John E.
McMurry
[Link]/chemistry/mcmurry
Chapter 7
Alkenes: Structure and Reactivity
Paul D. Adams • University of Arkansas
Alkene - Hydrocarbon With Carbon-
Carbon Double Bond
Also called an olefin but alkene is better
Hydrocarbon that contains a C-C double bond
Includes many naturally occurring materials
Flavors, fragrances, vitamins
Why this Chapter?
C=C double bonds are present in most organic and
biological molecules
To examine consequences of alkene stereoisomerism
To focus on an important alkene reaction: electrophilic
addition
7.1 Industrial Preparation and Use
of Alkenes
Ethylene and propylene are important organic
chemicals produced
Thermal Cracking
Thermal cracking may take place w/o catalyst at very
high temperatures
7.2 Calculating Degree of
Unsaturation
Relates molecular formula to possible structures
Degree of unsaturation: number of multiple bonds or rings
Formula for a saturated acyclic compound is CnH2n+2
Alkene has fewer hydrogens than an alkane with the same number of carbons —C nH2n
because of double bond
Each ring or multiple bond replaces 2 H's
Example: C6H10
Saturated is C6H14
therefore 4 H's are not present
This has two degrees of unsaturation
Two double bonds?
or triple bond?
or two rings?
or ring and double bond?
Degree of Unsaturation With Other
Elements
Organohalogens (X: F, Cl, Br, I)
Halogen replaces hydrogen
C4H6Br2 and C4H8 have one degree of unsaturation
Degree of Unsaturation
(Continued)
Organoxygen compounds (C,H,O) – Oxygen forms 2
bonds
these don't affect the formula of equivalent
hydrocarbons
May be ignored in calculating degrees of
unsaturation
Organonitrogen Compounds
Nitrogen has three bonds
So if it connects where H was, it adds a connection
point
Subtract one H for equivalent degree of unsaturation
in hydrocarbon
Summary - Degree of Unsaturation
Count pairs of H's below CnH2n+2
Add number of halogens to number of H's (X equivalent
to H)
Ignore oxygens (oxygen links H)
Subtract N's - they have two connections
7.3 Naming Alkenes
Name the parent hydrocarbon
Number the carbons in chain so that double bond carbons have lowest possible numbers
Naming Alkenes (Continued)
Write the full name- Number substituents according to:
1) Position in chain, 2)Alphabetically
Rings have “cyclo” prefix
Many Alkenes Are Known by
Common Names
7.4 Cis-Trans Isomerism in
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
Subtractive interaction creates a anti-bonding orbital
Occupied orbital prevents rotation about -bond
Rotation prevented by bond - high barrier, about 268
kJ/mole in ethylene
Cis-Trans Isomerism in Alkenes
(Continued)
Rotation of bond is prohibitive
This prevents rotation about a carbon-carbon double
bond (unlike a carbon-carbon single bond).
Creates possible alternative structures
Cis-Trans Isomerism in Alkenes
(Continued)
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
Cis-Trans Isomerism in Alkenes
(Continued)
Cis-Trans Isomerization requires that end groups differ
in pairs
Bottom pair cannot be superposed without breaking
C=C
7.5 Alkene Stereochemistry and the E,Z
Designation
Cis-Trans naming system discussed thus far only
works with disubstituted alkenes
Tri- and Tetra substituted double bonds require
more general method
Method referred to as the E,Z system
Alkene Stereochemistry and the E,Z
Designation (Continued): 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
Alkene Stereochemistry and the E,Z
Designation (Continued): Cahn-Ingold-Prelog
Rules
RULE 1
Must rank atoms that are connected at comparison
point
Higher atomic number gets higher priority
Br > Cl > S > P > O > N > C > H
Alkene Stereochemistry and the E,Z
Designation (Continued): Cahn-Ingold-Prelog
Rules
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
Alkene Stereochemistry and the E,Z
Designation (Continued): Cahn-Ingold-Prelog
Rules
RULE 3
Multiple-bonded atoms are equivalent to the same number of
single-bonded atoms
Substituent is drawn with connections shown and no double or
triple bonds
Added atoms are valued with 0 ligands themselves
7.6 Stability of Alkenes
Cis alkenes are less stable than trans alkenes
Compare heat given off on hydrogenation: Ho
Less stable isomer is higher in energy
And gives off more heat
tetrasubstituted > trisubstituted > disubstituted >
monosusbtituted
hyperconjugation stabilizes
Stability of Alkenes (Continued):
Comparing Stabilities of Alkenes
Evaluate heat given off when C=C is converted to C-C
More stable alkene gives off less heat
trans-Butene generates 5 kJ less heat than cis-butene
Stability of Alkenes (Continued):
Hyperconjugation
Electrons in neighboring filled orbital stabilize vacant
antibonding orbital – net positive interaction
Alkyl groups are better than H
7.7 Electrophilic Addition of
Alkenes
General reaction
mechanism of
electrophilic addition
Attack on electrophile
(such as HBr) by bond
of alkene
Produces carbocation
and bromide ion
Carbocation is an
electrophile, reacting
with nucleophilic
bromide ion
Electrophilic Addition of Alkenes (Continued):
Electrophilic Addition Energy Path
Two step process
First transition state is high energy point
First step is slower than second
Electrophilic Addition of Alkenes
(Continued)
The reaction is successful with HCl and with HI as well
as HBr
HI is generated from KI and phosphoric acid
7.8 Orientation of Electrophilic Additions:
Markovnikov’s Rule
In an unsymmetrical alkene, HX reagents can add in two different
ways, but one way may be preferred over the other
If one orientation predominates, the reaction is regioselective
Markovnikov observed in the 19th century that in the addition of
HX to alkene, the H attaches to the carbon with more H’s and X
attaches to the other end (to the one with more alkyl substituents)
This is Markovnikov’s rule
Example of Markovnikov’s Rule
Addition of HCl to 2-methylpropene
Regiospecific – one product forms where two are possible
If both ends have similar substitution, then not regiospecific
Markovnikov’s Rule (restated)
More highly substituted carbocation forms as
intermediate rather than less highly substituted one
Tertiary cations and associated transition states are
more stable than primary cations
Markovnikov’s Rule (restated)
7.9 Carbocation Structure and
Stability
Carbocations are planar and the tricoordinate carbon is
surrounded by only 6 electrons in sp2 orbitals
the fourth orbital on carbon is a vacant p-orbital
the stability of the carbocation (measured by energy needed to
form it from R-X) is increased by the presence of alkyl
substituents
Carbocation Structure and Stability
(Continued)
A plot of DH dissociation shows that more highly
substitued alkyl halides dissociate more easily than
less highly substituted ones
Carbocation Structure and Stability
(Continued)
A inductive stabilized cation species
7.10 the Hammond Postulate
If a carbocation intermediate is more stable than another, why
is the reaction through the more stable one faster?
the relative stability of the intermediate is related to an
equilibrium constant (Gº)
the relative stability of the transition state (which describes
the size of the rate constant) is the activation energy (G‡)
the transition state is transient and cannot be examined
What does the Hammond Postulate state?
“the structure of a transition state resembles the structure of
the nearest stable species. Transition states for endergonic
steps structurally resemble products, and transition states
for exergonic steps structurally resemble reactants”
The Hammond Postulate (Continued):
Transition State Structures
A transition state is the highest energy species in a
reaction step
By definition, its structure is not stable enough to exist
for one vibration
But the structure controls the rate of reaction
So we need to be able to guess about its properties in
an informed way
We classify them in general ways and look for trends in
reactivity – the conclusions are in the Hammond
Postulate
Examination of the Hammond
Postulate
A transition state
should be similar
to an intermediate
that is close in
energy
Sequential states
on a reaction path
that are close in
energy are likely
to be close in
structure - G. S.
Hammond
Competing Reactions and the
Hammond Postulate
Normal Expectation: Faster reaction gives more stable
intermediate
Intermediate resembles transition state
7.11 Evidence for the Mechanism of
Electrophilic Addition: Carbocation
Rearrangments
Carbocations undergo
structural
rearrangements
following set patterns
1,2-H and 1,2-alkyl
shifts occur
Goes to give
moststable carbocation
Can go through less
stable ions as
intermediates
Hydride shifts in biological
molecules
Let’s Work a Problem
Addition of HCl to 1-isopropylcyclohexene yields a
rearranged product. Propose a mechanism, showing the
structures of the intermediates and using curved arrows
indicate electron flow in each step.
The hydrogen is approached by the There is a “Methyl” shift, creating a new C-H
nucleophilic double bond. A new C-H bond bond with the 1st 3˚ carbocation to give an
is formed, along with a 3˚ carbocation. At isomeric 3˚ carbocation that is less
the same time, Cl takes on 1more electron, hindered.
making it a Cl anion.
The Cl-ion then approaches the new
carbocation. A Cl-C bond is formed which
gives charged neutral product.
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