6.

Alkenes: Structure and

Reactivity
Based on McMurry’s Organic Chemistry, 6th edition
©2003 Ronald Kluger
Department of Chemistry
University of Toronto
Alkene - Hydrocarbon With Carbon-
Carbon Double Bond
 Also called an olefin but alkene is better
 Includes many naturally occurring materials
 Flavors, fragrances, vitamins
 Important industrial products
 These are feedstocks for industrial processes

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6.2 Degree of Unsaturation
 Relates molecular formula to possible structures
 Degree of unsaturation: number of multiple bonds or rings
 Formula for saturated a acyclic compound is CnH2n+2
 Each ring or multiple bond replaces 2 H's

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Example: C6H10
 Saturated is C6H14 H H H H
 Therefore 4 H's are not C C CH3
present H 3C C C
 This has two H H H H
degrees of
unsaturation
 Two double bonds?
 or triple bond?
 or two rings
 or ring and double bond

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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 - if connected by single bonds
 These don't affect the total count of H's

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Degree of Unsaturation and
Variation
 Compounds with the same degree of unsaturation can
have many things in common and still be very different

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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
 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 links H)
 Subtract N's - they have two connections

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6.3 Naming of Alkenes
 Find longest continuous carbon chain for root
 Number carbons in chain so that double bond carbons
have lowest possible numbers
 Rings have “cyclo” prefix

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Many Alkenes Are Known by
Common Names
 Ethylene = ethene
 Propylene = propene
 Isobutylene = 2-
methylpropene
 Isoprene = 2-methyl-1,3-
butadiene

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6.4 Electronic Structure of Alkenes
 Carbon atoms in a double bond are sp2-hybridized
 Three equivalent orbitals at 120º separation in plane
 Fourth orbital is 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
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Rotation of  Bond Is Prohibitive

 This prevents rotation about a carbon-carbon double

bond (unlike a carbon-carbon single bond).
 Creates possible alternative structures

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6.5 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

 180°rotation superposes
 Bottom pair cannot be
superposed without
breaking C=C

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6.6 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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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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Ranking Priorities: Cahn-Ingold-
Prelog Rules
 Must rank atoms that are connected at comparison point
 Higher atomic number gets higher priority
 Br > Cl > O > N > C > H

In this case,The higher priority

groups are opposite:
(E )-2-bromo-2-chloro-propene

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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 0 ligands themselves

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6.7 Alkene Stability
 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 alkyl

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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

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

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6.8 Electrophilic Addition of HX to
Alkenes
 General reaction mechanism: electrophilic addition
 Attack of electrophile (such as HBr) on  bond of alkene
 Produces carbocation and bromide ion
 Carbocation is an electrophile, reacting with nucleophilic
bromide ion

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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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Electrophilic Addition Energy Path
 Two step process
 First transition state is high energy point

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Example of Electrophilic Addition
 Addition of hydrogen
bromide to 2-Methyl-
propene
 H-Br transfers proton to
C=C
 Forms carbocation
intermediate
 More stable cation
forms
 Bromide adds to
carbocation

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Energy Diagram for Electrophilic
Addition
 Rate determining
(slowest) step has highest
energy transition state
 Independent of
direction
 In this case it is the
first step in forward
direction
 “rate” is not the same
as “rate constant”

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Electrophilic Addition for
preparations
 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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6.9 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
 Regiospecific – one product forms where two are possible
 If both ends have similar substitution, then not
regiospecific

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Energy 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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6.10 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
 Therefore stability of carbocations: 3º > 2º > 1º > +CH3

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6.11 The Hammond Postulate
 If 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 look
carbocation like the intermediate
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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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6.12 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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