7.

Alkenes: Structure
and Reactivity

Based on McMurry’s Organic Chemistry, 8th edition

Alkene - Hydrocarbon With
Carbon-Carbon Double Bond
◼ Also called an olefin but alkene is better
◼ Includes many naturally occurring materials
◼ Flavors, fragrances, vitamins

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 Why this Chapter?
◼ C-C double bonds are present in most organic and biological molecules

◼ To examine consequences of alkene stereoisomerism

◼ To focus on general alkene reaction: electrophilic addition

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 7.1 Industrial Preparation and
Use of Alkenes
◼ Ethylene and propylene are the most important organic chemicals
produced

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 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
◼ Each ring or multiple bond replaces 2 H's

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Example: C6H10
◼ Saturated is C6H14
◼ Therefore 4 H's are not present

◼ C6H10 has two 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: one degree of unsaturation
◼ Organooxygen compounds (C,H,O) - if connected by single bonds
◼ These don't affect the total count of H's (Ignore!)
◼ 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)
◼ Ignore oxygens (oxygen links H)
◼ Subtract N's - they have two connections

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 7.3 Naming of Alkenes
◼ Name the parent hydrocarbon
◼ 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

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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

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

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 7.5 Sequence Rules: The E,Z
Designation
◼ Cis, trans nomenclature only works for disubstituted double bonds
◼ 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

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 Ranking Priorities: 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

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 Extended Comparison
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

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 Dealing With Multiple Bonds:
RULE 3
◼ Substituent is drawn with connections shown and no double or triple bonds

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Ranking Priorities: Examples

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 Ranking Priorities: Examples
◼ Worked Example 7.1

◼ Problem 7.11

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 7.6 Stability of Alkenes
◼ Cis alkenes are less stable than trans alkenes
◼ Cis-but-2-ene is less stable than trans-isomer by 2.8 kJ/mol

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 7.6 Stability of Alkenes
◼ Compare heat given off on hydrogenation: Ho

◼ Less stable isomer is higher in energy and gives off more heat

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 7.6 Stability of Alkenes
◼ Alkenes become more stable with increasing substitution

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 7.6 Stability of Alkenes
◼ Alkenes become more stable with increasing substitution
◼ Hyperconjugation (C=C π bonds C-H σ bonds) stabilizes
- The more substituents, the more hyperconjugation

◼ Bond strength
- sp2-sp3 is more stable than sp3-sp3
- Ratio of (sp2-sp3) to (sp3-sp3): Higher in highly substituted alkenes

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 7.7 Electrophilic Addition of
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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 Electrophilic Addition for
preparations
◼ The reaction is successful with HCl and with HI as well as HBr
◼ HI is generated from KI and phosphoric acid

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 7.8 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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 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

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 Markovnikov’s Rule
◼ Worked Example 7.2

◼ Worked Example 7.3

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 Markovnikov’s Rule
◼ Problem 7.14

◼ Problem 7.15

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 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

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 Inductive stabilization of cation
species
◼ Why are more highly substituted carbocations more stable?
◼ Inductive Effect (Shifting of σ electrons in response to EN of nearby
atoms: Electrons from larger, more polarizable alkyl group)

◼ Hyperconjugation

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 7.10 The Hammond Postulate
◼ If carbocation intermediate is more stable than another, why is the reaction
through the more stable one faster?
◼ Stability of carbocation intermediate: Free-energy change (Gº)
◼ Reaction rate: Activation energy (G‡)
◼ No direct relationship between Gº and G‡
◼ Intuitive relationship between Gº and G‡
◼ Generally, more stable intermediate forms faster than less stable one
◼ (a) is more typical than (b)

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 Hammond Postulates
◼ A transition states represent energy maxima
◼High-energy activated complexes transiently occurring during reaction
◼ Immediately go on to a more stable species
◼ Cannot be observed (No finite lifetime)
◼ Hammond Postulate
◼ The structure of a TS resembles the structure of the nearest stable
species
◼ TS for endergonic steps: Product-like
◼ TS for exergonic steps: Reactant-like

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 Electrophilic Addition Reaction &
Hammond Postulate
◼ Electrophilic Addition: Endergonic Reaction (Product-like TS)
◼ TS = Carbocation intermediate-like
◼ Factors stabilizing carbocation will stabilize the nearby TS
◼ Increasing alkyl substituents stabilize TS: Faster reaction
- Hyperconjugation & inductive effect stabilize the TS

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Evidence for Mechanism of Electrophilic Addition:
Rearrangements of Carbocations
◼ Mechanism?
◼ Plausible but Not completely certain
◼ The best?: Proposed mechanism consistent with all known facts
◼ Carbocations undergo structural rearrangements following set patterns

◼ Multistep reaction rather than single step reaction

◼ 1,2-H and 1,2-alkyl shifts occur to give more stable carbocation

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Evidence for Mechanism of Electrophilic Addition:
Rearrangements of Carbocations
◼ Problem 7.19
◼ Mechanism?

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