Alkenes

Structure, Nomenclature, and an

introduction to Reactivity
Thermodynamics and Kinetics

ANEES BABER
MSc Chemistry
 ALKENES
The general molecular formula for a noncyclic alkane is
Cn H2n+2 and the general formula for Cyclic alkene Cn H2n
The general molecular formula for an acyclic alkene is also
CnH2n because the double bond means the alkene has two
fewer hydrogens than an alkane with the same number of
carbons.
Thus, the general molecular formula for a cyclic alkene must be
CnH2n-2 .

molecular formula= CnH2n+2 – 2 hydrogens for every π bond or ring

degree of unsaturation = the total numbers of π bonds and ring
 Compounds with Molecular Formula = C8H14
CnH2n+2 = C8H18
Thus, the general molecular formula for a hydrocarbon is CnH2n+2
minus two hydrogens for every π bond or ring in the molecule
The total number of π bonds and rings is called the compound’s
degree of unsaturation . Thus, C8H14 , which has four fewer
hydrogens than an acyclic alkane with eight carbons (CnH2n+2 =
C8H18 ), has two degrees of unsaturation. So we know that the sum
of the compound’s π bonds and rings is two.

Therefore, C8H14 has two degrees of unsaturation.

 Saturated and
Unsaturated Hydrocarbons

Saturated hydrocarbons have no double bonds.

Unsaturated hydrocarbons have one or more double bonds.
 Nomenclature of Alkenes

Replace “ane” of alkane with “ene.”

1- The functional group gets the lowest possible number.

Number the longest continuous chain containing the functional group in the
direction that gives the functional group suffix the lowest possible number.
 Nomenclature of Dienes
2- For a compound with two double bonds, the “ne” ending of
the corresponding alkane is replaced with “diene.”

two double bonds = diene

3- The name of a substituent is stated before the name of the

longest continuous chain that contains the functional group,
together with a number to designate the carbon to which the
substituent is attached. if a compound’s name contains both a
functional group suffix and a substituent, the functional group
suffix gets the lowest possible number.
 Nomenclature of Alkenes

Number in the direction so that the functional

group gets the lowest number.
 Nomenclature of Alkenes
4- If a chain has more than one substituent, the substituents are
stated in alphabetical order. Then the appropriate number is
assigned to each substituent.

Substituents are stated in alphabetical order.

 Nomenclature of Alkenes
5- If counting in either direction results in the same number for
the alkene functional group suffix, the correct name is the one
containing the lowest substituent number.
 Nomenclature of Cyclic Alkenes
6- A number is not needed to denote the position of the double bond
in a cyclic alkene because the ring is always numbered so that the
double bond is between carbons 1 and 2. To assign numbers to any
substituents, count around the ring in the direction (clockwise or
counterclockwise) that puts the lowest number into the name.

Notice that 1,6-dichlorocyclohexene is not called 2,3-dichlorocyclohexene

because the former has the lowest substituent number (1), even though it does
not have the lowest sum of substituent numbers ( 1 + 6 = 7 versus 2 + 3 = 5 ).
 Nomenclature of Alkenes
7- If counting in either direction leads to the same number for
the alkene functional group suffix and the same lowest number
or numbers for one or more of the substituents, then ignore
those substituents and choose the direction that gives the
lowest number to one of the remaining substituents.
 IUPAC Nomenclature of Dienes

• Find the longest chain containing both double

bonds

CH2CH2CH2CH3
CH2 CHCHCH CH2
1 2 3 4 5

3-butyl-1,4-pentadiene

Chapter 4 12
 IUPAC Nomenclature of Dienes

• Use corresponding alkane name but replace

the “ne” ending with “diene”

CH2CH2CH2CH3
CH2 CHCHCH CH2

3-butyl-1,4-pentadiene

“pentane” changed to “pentadiene”

Chapter 4 13
 IUPAC Nomenclature of Dienes
• Number in the direction that gives the
lowest number to a double bond
CH2 CHCH2CH2CH CHCH3

1,5-heptadiene
not 2,6-heptadiene

Chapter 4 14
 IUPAC Nomenclature of Dienes

• List substituents in alphabetical order

CH3 CH2CH3
CH3C CHCH CCH2CH3

5-ethyl-2-methyl-2,4-heptadiene

Chapter 4 15
 IUPAC Nomenclature of Dienes
• Place numbers indicating the double bond
positions either in front of the parent
compound or in the middle of the name
immediately before the diene suffix
CH3 CH2CH3
CH3C CHCH CCH2CH3

5-ethyl-2-methyl-2,4-heptadiene
or 5-ethyl-2-methyl-hepta-2,4-diene

Chapter 4 16
 Vinylic and Allylic Carbons
vinylic carbon: the sp2 carbon of an alkene

allylic carbon: a carbon adjacent to a vinylic carbon

 Nomenclature
Notice how these Groups and some others can be used as substituents
names in Systematic nomenclature;
 Double Bonds Have Restricted Rotation
Each double-bonded carbon of an alkene has three sp2 orbitals. Each of
these orbitals overlaps an orbital of another atom to form a σ bond, one of
which is one of the bonds in the double bond. Thus, the σ bond of the
double bond is formed by the overlap of an sp2 orbital of one carbon with
an sp2 orbital of the other carbon, and the other bond of the double bond
is a π bond formed from side-to-side overlap of the remaining π orbital
on each of the sp2 carbons.

For the two p orbitals to be

parallel, all six atoms of the
double-bond system must be
in the same plane.

Rotation about a
double bond breaks
the π bond.
Stereoisomers are Named Using
a cis or trans Prefix
 Six Atoms of an Alkene are in the
Same Plane

© 2014 Pearson
Education,Inc.
 Alkenes Have Cis–Trans Isomers

Cis: Hydrogen on same side of the ring

Trans: The hydrogens are on opposite

sides of the ring.

• They have different configurations; they can be
separated.
?
 The E,Z System of Nomenclature
The E,Z system of nomenclature was devised for alkenes that
do not have a hydrogen attached to each of the sp2 carbons.
To name an isomer by the E,Z system, we first determine the
relative priorities of the two groups bonded to one of the sp2
carbons and then the relative priorities of the two groups bonded
to the other sp2 carbon

Z = Zusammen (together) E = Entgegen (opposite)

 Relative Priorities

The relative priorities of the two groups depends on the

atomic numbers of the atoms attached to the sp2 carbon.
 The E and Z Isomers
If the two atoms attached to an sp2 carbon are the same (there is a
tie), then consider the atomic numbers of the atoms that are
attached to the “tied” atoms.

The C of the CH2Cl group is bonded to Cl, H, H, and the C of the CH2
CH2Cl group is bonded to C,H,H. Cl has a greater atomic number than
C, so the CH2Cl group has the higher priority.
Both atoms attached to carbon on the right are Cs (in a CH2OH group and a
CH(CH3) 2 group), so there is a tie on this side as well. The C of the CH 2O H
group is bonded to O , H , H, and the C of the CH(CH 3) 2 group is bonded
to C,
C , H. Of these six atoms, O has the greatest atomic number, so CH2 OH
has the higher priority.
 E and Z
If an atom is doubly bonded to another atom, the priority system
treats it as if it were singly bonded to two of those atoms. If an
atom is triply bonded to another atom, the priority system treats it
as if it were singly bonded to three of those atoms.

The groups attached to the CH2 groups to break the tie. One of these groups is
CH2OH, and the other is C≡CH; the C of the CH2OH group is bonded to H, H , O;
the triple-bonded C is considered to be bonded to C,C,C. Of the six atoms, O has
the greatest atomic number, so CH2OH has the higher priority.
On the right, the first carbon of the CH2CH3 group is bonded to C,H,H ; the first
carbon of the CH=CH2 group is bonded to an H and doubly bonded to a C, so it is
considered to be bonded to H, C , C . One C cancels in each of the two groups,
leaving H and H in the CH2 CH3 group and H and C in the CH=CH2 group. C has
a greater atomic number than H, so CH=CH2 has the higher priority.
 E and Z
If two isotopes (atoms with the same atomic number, but
different mass numbers) are being compared, the mass
number is used to determine the relative priorities.

The Cs that are attached to the sp2 carbon on the right are both
bonded to C,C,H, so we must go to the next set of atoms to
break the tie. The second carbon of the CH(CH3)2 group is
bonded to H,H,H, whereas the second carbon of the CH=CH2
group is bonded to H, H, C .
 Reactions of Alkenes
All compounds with a carbon–carbon double bond react in
the same way, whether the compound is a small molecule like
ethene or a large molecule like cholesterol.

Alkenes undergo Electrophilic or Nucleophilic addition reaction

 Electrophiles
ELECTROPHILE: Electron loving (likes minus: e- and anions)

An electrophile has:
a positive charge,
a partial positive charge,
or an incomplete octet.
 Nucleophiles
NUCLEOPHILE: Nuclei loving (likes protons: H+)
Nucleophiles: electron-rich atoms or molecules that react with
electrophiles.
A nucleophile has
a negative charge
or a lone pair of electrons

An alkene is an electron rich molecule, a nucleophile?

Electrophiles are Lewis acids and nucleophiles are

Lewis bases.
 Nucleophiles
The π bond is localized above and below the C– C σ bond. The π
electrons are relatively far away from the nuclei and are therefore
loosely bound.

An electrophile will attract those electrons, and can pull them away to
form a new bond. This leaves one carbon with only 3 bonds and a +ve
charge (carbocation).

The double bond acts as a nucleophile (attacks the electrophile).

 Electrophilic Addition of HBr to Alkene
A two step reaction.
Mechanistic path of a reaction:
How reactants form products.

The step-by-step description of the process by which reactants (in this

case, alkene + HBr) are changed into products (an alkyl halide) is called
the mechanism of the reaction .

How can a mechanism be illustrated?

i.e. bond making & bond breaking

33
 Reaction Mechanisms
• We use curved arrows to indicate the movement of pairs of
electrons as two molecules, ions or atoms interact.
Each arrow represents the simultaneous movement of two electrons (an
electron pair) from an electron-rich center (at the tail of the arrow) toward
an electron-deficient center (at the point of the arrow). In this way, the
arrows show which bonds are formed and which bonds are broken.

34
A Nucleophile Reacts with an
Electrophile

is a two-step reaction.
 Reaction Mechanism
An arrow is drawn to show that the two electrons of the π bond of the alkene are
attracted to the partially positively charged hydrogen of HBr. The hydrogen is not
immediately free to accept this pair of electrons because it is already bonded to a
bromine. However, as the π electrons of the alkene move toward the hydrogen,
the H–Br bond breaks, with bromine keeping the bonding electrons. Notice that
the π electrons are pulled away from one sp2 carbon, but remain attached to the
other. Thus, the two electrons that originally formed the π bond now form a new
σ bond between carbon and the hydrogen from HBr. The product is positively
charged, because the sp2 carbon that did not form the new bond with hydrogen
has lost a share in an electron pair
First step of the reaction
 Curved Arrows
In the second step of the reaction, a lone pair on the negatively charged
bromide ion forms a bond with the positively charged carbon of the
carbocation. Notice that in both steps of the reaction, a nucleophile reacts
with an electrophile.
Second step of the reaction

The curved arrow shows where the electrons start from and where
they end up.
 Reaction Mechanisms
• Curved arrows are drawn only from the
electron-rich site to the electron deficient site

The overall reaction involves the addition of 1 mole of HBr to 1

mole of the alkene. The reaction, therefore, is called an addition
reaction . Because the first step of the reaction is the addition of
an electrophile ( H+) to the alkene, the reaction is more
precisely called an electrophilic addition reaction .

38
 How to Draw Curved Arrows
An arrow is used to show both the bond that forms and the bond that
breaks. Draw the arrows so that they point in the direction of the electron
flow; the arrows should never go against the flow. This means that an
arrow will point away from a negatively charged atom or toward a
positively charged atom.
 How to Draw Curved Arrows
Curved arrows are meant to indicate the movement of electrons. Never
use a curved arrow to indicate the movement of an atom. For example,
do not use an arrow as a lasso to remove a proton, as shown in the
equation on the right:

The head of a curved arrow always points at an atom or at a bond. Never

draw the head of the arrow pointing out into space.
 How to Draw Curved Arrows

A curved arrow starts at an electron source; it does not start at an atom.

In the following example, the arrow starts at the electron-rich π bond, not
at a carbon atom:
 Relative Stabilities of Alkenes

The more alkyl substituents attached to a double bond

the more stable the double bond.

42
 Thermodynamics and Kinetics
To understand the energy changes that take place in a reaction
such as the addition of HBr to an alkene, we need to understand
some of the basic concepts of thermodynamics, which
describes a reaction at equilibrium, and kinetics , which explains
the rates of chemical reactions;
A Reaction Coordinate Diagram

The more stable the species, the lower its energy.

 The Equilibrium Constant
Thermodynamics is the field of chemistry that describes the
properties of a system at equilibrium.
The relative concentrations of reactants and products at
equilibrium can be expressed by an equilibrium constant, Keq

The relative concentrations of products and reactants at equilibrium

depend on their relative stabilities: the more stable the compound,
the greater its concentration at equilibrium. Thus, if the products are
more stable (have a lower free energy) than the reactants , there will
be a higher concentration of products than reactants at equilibrium,
and Keq will be greater than 1.
If the reactants are more stable than the products, there will be a
higher concentration of reactants than products at equilibrium, and K
eq will be less than 1.
 Exergonic and Endergonic Reactions
The difference between the free energy of the products and the
free energy of the reactants under standard conditions is called
the Gibbs free-energy change. ΔG0

Gibbs free-energy change , or ΔG0 .

The symbol indicates standard conditions, which means that all
species are at a concentration of 1 M, a temperature of 25 °C, and
a pressure of 1 atm.
 Thermodynamics

G° will be negative if

the products have a lower
free energy (are more
stable) than the reactants.
In other words, the
reaction will release more
energy than it consumes;
such a reaction is called
an exergonic reaction .

• When G° is negative the reaction is exergonic

47
 Thermodynamics

If the products have a higher

free energy (are less stable)
than the reactants, G° will
be positive, and the reaction
will consume more energy
than it releases; such a
reaction is called an
endergonic reaction

• When G° is positive the reaction is

endergonic
48
 Thermodynamics
So, We have seen that whether reactants or products are favored
at equilibrium can be indicated by the equilibrium constant ( Keq )
or by the change in free energy (G° ). These two quantities are
related by the equation;

A small change in G° corresponds to a large change in Keq

and, therefore, a large change in the amount of product
obtained at equilibrium
 ?
• The G° for conversion of “axial” fluorocyclohexane to “equatorial”
fluorocyclohexane at 25C is -0.25kcal/mol . Calculate the percentage
of fluorocyclohexane molecules that have the fluoro substituent in an
equatorial position at equilibrium.
 Gibbs Free-Energy Change (∆G°)

The enthalpy term ( H ) is the heat given off or the heat consumed
during the course of a reaction. Heat is given off when bonds are
formed, and heat is consumed when bonds are broken.

If the bonds that are formed in a reaction are stronger than the
bonds that are broken, more energy will be released in the bond-
forming process than will be consumed in the bond-breaking
process, and ∆H0 will be negative. A reaction with a negative ∆H0 is
called an exothermic reaction . If the bonds that are formed are
weaker than those that are broken, ∆H0 will be positive. A reaction
with a positive ∆H0 is called an endothermic reaction
Calculating ∆H°
 Entropy

Entropy ∆S0 is a measure of the freedom of motion in a system.

Restricting the freedom of motion of a molecule decreases its entropy. For
example, in a reaction in which two molecules come together to form a
single molecule, the entropy of the product will be less than the entropy of
the reactants because two separate molecules can move in ways that are
not possible when they are bound together in a single molecule. In such a
reaction, ∆S0 will be negative. In a reaction in which a single molecule is
cleaved into two separate molecules, the products will have greater
freedom of motion than the reactant, and ∆S0 will be positive.
 Entropy

• A reaction with a negative G° has a favorable equilibrium

constant (Keq > 1); that is, the reaction is favored as written
from left to right because the products are more stable than
the reactants. If you examine the expression for the Gibbs
standard free-energy change, you will find that negative
values of ∆H0 and positive values of ∆S0 contribute to make
G° negative. In other words, the formation of products
with stronger bonds and greater freedom of motion causes
G° to be negative. Notice that the entropy term is
temperature dependent and, therefore, becomes more
important as the temperature increases. As a result, a
reaction with a positive ∆S0 may be endergonic at low
temperatures, but exergonic at high temperatures.
 Kinetics
• Kinetics is the field of chemistry that studies the
rates of chemical reactions and the factors that affect
those rates.
• G° of a reaction will not tell us how fast it will
occur or if it will occur at all
• G°describes only the difference between the
stability of the reactants and the stability of the
products.
• We need to know the rate of reaction
• The rate of a reaction is dependant on the height
of the energy barrier for the reaction, G‡, called
the free energy of activation
• G‡= (free energy of the transition state) --
(free energy of the reactants)

57
 Reaction Coordinate Diagrams for Fast and Slow
Exergonic and Endergonic Reactions

As G‡ decreases, the rate of the reaction increases. Thus,

anything that makes the reactants less stable or makes the
transition state more stable will make the reaction go faster.
 Free Energy of Activation (∆G‡)

Some exergonic reactions have small free energies of activation and

therefore can take place at room temperature. In contrast, some exergonic
reactions have free energies of activation that are so large that the reaction
cannot take place unless energy is supplied in addition to that provided by
the existing thermal conditions .

The free energy of activation

is the energy barrier of the reaction.
Thermodynamic Vs Kinetic Stability
 Rate of reaction
1- The number of collisions that take place between the
reacting molecules in a given period of time. The rate of
the reaction increases as the number of collisions
increases.
2- The fraction of collisions that occur with sufficient
energy to get the reacting molecules over the energy
barrier. If the free energy of activation is small, then
more collisions will lead to reaction than if the free
energy of activation is large.
3- The fraction of collisions that occur with the proper
orientation. 2-Butene and HBr will react only if the
molecules collide with the hydrogen of HBr
approaching the π bond of 2-butene. If a collision
occurs with the hydrogen approaching a methyl group
of 2-butene, no reaction will take place, regardless of
the energy of the collision.
 Rate of a Reaction

Increasing the concentration increases the rate.

Increasing the temperature increases the rate.

The rate of a reaction can also be increased by a catalyst

 The Rate of a Reaction versus
The Rate Constant for a Reaction

The rate constant tells us how easy it is to reach the transition state
(how easy it is to get over the energy barrier). Low-energy barriers
are associated with large rate constants , whereas high-energy
barriers are associated with small rate constants
The rate of a reaction is a measure of the amount of product
that is formed per unit of time.
The rate is the product of the rate constant and the reactant
concentration(s), so reaction rates depend on concentration,
whereas rate constants are independent of concentration.
 Kinetics
Therefore, when we compare two reactions to see which one occurs more
readily, we must compare their rate constants and not their concentration-
dependent rates of reaction.
Although rate constants are independent of concentration, they are
dependent on temperature. The Arrhenius equation relates the rate constant
of a reaction to the experimental energy of activation and to the temperature
at which the reaction is carried out:

The value of A pertains to the frequency and orientation of

collisions that occurs with the proper orientation for the reaction

e–Ea/RT is the fraction of collisions with the minimum energy ( Ea )

needed for reaction. ( R is the gas constant, T is the temperature in
kelvins, and Ea is the experimental energy of activation, which is an
approximate value of the activation energy;
 An Electrophilic Addition Reaction
We have seen that the addition of HBr to 2-butene is a two-step
process. In each step, the reactants pass through a transition
state as they are converted into products. The structure of the
transition state for each of the steps is shown here in brackets.

Transition states have partially formed bonds.

 Reaction Coordinate Diagram
A reaction coordinate diagram can be drawn for each step of a reaction.
In the first step of the addition reaction, the alkene is converted into a
carbocation that is higher in energy (less stable) than the reactants. The
first step, therefore, is endergonic (G° > 0). In the second step, the
carbocation reacts with a nucleophile to form a product that is lower in
energy (more stable) than the carbocation reactant. This step, therefore,
is exergonic (G°is < 0).
 Reaction Coordinate Diagram for
the Addition of HBr to 2-Butene

The rate-limiting step of the reaction is the step that has its transition state
at the highest point of the reaction coordinate diagram.
 Rate-Determining Step
• Formation of the carbocation intermediate is the slower
of the two steps
• It is the rate-determining step
• Carbocation intermediates are consumed by bromide
ions as fast as they are formed

68
 Transition States and Intermediates
• It is important to distinguish between a transition
state and a reaction intermediate
• A transition state
– is a local maximum in the reaction coordinate diagram
– has partially formed and partially broken bonds

69
 Transition States and Intermediates
• An intermediate
– is at a local minimum energy in the reaction
coordinate diagram
– may be isolated in some cases

70
 A Catalyst

A catalyst provides a pathway for a reaction with a lower

energy barrier.

A catalyst does not change the energy of the starting

point (the reactants) or the energy of the end
point (the products).
 Enzymes
Most biological reactions require a catalyst.
Most biological catalysts are proteins called enzymes.

The reactant of a biological reaction is called a substrate.

 The Active Site of an Enzyme

An enzyme binds its substrate at its active site.

 Enzyme Side Chains that Bind the
Substrate

Some enzyme side chains bind the substrate.

Some enzyme side chains are acids, bases, and
nucleophiles that catalyze the reaction.
Enzyme Side Chains that Catalyze the
Reaction

Some enzyme side chains are acids, bases, and

nucleophilesthat catalyze the reaction.
Calculating Kinetic Parameters
Bases in Nucleic acids
Isomers for Compounds with
Two Double Bonds