Unit V:

Reactions of Alkenes and

UST Faculty of pharmacy
Alkynes
Chem200 Organic Chemistry
E. D. Gloria

Contents
1. Kinds of organic reactions
2. Organic reaction intermediates
3. Electrophilic addition reactions
1. Classification tests for hydrocarbons

4.
5.
6.
7.
8.

Reaction energy diagrams and transition states

Reactions of alkenes, dienes, and alkynes
Preparation of alkenes and alkynes
Alkyne acidity
Structure elucidation

Kinds of Organic Reactions

Characteristic Reactions of Alkanes

1. Oxidation

Characteristic Reactions of Alkanes

1. Oxidation
2. Thermal Cracking

Characteristic Reactions of Alkanes

1. Oxidation
2. Thermal Cracking
3. Catalytic re-forming

Kinds of Organic Reactions:

Alkenes
REACTION MECHANISMS

4 General Types of Organic Reactions

1.
2.
3.
4.

Additions
Eliminations
Substitutions
Rearrangements

Addition
Occurs when two reactants add together to form a single product
with no atoms left over

Characteristic Reactions of Alkenes

Hydrochlorination (hydrohalogenation)
Hydration
Bromination (halogenation)
Hydroboration
Hydrogenation (reduction)

Halogenation
Introduction of halogen into the molecule: chlorine, bromine, etc.

Elimination
Occur when a single reactant splits into two products, often with the
formation of a small molecule such as water or HBr.

Stability and Ease of Formation of Alkenes

CH2=CH2 < RCH=CH2 < R2C=CH2 = RCH=CHR < R2C=CHR < R2C=CR2
Dehydration and dehydrohalogenation. If elimination can result in the
formation of more than one alkene, the most stable alkene is formed
predominantly. The most stable alkene is the one most highly substituted with
alkyl groups.

Dehydrohalogenation
A reaction in which hydrogen and halogen are eliminated from a
molecule

Dehydration
The reaction in which the elements of water are eliminated from a
molecule

Substitution
occur when two reactants exchange parts to give two new products.

Reaarangement
occur when a single reactant undergoes a reorganization of bonds
and atoms to yield an isomeric product.

Characteristic Reactions of Alkenes

Addition

Hydrochlorination (hydrohalogenation)
Hydration
Bromination (halogenation)
Hydroboration
Hydrogenation (reduction)

Reaction Mechanism

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)
21

Reaction Mechanism
An overall description of how a reaction occurs
Two ways in which a covalent two-electron bond can break:
Symmetrical homolytic
Unsymmetrical heterolytic

Two ways in which a covalent two-electron bond can form:

Symmetrical
Unsymmetrical

Usual sites of reactions:

1. Multiple bonds more reaction active sites than single bonds. Pi
bonds are more prone to attacking species.
2. Polar bonds covalent bonds with uneven sharing of electron pairs
between atoms of different electronegativity
3. Lewis acids and bases

Lewis Acid
Electrophile
Accepts electrons

Lewis Base
Nucleophile
Donates electrons
Substance with
nonbonding electron
pair

Breaking

Bonding

Radical Reactions
Processes involving symmetrical bon-breaking and bondmaking
Radical also called free radical, is a neutral chemical species
that contain an odd number of electrons and thus has a single,
unpaired electron in one of its orbital

1
2

1
2

Polar Reactions
Processes involving unsymmetrical bon-breaking and bondmaking
Involve species that have an even number of electrons and thus
have only electron pairs in their orbitals. More common processes.

Hydrogen atom on HBr

attacked by nucleophilic
double bond

Bromide ion donates an

electron pair to positively
charges carbon atom

Using curved arrows in polar reaction

mechanisms
1. Electrons move from a nucleophilic source (Nu: or Nu:-) to an
electrophilic sink (E or E+)

Using curved arrows in polar reaction

mechanisms
1. Electrons move from a nucleophilic source (Nu: or Nu:-) to an
electrophilic sink (E or E+)
2. The nucleophile can be either negatively charged or neutral.

Using curved arrows in polar reaction

mechanisms
1. Electrons move from a nucleophilic source (Nu: or Nu:-) to an
electrophilic sink (E or E+)
2. The nucleophile can be either negatively charged or neutral.
3. The electrophile can be either positively charges or neutral.

Using curved arrows in polar reaction

mechanisms
1. Electrons move from a nucleophilic source (Nu: or Nu:-) to an
electrophilic sink (E or E+)
2. The nucleophile can be either negatively charged or neutral.
3. The electrophile can be either positively charges or neutral.
4. The octet rule must be followed.

Example

Example

Reaction Intermediates

Reaction Intermediates
Intermediates are intermediate structures in going from the starting
material to the product.

Kinds of Reaction Intermediates

1. Carbocation
2. Free radical
3. Carboanion

Reasons why an intermediate is unstable:

1. The particle is charged (carbocation and carboanion)
2. The particle does not have an octet of electrons in the outer shell
(carbocation, free radical)

Energy Diagrams and Transition

States

Thermodynamics

Enthalpy
the amount of heat content used or released in a system at
constant pressure.

Energy Diagram
The point on the
reaction
coordinate at
which the energy
is at a maximum.

Heat of Reaction
The difference in energy between the reactants and products
Exothermic if the energy of the products is lower than that of the
reactants
Endothermic if the energy of the products is higher that that of the
reactants

Energy Diagram

Entropy
Measure of disorder associated with a system.
The ultimate measure for determining whether or not a reaction can
occur.
The large number of possible states corresponds with a larger entropy

Gibbs free energy

Equilibria

Conclusion
The thermodynamics of a reaction is based on the difference
in energy between starting materials and products.

Kinetics

Energy of activation
The energy barrier between the reactants and the products