6.

Alkenes: Structure and

Reactivity

Based on McMurry’s Organic Chemistry, 6th edition

©2003
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

McMurry Organic Chemistry 6th edition Chapter 2

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 3

6 (c) 2003
Example: C6H10
◼ Saturated is H H H H
C6H14 C C CH3
◼ Therefore 4 H's are not H3C C C
present H H H H
◼ This has two
degrees of
unsaturation
◼ Two double bonds?
◼ or triple bond?
◼ or two rings
◼ or ring and double bond

McMurry Organic Chemistry 6th edition Chapter 4

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 5

6 (c) 2003
Degree of Unsaturation and
Variation
◼ Compounds with the same degree of unsaturation can
have many things in common and still be very different

McMurry Organic Chemistry 6th edition Chapter 6

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 7

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 8

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 9

6 (c) 2003
Many Alkenes Are Known by
Common Names
◼ Ethylene = ethene
◼ Propylene = propene
◼ Isobutylene = 2-
methylpropene
◼ Isoprene = 2-methyl-1,3-
butadiene

McMurry Organic Chemistry 6th edition Chapter 10

6 (c) 2003
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
McMurry Organic Chemistry 6th edition Chapter 11
6 (c) 2003
Rotation of  Bond Is Prohibitive

◼ This prevents rotation about a carbon-carbon double

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

McMurry Organic Chemistry 6th edition Chapter 12

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 13

6 (c) 2003
 Cis, Trans Isomers Require That End
Groups Must Differ in Pairs

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

McMurry Organic Chemistry 6th edition Chapter 14

6 (c) 2003
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
McMurry Organic Chemistry 6th edition Chapter 15
6 (c) 2003
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”

McMurry Organic Chemistry 6th edition Chapter 16

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 17

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 18

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 19

6 (c) 2003
Dealing With Multiple Bonds
◼ Substituent is drawn with connections shown and no
double or triple bonds
◼ Added atoms are valued with 0 ligands themselves

McMurry Organic Chemistry 6th edition Chapter 20

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 21

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 22

6 (c) 2003
Hyperconjugation
◼ Electrons in neighboring filled  orbital stabilize vacant
antibonding  orbital – net positive interaction
◼ Alkyl groups are better than H

McMurry Organic Chemistry 6th edition Chapter 23

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 24

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 25

6 (c) 2003
Electrophilic Addition Energy Path
◼ Two step process
◼ First transition state is high energy point

McMurry Organic Chemistry 6th edition Chapter 26

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 27

6 (c) 2003
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”

McMurry Organic Chemistry 6th edition Chapter 28

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 29

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 30

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 31

6 (c) 2003
Energy of Carbocations and
Markovnikov’s Rule
◼ More stable carbocation forms faster
◼ Tertiary cations and associated transition states are more
stable than primary cations

McMurry Organic Chemistry 6th edition Chapter 32

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 33

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 34

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 35

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 36

6 (c) 2003
 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
McMurry Organic Chemistry 6th edition Chapter 37
Reaction 6 (c) 2003
Competing Reactions and the
Hammond Postulate
◼ Normal Expectation: Faster reaction gives more stable
intermediate
◼ Intermediate resembles transition state

McMurry Organic Chemistry 6th edition Chapter 38

6 (c) 2003
“Non-Hammond” Behavior
◼ More stable intermediate from slower reaction
◼ Conclude: transition state and intermediate must not be
similar in this case – not common

McMurry Organic Chemistry 6th edition Chapter 39

6 (c) 2003
Transition State for Alkene
Protonation
◼ Resembles carbocation
intermediate
◼ Close in energy and
adjacent on pathway
◼ Hammond Postulate says
they should be similar in
structure

McMurry Organic Chemistry 6th edition Chapter 40

6 (c) 2003
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

McMurry Organic Chemistry 6th edition Chapter 41

6 (c) 2003