Organic Chemistry

6th Edition
Paula Yurkanis Bruice
Chapter 3
Alkenes:

Structures, Nomenclature, and

an Introduction to Reactivity

Thermodynamics
and Kinetics

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Alkenes Are an Important Part of Our Lives

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 Systematic Nomenclature of Alkenes
CnH 2 nt
1. Longest continuous chain containing the
functional group:
CnHan

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2. For a compound with two double bonds, the suffix is
“diene”:

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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5. In a cyclic alkene, the alkene functional group is given the
number 1, but the -1- is left out of the name:

6. The alkene substituent is given the lower number:

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Special Nomenclatures

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

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Structure of Alkene

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Alkene Isomers

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Dipole Moments of Alkene Isomers

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Conversion of alkene isomers requires breaking of
the p bond between the two sp2 carbons

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Cis-Trans Interconversion in Vision

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 Fats: Kinky, Saturated, and Trans

Saturated fats are Trans fats structurally

Cis alkenes groups produce kinks solids because stacking resemble saturated fats.
in the chain. Unsaturated fats are of chains is possible. Both are considered
oils because stacking of kinked unhealthy.
chains is not possible.

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tons "

8 E and Z Nomenclature:

E,Z is from German:

Z, Zusammen (together) E, Entgegen (opposite)
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 Naming by the E,Z System
Rule 1: Consider the atomic number of the atoms bonded
directly to a specific sp2 carbon:

Higher atomic number has higher priority

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Rule 2: If there is a tie, consider the atoms
attached to the tied atoms:

Rule 3: Multiple bonds are treated as attachment of multiple

single bonds using “divide-duplicate.”

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 Using divide-duplicate:
• Divide -bonds.
• Duplicate atoms attached to each -bond.

Rule 4: Rank the priorities by mass number in isotopes:

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 ÷

^
Electron-rich atoms or molecules (nucleophiles) are attracted
to electron-deficient atoms or molecules (electrophiles):

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Your First Reaction: 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.

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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. The arrow must originate at the electron source.

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3. The head of the curved arrow always points to the
destination of the electrons.
correct incorrect

4. Half-headed arrows are used for radical processes.

Bond breaking and bond formation both require two half-
headed arrows.

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 Thermodynamics and Kinetics
Kinetics: The k1 and k-1 values that
provide the rate at which the reaction
comes to equilibrium.

Thermodynamics:The Keq value

that provides the concentration at Z
and Y at equilibrium.

Thermodynamics describes a reaction at equilibrium.

Kinetics explains the rates of chemical reactions.
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A Reaction Coordinate Diagram Describes
the Reaction Pathway

Transition states have partially formed bonds

Intermediates have fully formed bonds
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Thermodynamics: How much product is formed?

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 Thermodynamic Parameters
DGo = DHo -
TDSo
DGo = -RTlnKeq
Gibbs standard free-energy change (DGo)

Enthalphy (DHo): the heat given off or absorbed

during a reaction

Entropy (DSo): a measure of freedom of motion

If DSo is small compared to DHo, DGo ~ DHo

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 …

Exergonic Reaction Endergonic Reaction

-DGo +DGo
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DHo can be calculated from bond dissociation
energies

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 Entropic Reactions
• An entropic reaction results in a massive change in
volume without heat evolution.
• Air bag deployment is a common entropic reaction.
• TATP is an entropic explosive used by terrorists.

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Kinetics: How fast is the product formed?

Rate of a reaction =
number of collisions fraction with fraction with
per unit of time X sufficient energy X proper orientation

The rate-limiting step controls the overall rates of the reaction

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The free energy between the transition state
and the reactants

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 DG‡ = DH‡ -TDS‡
DG‡ :
(free energy of transition state)- (free energy of reactants)

DH‡ :
(enthalpy of transition state) - (enthalpy of reactants)

DS‡ :
(entropy of transition state) - (entropy of reactants)

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 Rates and Rate Constants
First-order reaction Second-order reaction

A B A+B C+D
rate = k[A] rate = k[A][B]
Units of first-order rate constant
k is time-1
A+A B

rate = k[A]2
Units of the rate is M time-1
Units of second-order rate constant
k is M-1time-1

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 The Arrhenius Equation
k = Ae
-
Ea = D
DH‡ + RT
Ea/RT
A is the pre-exponential factor. Its value pertains to the
frequency and orientation of collisions.

The term provides the fraction of molecules with the

activation energy (Ea) at temperature T (oK). R is the gas
constant.
If Ea = 0, the reaction is encounter controlled with k =
A. The second order encounter-controlled k value in
water is 1010 M-1sec-1.
The Arrhenius equation predicts that the rate of a
reaction will double with each 10oK increase in
temperature.
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Transition State Versus Intermediate

intermediate

intermediate

Transition states have partially formed bonds

Intermediates have fully formed bonds

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Electrophilic Addition of HBr to 2-Butene

The rate-limiting step controls the overall rates of the

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