Chapter 7

Alkenes: Structure and Reactivity

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李家琳 chlilee@mail.cmu.edu.tw
 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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 Industrial Preparation and Use of Alkenes
 Ethylene and propylene are the most important organic chemicals
produced industrially (by thermal cracking, 熱裂解)

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Compounds derived industrially from
ethylene and propylene

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 不飽和度

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
 This has two degrees of unsaturation

 two double bonds?  two rings?

 ring and double bond?  triple bond?

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Degree of Unsaturation With Other Elements
 Organohalogen compounds (C, H, X, where X= F, Cl, Br, I)
 Halogen replaces hydrogen
 C4H6Br2 and C4H8 have one degree of unsaturation

C4H8+2

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Degree of Unsaturation With Other Elements

 Organoxygen compounds (C, H, O) -if connected by

single bonds

 These don't affect the total count of H's

C5H10+2

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Degree of Unsaturation With Other Elements
 Organonitrogen compounds (C, H, N)

 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

C5H10+2

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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 the number of oxygens (oxygen links H)

 Subtract the number of nitrogens from the number of

hydrogens -they have two connections

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 CnH2n+2
Calculate the degree of unsaturation in each of the following formulas

C3H4 C6H5N C6H5NO2

3x2+2 = 8 6x2+2 = 14 6x2+2 = 14

(8-4)/2 = 2 [14-(5-1)] / 2 = 5 [14-(5-1)] / 2 = 5

C8H9Cl3 C20H32ClN

8x2+2 = 18 20x2+2 = 42

[18-(9+3)] / 2 = 3 [42-(32+1-1)] / 2 = 5

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 Naming Alkenes -ane >> -ene

 Step 1- Name the parent hydrocarbon (including double bond)

 Step 2- Number carbons in the chain so that double bond
carbons have lowest possible numbers
 Step 3- Write the full name (Rings have “cyclo” prefix)

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 Nomenclature of Alkenes

4 6
5 5
3
1
4
1 2
2
3

cyclopentene
cyclohexene
methyl-
ethyl-
methyl-

3-Methylcyclopentene 4-Ethyl-1-methylcyclohexene
5-Methylcyclopentene (X) 5-Ethyl-2-methylcyclohexene (X)

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 Some alkenes, particularly low-molecular-weight ones, are known almost
exclusively by their common names. 俗名

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 Nomenclature of Alkenes
 Some alkenes, particularly low-molecular-weight ones,
are known almost exclusively by their common names.
俗名
CH3
CH2 =CH2 CH3 CH=CH2 CH3 C=CH2
IUPA C: Ethene Propene 2-Methylprop ene
Common: Ethylene Propylene Isobutylene

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Introduction to organic chemistry; fourth edition; William Brown & Thomas Poon
 Cis-Trans Isomerism in Alkenes
 Carbon atoms in a double bond are sp2-hybridized
 Three equivalent orbitals at 120º separation in plane
 The fourth orbital is atomic p orbital

 Combination of electrons in two sp2 orbitals of two atoms forms σ bond

between them

 Additive interaction of p orbitals creates a π bonding orbital

 Subtractive interaction creates a π anti-bonding orbital

 Occupied π orbital prevents rotation about σ-bond

 Rotation prevented by π bond -high barrier, about 268 kJ/mole in ethylene

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 Rotation of π Bond Is Prohibitive
 This prevents rotation about a carbon-carbon double bond
(unlike a carbon-carbon single bond).

 Creates possible alternative structures

350 kJ/mol
(84 kcal/mol)

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 Structure of Alkenes

 According to the orbital overlap model, a double bond consists of

• a s bond formed by overlap of sp2 hybrid orbitals.
• a p bond formed by overlap of parallel 2p orbital.

 Rotating by 90°breaks the pi bond. The energy is considerably

greater than the thermal energy
available at room temperature,
and, as a consequence, rotation
about a carbon-carbon double
264 kJ/mol bond is severely restricted.
(63 kcal/mol)

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Introduction to organic chemistry; fourth edition; William Brown & Thomas Poon
  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

180° rotation superposes

They cannot be superposed without

breaking C=C

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Alkene Stereochemistry and 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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 E, Z Stereochemical Nomenclature
 Priority rules of Cahn, Ingold, and Prelog 序列法則

 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 (Sequence Rule)

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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

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 Dealing With Multiple Bonds
 Rule 3
 Multiple-bonded atoms are equivalent to the same number of single-
bonded atoms
 Substituent is drawn with connections shown and no double or triple bonds
 Added atoms are valued with ligands themselves

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 Configuration - E,Z

H CH3
2 3 Cl H
5 2 3
4 4 5
1 H3C CH3 1
H3C CH2CH3
H3C

(Z)-3,4-dimethyl-2-pentene (E)-2-chloro-2-pentene

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 Configuration - E,Z

F 3C

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 Configuration - E,Z

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32
 Stability of Alkenes

 Cis alkenes are less stable than trans alkenes

 Compare heat given off on hydrogenation: ΔHo
 Less stable isomer is higher in energy

 And gives off more heat

 tetrasubstituted > trisubstituted > disubstituted >
monosusbtituted
 Hyperconjugation (超共軛) stabilizes

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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 4 kJ
34 less heat than cis-butene
 ΔHo: Heats of hydrogenation

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36
  The stability order of substituted alkenes is due to a
combination of two factors

 One is a stabilizing interaction between the C=C π bond

and adjacent C-H σ bonds on substituents.

>> In valence-bond language, the interaction is called

hyperconjugation.

>> In a molecular orbital description, there is a bonding MO

that extends over the four-atom C=C-C-H grouping. The
more substituents present on the double bond, the more
hyper conjugation occurs and the more stable the alkene.

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 Hyperconjugation 超共軛效應

 Hyperconjugation is a stabilizing interaction between the

C=C π bond and adjacent C-H σ bonds on substituents.

 Alkyl groups are better than H

C=C-C-R R: alkyl group is better than H

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 Hyperconjugation In Substituted Alkenes
 In Organic Chemistry, hyperconjugation is the interaction of the
electrons in a σ bond (usually C–H or C–C) with an adjacent empty
(or partially filled) non-bonding π-orbital or antibonding π orbital or
filled π orbital, to give an extended molecular orbital that increases
the stability of the system.

超共軛效應在有機化學中是指一個σ鍵裡的電子（通常是C-H或C-C）和一個臨近的
半滿或全空的非鍵p軌域或反鍵的π軌域或全滿的π軌域之間的相互作用，該相互作
用能夠使整個體系變得更穩定。這是由於該作用能夠生成一個較大的分子軌道。

C=C-C-R

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 A second factor that contributes to alkene stability involves bond strengths

bonds stronge: sp3 - sp2 bonds stronger > sp3 - sp3

A bond between an sp2 carbon and an sp3 carbon is somewhat stronger than a
bond between two sp3 carbons.

More highly substituted alkenes always have a higher ration of sp3 - sp2 bonds to
sp3 - sp3 bonds than less highly substituted alkenes and are therefore more
stable.
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 Electrophilic Addition of Alkenes

 General reaction mechanism:

electrophilic addition

 Attack of electrophile (such as HBr) on π

bond of alkene

 Produces carbocation and bromide ion

 Carbocation is an electrophile, reacting

with nucleophilic bromide ion

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 Electrophilic Addition Energy Path

 Two step process

 First transition state is

high energy point

 The first step is slower

than the second step

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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 usually

generated in the reaction
mixture by treating KI and
phosphoric acid

 A strong acid catalyst is needed

for the addition of water

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 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 (位置特

異性)

 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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 mixture

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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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48
 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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 A plot of dissociation enthalpy versus substitution pattern for the gas-phase dissociation of alkyl
chlorides to yield carbocations.

50 >> More highly substituted alkyl halides dissociate more easily than less highly substituted ones.
  Why are more highly substituted carbocations more stable than
less highly substituted ones?

The more alkyl groups attached to the

 Two reasons positively charged carbon, the more electron
density shifts toward the charge and the more
 Inductive effect inductive stabilization of the cation occurs.

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  Why are more highly substituted carbocations more stable than
less highly substituted ones?

 Two reasons
Hyperconjugation, in connection with the stabilities of
 Hyperconjugation substituted alkenes, is the stabilizing interaction
between a p orbital and properly oriented C-H σ bonds
on neighboring carbons that are roughly parallel to the
p orbital.

The more alkyl groups there are

on the carbocation, the more
possibilities there are for
hyperconjugation and the more
stable the carbocation.

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 Summary-electrophilic addition reactions
 Electrophilic addition to an unsymmetrically substituted alkene gives the more
highly substituted carbocation intermediate.

 A more highly substituted carbocation forms faster than a less highly substituted
one and, once formed, rapidly goes on to give the final product.

 A more highly substituted carbocation is more stable than a less highly

substituted one.

 That is, the stability order of carbocations is

tertiary (3o) > secondary (2o) > primary (1o) > methyl

What we have not yet seen is how these two points are related.

Why does the stability of the carbocation intermediate affect the rate at which it’s
53 formed and thereby determine the structure of the final product?
 The Hammond Postulate (哈蒙德假說)
 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 (ΔGº, free-energy change)

 The relative stability of the transition state (which describes the

size of the rate constant) is the activation energy (ΔG‡)

Reaction rate
 The transition state is transient and cannot be examined

 The two quantities (ΔGº & ΔG‡) aren’t directly related.

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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 (哈蒙德假說)

The explanation of the relationship between reaction rate and intermediate stability goes like this.
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 Examination 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

根據Hammond Postulate 假說：TS 最像能量與它接近的穩定物質。即在吸熱反應，

TS 比較像產物而不是反應物；在放熱反應，TS 比較像反應物而不是產物。
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Competing Reactions and the Hammond Postulate
 Normal Expectation: Faster reaction gives more stable intermediate
 Intermediate resembles transition state

1o This transition state is

stabilized by
hyperconjugation and
inductive effects in the
same way as the
product carbocation.

3o The more alkyl groups

that are present, the
greater the extent of
stabilization and the
57 faster the transition
state forms.
 The hypothetical structure of a transition state for alkene protonation. The transition
state is closer in both energy and structure to the carbocation than to the alkene.

Thus, an increase in carbocation stability (lower ΔGº) also causes an increase in

transition-state stability (lower ΔG‡), thereby increasing the rate of its formation.

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 Evidence for the Mechanism of Electrophilic
Addition: Rearrangements of Carbocations
 Carbocations undergo structural rearrangements following set patterns
 1,2-H (Hydride) and 1,2-alkyl shifts occur
 Goes to give more stable carbocation
 Can go through less stable ions as intermediates

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 1,2-shift-1,2-H (Hydride)

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 1,2-shift-1,2-alkyl

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 Hydride shifts in biological molecules
(during the biosynthesis of cholesterol)

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