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
2
Alkenes
3
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
5
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
8
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
9
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
22
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)
44
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
48
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
74
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
86
“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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Limonene biosynthesis
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