Essential Organic Chemistry

Paula Yurkanis Bruice

Chapter 4

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  bond 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 
121.7
H H

109.6
H

compared to alkanes, bond angles increase in alkenes

 Introduction
 Typical representatives are
• Ethene, plant growth hormone, affects seed
germination, flower maturation, and fruit ripening.

H H

H H
 Introduction
 Typical representatives are
• citronellol, in rose and geranium oils

4 3 2

5
6 1 OH
7
8

7 Geranium “Mavis Simpson”

8 5 4 1
6
3 2
 Introduction
 Typical representatives are
• limonene, in lemon and orange oils

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

Citrus limon
 Introduction
 Typical representatives are
-phellandrene, in oil of eucalyptus

1 1
2 6 2 6

5 3 5
3
4 4

Eucalyptus globulus
 4.1 Molecular Formulas
 Alkane: CnH2n+2
 Alkene: 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 Formulas
 Alkane: CnH2n+2
 Ring: 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 Formulas
 Alkene:
CnH2n+2- 2P-2R
P = number of double bonds
R = number of rings.
 4.2 Nomenclature of Alkenes
 The functional group is the center of
reactivity in a molecule.
 The IUPAC system uses a suffix to denote
certain functional groups.
 Nomenclature of Alkenes
 1-1. Find the longest carbon chain.

 1-2. Enumerate the carbons such that the

functional group, here the double bond, gets the
lowest possible number.
 Nomenclature of Alkenes
 2. Substituents are cited before the parent
longest chain, along with a number indicating
its position at the chain.
 Nomenclature of Alkenes
 3. If a chain has more than one double bond, we
first identify the chain by its alkane name,
replacing the “ne” ending with the appropritate
suffix: diene, triene, etc.

 4. If a chain has more than one substitutent,

substituents are cited in alphabetical order.
 Nomenclature of Alkenes
 5. If the same number for alkene is obtained in
both directions, the correct name is the name
that contains the lowest substituent number.
 Nomenclature of Alkenes
 6. A number is not needed to denote the position of the
double bond in a cyclic alkene because the double bond
is always placed between carbons 1 and 2.

 7. Numbers are needed if the ring has more than one

double bond.
 Nomenclature of Alkenes

 Remember that the name of a substituent is stated

before the name of the parent hydrocarbon, and
the functional group suffix is stated after that.

[substitutent] [parent hydrocarbon] [fucntional group

suffix]
Nomenclature of Alkenes
 4.3 The Structure of Alkenes
 All six atoms of the double bond system are
in the same plane.
 4.4 Cis-Trans Isomerism
 Because rotation about a double bond does
not readily occur, an alkene such as 2-
butene can exist in two distinct forms.
 cis/trans Isomers

sp2-sp2  bond p-p  bond p-p  bond

side view front view

The 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  bond of  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
4.5 The E,Z System of Nomenclature

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- Rule 1
The relative priorities of the two groups depend on the
atomic numbers of the atoms bonded directly to the sp2
carbon. The greater the atomic number, the higher is the
priority of the group.
 E/Z System
Priorities are first assigned based on atomic numbers.
I H
1 2
I>C F>H
2 H3C F 1
E-configuration

1 I F 1
I>C F>H
2 2
H3C H
Z-configuration
 E/Z System- Rule 2
If the two substituents attached to the sp2 carbon start
with the same atom, you must move outward and
consider the atomic numbers that are attached to the
“tied” atoms.
 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- Rule 3
If an atom is doubly (or triply) bonded to another atom,
the priority system treats it as if it were singly bonded
to two (or three) of those atoms.
 E/Z System
path goes to C,
Atoms in double bonds not H
are “replicated” at either
C H
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
4.6 The Relative Stabilities of Alkenes
Alkyl substituents that are bonded to the sp2 carbons
of an alkene have a stabilizing effect on the alkene.

The more alkyl substituents bonded to the sp2

carbons of an alkene, the greater is its stability.
 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 (Steric strain) is responsible for
energy differences among the disubstituted alkenes

H3C H H H H3C H
> >
H3C H H3C CH3 H CH3
4.7 How Alkenes React ; Curved Arrows

The functional group is the center of reactivity of a

molecule.
In essence, organic chemistry is about the interaction
between electron-rich atoms or molecules and electron-
deficient atoms or molecules. It is these forces of
attraction that make chemical reactions happen.
A very simple rule:
Electron-rich atoms or molecules are attracted to
electron-deficient atoms or molecules!
 Electrophiles vs Nucleophiles
Electrophile: electron-deficient atom or molecule that
can accept a pair of electrons.

H CH3CH2 BF3

Nucleophile: electron-rich atom or molecule that has a

pair of electrons to share.

HO Cl CH3NH2 H2O

A very simple rule restated:

A Nucleophile reacts with an electrophile!
 Electrophiles vs Nucleophiles
Nucleophiles:
Organic molecules with double bonds
(alkenes, alkynes) are also nucleophilic.
Examples:

CH3
H3C C CH
H3C
 Reactions

 Alkenes are similar in structure and do

similar reactions.
• All contain a double bond
• All contain the same functional group
 Reactions are categorized through different
types of mechanisms.
 Reactions
Typical for unsaturated systems
is the addition reaction: A+B  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

 
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
 Mechanism
Summarizing our reaction, we realize
it is a 2-step mechanism
 
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.
A Few Words about Curved Arrows
4.8 Using a Reaction Coordinate Diagram
(Energy Profile) to Describe a Reaction
Transition State
 Transition state TS 1
The chemical species that exists 
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
O 
H3C
CH2 H H
 
H2C C Br
H CH3 bond
forming
 Reactions
Overall reaction coordinate