Chapter 5

Alkenes
Structure, Nomenclature,
and an Introduction to
Reactivity
•
Thermodynamics
and Kinetics

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 Alkenes Are an Important Part of Our Lives
Ethene (a plant Hormone)
controls growth and other
changes in the plant’s tissues.

Tomatoes are shipped green so

they will arrive unspoiled.
Ripening can be started by
exposure to ethene. 2
 5.1 MOLECULAR FORMULAS AND
THE DEGREE OF UNSATURATION
• noncyclic alkane is CnH2n+2
• cyclic alkane is CnH2n Noncyclic = acyclic
• acyclic alkene is also CnH2n CnH2n+2  2 H for every  bond or ring
• cyclic alkene is CnH2n-2

a saturated hydrocarbon an unsaturated hydrocarbon

Degree of unsaturation (DU): the total # of  bonds and rings.

C8H14 missing four hydrogens from CnH2n+2 has two DU. Then, the
sum of its  bonds and rings is two.
Cf) DU = (18 – 14)/2 = 2

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Alkenes
 Hydrocarbons containing a C=C [double bond]
 common name ~ olefin [oil-forming]
 alkane ~ paraffin [little affinity]
 unsaturated, CnH2n
 alkane ~ saturated, CnH2n+2

 degree of unsaturation [DU]

–2H

–2H –2H

DU = 0 DU = 1 DU = 1 DU = 2

 1 DU per 1  bond or 1 ring by – 2 H

 DU = (max # of H - # of H)/2 4
 5.2 THE NOMENCLATURE OF ALKENES
Replace “ane” of alkane with “ene.”

1. The longest continuous chain containing the functional

group is numbered in the direction that gives the
functional group suffix the lowest possible numer.

The stereoisomers of an alkene are

named using a cis or trans prefix (in
italics).
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2. For a compound with two or more double bonds, the
suffix is “diene”, “triene”, “tetraene”, and so on:

3. When there are both a functional group and a

substituent, the functional group gets the lowest
number:

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4. Cite the substituents in alphabetical order:

5. Name with the lowest functional group number and

then the lowest substituent numbers:

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6. In a cyclic alkene, a number is not needed to denote the position of
the double bond because the double bond is between C1 and C2.
For substituents, count around the ring in the direction that puts
the lowest number into the name:

even though
1+6 > 2+3

7. Give the lowest number to one of the remaining substituents:

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 Special Nomenclatures
allyl from allene
vinylic carbon: the sp2 carbon of an alkene CH2=C=CH2
allylic carbon: a carbon adjacent to a vinylic carbon propadiene
allene

in systematic nomenclature:

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 (cf.) What is an Omega Fat?
This nomenclature is not IUPAC (both Greek letters and numbers
are used). This naming is commonly used in labeling and by
nutritionists.

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5.3 THE STRUCTURE OF ALKENES

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[Review 4.2] Naming Alkenes Using E,Z System
 cis-trans designation for 1,2-disubstituted alkenes only

cis-trans
2 H’s on the same-opposite side

no isomer
1 comp’d

 for tri- or tetrasubstituted ~ Z-E designation

Z isomer E isomer 12
zusammen [‘together’] entgegen [‘opposite’]
 Z-E designation
 rules for priority
 Cahn-Ingold-Prelog sequence rule [CIP system]
1. higher priority for higher atomic number
2. higher atomic number at the first point of difference
3. divide-duplicate multiple bond
4. for isotopes use mass #

CHH OHH CHH

CCH
CCH

Cl H H OHH
CCC
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 Using divide-duplicate multiple bond:
• Divide -bonds.
• Duplicate atoms attached to each -bond.

 Stereoisomers for Compounds with Two Double Bonds

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5.4 HOW AN ORGANIC COMPOUND REACTS
DEPENDS ON ITS FUNCTIONAL GROUP
The functional group determines the kinds of reactions
a compound will undergo.

Organic compounds can be divided into families, and all

the families in a group react in similar ways.

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 5.5 HOW ALKENES REACT • CURVED
ARROWS SHOW THE FLOW OF ELECTRONS
Electron-deficient atoms or molecules (electrophiles)
are attracted to electron-rich atoms or molecules
(nucleophiles):

An electrophile [E+] has

a positive charge,
a partial positive charge,
or an incomplete octet (empty orbital) 16
A nucleophile [Nu:] has
a negative charge,
a lone pair,
or a π bond.

17
 Addition of HBr to an Alkene

• 1st Step: Addition

of a proton to the
alkene. The
proton is the
electrophile.

• 2nd Step:
Bromide traps the
carbocation.
Bromide is the
nucleophile.
Curved arrows show where the electrons start from and where they end up. 18
Arrows in Organic Chemistry: Moving Electrons

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Arrows in Organic Chemistry: Showing Processes

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 Rules on Using Curved Arrows
1. Full-headed arrows are drawn in the direction of
two-electron flow:

2. Curved arrows are meant to indicate the movement

of electrons (not for the movement of an atom!):

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3. The head of the curved arrow always points at an atom
or a bond (destination, not pointing out into space)

4. A curved arrow starts at an electron source (not at

an atom):

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A Reaction Coordinate Diagram Describes the Reaction Pathway

A reaction coordinate diagram shows the energy changes

that take place in each step of a reaction.
The more stable the species, the lower its energy
Transition states have partially broken and partially formed bonds.
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5.6 THERMODYNAMICS:
HOW MUCH PRODUCT IS FORMED

Kinetics: The k1 and k-1 values that

provide the rate at which the
k1 reaction comes to equilibrium.
Y Z
Thermodynamics:The Keq value
k-1
that provides the concentration
k1 [Z] of Z and Y at equilibrium.
Keq = =
k-1 [Y]
Thermodynamics describes a reaction at equilibrium.
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Kinetics explains the rates of chemical reactions.
Thermodynamics: How much product is formed?

The equilibrium constant gives the relative concentration of

reactants and products at equilibrium.
The more stable the compound, the greater its concentration
at equilibrium.

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, so Keq will be greater than 1.
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Exergonic Reaction DGo :  Endergonic Reaction DGo : +

products are
less stable
products are
more stable

R: gas const. (1.986 x 10-3 kcal mol-1 K-1)

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T: temp in kelvins
Thermodynamic Parameters
: standard conditions
Gibbs standard free-energy change (DGo) (at 1 M, 25oC, 1 atm)
Enthalphy (DHo): the heat given off or absorbed during a reaction
Entropy (DSo): a measure of the freedom of motion

forming

The formation of products with stronger bonds and greater freedom of

motion causes DGo to be negative, i.e., favorable reaction.
 DH° < 0, exothermic; DH° > 0, endothermic
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 DH° can replace DG° when TDS° is small [either low T or DS]
 5.7 INCREASING THE AMOUNT OF
PRODUCT FORMED IN A REACTION
Le Chatelier’s Principle: if an equilibrium is disturbed,
the system will adjust to offset the disturbance

Coupled Reactions: an endergonic reaction followed by an exergonic reaction

The exergonic reaction drives the endergonic

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reaction that precedes it.
 5.8 CALCULATNG DHo VALUES
DHo can be calculated from bond dissociation enthalpies (DH)

DGo  DHo with small DSo and in the gas phase 29

(No solvation issue)
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5.9 USING DHo VALUES TO DETERMINE
THE RELATIVE STABILITIES OF ALKENES

Catalytic Hydrogenation

reduction reactions
(the number of C-H bonds increases)
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Catalytic Hydrogenation

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Using ∆H° Values to Determine the
Relative Stabilities of Alkenes

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Using ∆H° Values to Determine the
Relative Stabilities of Alkenes

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 The more alkyl groups bonded to the sp2
carbon, the more stable the alkene
why? hyperconjugation
- Stabilizing interaction betw C=C  bond and adjacent C-H 
bonds on substituents [ - *]

The more the # of α hydrogen, the more the stability of compound !

https://www.youtube.com/watch?v=TgfQ2Vaf06s 35
A Trans Alkene is More Stable Than a Cis Alkene

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5.10 KINETICS: HOW FAST IS THE PRODUCT FORMED?
DG‡ = free energy of transition state – free energy of the reactants

fast exergonic reaction

fast endergonic reaction

slow exergonic reaction

slow endergonic reaction

The higher the energy barrier, the slower is the reaction.

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Free Energy of Activation (∆G‡)

The free energy of activation is

the energy barrier of the reaction.

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 Kinetic and Thermodynamic Stability

Kinetic Stability is indicated by ∆G‡

If ∆G‡ is large, the reactant is kinetically stable because it reacts slowly.

If ∆G‡ is small, the reactant is kinetically unstable because it reacts rapidly.
cf) Similarly, if ∆G‡ for the reverse reaction is large, the product is kinetically stable.
if ∆G‡ for the reverse reaction is small, the product is kinetically unstable.

Thermodynamic Stability is indicated by ∆G°

If ∆G° is negative,
the product is thermodynamically stable compared to the reactant.
If ∆G° is positive,
the product is thermodynamically unstable compared to the reactant.

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 5.11 THE RATE OF A CHEMICAL 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. For example,
2-butene and HBr will react only if the molecules collide with the hydrogen of HBr
approaching the  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.

conc’n of reactants catalyst may help

rxn temperature 40
Boltzmann distribution curves at two different temperatures

DGǂ

At a higher temperature, there will be more molecules with sufficient energy to

get over the energy barrier.

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

The rate of reaction depends on concentration,

whereas the rate constant is independent of concentration.
To see which one occurs more readily, we must compare their rate 42
constants, not rates of reaction.
 The Arrhenius Equation

The value of A pertains to

the frequency and orientation of collisions.

e−Ea/RT
e–Ea/RT is the fraction of the collisions with
the minimum energy needed for a reaction.

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How are Rate Constants Related to
the Equilibrium Constant?

Box p251
True activation energy is DGǂ.
DGǂ = DHǂ – TDSǂ
Ea = DHǂ + RT
Ea is an approximate DGǂ,
and lowered by catalyst.

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 5.12 A REACTION COORDINATE DIAGRAM
DESCRIBES THE ENERGY CHANGES THAT
TAKE PLACE DURING A REACTION

Transition State Versus Intermediate

Transition states have partially formed bonds

Intermediates have fully formed bonds 45
Reaction Coordinate Diagram for Each Step of the
Addition of HBr to 2-Butene

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Electrophilic Addition of HBr to 2-Butene

The rate-determining (rate-limiting) step has its transition state at the

highest point on the reaction coordinate diagram.

The RDS controls the overall rates of the reaction. 47

 5.13 CATALYSIS

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).

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 5.14 CATALYSIS BY ENZYMES
All reactions occurred in biological systems are
reactions of organic compounds.

Most biological catalysts are proteins called enzymes.

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 Molecular recognition

Enzyme Side Chains That Enzyme Side Chains That

Bind the Substrate Catalyze the Reaction

Enzyme side chains bind the substrate using Some enzyme side chains are acids, bases,
hydrogen bonds, London dispersion forces, and and nucleophiles that catalyze the reaction.
dipole-dipole interactions.
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