5.

Alkenes: Structure
and Reactivity

Assoc. Prof. Ph. D. Tran Thuong Quang

Department of Organic Chemistry
School of Chemical Technology
HUST
5.1Alkene - Hydrocarbon With
Carbon-Carbon Double Bond
◼ Includes many naturally occurring
materials
◼ Flavors, fragrances, vitamins
◼ Important industrial products
◼ These are feedstocks for industrial
processes

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Alkenes

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5.2 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
◼ Each ring or multiple bond replaces 2 H's

4
Example: C6H10
◼ Saturated is C6H14
◼ Therefore 4 H's are missing
◼ This has two degrees of unsaturation
◼ Two double bonds?
◼ or triple bond?
◼ or two rings
◼ or ring and double bond

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Other Examples of C6H10:

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Degree of Unsaturation With Other
Elements
◼ Organohalogens (X: F, Cl, Br, I)
Halogen replaces hydrogen
◼

◼ C4H6Br2 and C4H8 have one degree of unsaturation

◼ Oxygen atoms: these don't affect the total count of H's

C4H8O3 7
Degree of Unsaturation With Other
Elements

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If C-N Bonds Are Present
◼ Nitrogen has three bonds
◼ So if it connects where H was, it adds a connection point, and
there an extra H
◼ Subtract one H for equivalent degree of unsaturation in
hydrocarbon

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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)
◼Don't count oxygens (oxygen
does not affect the # of H’s)
◼Subtract N's - they have three
connections
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 5.3 Naming of Alkenes
◼ Find longest continuous carbon chain for root of the name
◼ Number carbons in chain so that double bond carbons have lowest
possible numbers
◼ Double bond carbons must be numbered consecutively

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Alkene Nomenclature: longest
chain must contain the C=C

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Alkene Nomenclature

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Cycloalkene nomenclature

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 Cycloalkene nomenclature

1 CH3 CH3 CH3

3 4

2 2 1
1 2

1-methylcyclohexene 3-methylcyclohexene 4-methylcyclohexene

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Problem 5.1 IUPAC

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Problem 5.2

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Many Alkenes Are Known by
Common Names

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Alkene Group Names

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5.4 Electronic Structure of Alkenes

◼ Carbon atoms in a double bond are sp2-

hybridized
◼ Three equivalent orbitals at 120º separation in
plane
◼ Fourth orbital is an unhybridized p orbital

◼ Combination of an electron pair in an orbital

formed by the overlap of two sp2 orbitals of
two atoms forms  bond between them

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5.4 Electronic Structure of Alkenes

◼ Additive interaction (overlap) of p orbitals

creates a  bonding orbital
◼ Subtractiveinteraction creates a  anti-
bonding orbital
◼ Occupied  orbital prevents rotation about
-bond
◼ Rotation prevented by  bond - high barrier,
about 268 kJ/mole in ethylene

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 Rotation of  Bond Is Energetically
Costly
◼ This prevents
rotation about a
carbon-carbon
double bond (unlike
a carbon-carbon
single bond).
◼ Creates possible
geometric isomers
(cis/trans)

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5.5 Cis-Trans Isomerism in Alkenes

◼ The presence of a carbon-carbon double 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

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Cis, Trans Isomers Require That End
Groups Must Differ in Pairs

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 5.6 Sequence Rules: The E,Z
Designation

◼ Neither compound is
clearly “cis” or “trans”
◼ Substituents on C1 are
different than those on
C2
◼ We need to define
“similarity” in a precise
way to distinguish the
two stereoisomers
◼ Cis, trans nomenclature
only works for
disubstituted double
bonds
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 Develop a System for Comparison of
Priority of Substituents

◼ Assume a valuation
system
◼ If Br has a higher
“value” than Cl
◼ If CH3 is higher than H
◼ Then, in A, the higher
value groups are on
opposite sides
◼ In B, they are on the same
side
◼ Requires a universally
accepted “valuation”
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Ranking Priorities: Cahn-Ingold-
Prelog Rules
◼ Must rank atoms that are connected at
comparison point
◼ Higher atomic number gets higher priority

In this case,The higher priority

groups are opposite:
(E )-1-bromo-1-chloro-propene

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 E,Z Stereochemical Nomenclature

◼ Priority rules of
Cahn, Ingold, and
Prelog
◼ Compare where
higher priority group
is with respect to
bond and designate
as prefix
◼ E -entgegen,
opposite sides
◼ Z - zusammen,
together on the
same side
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2-chloro-2-butenes

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Extended Comparison
◼ 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

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Dealing With Multiple Bonds
◼ Substituent is drawn with connections shown and no double
or triple bonds
◼ Added atoms are valued with no ligands themselves

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Some Examples:

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Practice problem 5.1

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Solution

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Problem 5.3 E, Z

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Problem 5.4 E or Z?

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5.7 Alkene Stability
◼ Cis alkenes are usually less stable than trans
alkenes

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5.8 Alkene Stability
◼ Compare heat given off on hydrogenation:
Ho
◼ Less stable isomer is higher in energy and
gives off more heat
◼ tetrasubstituted > trisubstituted >
disubstituted > monosusbtituted

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Comparing Stabilities of Alkenes
◼ Evaluate heat given off when C=C is
converted to C-C (catalytic hydrogenation)
◼ More stable alkene gives off less heat (H)

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Heats of hydrogenation of butenes

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Equilibration of 2-butenes

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Alkene Stability
◼ Compare heat given off on hydrogenation:
Ho
◼ Less stable isomer is higher in energy and
gives off more heat
◼ tetrasubstituted > trisubstituted >
disubstituted > monosusbtituted

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49
Alkene Stabilities from H’s:

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Hyperconjugation
◼ Electrons in neighboring filled  orbital stabilize vacant
antibonding  orbital – net positive interaction
◼ Alkyl groups are more stabilizing than H

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Bond strengths/hybridization effects

◼ sp3-sp3 bond is weaker than sp3-sp2, sp2-sp2

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Name each; which is more stable?
Problem 5.5

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5.9 Electrophilic Addition Reactions
of Alkenes
◼ General reaction mechanism: electrophilic
addition
◼ Attack of electrophile (such as HBr) on 
bond of alkene produces carbocation and
bromide ion
◼ Carbocation is itself an electrophile, reacting
with nucleophilic bromide ion

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Examples:

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Writing Organic Reactions

◼ No established convention – shorthand

◼ Can be formal kinetic expression
◼ Not necessarily balanced
◼ Reactants can be before or on arrow
◼ Solvent, temperature, details, on arrow

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For Example:

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Addition of
HBr to 2-
methylpropene

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Electrophilic Addition Energy Diagram:

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Electrophilic Addition for Syntheses
◼ The reaction is successful with HCl and with HI as well as
HBr. Note that HI is generated from KI and phosphoric acid

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5.10 Orientation of Electrophilic Addition:
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
regiospecific
◼ Markovnikov observed in the 19th century that in
the addition of HX to alkene, the H attaches to
the carbon with the most H’s and X attaches to
the other end (to the one with the most alkyl
substituents)
◼ This is Markovnikov’s rule

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Example of Markovnikov’s Rule
◼ Addition of HCl to 2-methylpropene is regiospecific – one
product forms where two are possible
◼ If both ends have similar substitution, then the reaction is not
regiospecific

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Examples:

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But:

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Practice Problem 5.2

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Solution:

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Practice Problem 5.3 :

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Solution:

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Problem 5.6: Major products?

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Problem 5.7: Which alkene would
you add HX to?

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Stability of Carbocations and
Markovnikov’s Rule
◼ More stable carbocation forms faster
◼ Tertiary cations and associated transition states are more stable than
primary cations

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Mechanistic Source of Regiospecificity in
Addition Reactions

◼ If addition involves a
carbocation intermediate
◼ and there are two
possible ways to
add
◼ the route producing
the more alkyl
substituted cationic
center is lower in
energy
◼ alkyl groups
stabilize carbocation
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5.11 Carbocation Structure and
Stability
◼ Carbocations are planar
◼ The positively charged carbon is
surrounded by only 6 electrons in
2
three sp orbitals
◼ The fourth orbital on carbon is a
vacant p-orbital

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5.12 Carbocation Structure and
Stability

◼ The stability of the carbocation

(measured by energy needed to form it
from R-X) is increased by the presence
of alkyl substituents
◼ Therefore stability of carbocations:

3º > 2º > 1º > +CH3

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Heterolytic bond dissociations
energies:

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Stabilizing Carbocations:

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Stabilizing Carbocations:

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Problem 5.8 : carbocation structure?

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5.13 The Hammond Postulate

◼ If one 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
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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
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 Statement 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

In a reaction
involving a
carbocation, the
G transition states
carbocation look like the
intermediate 85
Reaction
Competing Reactions and the
Hammond Postulate
◼ Normal Expectation: Faster reaction gives more stable
intermediate
◼ Intermediate resembles transition state

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“Non-Hammond” Behavior
◼ More stable intermediate from slower reaction
◼ Conclude: transition state and intermediate must
not be similar in this case – not common

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 Transition State for Alkene
Protonation
◼ Resembles carbocation intermediate
◼ Close in energy and adjacent on pathway
◼ Hammond Postulate says they should be similar in structure

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Transition State resembles cation

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Energy Diagrams for Markovnikov
& Anti-Markovnikov Addition

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5.14 Mechanism of Electrophilic Addition:
Rearrangements of Carbocations

◼ Carbocations undergo structural

rearrangements following set patterns
◼ 1,2-H and 1,2-alkyl shifts occur
◼ Goes to give more stable carbocation
◼ Can go through less stable ions as
intermediates

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Carbocation rearrangements:

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Hydride Shifts

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Alkyl (methyl) shifts

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Cholesterol Biosynthesis:

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Problem 5.9: What will be the
rearranged cations?

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Problem 5.10: mechanism?

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 HBr
H

H-shift

Br-1
Br

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Problem 5.11: mechanism?

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Problem 5.12: mechanism?

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H3C H3C

CH2 CH3

CH3 CH3

CH3
CH3

CH3
CH3

CH3
CH3
Cl
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Terpenes

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Terpenes

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Terpene Biosynthesis

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105
Limonene biosynthesis

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