CH1012

Dr. Ireshika De Silva

1
 Alkenes (Olefins)
• Alkenes contain carbon—carbon double bonds.

• The double bond consists of a  bond and a  bond.

• Each carbon is sp2 hybridized and trigonal planar, with bond
angles of approximately 120.

2
➢ 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.

3
 Cis-Trans Isomerism in Alkenes

➢ Trans alkenes are generally more stable than cis alkenes.

➢ Stability of an alkene increases as the number of R groups on the

C=C increases

Monosubstituted
Tetrasubstituted Trisubstituted Disubstituted

➢ The cis-trans naming system works only with disubstituted alkenes4

 E/Z geometric isomers of alkenes

➢ E/Z system used for describing trisubstituted and tetrasubstituted alkenes

➢ Rank the substituents in each of the double-bond carbons separately

according to the Cahn-Ingold-Prelog sequence role. (an atom with higher
atomic number an atom with lower atomic number)

➢ Z geometry: If the higher ranked groups on each carbon are on the

same side of the double bond

➢ E geometry: If the higher ranked groups on each carbon are on the

opposite sides of the double bond

5
Introduction to Addition Reactions
➢The characteristic reaction of alkenes is addition—the …… bond
is broken and ……………………………. bonds are formed.

➢ Alkenes are electron ………., with the electron density of the 

bond concentrated above and below the plane of the molecule.

➢ Because alkenes are electron ……….., simple alkenes ………

…… with nucleophiles or bases, reagents that are themselves
electron rich.
➢ Alkenes react with …………………………… 6
• Because the carbon atoms of a double bond are both ……………..,
the elements of X and Y can be added to them from the ……………
or from …………………………….

• The terms syn and anti describe stereochemistry of a process—for

example, how two groups are added to a double bond.

7
Five important Addition Reactions of Alkenes

8
 Reactions of Alkenes

(1) 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 with
Cs—one to H and one to X.

➢ Recall that 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-

9
rich double bond, these reactions are called electrophilic additions.
 Hydrohalogenation

➢Addition reactions are ……………….... 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.

10
 Hydrohalogenation

• The mechanism of electrophilic addition consists of ……….........

………………….. Lewis acid-base reactions.

• In step 1 - The alkene is the Lewis base that donates an electron

pair to H—Br, the Lewis acid.

• In step 2 - Br¯ is the Lewis base that donates an electron pair to

the carbocation, the Lewis acid.

11
 Hydrohalogenation

➢ In the representative energy diagram below, each step has its own
energy barrier with a transition state energy maximum.
➢Since step 1 has a higher energy transition state, it is rate-determining.
H for step 1 is positive because more bonds are broken than formed,
whereas H for step 2 is negative because only bond making occurs.

12
 Hydrohalogenation
Hydrohalogenation follows 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 …………………………………………
……………………………………………..—that is, the carbon that has
the greater number of H atoms to begin with.
13
 Hydrohalogenation

➢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 ………… substituted carbon to form the ………….
stable, ………………. substituted carbocation.

14
 Hydrohalogenation

What would be the major product of the reaction? Write the stepwise mechanism

15
 Reactions of Alkenes

(2) Hydration of Alkenes — Electrophilic Addition of Water

➢ Hydration is the addition of water to an alkene to form an

alcohol.

16
Hydration of alkene

17
 Reactions of Alkenes

(3) Halogenation of Alkenes — Addition of Halogen

➢ Halogenation is the addition of X2 (X = Cl or Br) to an alkene to
form a ………………………...

18
 Halogenation

Carbocations are unstable because they

have only six electrons around carbon.
Halonium ions are unstable because of
ring strain.
19
 Halogenation
Reaction Stereochemistry
➢ Consider the chlorination of cyclopentene to afford both enantiomers of
trans-1,2-dichlorocyclopentene, 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.

20
 Halogenation

➢ In the second step, nucleophilic attack of Cl¯ must occur from the
……………………… of the bridged halogen atom.

➢ 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 a racemic mixture.

21
 Halogenation

What are the products of the following reactions?

22
 Reactions of Alkenes

(4) 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.

23
 Halohydrin Formation

➢ Even through 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. 24
 Halohydrin Formation

➢ Because the bridged halonium ion is opened by backside attack of H2O,

addition of X and OH occurs in an ……….. fashion and ……… products
are formed.

➢ With unsymmetrical alkenes, the preferred product has the electrophile

X+ bonded to the ……….. substituted carbon, and the nucleophile (H2O)
bonded to the ……….. substituted carbon.

25
 Halohydrin Formation

➢ 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.

26
 Reactions of Alkenes

(5) Hydroboration—Oxidation of Alkenes

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

, THF

27
➢ With unsymmetrical alkenes, the larger boron atom bonds to the
…………. substituted carbon atom (less sterically hindered, more
accessible carbon atom)

➢ alkyl groups stabilize a positive charge, the more stable transition

state has the partial positive charge on the more substituted carbon

28
➢ 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 …… addition of the

elements of H and OH to a double bond.

➢ Overall reaction follows the ……………………………..

29
30
 Reactions of Alkenes

(6) Oxymercuration-Demercuration
➢ A useful laboratory procedure for synthesizing alcohols from alkenes that
avoids rearrangement
➢ Two-step reaction and both steps carried out in the same vessel.

➢ This reaction follows Markovnikov’s rule.

➢ Step 1: Oxymercuration: Mercuric acetate and water add to the double bond
to form (hydroxyalkyl)mercury compound.

➢ Step 2: Demercuration: Sodium borohydride reduces the acetoxymercury

group and replaces it with hydrogen.

31
What are the products of the following reactions of alkenes?

32
 Reactions of Alkenes

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.

33
 Oxidation of Alkenes
(1) Epoxidation of Alkenes
➢ Epoxidation is the ………………………….. atom to an alkene to
form an epoxide.
➢ Epoxidation is typically carried out with a ……………………...

34
 Oxidation of Alkenes
(2) Dihydroxylation of Alkenes

➢ Dihydroxylation is the …………………………. groups to a double

bond, forming a 1,2-diol or glycol.

➢ Depending on the reagent, the two new OH groups can be added

to the opposite sides (anti addition) or the same side (syn
addition) of the double bond.

35
Anti dihydroxylation

➢ Anti dihydroxylation is achieved in two steps—epoxidation

followed by ring opening with aqueous acid or base.

36
Syn dihydroxylation

➢ Syn hydroxylation results when an alkene is treated with either

KMnO4 or OsO4.

cold

37
➢ 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.

38
 Oxidative Cleavage of Alkenes
➢ Oxidative cleavage of an alkene breaks both the  and  bonds of the
double bond to form two carbonyl compounds.

➢ Cleavage with ozone (O3) is called ozonolysis.

39
What is the product of the following reaction?

40