CHE 121 Alkene

Sumani Jey

1
 Alkenes
• Alkenes are also called olefins.
• Alkenes contain a carbon—carbon double bond (their
functional group).
• Terminal alkenes have the double bond at the end of the
carbon chain.
• Internal alkenes have at least one carbon atom bonded
to each end of the double bond.
• Cycloalkenes contain a double bond in a ring.

2
• Recall that the double bond consists of a  bond and a 
bond (the two bonds have a total of 4 electrons)

• Each carbon of the double bond is sp2 hybridized and

trigonal planar, with bond angles of approximately 120°.

• Since there are fewer hydrogen atoms in alkenes as a

result of the double bond, alkenes are referred to as
unsaturated.
3
• Bond dissociation energies of the C—C bonds in ethane
(a  bond only) and ethylene (one  and one  bond) can
be used to estimate the strength of the  component of
the double bond.

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5
there are two 2-butenes:

H H H CH3
C C C C
H3C CH3 H3C H
cis-2-butene trans-2-butene

“geometric isomers” (diastereomers)

Nomenclature of Alkenes

7
Naming an alkene in which the longest carbon chain does not
contain both atoms of the double bond

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• Compounds with two double bonds are named as dienes by
changing the “-ane” ending of the parent alkane to the suffix “–
adiene”. Compounds with three double bonds are named as triene,
and with 4 double bonds as tetraene.

• Always choose the longest chain that contains both atoms of the
double bond.

• In naming cycloalkenes, the double bond is located between C1 and

C2, and the “1” is usually omitted in the name. The ring is numbered
clockwise or counterclockwise to give the first substituent the lower
number.

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10
Naming compounds with more than one double bond
Give the UIPAC names of the following compounds
• Some alkene or alkenyl substituents have common names.
• The simplest alkene, CH2=CH2, named in the IUPAC system as
ethene, is often called ethylene.

Naming alkenes with common substituent names

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Physical Properties
• Most alkenes exhibit only weak van der Waals interactions, so
their physical properties are similar to alkanes of comparable
molecular weight.

• Alkenes have low melting points and boiling points.

• Melting and boiling points increase as the number of carbons

increases because of increased surface area which increases
van der Waals forces.

• Alkenes are soluble in organic solvents and insoluble in water.

• The C—C single bond between an alkyl group and one of the
double bond carbons of an alkene is slightly polar because the
sp3 hybridized alkyl carbon donates electron density to the sp2
hybridized alkenyl carbon.
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16
• A consequence of this dipole is that cis and trans isomeric
alkenes often have somewhat different physical properties.

• cis-2-Butene has a higher boiling point than trans-2-butene .

• In the cis isomer, the two Csp3—Csp2 bond dipoles reinforce each
other, yielding a small net molecular dipole. In the trans isomer,
the two bond dipoles cancel.

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Preparation of Alkenes
• Alkenes can be prepared from alkyl halides and alcohols via
elimination reactions. Reactions which removes a potion of the
molecule.

dehydrohalogenation and detosylation

dehydration
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 Curved (Curly) arrows

• They show movement of an electron pair

• They start on a lone pair of electrons or a full

blown negative charge or on a covalent bond

• Remember to show clearly the molecule or ion

produced after each stage of the mechanism.
Don’t forget charges on ions. It also helps when
the atoms/groups involved are clearly shown.
 For example
xx -
N C -
Cl
H3C C N +
H3C Cl

The examiner is very strict about curly

arrows in mechanisms.
The C bonded to N is donation its two
electrons to C bonded to Cl. The C bonded
to Cl has a partial positive charge and
therefore it can accept electrons and release
the Cl.
• Elimination reactions are stereoselective and
regioselective, so the most stable alkene is usually
formed as the major product.

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• Regiospecific/Regioselective – a reaction that yields only
one product (or a predominance of one product) when two
or more products are possible.
• Stereoselectivity – single starting material can give two
or more stereoisomeric products to yields one of them in
greater amounts than the other (or even to the exclusion of
the other).

• Stereoisomeric products has a carbon with four

different groups attached to it. Two groups lies in the
plane and the remaining two groups lies in such a way
that one group point towards the observer while the other
group points away from the observer.

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 H H H H
H C2H5ONa
H
H Br H H

H H
H H
O H
H H H
H Br

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 Dehydrohalogenation
-
X X
C C C C + HB + X-
H H
:B B
-
The double bond is partially formed in the transition state
and therefore the transition state resembles an alkene.
Thus the factors which stabilize alkenes will stabilize this
nascent alkene.

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 Alkenes: Acid Catalyzed Dehydration

CH3
CH2
20% H2SO4
H 3C OH
+ H2 O
85 oC
CH2 H 3C CH3

• 3° Alcohols Exceptionally Easy to Dehydrate

• Can Use Dilute Acid, Lower Temperatures

• Relative Ease of Reaction:

3° > 2° > 1° 25
 CH3 CH3

H3 C OH H 3C OH2
+
H
CH2 CH2
H H

-H2O

Base
CH2 CH3
-H+
+ H 2O H
H3C CH3 C CH3
H2
 Introduction to Addition Reactions
• The characteristic reaction of alkenes is addition—the  bond is
broken and two new  bonds are formed.

• Alkenes are electron rich, with the electron density of the  bond
concentrated above and below the plane of the molecule.

27
•Because alkenes are electron rich, simple alkenes do not
react with nucleophiles or bases, reagents that are
themselves electron rich. Alkenes react with electrophiles.
• Because the carbon atoms of a double bond are both
trigonal planar, the elements of X and Y can be added to
them from the same side or from opposite sides.

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Five addition reactions of cyclohexene

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Hydrohalogenation—Electrophilic Addition of HX

• Two bonds are broken in this reaction—the weak  bond of the

alkene and the HX bond—and two new  bonds are formed—one
to H and one to X.

• The H—X bond is polarized, with a partial positive charge on H.

Because the electrophilic H end of HX is attracted to the
electron-rich double bond, these reactions are called
electrophilic additions.

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To draw the products of an addition reaction:

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• Addition reactions are exothermic because the two  bonds
formed in the product are stronger than the  and  bonds
broken in the reactants. For example, H° for the addition of HBr
to ethylene is –14 kcal/mol, as illustrated below.

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• The mechanism of electrophilic addition consists of two
successive Lewis acid-base reactions. In step 1, the alkene is the
Lewis base that donates an electron pair to H—Br, the Lewis
acid, while in step 2, Br¯ is the Lewis base that donates an
electron pair to the carbocation, the Lewis acid.

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Eletrophiles – species that are electron deficient
(they may have a partial positive charge or a full
blown positive charge – electron loving

Nucleophile- species that are electron rich (have

lone pairs of electrons or are negatively charged) –
nucleus loving

Carbocation is a positive intermediate form of a

carbon. It has an empty P orbital which can
accept electrons from a nucleophile

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 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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 Carbocation is an electrophile and has a trigonal
planar geometry

Carbocations are
•classified as 1°, 2°, or 3° depending on the
number of carbons bonded to the carbon bearing
the positive charge

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Alkyl groups are weak electron donors.

They stabilise the carbocation by 2 ways

1. By donating electron density by induction (through

sigma bonds). Inductive effects: Alkyl groups donate (shift)
electron density through sigma bonds to electron deficient
atoms. This stabilizes the carbocation

2. By hyperconjugation
filled sigma bonds of the C-H
interacting with the positively
charged carbon.

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Mechanism of Electrophilic Addition: Rearrangements
of Carbocations
• Carbocations can undergo structural rearrangements
following set patterns
• It can be a 1,2-hydride shift or 1,2-alkyl shift
• The driving force is the formation of the stable
carbocation

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39
Methyl shift can also occur as shown below

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 Hydrohalogenation—Markovnikov’s Rule

• With an unsymmetrical alkene, HX can add to the double

bond to give two constitutional isomers, but only one is
actually formed:

• This is a specific example of a general trend called

Markovnikov’s rule.
• Markovnikov’s rule states that in the addition of HX to an
unsymmetrical alkene, the H atom adds to the less
substituted carbon atom—that is, the carbon that has the
greater number of H atoms to begin with. 41
• The basis of Markovnikov’s rule is the formation of a carbocation
in the rate-determining step of the mechanism.
• In the addition of HX to an unsymmetrical alkene, the H atom is
added to the less substituted carbon to form the more stable, more
substituted carbocation.

• Trigonal planar atoms react with reagents from two directions with
equal probability. 42
• This is the case because the nucleophilic attack of Cl¯ on the
trigonal planar carbocation occurs from two different directions

43
• Hydrohalogenation occurs with syn and anti addition of HX.
• The terms cis and trans refer to the arrangement of groups in a
particular compound, usually an alkene or disubstituted
cycloalkene.
• The terms syn and anti describe stereochemistry of a process—
for example, how two groups are added to a double bond.
• Addition of HX to 1,2-dimethylcyclohexene forms syn and anti
products

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Reaction of 1,2-dimethylcyclohexene with HCI

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Rate determining step is the slowest step in a
reaction which determine how fast the reaction
can go to form the product.
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Hydration—Electrophilic Addition of Water
• Hydration is the addition of water to an alkene to form an
alcohol.

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48
• Alcohols add to alkenes, forming ethers by the same
mechanism. For example, addition of CH3OH to 2-
methylpropene, forms tert-butyl methyl ether (MTBE), a
high octane fuel additive.

• Note that there are three consequences to the

formation of carbocation intermediates:
1. Markovnikov’s rule holds.
2. Addition of H and OH occurs in both syn and anti
fashion.
3. Carbocation rearrangements can occur. 49
 Halogenation—Addition of Halogen

• Halogenation is the addition of X2 (X = Cl or Br) to an

alkene to form a vicinal dihalide.

50
• Halogens add to  bonds because halogens are polarizable.

• The electron rich double bond induces a dipole in an

approaching halogen molecule, making one halogen atom
electron deficient and the other electron rich (X+—X–).

• The electrophilic halogen atom is then attracted to the

nucleophilic double bond, making addition possible.

• Two facts demonstrate that halogenation follows a different

mechanism from that of hydrohalogenation or hydration.
No rearrangements occur
Only anti addition of X2 is observed
These facts suggest that carbocations are not
intermediates.
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Carbocations are unstable because
they have only six electrons around
carbon. Halonium ions are unstable
52
because of ring strain.
 Halogenation—Reaction Stereochemistry
• Consider the chlorination of cyclopentene to afford trans-1,2-
dichlorocyclopentane, with no cis products.

• Initial addition of the electrophile Cl+ from (Cl2) occurs from

either side of the planar double bond to form a bridged
chloronium ion.

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• In the second step, nucleophilic attack of Cl¯ must occur from
the backside.

• Since the nucleophile attacks from below and the leaving group
departs from above, the two Cl atoms in the product are oriented
trans to each other.

• Backside attack occurs with equal probability at either carbon of

the three-membered ring to yield the 2 products in 1:1 ratio

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cis-2-Butene yields two products, whereas trans-2-butene
yields a single product.

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Halohydrin Formation
Treatment of an alkene with a halogen X2 and H2O forms a
halohydrin by addition of the elements of X and OH to the
double bond.

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Even though X¯ is formed in step [1] of the mechanism, its
concentration is small compared to H2O (often the
solvent), so H2O and not X¯ is the nucleophile.
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Because the bridged halonium ion is opened by backside attack of
H2O, addition of X and OH occurs in an anti fashion and trans
products are formed.

With unsymmetrical alkenes, the preferred product has the

electrophile X+ bonded to the less substituted carbon, and the
nucleophile (H2O) bonded to the more substituted carbon.

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The nucleophilic attack occurs at the more substituted
carbon end of the bridged halonium ion because that
carbon is better able to accommodate the partial positive
charge in the transition state.

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60
Hydroboration—Oxidation
Hydroboration—oxidation is a two-step reaction sequence
that converts an alkene into an alcohol.

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Hydroboration—oxidation results in the addition of H2O to
an alkene.

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BH3 is a reactive gas that exists mostly as a dimer, diborane (B2H6).
Borane is a strong Lewis acid that reacts readily with Lewis bases.
For ease of handling in the laboratory, it is commonly used as a
complex with tetrahydrofuran (THF).

The first step in hydroboration—oxidation is the addition of the

elements of H and BH2 to the  bond of the alkene, forming an
intermediate alkylborane.

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• The proposed mechanism involves concerted addition of
H and BH2 from the same side of the planar double bond:
the  bond and H—BH2 bond are broken as two new 
bonds are formed.
• Because four atoms are involved, the transition state is
said to be four-centered.

64
Because the alkylborane formed by the reaction with one
equivalent of alkene still has two B—H bonds, it can react
with two more equivalents of alkene to form a
trialkylborane.

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Since only one B—H bond is needed for hydroboration,
commercially available dialkylboranes having the general
structure R2BH are sometimes used instead of BH3. A
common example is 9-borabicyclo[3.3.1]nonane (9-BBN).

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With unsymmetrical alkenes, the boron atom bonds to the
less substituted carbon atom.

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• This regioselectivity can be explained by considering
steric factors. The larger boron atom bonds to the less
sterically hindered, more accessible carbon atom.

• Electronic factors are also used to explain this

regioselectivity. If bond making and bond breaking are
not completely symmetrical, boron bears a - charge in
the transition state and carbon bears a + charge. Since
alkyl groups stabilize a positive charge, the more stable
transition state has the partial positive charge on the
more substituted carbon.

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Hydroboration of an unsymmetrical alkene

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• Since alkylboranes react rapidly with water and
spontaneously burn when exposed to air, they are
oxidized, without isolation, with basic hydrogen
peroxide (H2O2, ¯OH).

• Oxidation replaces the C—B bond with a C—O bond,

forming a new OH group with retention of configuration.

• The overall result of this two-step sequence is syn

addition of the elements of H and OH to a double bond
in an “anti-Markovnikov” fashion.

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 Predict the Product

Predict the product when the given alkene

reacts with borane in THF, followed by
oxidation with basic hydrogen peroxide.

CH3 (1) BH3, THF H

CH3
-
(2) H2O2, OH OH
D D
syn addition
=>
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Heating the borane intermediate result in shifting of the
borane to the terminal carbon (1o carbon). Some books
use trialkyl borane as an intermediate for this reaction.

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 Oxymercuration
• Reagent is mercury(II) acetate which dissociates
slightly to form +Hg(OAc).
• +Hg(OAc) is the electrophile that attacks the pi
bond.
O O O O
_ +
CH3 C O Hg O C CH3 CH3 C O Hg O C CH3

• The intermediate is a cyclic mercurinium ion, a

three-membered ring with a positive charge.

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 OAc
+
Hg
+
C C Hg(OAc) C C

• Water approaches the mercurinium ion from the side

opposite the ring (anti addition).
• Water adds to the more substituted carbon to form the
Markovnikov product.
OAc OAc OAc
+ Hg
Hg Hg
C C C C C C
+
H O O
H2O H H
H2O
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 Demercuration
Sodium borohydride, a reducing agent, replaces the
mercury with hydrogen.
OAc
Hg H
_
4 C C + NaBH4 + 4 OH 4 C C + NaB(OH)4
_
O O
+ 4 Hg + 4 OAc
H H

75
 Predict the Product
Predict the product when the given alkene reacts
with aqueous mercuric acetate, followed by
reduction with sodium borohydride.

CH3 OH
(1) Hg(OAc) 2, H2O
CH3
D
(2) NaBH4
D H

anti addition

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• Oxymercuration-Demercuration
– Markovnikov product formed
– Anti addition of H-OH
– No rearrangements

• Hydroboration-Oxidation
– Anti-Markovnikov product formed
– Syn addition of H-OH

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 Oxidative Cleavage
• Both the pi and sigma bonds break.
• C=C becomes C=O.
• Two methods:
– Warm or concentrated or acidic KMnO4.
– Ozonolysis
• Used to determine the position of a double
bond in an unknown alkene.

78
 Cleavage with MnO4 -

• Permanganate is a strong oxidizing agent.

• Glycol initially formed is further oxidized.
• Disubstituted carbons become ketones.
• Monosubstituted carbons become
carboxylic acids.
• Terminal =CH2 becomes CO2.

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 Example
H CH3
H CH3 KMnO4
C C H3C C C CH3
CH3 CH3 (warm, conc.)
OH OH

H CH3
H3C C + C CH3
O O

OH
H3C C
O
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 Ozonolysis
• Reaction with ozone forms an ozonide.

• Ozonides are not isolated, but are treated with a

mild reducing agent like Zn or dimethyl sulfide.

• Milder oxidation than permanganate.

• Products formed are ketones or aldehydes.

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 Ozonolysis Example
O
H CH3 O3 H CH3
C C C C
CH3 CH3 O O
H3C CH3
Ozonide

H O
(CH3)2S CH3
C O O C + CH3 S CH3 =>
H3C CH3
DMSO

Chapter 8 82
 Dihydroxylation of Alkenes
• Alkene is converted to a cis-1,2-diol,
• Two reagents:
– Osmium tetroxide ( very expensive!), followed by
hydrogen peroxide or followed by aqueous sodium
hydrogen sulfate
– Cold, dilute aqueous potassium permanganate,
followed by hydrolysis with base

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• Each reagent adds two oxygen atoms in a syn
fashion.
• Hydrolysis of the cyclic intermediate cleaves the
metal oxygen bonds, forming a cis-1,2-diol.

84
Reduction of Alkenes—Catalytic Hydrogenation

• The addition of H2 occurs only in the presence of

a metal catalyst, and thus it is called catalytic
hydrogenation.
• The catalyst consists of a metal—usually Pd, Pt,
or Ni, adsorbed onto a finely divided inert solid,
such as charcoal.
• H2 adds in a syn-fashion.
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Because of the fact that these reactions take place on
a surface, hydrogenation of substituted cycloalkenes
produces cis products

86
Alkenes in Organic Synthesis
Suppose we wish to synthesize 1,2-dibromocyclohexane from
cyclohexanol.

To solve this problem we must:

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Working backwards from the product to determine the starting
material from which it is made is called retrosynthetic analysis.

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 Polymer
• A polymer is a compound of very high formula
mass whose long chain molecules are made of
repeating units.
• Monomer is the fundamental repeating unit of a
polymer.
• There are two major types of polymers:
– Addition polymers
– Condensation polymers

Section 14.5
 Addition Polymers
• Addition polymers are formed when molecules of an
alkene monomer add to one another.

• Recall that alkenes have a double bond between two

carbon atoms.

• Under the proper reaction conditions the double bond

opens up and attaches itself by single bonds to two other
monomer molecules.

• Each of these monomers will then in turn attach to

another monomer, and so on and on…
14 | 90
Section 14.5
 Polymerization of Ethene

• The subscripted n on polyethylene indicates that

the unit shown in brackets is repeated thousands
of times for a ‘big polymer’.
• Polyethylene is the simplest of the synthetic
polymers.
– It is significantly chemically inert and is used to make
containers.
14 | 91
Section 14.5
 Teflon
• Teflon is made by the polymerization of
tetrafluoroethene.

• This polymer is a hard, strong, chemically

resistant compound with a high melting point and
very low surface friction.

14 | 92
Section 14.5
Drawing the Structure of an Addition
Polymer - An Example
• An addition polymer prepared from vinylidene chloride,
CH2==CCl2. Draw the structure of the polymer.
• To form the polymer the double bonds of all the
monomers (CH2==CCl2) must open up and repeatedly
bond to the growing chain of monomers.
• The structure is shown as:

14 | 93
Section 14.5
Section 14.5
 Condensation Polymers
• Condensation polymers are formed from molecules of
two or more reactive groups.
– Water is the other product, hence the name condensation
polymers.
• Polyethylene terephthalate (PET) is formed from the
polymerization of tetephthalic acid and ethylene glycol.

14 | 95
Section 14.5
 Nylon – A Condensation Polymer
• Nylon was first introduced to the public in 1939 at the
New York World’s Fair.
• Nylon is formed from the polymerization of adipic acid
and hexamethylenediamine.

14 | 96
Section 14.5
• Three methods of making additional
polymers:
– Cationic, a carbocation intermediate
– Free radical
– Anionic, a carbanion intermediate (rare)

97
Cationic Polymerization

98
 Termination Step of Cationic
Polymerization

• The chain growth ends when a proton is abstracted by the

weak base of the acid used to initiate the reaction.
• The loss of a hydrogen forms an alkene and ends the chain
growth so this is a termination step.

99
Cationic Polymerization Using BF3
as Catalyst

100
 Radical Polymerization

• In the presence of an initiator such as peroxide,

free-radical polymerization occurs.
101
 Anionic Polymerization
For an alkene to gain electrons, strong
electron-withdrawing groups such as nitro, cyano, or
carbonyl must be attached to the carbons in the double
bond.

102