Essential Organic Chemistry

Paula Yurkanis Bruice

Chapter 5
Alkenes: Structure, Nomenclature,
Stability, and an Introduction to
Reactivity
 Introduction

Alkenes contain a C=C double bond

H H

H H

C=C double bond consists of

sp2-sp2 s bond p-p p bond

 Introduction
compared to alkanes, bond lengths decrease in alkenes

133 pm 154 pm

108 pm 109 pm
H H H H
116.6o C C C C H
H
H o
121.7
H H
o
109.6
H

compared to alkanes, bond angles increase in alkenes

 Introduction
ØTypical representatives are
• Ethene, plant growth hormone

H H

H H
 Introduction
ØTypical representatives are
• citronellol,

4 3 2

5
6 1 OH
7
8
Geranium “Mavis Simpson”
7
8 5 4 1
6
3 2
 Introduction
ØTypical representatives are
• limonene,

1 6
2 1 6
2 5
5
3 4 3 4

Citrus limon
 Introduction
ØTypical representatives are
• b-phellandrene,

1 1
2 6 2 6

5 3 5
3
4 4

Eucalyptus globulus
 Molecular Formula
ØAlkane: CnH2n+2
ØAlkene: CnH2n
• or CnH2n+2- 2P
• P = number of double bonds

H H H H H H
H H H H
H H H H H H
+ 2H
 Molecular Formula
ØAlkane: CnH2n+2
ØRing: CnH2n
• or CnH2n+2- 2R
• R = number of rings

H H H H H H
H H H H H H
H H H H + 2H
 Molecular Formula
ØAlkene:

CnH2n+2- 2P-2R

P = number of double bonds

R = number of rings.
 Nomenclature of Alkenes
ØFind the longest carbon chain.
ØEnumerate the carbons such that the
functional group, here the double bond, gets
the lowest possible number.
ØSubstituents are cited before the parent
longest chain, along with a number
indicating its position at the chain.
 Nomenclature of Alkenes
3
1
4
2

2-butene
High electron density

3
4 1
Electrostatic map shows 2
high electron density
at double bond
Low electron density
Nomenclature of Alkenes

5 3
1
6
4 2
2-hexene

p bond
Nomenclature of Alkenes
5 3 1
CH3
6 H3C 2
4
CH3
2-methyl-3-hexene

3
6 5 4
1
2

Copyright © 2010 Pearson

Education, Inc.
Nomenclature of Alkenes
7
H3C H
6
3 1
5 CH3
H3C 4 2

H
5-methyl-3-heptene

4 2
6 5 3
7 1
Copyright © 2010 Pearson
Education, Inc.
 Nomenclature of Alkenes
ØIf there is more than one double bond,
suffixes di, tri, tetra, ..., are used

4 3
6 5 2 1

5 3
1
6
4 2
2,4-hexadiene
 Nomenclature of Alkenes
ØIf there is more than one double bond,
suffixes di, tri, tetra, ..., are used
4 2
6 3 1
7 5

7 5 3 1

6 4 2
5-methyl-1,3-heptadiene
 Nomenclature of Alkenes
ØIf there is more than one double bond,
suffixes di, tri, tetra, ..., are used

2 H3C CH3
3
CH3
1 6
5 1
4
7 4 2
5
6 3
cyclo-heptatriene 1,6,6-trimethylcylcohexa-1,4-diene
 cis/trans Isomers

sp2-sp2 s bond p-p p bond p-p p bond

side view front view

The p-p p bond restricts free rotation.

 cis/trans Isomers

Upon rotation we lose p-p overlap, thus

rotation doesn’t happen (easily).

Consequently, geometrical isomers exist.

 cis/trans Isomers

cis trans
H H R H

R R H R
All substituents are All substituents are
on one side on different sides
of p bond of p bond
 cis/trans Isomers
3 2

5
4 1
cis-2-pentene

3 2 3
5 5 2
4
4 1
1
 cis/trans Isomers
2
1
4
3
6
5
7 trans-3-heptene

2
6 4 1 2
3 6
7 5 4 3 1
7 5
 cis/trans Isomers
The main chain determines cis/trans in the name
6 1
1 4 H3C CH3
H3C 5
3 2 3
2 5
4
CH3
6
cis-3-methyl-2-hexene trans-3-methyl-2-hexene
This compound is cis This compound is trans
but the two methyl but the two methyl
groups are groups are
… trans to each other. … cis to each other.
cis and trans are also used to designate
the relative position of two groups.
 E/Z System
For more than two substituents the cis/trans
system cannot be used.

A new system, the E/Z system is introduced.

To use the E/Z system we need to assign

priorities to each substituent on each
carbon.
 E/Z System
high priority high priority low priority high priority

low priority low priority high priority low priority

In case high priorities In case high priorities

are on the same side, are on opposite sides,
we assign a we assign an
Z configuration. E configuration.
 E/Z System
Priorities are first assigned based on atomic numbers.

1
I H 2
I>C F>H
2 H3C F 1

(E)-3-fluoro-2-iodo-2-propene

1 I F 1
I>C F>H
2 2
H3C H
(Z)-3-fluoro-2-iodo-2-propene
 E/Z System
If you can’t decide using the first atoms attached, go
out to the next atoms attached. If there are
nonequivalent paths, always follow the path with
atoms of higher atomic number.
path goes to O,
H not H
1 H3C CH2 OH 1 C O
H comparison
2 H CH2 CH3 2 H stops here

C C
H
path goes to C,
Z-configuration not H
 E/Z System
path goes to C,
Atoms in double bonds not H
are “replicated” at
C H
either end of the double
bond. CH CH2 C C C
H H
H H
CH2 CH3 C C H
H H
2 H CH CH2 1

1 H3C CH2 CH3 2

E-configuration
 E/Z System
Name the following compound:

CH3
H

H3C CH2

?
 E/Z System
Name the following compound: Answer

7
CH3 2
5
2 H
6
3 4
1
1 H3C CH CH2 1
2

(Z)-4-ethenyl-3-heptene
 Stability
The stability of alkenes depends
upon number of substituents

R H R H R H R R
< < <
H H H R R R R R

The more substituents, the more stable

 Stability
Steric repulsion is responsible for energy differences
among the disubstituted alkenes

H3C H H H H3C H
> >
H3C H H3C CH3 H CH3
 Reactions
ØAlkenes are similar in structure and do
similar reactions.
• All contain a double bond
• All contain the same functional group
ØReactions are categorized through different
types of mechanisms.
 Reactions
Typical for unsaturated systems
is the addition reaction: A+B à C
CH2 CH3 HBr(aq) CH2 CH3
H2C C H2C C Br
CH3 H CH3

CH3
CH3
C HBr(aq) C Br
C C
H H H
 Reactions

A LOOK AT THE
REACTANTS
 Reactions

CH2 CH3 CH2 CH3

H2C C + HBr(aq) H2C Br
CH3 H CH3

WHAT IS THE NATURE

OF THIS REAGENT?
 Reactions
electrophile

d+ d-
HBr + H2O Br + H3O

Hydrogen bromide is a strong acid and forms

hydronium ions, H3O+, and bromide, Br–, when
dissolved in water.
H3O+ is positively charged,
thus it is electron deficient
it is electrophilic “electron loving”
 Reactions
In the presence of an electron-rich species
the hydronium ion reacts:

H3C H2C H H3C H2C

C CH2 + O H C CH2 + H2O
H3C H H3C H

electrophile

A new positively charged species is formed.

 Reactions

The newly formed species, a carbocation, is

again electron deficient, thus it is electrophilic.

CH2 CH3
H2C C
H CH3
electrophile
 Reactions

One species present that is rich in electrons is Br–.

Since Br– bears a negative charge it seeks for
neutralization.

It is nucleophilic (nuclei are positively charged).

 Reactions
The two species, electrophile and nucleophile, combine
and form a new compound.

CH2 CH3 CH2 CH3

H2C C + Br H2C Br
H CH3 H CH3
electrophile nucleophile
 Reactions
ØElectrophiles:
molecules that contain atoms with empty
orbitals, which can accommodate electrons.
Typically, these are positively charged.

ØExamples:
H CH3CH2 BF3
Boron has only 6 valence electrons.
BF3 is a Lewis acid.
 Reactions
ØNucleophiles:
molecules that contain atoms with lone pairs,
which can donate electrons. Often these are
negatively charged. Almost all the time they
contain elements from groups 15–17 of the
periodic table, since those have lone pairs.

ØExamples:

HO Cl CH3NH2 H2O
 Reactions
Nucleophiles:
Organic molecules with double bonds
(alkenes, alkynes) are also nucleophilic.
Examples:

CH3
H3C C CH
H3C
 Mechanism
Summarizing our reaction, we realize
it is a 2-step mechanism
d+ d-
HBr + H2O Br + H3O

H3C H2C H H3C H2C

C CH2 + O H C CH2 + H2O STEP 1
H3C H H3C H

CH2 CH3 CH2 CH3

H2C C + Br H2C STEP 2
Br
H CH3 H CH3
 Mechanism
Step 1 reaches a carbocation “intermediate.”
One new bond is formed.

Intermediates are species with a very short lifetime.

However, their stability (energy) often determines
the outcome of a reaction.
Step 2 completes the reaction by forming a second
bond. Again, it is the interplay between positively
charged (electrophilic) and negatively charged
(nucleophilic) species.
 ENERGY PROFILE 1st step

energy maximum

activation
energy
ENERGY PROFILE 2nd step

energy maximum

activation
energy
 Transition state TS 1
The chemical species that exists dd+
at the transition state, with old
bonds in the process of breaking
and new bonds in the process of bond
bond breaking H
forming: forming
TS 2
H3C O dd+
CH2
d+ d- H H
H2C C Br
H CH3 bond
forming
 Reactions
Overall reaction coordinate