering system must be used. According to the IUPAC
system,
1. Identify the longest continuous carbon chain or largest carbon ring that contains the
entire C = C
2. Number the longest carbon chain that contains the double bond in the direction that gives
the carbon atoms of the double bond the lowest possible numbers.
3. Indicate the location of the double bond by the number of its first carbon.
4. Name branched or substituted alkenes in a manner similar to alkanes.
5. Number the carbon atoms, locate and name substituent groups, locate the double bond,
and name the main chain.

Example:
 Sample Problem 7.1
Write the IUPAC name of each alkene.

Think:
What is the longest carbon chain that entirely contains the C = C? What is the corresponding
root name? On which end of the chain should numbering begin to allow the C = C group to be
encountered the earliest? Which locator number of the C=C atoms should be included in the IUPAC
name?

Solve:
a.) 4-ethyl-3,3-dimethyl-1-octene b.) 2-methyl-2-butene

B. Common Names
Some alkenes, particularly those of low molecular weight, are known almost exclusively by their
common names, as illustrated by the common names of these alkenes

C. Systems for Designating Configuration in Alkenes

The Cis,Trans System

The most common method for specifying the configuration in alkenes uses the prefixes
cis and trans. For more complex alkenes, the orientation of the atoms of the parent chain
determines whether the alkene is cis or trans. On the right is a structural formula for the cis
 isomer of 3,4-dimethyl-2-pentene. In this example, carbon atoms of the main chain (carbons 1
and 4) are on the same side of the double bond and, therefore, this alkene is cis.
Cis alkenes with double bonds in open chains are less stable than their trans isomers
because of steric strain between alkyl substituents on the same side of the double bond.

Sample Problem 7.2

Name each alkene and show the configuration about each double bond using the cis, trans
system.

Solution:
(a) The chain contains seven carbon atoms and is numbered from the end that gives the lower
number to the first carbon of the double bond. Its name is trans-3-heptene.

(b) The longest chain contains eight carbon atoms and is numbered from either end of the chain so
that the first carbon of the double bond is carbon 4 of the chain. Its name is cis-4-octene.

The E,Z System

This system uses the priority rules of the R,S system to assign priority to the substituents on each
carbon of a double bond. Using these rules, we decide which group on each carbon has the higher
priority. If the groups of higher priority are on the same side of the double bond, the configuration of
the alkene is Z (German: zusammen, together). If they are on opposite sides of the double bond, the
alkene is E (German: entgegen, opposite).
 Sample Problem 7.3
Name each alkene and specify its configuration by the E,Z system.

Solution:

a) The group of higher priority on carbon 2 is methyl; that of higher priority on carbon 3 is
isopropyl. Because the groups of higher priority are on the same side of the double bond, the
alkene has the Z configuration. Its name is (Z)-3,4-dimethyl-2-pentene.

b) Groups of higher priority on carbons 2 and 3 are -Cl and -CH2CH3. Because these groups are
on opposite sides of the double bond, the configuration of this alkene is E, and its name is
(E)-2-chloro-2-pentene.

c) The groups of higher priority are on opposite sides of the double bond; the configuration is
E. The name of this bromoalkene is (E)-1-bromo-4-isopropyl-5-methyl-4-octene.

D. Cycloalkenes

In naming cycloalkenes, the carbon atoms of the ring double bond are numbered 1 and 2 in the
direction that gives the substituent encountered first the smaller number.

Sample Problem 7.4

Write the IUPAC name of each cycloalkene.

 Solution:
a. 3,3-dimethylcyclohexene
b. 1,2-dimethylcyclopentene
c. 4-(1-methylethyl)-1-methylcyclohexene

G. Dienes, Trienes, and Polyenes

For alkenes containing two or more double bonds, the infix -en- is changed to -adien-, -atrien-,
and so on. Those that contain several double bonds are also referred to more generally as polyenes
(Greek: poly, many). Following are examples of three dienes.

H. Cis, Trans Isomerism in Dienes, Trienes, and Polyenes

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 which can show
cis, trans isomerism 2n stereoisomers are possible.

Sample Problem 7.5

How many stereoisomers are possible for 2,4-heptadiene?

Solution:
This molecule has two carbon-carbon double bonds, each of which shows cis, trans isomerism.
As shown in this table, there are 22 = 4 stereoisomers. Two of these are drawn on the right.
 Your Turn Exercise 7.1
1. Draw the line bond, condensed, and skeletal structure of the following alkenes.
a. 1-hexene b. 4-isopropyl-2-methyl-1-nonene
2. Draw the skeletal structure of the following alkenes.
a. Trans-2-pentene b. Cis-2-methyl-3-hexene
3. Name the following alkenes (include cis- or tans- for the alkenes when applicable)

a. e.
b. CH2=CHCH2CH2CH2CH2CH2CH3

c. CH3CHCH2CH=CH2CH2CH3
CH3

d. f.

7.3 PHYSICAL PROPERTIES OF ALKENES

Density of Alkenes
The physical properties of the homologous series of alkenes (C nH2n) are similar to those
of the homologous series of alkanes (CnH2n+2). Alkenes have densities ranging from 0.6 to 0.8 g
cm3. Alkenes are either nonpolar or very slightly polar. Thus, they are insoluble in water but
soluble in nonpolar solvents such as hexane. They are also soluble in diethyl ether and
halogenated solvents.

Polarity of Alkenes
Alkenes are nonpolar compounds, and the only attractive forces between their molecules
are dispersion forces.

Boiling Points of Alkenes

Alkenes that contain fewer than five carbon atoms are gases at room temperature. The
boiling points of the alkenes, like those of alkanes, increase with an increasing number of carbon
atoms because the London forces increase. And, like alkanes, alkenes with branched alkyl
groups have lower boiling points. Branched alkenes have more compact structures than the
unbranched isomers, and thus less intermolecular contact, which diminishes the intermolecular
London forces.
 Because geometric isomers have different polarities, their boiling points differ. For example, the
boiling points of cis- and trans-1,2-dichloroethenes are 60 and 47 °C, respectively. The two C-Cl bond
moments of the trans isomer cancel each other, so it has no net dipole moment. In contrast, the cis isomer
has a net dipole moment because the two C-Cl bond moments reinforce each other. Therefore, the cis
isomer is polar and has the higher boiling point.
7.4 REACTIONS OF ALKENES

The most characteristic reaction of alkenes is addition to the carbon-carbon double bond in
such a way that the 𝜎 bond is broken and, in its place, 𝜎 bonds form to two new atoms or groups of
atoms.
Characteristic Alkene Addition Reactions
 Another addition reaction of alkenes is the formation of chain-growth polymers (Greek: poly,
many, and meros, part). In the presence of certain catalysts called initiators, many alkenes form polymers
made by the addition of monomers (Greek: mono, one, and meros, part) to a growing polymer chain as
illustrated by the formation of polyethylene from ethylene.

Electrophilic addition
A common type of reaction with alkenes in which an electrophilic species adds to a 𝜎bond.
There are at least three characteristic features that can make a molecule or ion electrophilic.
 The most common of these features is a region of low electron density, reflected by a
partial or full positive charge.
 A second common feature of some electrophiles is the lack of an octet on an atom.
 The third characteristic that can make a molecule or ion electrophilic is a relatively weak
bond to an atom that can depart as a stable ion or molecule. These electrophilic species
can be considered as electron seeking because their reactions with nucleophiles create
stronger bonds and therefore more stable molecules.

A. Addition of Hydrogen Halides

The hydrogen halides HCl, HBr, and HI add to alkenes to give haloalkanes (alkyl
halides). These additions may be carried out either with the pure reagents (neat) or in the
presence of a polar solvent such as acetic acid. HCl reacts sluggishly compared to the other two
acids. Addition of HBr to ethylene gives bromoethane (ethyl bromide):

Addition of HBr to propene gives 2-bromopropane (isopropyl bromide); hydrogen adds

to carbon 1 of propene, and bromine adds to carbon 2. If the orientation of addition were
reversed, 1-bromopropane (propyl bromide) would be formed. The observed result is that 2-
bromopropane is formed to the virtual exclusion of 1-bromopropane. We say that addition of
HBr to propene is highly regioselective. A regioselective reaction is a reaction in which one
direction of bond forming or breaking occurs in preference to all other directions of bond
forming or breaking.
 This regioselectivity was noted by Vladimir Markovnikov who made the generalization
known as Markovnikov’s rule: in the addition of H-X to an alkene, hydrogen adds to the
double-bonded carbon that has the greater number of hydrogens already bonded to it.

Sample Problem 7.6

Name and draw a structural formula for the product of each alkene addition
reaction:

Think: Remember the Markovnikov’s rule,

Solve:

B. Addition of Water: Acid-Catalyzed Hydration

The acid-catalyzed addition of water to the double bond of an alkene (hydration of an
alkene) is a method for the preparation of low-molecular-weight alcohols. This reaction has its
greatest utility in large-scale industrial processes. The acids most commonly used to catalyze the
hydration of alkenes are dilute aqueous solutions of sulfuric acid and phosphoric acid. These
reactions, too, are usually regioselective, and the addition of water to the double bond follows
Markovnikov’s rule. In general, the reaction takes the form that follows:
Example:

In the case of simple alkenes, H adds to the carbon of the double bond with the greater number
of hydrogens, and OH adds to the carbon with the fewer hydrogens. Thus, H-OH adds to alkenes in
accordance with Markovnikov’s rule.

Sample Problem 7.6

Draw a structural formula for the product of the acid-catalyzed hydration of 1-
methylcyclohexene.

Solution:

C. Addition of Bromine and Chlorine

Alkenes react rapidly with bromine and chlorine in nonnucleophilic solvents to form vicinal
dihalides. Chlorine, Cl2, and bromine, Br2, react with alkenes at room temperature by adding halogen
atoms to the two carbon atoms of the double bond with formation of two new carbon-halogen bonds.

Fluorine, F2, adds to alkenes, but, because its reactions are very fast and difficult to control, this
reaction is not a useful laboratory procedure. Iodine, I2, also adds, but the reaction is not preparatively
useful. Halogenation with bromine or chlorine is generally carried out either with the pure reagents or by
mixing them in an inert solvent such as CH2Cl2.
 The addition of bromine or chlorine to a cycloalkene gives a trans -dihalocycloalkane formed
as a racemic mixture. The addition of bromine to cyclohexene, for example, gives trans -1,2-
dibromocyclohexane:

Sample Problem 7.7

Complete these reactions, showing the stereochemistry of the product.

Solution:
Addition of both Br2 and Cl2 occurs with anti stereoselectivity, which means that the halogen
atoms are trans to each other in each product.

D. Addition of HOCl and HOBr

 Treating an alkene with Br2 or Cl2 in the presence of water results in addition of OH and Br, or
OH and Cl, to the carbon-carbon double bond to give a halohydrin. Halohydrin is a compound
containing a halogen atom and a hydroxyl group on adjacent carbons; those containing Br and OH are

bromohydrins, and those containing Cl and OH are chlorohydrins.

Addition of HOCl and HOBr is regioselective (halogen adds to the less substituted carbon
atom) and anti stereoselective.

Sample Problem 7.8

Draw the structure of the bromohydrin formed by treating 2-methylpropene with
Br2/H2O.

Solution:
Addition is regioselective, with -OH adding to the more substituted carbon and -Br adding to
the less substituted carbon.

E. Addition of H2 or Catalytic Reduction

In the presence of an appropriate transition metal, H2 reduces alkenes to alkanes with syn
stereoselectivity and without rearrangement. The reaction can be stereospecific because Z alkenes can
give different products than E alkenes. The mechanism involves cleavage of the alkene 𝜎 bond through
adsorption onto the surface of the transition metal. This step is followed by formation of two carbon-
hydrogen bonds from the same face of the alkane molecule as it desorbs.
Sample Problem 7.9
Write the complete reaction of propene with hydrogen.

Solution:
CH2=CHCH3 + H2 → CH2CH2CH3

References:
1. Organic Chemistry, 8th ed. By William H. Brown, Brent L, Iverson, Eric V. Anslyn,
Christopher S. Foote, Bruce M. Novak, c 2018 Cengage Learning
2. Solomons Organic Chemistry, 11th ed.pdf downloaded from https://chemistry.com.pk/free-
download-chemistry-books/
3. Organic Chemistry: Structure, Mechanism, and Synthesis by Robert J. Ouellette and J. David Rawn.pdf
downloaded from https://chemistry.com.pk/free-download-chemistry-books/
4. https://chem.libretexts.org
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apter- 8-alkenes-and-alkynes-i-properties-and-
synthesis&psig=AOvVaw0QqwDea3nQIEAPcALEaD9C&ust=1603613242649000&source=imag
es&cd=vf e&ved=0CA0QjhxqFwoTCJi_tsyszuwCFQAAAAAdAAAAABAD