Chapter 7

Alkenes and Alkynes I:

Properties and Synthesis.

NEPHAR 109 Organic Chemistry

Assist.Prof. Banu Keşanlı
 Unsaturated Hydrocarbons
Lecture Outline
ƒ Class odds and ends
ƒ Defining unsaturation in hydrocarbons
ƒ Naming alkenes and alkynes
ƒ Cis and trans isomers
ƒ Synthesis of hydrocarbons
ƒ Reactions of alkenes and alkynes
o Hydrogenation
o Halogenation
o Hydrohalogenation
o Hydration
o oxidation
 Unsaturated Hydrocarbons
Compare the following structures of ethane, ethene
and ethyne.
1. What difference do you notice among the first and the
last two structures? (Ethane is saturated and ethene
and ethyne are unsaturated?
2. How would you define unsaturated hydrocarbons?
Ethane

H H

H C C H

H H
Types of Hydrocarbons
ƒ Saturated: All C—C bonds are single bonds
ƒ Unsaturated: Hydrocarbons with one or more multiple
bonds
ƒ The term unsaturated is used because C could bind
more H (become saturated) if no multiple bonds existed.
H H
1. Alkenes (ethylene)  C C
H H 
 

2. Alkynes (acetylene)  H C C H 

H
H H
3. Aromatics (benzene) 
H H
H  
 
 
Bond Angles in Alkenes and
Alkynes
According to VSEPR theory:
ƒ Three groups in a double
bond are bonded at 120°
angles.
ƒ Alkenes are flat, because
the atoms in a double
bond lie in the same
plane.
ƒ The groups attached to a
triple bond are at 180°
angles. Copyright © 2007 by Pearson Education, Inc.
Publishing as Benjamin Cummings
Naming Alkenes
Look and study the names of the following alkenes
Alkene IUPAC Common
H2C=CH2 ethene ethylene
H2C=CH─CH3 propene propylene
cyclohexene

CH2=CH─CH2─CH3 1-butene
CH3─CH=CH─CH3 2-butene
Naming Alkynes
Naming of alkynes is done in a fashion similar to that of
alkenes.
Alkyne IUPAC Common
HC≡CH ethyne acetylene
HC≡C─CH3 propyne
Br

H3C CH C C CH3 4-Bromo-2-pentyne

5 4 3 2 1

cycloheptyne
 Naming Alkenes and Alkynes with
Substituents
Now what if the alkene or alkyne has a substituent? Here is an
example. Write the IUPAC name for
CH3
│
CH3─CH─CH=CH─CH3

STEP 1 Name the longest carbon chain pentene

STEP 2 Number the chain from the double bond

CH3
H
CH 3 C
H3C 4 C 2 CH3 2-pentene
5 H 1

STEP 3 Give the location of each substituent: 4-methyl- 2-pentene

 Naming Alkynes with Substituents
Write the IUPAC name for
CH3
│
HC≡C─CH─CH3
Summary: Naming Alkenes and Alkynes

To summarize the rules for naming alkenes and

alkynes:

ƒ Name the longest carbon chain with a double or triple

bond
ƒ Indicate the location of the double or triple bond in
the main chain by number, starting at the end closer
to the double or triple bond
ƒ Cycloalkenes do not require the numerical prefix but
the bonds are given numbers 1 and 2
ƒ Give the location and name of each substituent
(alphabetical order) as a prefix to the name
Learning Check

Write the IUPAC name for each of the following:

Solution
1. CH2=CH─CH2─CH3 1) ______________
2. CH3─CH=CH─CH3 2) ______________
CH3
|
3) ______________
3. CH3─CH=C─CH3

4. CH3─C≡C─CH3 4) ______________
Learning Check
Write the structural formula for each of the following:
Solution
A. 2-pentyne a) _______________

B. 3-methyl-2-pentene b) ________________
Cis and Trans Isomers
In an alkene, cis and trans isomers are possible
because the double bond
ƒ Is rigid.
ƒ Cannot rotate.
ƒ Has groups attached to the carbons of the double
bond that are fixed relative to each other.
CH3 CH3 CH3

CH = CH CH = CH
cis trans CH3
Cis-Trans Isomers
Cis-trans isomers occur when
different groups are attached to
the double bond.
ƒ In a cis isomer, groups are
attached on the same side of
the double bond.
ƒ In the trans isomer, the groups
are attached on opposite
sides.

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Publishing as Benjamin Cummings
Cis-Trans Isomerism
ƒ Cis-trans isomers do not occur if a carbon atom in the
double bond is attached to identical groups.

Identical Identical

HH Br
H
Br H Br
C C C C
HH CH3 H Br
2-bromopropene 1,1-dibromoethene
(not cis or trans) (not cis or trans)
Naming Cis-Trans Isomers
ƒ The prefixes cis or trans are placed in front of the
alkene name when there are cis-trans isomers.
cis trans

Br Br Br H
C C C C
H H H Br

cis-1,2-dibromoethene trans-1,2-dibromoethene
Learning Check
Name each, using cis-trans prefixes when needed.
Br Br
A. C C
H H

CH3 H
B. C C
H CH3

CH3 Cl
C. C C
H Cl
 Relative Stabilities of Alkenes
„ Generally cis alkenes are less stable than trans
alkenes because of steric hinderance

Heat of Hydrogenation
„ The relative stabilities of alkenes can be measured

using the exothermic heats of hydrogenation

• The same alkane product must be obtained to
get accurate results
The (E)-(Z) System for Designating Alkene Diastereomers

„ The Cahn-Ingold-Prelog convention is used to assign

the groups of highest priority on each carbon

• If the group of highest priority on one carbon is on

the same side as the group of highest priority on
the other carbon the double bond is Z (zusammen)

• If the highest priority groups are on opposite sides

the alkene is E (entgegen)
Synthesis of Alkenes via Elimination Reactions

z Dehydrohalogenation
ÎReactions by an E2 mechanism are most
useful
• E1 reactions can be problematic
ÎE2 reaction are favored by:
• Secondary or tertiary alkyl halides
• Alkoxide bases such as sodium ethoxide
or potassium tert-butoxide
ÎBulky bases such as potassium tert-butoxide
should be used for E2 reactions of primary
alkyl halides
Zaitzev’s Rule: when two different alkene
products are possible in an elimination, the
most highly substituted (most stable) alkene
will be the major product
• This is true only if a small base such as
ethoxide is used

(69 %, more stable)

(31 %, less stable)

z Formation of the Least Substituted Alkene
Using a Bulky Base
ÎBulky bases such as potassium tert-butoxide
have difficulty removing sterically hindered
hydrogens and generally only react with
more accessible hydrogens (e.g. primary
hydrogens)
 Acid Catalyzed Dehydration of Alcohols

ÎRecall that elimination is favored over

substitution at higher temperatures
ÎTypical acids used in dehydration are
sulfuric acid and phosphoric acid
ÎThe temperature and concentration of acid
required to dehydrate depends on the
structure of the alcohol
• Primary alcohols are most difficult to
dehydrate, tertiary are the easiest
Rearrangements of the carbon skeleton can occur
Carbocation Stability and the Transition State
¾ Recall the stability of carbocations is:

¾ The second step of the E1 mechanism in which

the carbocation forms is rate determining
¾ The transition state for this reaction has
carbocation character
¾ Tertiary alcohols react the fastest because
they have the most stable tertiary carbocation-
like transition state in the second step
 Chapter 8

Alkenes and Alkynes II:

Addition Reactions

NEPHAR 109 Organic Chemistry

Assist.Prof. Banu Keşanlı
28
Addition Reactions
There are four addition reactions we will study,
summarized in table below.
TABLE
Introduction: Additions to Alkenes

ÎGenerally the reaction is exothermic

because one π and one σ bond are converted
to two σ bonds

30
Hydrogenation
Question: what happens in hydrogenation? Study the
examples given below to answer this question?
(Side note: a catalyst such as Pt or Ni is used to speed up the reaction)

H H
Pt
H2C CH2 + H2 H2C CH2

H H
Ni
HC CH + 2H2 HC CH
H H
ÎIn heterogeneous catalysis the hydrogen
and alkene adsorb to the catalyst surface
and then a step-wise formation of C-H bonds
occurs
Hydrogenation of Oils

Adding H2 to double
bonds in vegetable
oils produces
ƒ Compounds with
higher melting points.
ƒ Solids at room
temperature such as
margarine,
soft margarine,
Copyright © 2007 by Pearson Education, Inc.
Publishing as Benjamin Cummings

and shortening.
Trans Fats
In vegetable oils, the unsaturated fats usually contain
cis double bonds.
ƒ During hydrogenation, some cis double bonds are
converted to trans double bonds (more stable)
causing a change in the fatty acid structure
ƒ If a label states “partially” or “fully hydrogenated”,
the fats contain trans fatty acids.
 Learning Check
Write the product of each the following reactions:

Pt
CH3─CH=CH─CH3 + H2

Pt
+ H2
 Halogenation
Question: What happens in halogenation reaction?
Think about the following reactions.

Br Br
H2C CH2 + Br2 H2C CH2

Cl Cl

HC C CH3 + 2Cl2 HC C CH3

Cl Cl
Addition of Bromine and Chlorine to Alkenes

ÎAddition produces vicinal dihalides

37
• This reaction is used as a test for alkenes
because the red color of the bromine reagent
disappears when an alkene (or alkyne) is
present

• Alkanes do not react with bromine in the

dark

38
Learning Check

Write the product of the following addition reactions:

1. CH3─CH=CH─CH3 + Cl2

2. + Br2
Hydrohalogenation
What happens in hydrohalogenation reactions?
Again, think about where atoms of a hydrogen
halide end up.

H Cl
CH3 CH CH CH3 + HCl CH3 CH CH CH3

H
+ HBr

Br
41
Addition of Hydrogen Halides to Alkenes:
Markovnikov’s Rule

ÎAddition of HBr to propene occurs to give 2-

bromopropane as the major product

42
Markovnikov’s Rule (Original): addition of HX to
an alkene proceeds so that the hydrogen atom
adds to the carbon that already has the most
hydrogen atoms

43
Theoretical Explanation of Markovnikov’s Rule

ÎThe product with the more stable

carbocation intermediate predominates

ÎThe most stable carbocation is formed

fastest because it has a lower ΔG‡
• The transition state for the rate
determining step (first step) resembles a
carbocation and is stabilized by factors
which stabilize carbocations

44
45
ÎAddition of HBr to 2-methylpropene gives
only tert-butyl bromide

46
Modern Statement of Markovnikov’s Rule: In
the ionic addition of an unsymmetrical reagent
to a double bond, the positive portion of the
adding reagent attaches itself to a carbon
atom of the double bond so as to yield the
more stable carbocation as an intermediate

Regioselective Reaction: When a reaction

that can potentially yield two or more
constitutional isomers actually produces only
one or a predominance of one isomer

47
Hydration
In the addition reaction called hydration
ƒ An acid H+ catalyst is required.
ƒ Water (HOH) adds to a double bond.
ƒ An H atom bonds to one C in the double bond.
ƒ An OH bonds to the other C.
H OH
H+ │ │
CH3─CH=CH─CH3 + H─OH CH3─CH─CH─CH3
Hydration
When hydration occurs with a double bond that has an
unequal number of H atoms,
ƒ The H atom bonds to the C in the double bond with
the most H.
ƒ The OH bonds to the C in the double bond with the
fewest H atoms.
OH H
H+ │ │
CH3─CH=CH2 + H─OH CH3─CH─CH2
(1H) (2H)
Addition of Water to Alkenes: Acid-Catalyzed
Hydration

ÎThe reaction of alkenes with dilute aqueous

acid leads to Markovnikov addition of water

50
• The hydration of alkenes and the dehydration of
alcohols are simply reverse reactions of one other
• The reaction is governed by the position of all
the equilibria
• Hydration is favored by addition of a small
amount of acid and a large amount of water
• Dehydration is favored by concentrated acid
with very little water present (removal of water
produced also helps favor dehydration)
• Carbocation rearrangements can occur

51
Learning Check
Write the product for the hydration of each of the
following:
H+
1. CH3─CH2─CH=CH─CH2─CH3 + HOH
CH3
│ H+
2. CH3─C=CH─CH2─CH3 + HOH

H+
3. + HOH
Learning Check
Write the products of each reaction

A. CH3 CH CH2 + Cl2

CH3 CH CH CH3 + HOH H+

B.

Pt
C. + H2
 Oxidations of Alkenes:
Syn 1,2-Dihydroxylation

ÎKMnO4 will give 1,2 diols (glycols)

54
Mechanism for Syn Hydroxylation of Alkenes

• Cyclic intermediates result from reaction

of the oxidized metals
• The initial syn addition of the oxygens is
preserved when the oxygen-metal bonds
are cleaved and the products are syn diols

55
 Oxidative Cleavage of Alkenes
ÎReaction of an alkene with hot KMnO4
results in cleavage of the double bond and
formation of highly oxidized carbons
• unsubstituted carbons become CO2
• monosubstituted carbons become
carboxylates
• disubstituted carbons become ketones

56
ÎThis be used as a chemical test for alkenes in
which the purple color of the KMnO4 disappears
and forms brown MnO2 residue if alkene
(or alkyne) is present

57
Reactions of Alkynes

58
Addition of Bromine and Chlorine to Alkynes
ÎAddition of halogen to alkynes can occur
once or twice depending on how many
equivalents of the halogen are added
ÎAddition of one equivalent usually proceeds
to give the trans dihalide

59
60
 Addition of Hydrogen Halides to Alkynes

ÎAddition of hydrogen halides occurs once or

twice depending on how many molar
equivalent of hydrogen halide are added
ÎBoth additions are Markovnikov and give
gem-halides

61
Î HBr can be generated by reaction of acetyl
bromide and alumina

ÎAnti-Markovnikov addition of HBr occurs in the

presence of peroxide

62
 Oxidative Cleavage of Alkynes
ÎReaction of alkynes with ozone or basic
potassium permanganate both lead to
formation of carboxylic acids
Unsaturated Hydrocarbons

Aromatic Compounds

Copyright © 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings
Benzene Structure
Benzene
ƒ Has 6 electrons shared equally among the 6 C atoms.
ƒ Is also represented as a hexagon with a circle drawn
inside.

Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

Aromatic Compounds in Nature
and Health
O
Vanillin Aspirin O
CH
COH O
C O CH3

OCH3
OH O

NH C CH3
Ibuprofen Acetaminophen
CH3 CH3 O
H3C CH CH2 CH COH
OH