Unsaturated Hydrocarbons

Lecture Outline
Class odds and ends
Defining unsaturation in hydrocarbons
Naming alkenes and alkynes
Cis and trans isomers
Reactions of alkenes and alkynes
o Hydrogenation
o Halogenation
o Hydrohalogenation
o hydration
Polymers
Aromatic compounds
Properties of aromatic compounds
1

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
2

Bond Angles in Alkenes and

Alkynes
According to VSEPR theory:
Three groups in a double
bond are bonded at 120
angles.
Alkenes are flat, because
the atoms in a double
bond lie in the same
plane.
The groups attached to a
triple bond are at 180
angles.

Copyright 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings
3

Naming Alkenes
Look and study the names of the following alkenes
Alkene

IUPAC

Common

H2C=CH2

ethene

ethylene

H2C=CHCH3

propene

propylene

cyclohexene
CH2=CHCH2CH3

1-butene

CH3CH=CHCH3

2-butene

How is the naming of alkenes done? Talk over with

your group members

Naming Alkynes
Now, lets look at the case of alkynes. Naming is done in
a fashion similar to that of alkenes.
Alkyne

IUPACCommon

HCCH

ethyne

HCCCH3

propyne

acetylene

Br
H3C

CH C
4
3

C
2

CH3
1

4-Bromo-2-pentyne
cycloheptyne
5

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

CH3CHCH=CHCH3
STEP 1 Name the longest carbon chain

pentene

STEP 2 Number the chain from the double bond

CH3
CH
H3C

H
C

C
H

CH3
1

2-pentene

STEP 3 Give the location of each substituent:

4-methyl- 2-pentene
6

Naming Alkynes with Substituents

Write the IUPAC name for
CH3

HCCCHCH3

Summary: Naming Alkenes and Alkynes

Okay, so lets summarize the rules for naming alkenes
and alkynes. Here is what we do:
Name the longest carbon chain with a double or triple
bond
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
Cycloalkenes do not require the numerical prefix but
the bonds are given numbers 1 and 2
Give the location and name of each substituent
(alphabetical order) as a prefix to the name
8

Learning Check
Write the IUPAC name for each of the following:
1. CH2=CHCH2CH3

Solution
1) ______________

2. CH3CH=CHCH3

2) ______________

CH3
|
3. CH3CH=CCH3
4. CH3CCCH3

3) ______________
4) ______________
10

Learning Check
Write the structural formula for each of the following:
Solution
a) _______________
A. 2-pentyne

B. 3-methyl-2-pentene
b) ________________

11

Cis and Trans Isomers

In an alkene, cis and trans isomers are possible
because the double bond
Is rigid.
Cannot rotate.
Has groups attached to the carbons of the double
bond that are fixed relative to each other.
CH3
CH = CH
cis

CH3

CH3
CH = CH
trans

CH3

12

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

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Publishing as Benjamin Cummings

13

Cis-Trans Isomerism
Cis-trans isomers do not occur if a carbon atom in the
double bond is attached to identical groups.
Identical

Identical

Br
H
Br

HH

C C
HH

Br

H
C C

CH3

2-bromopropene
(not cis or trans)

Br

1,1-dibromoethene
(not cis or trans)
14

Naming Cis-Trans Isomers

The prefixes cis or trans are placed in front of the
alkene name when there are cis-trans isomers.
cis
trans

Br

Br
C C
H

Br
C C

cis-1,2-dibromoethene

Br

trans-1,2-dibromoethene
15

16

Learning Check
Name each, using cis-trans prefixes when needed.
Br

Br
C C

A.

CH3
C C

B.
H

CH3
Cl

CH3
C.

C C
H

Cl

17

Lecture 3 Unsaturated Hydrocarbons

Reactions of Alkenes and Alkynes

Copyright 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings
18

Addition Reactions
There are four addition reactions we will study,
summarized in table 12.2
TABLE 12.2

19

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)

H2C CH2 + H2
HC CH + 2H2

Pt

H H
H2C CH2

Ni

H H
HC CH
H H

Your conclusion about hydrogenation:

20

Hydrogenation of Oils
Adding H2 to double
bonds in vegetable
oils produces
Compounds with
higher melting points.
Solids at room
temperature such as
margarine,
soft margarine,

Copyright 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings

and shortening.
21

Learning Check
Write an equation for the hydrogenation of 1-butene
using a platinum catalyst.

22

Trans Fats
In vegetable oils, the unsaturated fats usually contain
cis double bonds.
During hydrogenation, some cis double bonds are
converted to trans double bonds (more stable)
causing a change in the fatty acid structure
If a label states partially or fully hydrogenated,
the fats contain trans fatty acids.

23

Learning Check
Write the product of each the following reactions:
Pt
CH3CH=CHCH3 + H2

Pt
+ H2

24

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

Your conclusion about halogenation of alkenes and alkynes is that

25

Learning Check
Write the product of the following addition reactions:
1. CH3CH=CHCH3 + Cl2
2.

+ Br2

26

Testing for Unsaturation

Br2

When bromine (Br2) is

added to an alkane, the
red color of bromine
persists.

When bromine (Br2) is

added to an alkene or
alkyne, the red color of
bromine disappears
immediately.

Br2

27
Copyright 2007 by Pearson Education, Inc.
Publishing as Benjamin Cummings

15

Hydrohalogenation
What happens in hydrohalogenation reactions?
Again, think about where atoms of a hydrogen
halide end up.
H
CH3 CH CH CH3 + HCl

CH3

Cl

CH CH CH3

+ HBr
Br

28

Markovnikovs Rule
When an unsymmetrical alkene undergoes
hydrohalogenation, the H in HX adds to the carbon
in the double bond that has the greater number of
H atoms .
H Cl
CH3 CH CH2 Does not form
CH3

CH CH2 + HCl
Cl
CH3

C with the most H

H

CH CH2

Product that forms

29

Hydration
In the addition reaction called hydration
An acid H+ catalyst is required.
Water (HOH) adds to a double bond.
An H atom bonds to one C in the double bond.
An OH bonds to the other C.
H OH
H+

CH -CH3CH=CHCH3 + HOH
CH3CHCHCH3
3

30

Hydration
When hydration occurs with a double bond that has an
unequal number of H atoms,
The H atom bonds to the C in the double bond with
the most H.
The OH bonds to the C in the double bond with the
fewest H atoms.
OH H
H+

CH3CH=CH2 + HOH
CH3CHCH2
(1H)

(2H)

31

Learning Check
Write the product for the hydration of each of the
following:
H+
1. CH3CH2CH=CHCH2CH3 + HOH
CH3

H+
2. CH3C=CHCH2CH3 + HOH

H+
3.

+ HOH
32

Learning Check
Write the products of each reaction
A.

B.

C.

CH3 CH CH2 + Cl2

CH3 CH CH CH3 + HOH

+ H2

H+

Pt

33

Markovnikovs Rule
The electrophile adds to the sp2 carbon that is bonded
to the greater number of hydrogens:

In a regioselective reaction, one constitutional isomer is t

major or the only product.

34

Markovnikovs Rule
The positive part of the reagent becomes attached to
the double bond carbon which bears the greatest
number of hydrogen atoms

Markovnikovs Rule

The acid proton will bond to carbon 3 in order

to produce the most stable carbocation
possible.

Example

Solved Problem 1
Show how you would accomplish the following synthetic
conversions.
(a) Convert 1-methylcyclohexene to 1-bromo-1methylcyclohexane.

Solution

This synthesis requires the addition of HBr to an alkene

with Markovnikov orientation. Ionic addition of HBr gives
the correct product.

Anti-Markovnikovs Rule
Free Radical Additon of HBr:
In the presence of peroxides, (ROOR), HBr adds to an
alkene to form the anti-Markovnikov product.
Peroxides produce free radicals.
Only HBr has just the right reactivity for each step of the
free-radical chain reaction to take place.
The peroxide effect is not seen with HCl or HI because the
reaction of an alkyl radical with HCl or HI is strongly
endothermic.
Atom H attached to C atom with fewer hydrogen atom.

OXIDATION REACTION OF
ALKENES

1) OZONOLYSIS
Ozone, O3, adds to alkenes to form molozonide
Molozonideis converted to ozonide that may be reduced to obtain ketones and/or aldehydes

E.g:

2) HYDROXYLATION

Example

3) OXIDATION WITH HOT

KMnO
Alkene react
4 with hot/concentrated KMnO4 to give compounds
containing C=O group (form ketone and/or acids)
In the reaction, C=C is cleavage and bond to oxygen
R1 C = C R4

KMnO4

R2 R3
R1 C = C H

R2 H

R2
KMnO4

R2 R3
R1 C = C H

R1 C = O

R1 C = O
R2

KMnO4

R1 C = O
R2

O = C R4
R3

O = C OH
R3
+ CO2 + H2O

4) OXYMERCURATION
DEMERCURATION REACTION

Reagent is mercury(II) acetate, which dissociates slightly

to form +Hg(OAc).
+Hg(OAc) is the electrophile that adds to the pi bond.
The intermediate is a three-membered ring called the
mercurinium ion.
Overall, the addition of water follows Markovnikovs rule.

5) HYDROBORATION OF
ALKENES

46

SYNTHESIS OF ALKENES
- ELIMINATION RXNS

1) DEHYDRATION OF
ALCOHOL
Alkenes are also generally prepared by the dehydration of
alcohols in the presence of a strong acid.

OH

H+
heat

+ H2O

Sulfuric and phosphoric acids are often used for this reaction.
Industrial processes use flow reactors with the alcohol in the gas phase
passing over a solid Lewis acid such as alumina, Al2O3, with heating.

Characteristics of the Dehydration Reaction

(1) The conditions (acid strength and temperature) required for the
dehydration depend on the structure of the alcohol.
CH3CH2OH
primary alcohol
CH3
CH3COH
CH3
tertiary alcohol

conc. H2SO4
180o

20% H2SO4
85o C

CH2=CH2 + H2O

CH2=C CH3 + H2O

CH3

General Order of Reactivity

R
R-C-OH
R
tertiary alcohol

>

R
R-C-OH
H

secondary alcohol

>

H
R-C-OH
H
primary alcohol

2) DEHYDROGENATIONS OF
ALKYL HALIDES
KOH,

CC

C=C

H2O + KX

alcohol

Elimination reaction of hydrogen halide (HX) from alkyl halide (RX)

Reagents used commonly KOH dissolved in alcohol and NaOH
dissolved in alcohol
E.g:

KOH
Br

Br
KOH

Polymers
Polymers are
Large, long-chain molecules.
Found in nature, including cellulose in plants,
starches in food, proteins and DNA in the body.
Also synthetic such as polyethylene and
polystyrene, Teflon, and nylon.
Made up of small repeating units called
monomers.
Made by reaction of small alkenes.

51

Polymerization
In polymerization, small repeating units called monomers
join to form a long chain polymer.
monomer unit repeats

n
52

Common Synthetic Polymers

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53

Polymers from Addition Reactions

TABLE 12.3

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54

More Monomers and Polymers

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55

Learning Check
What is the starting monomer for polyethylene?

56

Learning Check
Name the monomer used to make Teflon and write a
portion of a Teflon polymer using four monomers.

57

Recycling Plastics
Recycling is simplified by using codes found
on plastic items.
1
2
3
4
5
6

PETE Polyethyleneterephtalate
HDPE High-density polyethylene
PV Polyvinyl chloride
LDPE Low-density polyethylene
PP Polypropylene
PS Polystyrene

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. Publishing as Benjamin Cummings

58

Lecture 3 Unsaturated Hydrocarbons

Aromatic Compounds

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Publishing as Benjamin Cummings

59

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

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

60

Aromatic Compounds in Nature

and Health
O
Vanillin

CH

Aspirin

COH O
C O CH3

OCH3
O

OH

NH C CH3

Ibuprofen
CH3

H3C CH CH2

Acetaminophen

CH3 O

CH COH
OH
61

Naming Aromatic Compounds

Aromatic compounds are named
With benzene as the parent chain.
With one side group named in front of benzene.
CH3

methylbenzene

Cl

chlorobenzene
62

Some Common Names

Some substituted benzene rings
Have common names used for many years.
With a single substituent use a common name or are
named as a benzene derivative.
CH3

toluene
(methylbenzene)

NH2

OH

aniline
(benzenamine)

phenol
(hydroxybenzene)
63

Aromatic Compounds with Two

Groups
Two naming systems are used when two groups are
attached to a benzene ring.
Number the ring to give the lowest numbers to the
side groups.
Use prefixes to show the arrangement:
ortho(o-) for 1,2meta(m-) for 1,3para(p-) for 1,4-

64

Aromatic Compounds with Two

Groups
Cl

CH3

OH
Cl

Cl
Cl

3-chlorotoluene
m-chlorotoluene

1,4-dichlorobenzene
p-dichlorobenzene

2-chlorophenol
o-chlorophenol

65

Learning Check
Select the correct name for each compound:
Cl
1) chlorocyclohexane
2) chlorobenzene
3) 1-chlorobenzene
1) 1,2-dimethylbenzene
2) m-xylene
3) 1,3-dimethylbenzene

CH3

CH3

66

Learning Check
Write the structural formulas for each of the following:
A. 1,3-dichlorobenzene

B. o-chlorotoluene

67

Learning Check
Identify the organic family for each:
A. CH3CH2CH=CH2
B.
C. CH3CCH
D.
68

Properties of Aromatic
Compounds
Aromatic compounds
Have a stable aromatic bonding system.
Are resistant to many reactions.
Undergo substitution reactions, which retain
the stability of the aromatic bonding system.

69

Substitution Reactions
In a substitution reaction, a hydrogen atom on a
benzene ring is replaced by an atom or group of
atoms.
Type of substitution

H on benzene replaced by

Halogenation

chlorine or bromine atom

Nitration

nitro group (NO2)

Sulfonation

SO3H group

70

Halogenation
In a halogenation
An H atom of benzene is replaced by a chlorine or
bromine atom.
A catalyst such as FeCl3 is needed in chlorination.
A catalyst such as FeBr3 is needed in bromination.

H
+
Benzene

Cl
Cl2

FeCl3

HCl

Chlorobenzene
71

Nitration
In the nitration of benzene
An H atom of benzene is replaced by a nitro (-NO2)
group from HNO3.
An acid catalyst such as H2SO4 is needed.

H
+ HNO3
Benzene

NO2
H2SO4

HOH

Nitrobenzene
72

Sulfonation
In a sulfonation
An H atom on benzene is replaced by a SO3H
group from SO3.
An acid catalyst such as H2SO4 is needed.
H
+ SO3
Benzene

SO3H
H2SO4
Benzenesulfonic acid
73

Learning Check
Write the equation for the bromination of benzene
including catalyst.

74