Epoxidation of Alkenes

Epoxides

are examples of heterocyclic compounds

three-membered rings that contain oxygen

ethylene oxide propylene oxide

H2C CH2 H2C CHCH3

O O
 Epoxide Nomenclature

Substitutive nomenclature:
named as epoxy-substituted alkanes.
epoxy precedes name of alkane
1,2-epoxypropane 2-methyl-2,3-epoxybutane
H3C 1
2 3 4
H2C CHCH3 C CHCH3

O H3C O
Problem 6.17 Give the IUPAC name, including
stereochemistry, for disparlure.

H O H

cis-2-Methyl-7,8-epoxyoctadecane
Epoxidation of Alkenes

C C + RCOOH
peroxy acid

C C + RCOH

O
 Example

+ CH3COOH

+ CH3COH
O
(52%)
 Epoxidation of Alkenes

C C + RCOOH

syn addition

C C + RCOH

O
 Relative Rates

Epoxidation

ethylene H2C=CH2 1
propene CH3CH=CH2 22
2-methylpropene (CH3)2C=CH2 484
2-methyl-2-butene (CH3)2C=CHCH3 6526
More highly substituted double bonds react faster.
Alkyl groups on the double bond make it
more electron rich.
Mechanism of Epoxidation
Mechanism of Epoxidation
Mechanism of Epoxidation
Mechanism of Epoxidation
Mechanism of Epoxidation
 6.19
Ozonolysis of Alkenes

Ozonolyis has both synthetic and analytical

applications.
synthesis of aldehydes and ketones
identification of substituents on the
double bond of an alkene
 Ozonolysis of Alkenes

First step is the reaction of the alkene with

ozone. The product is an ozonide.

O
C C + O3 C C
O O
 Ozonolysis of Alkenes

Second step is hydrolysis of the ozonide.

Two aldehydes, two ketones, or an aldehyde
and a ketone are formed.
O
C C + O3 C C
O O

H2O, Zn
C O + O C
 Ozonolysis of Alkenes

As an alternative to hydrolysis, the ozonide

can be treated with dimethyl sulfide.

O
C C + O3 C C
O O

(CH3)2S
C O + O C
Example
CH3 CH2CH3

C C
H CH2CH3

1. O3
2. H2O, Zn

CH3 CH2CH3

C O + O C (57%)
H (38%) CH2CH3
 Oxidation/Reduction
How do you recognize the reaction
whether oxidation/reduction or not

by using a balanced half-reaction

1. write a half-reaction showing one reactant and its product(s)

2. complete a material balance;

use H2O and H+ in acid solution,
use H2O and OH- in basic solution

3. complete a charge balance using electrons, e-

 Oxidation/Reduction
three balanced half-reactions

OH
CH3 CH= CH2 + H2 O CH3 CHCH3
Propene 2-Propanol

HO OH
CH3 CH= CH2 + 2 H2 O CH3 CHCH2 + 2 H+ + 2 e -
Propene 1,2-Propanediol

CH3 CH= CH2 + 2 H+ + 2 e - CH3 CH2 CH3

Propene Propane