Chapter 3
Alkenes and Alkynes: The Nature
of Organic Reactions
Jae Woong Jung
Kyung Hee University
에너지나노소재연구실
Energy Nanomateials Laboratory
3. Alkenes and Alkynes: The
Nature of Organic Reactions
Alkene s- Hydrocarbon with carbon-carbon double
Bonds
Also called an olefin but alkene is better
Alkynes - Hydrocarbons that contain carbon-carbon
triple bonds
Includes many naturally occurring materials
Flavors, fragrances, vitamins
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Why this Chapter?
C-C double bonds are present in most
organic and biological molecules
To examine consequences of alkene
stereoisomerism
To focus on general alkene reaction:
electrophilic addition
We will use alkyne chemistry to begin looking
at general strategies used in organic
synthesis
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3.1 Naming of Alkenes and Alkynes
Name the parent hydrocarbon
Number carbons in chain so that double bond carbons
have lowest possible numbers
Write the full name
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1. Name the parent hydrocarbon: suffix –ene in plase of -ane
2. Number carbons in chain so that double bond
carbons have lowest possible numbers
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3. Write the full name
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IUPAC changed its naming rules in 1993
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Many Alkenes Are Known by Common Names
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Alkynes
- General hydrocarbon rules apply with “-yne” as a
suffix indicating an alkyne
- Numbering of chain with triple bond is set so that
the smallest number possible for the first carbon of
the triple bond
Alkenyl and alkynyl groups
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3.2 Electronic Structure of Alkenes
Carbon atoms in a double bond are sp2-hybridized
Three equivalent orbitals at 120º separation in plane
Fourth orbital is atomic p orbital
Combination of electrons in two sp2 orbitals of two atoms
forms bond between them
Additive interaction of p orbitals creates a bonding
orbital
Occupied orbital prevents rotation about -bond
Rotation prevented by bond - high barrier, about 268
kJ/mole in ethylene
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3.3 Cis-Trans Isomers of Alkenes
The presence of a carbon-carbon double bond can
create two possible structures
cis isomer - two similar groups on same side of
the double bond
trans isomer - similar groups on opposite sides
Each carbon must have two different groups for these
isomers to occur
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Cis, Trans Isomers Require That End Groups
Must Differ in Pairs
180°rotation superposes
Bottom pair cannot be superposed without breaking C=C
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Interconversion of cis and trans alkene isomers
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3.4 Sequence Rules: The E,Z Designation
Neither compound is clearly “cis” or “trans”
Substituents on C1 are different than those on C2
We need to define “similarity” in a precise way to
distinguish the two stereoisomers
Cis, trans nomenclature only works for disubstituted
double bonds
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E,Z Stereochemical Nomenclature
Priority rules of Cahn, Ingold, and Prelog
Compare where higher priority groups are with
respect to bond and designate as prefix
E -entgegen, opposite sides
Z - zusammen, together on the same side
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Ranking Priorities: Cahn-Ingold-Prelog Rules
RULE 1
Must rank atoms that are connected at comparison point
Higher atomic number gets higher priority
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RULE 2
If atomic numbers are the same, compare at next
connection point at same distance
Compare until something has higher atomic number
Do not combine – always compare
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RULE 3
Substituent is drawn with connections shown and no
double or triple bonds
Added atoms are valued with 0 ligands themselves
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3.5 Kinds of Organic Reactions
In general, we look at what occurs and try to learn how
it happens
Common patterns describe the changes
- Addition reactions – two molecules combine
- Elimination reactions – one molecule splits into two
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- Substitution – parts from two molecules exchange
- Rearrangement reactions – a molecule undergoes
changes in the way its atoms are connected
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3.6 How Reactions Occur: Mechanisms
In a clock the hands move but the mechanism
behind the face is what causes the movement
In an organic reaction, we see the transformation
that has occurred. The mechanism describes the
steps behind the changes that we can observe
Reactions occur in defined steps that lead from
reactant to product
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Types of Reaction Mechanisms
Bond formation or breakage can be symmetrical or
unsymetrical
Symmetrical- homolytic : radical reactions
Unsymmetrical- heterolytic : polar reactions
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Indicating Steps in Mechanisms
Curved arrows indicate breaking
and forming of bonds
Arrowheads with a “half” head
(“fish-hook”) indicate homolytic
and homogenic steps (called
‘radical processes’)
Arrowheads with a complete head
indicate heterolytic and
heterogenic steps (called ‘polar
processes’)
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Polar Reactions
Molecules can contain local unsymmetrical electron
distributions due to differences in electronegativities
This causes a partial negative charge on an atom and a
compensating partial positive charge on an adjacent atom
The more electronegative atom has the greater electron
density
Elements such as O, F, N, Cl more electronegative than
carbon
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Generalized Polar Reactions
An electrophile, an electron-poor species,
combines with a nucleophile, an electron-rich
species
The combination is indicate with a curved arrow
from nucleophile to electrophile
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3.7 The Mechanism of an Organic
Reaction: Addition of HCl to Ethylene
HCl adds to the part of C-C double bond
The bond is electron-rich, allowing it to function as
a nucleophile
H-Cl is electron deficient at the H since Cl is much
more electronegative, making HCl an electrophile
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Mechanism of Addition of HCl to Ethylene
General reaction
mechanism:
electrophilic addition
Attack of electrophile
(such as HCl) on bond
of alkene
Produces carbocation
and chloride ion
Carbocation is an
electrophile, reacting
with nucleophilic
chloride ion
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3.8 Describing a Reaction: Transition
States and Intermediates
The highest energy point in a reaction step is
called the transition state
The energy needed to go from reactant to
transition state is the activation energy (DG‡)
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If a reaction occurs in more
than one step, it must
involve species that are
neither the reactant nor the
final product
These are called reaction
intermediates or simply
“intermediates”
Each step has its own free
energy of activation
The complete diagram for
the reaction shows the free
energy changes associated
with an intermediate
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3.9 Describing a Reaction: Catalysis
Catalyst: a substance that increases the rate of a
chemical transformation
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Terpens: Naturally Occurring Alkenes
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