OZONE

OZONE
electric discharge

O2
or cosmic rays

O3

:O

.. .. O O: + .. -

..

.. .. .. O+ O .. :O - ..

EQUIVALENT RESONANCE STRUCTURES

OZONOLYSIS

Ozonolysis
FORMATION OF AN OZONIDE
R1 C R2 C R4 R3 O O3 R1 O C R2 C R4 O R3 spontaneous rearrangement R1 R2 O C O O C R3 R4

unstable
an ozonide (1,2,4-trioxolane)

a molozonide (1,2,3-trioxolane)

HYDROLYSIS OF THE OZONIDE (WORKUP)

R1 R2 O C O O C R3 R4 Zn CH3COOH R1 C R2 O + O C R4 R3

aldehydes or ketones

FORMATION OF AN OZONIDE - MECHANISM

-: .. : O
:O ..
Addition is concerted

O+
ozone

..

CH2 Cl 2 0o C

.. O .. .. O ..

UNSTABLE

:O:

molozonide

.. O .. :O ..
ozonide

O+ C

..

carbonyl oxide

: O: :O C ..

.. O: .. -

.. O: .. C O: ..
ketone or aldehyde

O+

..

OVERALL RESULT OF THE REACTION WITH OZONE

Ph CH3 CH3 CH3 O O O

O3

Ph CH3

CH3 CH3

The double bond is replaced with the ozonide ring.

O O O

OZONIDE AND MOLOZONIDE STRUCTURES

molozonide
forms initially

ozonide
forms after rearrangement

SOME EVIDENCE FOR THE MECHANISM

EVIDENCE FOR THE MECHANISM

When ozonolysis is performed in an aliphatic hydrocarbon solvent (hexane) dimers of the carbonyl oxide intermediate sometimes form.

O+ C

..

-: .. O
..
O + ..

.. O: .. C

hexane

.. O .. ..
O: C

:O .. .. O ..

insoluble carbonyl oxide dimer

This dimerization proves the existence of the carbonyl oxide intermediate.

YET MORE MECHANISTIC EVIDENCE

If a foreign ketone is placed in the solution (e.g., benzophenone) it becomes incorporated into a portion of the ozonides formed.

CH3 CH3 Ph Ph
+

CH3 CH3 C O

O3
CH2 Cl2

CH3 CH3 Ph Ph

O O O O O O

CH3 CH3 CH3 CH3

EXPECTED

benzophenone traps the carbonyl oxide

Can you explain this with a mechanism ? HINT: The benzophenone reacts with the carbonyl oxide intermediate.
TRY THIS ON YOUR OWN

MORE EVIDENCE
When an unsymmetrical alkene undergoes ozonolysis, it is not uncommon for three different ozonides to form.

Ph CH3

CH3 CH3

O3

Ph CH3 CH3 CH3 Ph CH3

O O O O O O O O O

CH3
EXPECTED

CH3 CH3 CH3 Ph

cis & trans

The alkene must break in two and recombine.

Can you draw mechanisms that explain the formation all three ozonides ? TRY THIS ON YOUR OWN

CH3

WORKUP PROCEDURES FOR OZONOLYSIS

WORKUP PROCEDURES FOR OZONOLYSIS

After the ozonide is formed it is hydrolyzed (work-up). Two types of work-up (decomposition of the ozonide) are possible : Oxidative Workup Add aqueous acid (H3O+) H2SO4 + H2O

Reductive Workup A) Zn, acetic acid or Zn, H2O Two methods :

CH3COOH

B) Pd/H2 followed by aqueous acid

OXIDATIVE WORKUP

OXIDATIVE WORKUP (acid)

Just add H3O+ ( = H20 and acid ) O O O Aldehydes are oxidized to carboxylic acids. Formaldehyde is oxidized to carbon dioxide, which is lost as a gas. These oxidations occur because H2O2 is a hydrolysis product. The general hydrolysis mechanism follows.
You do not have to known this mechanism. H3O+

O O

OXIDATIVE WORKUP
Ph H CH3 CH3
O3

(acid + water)
O O + O H CH3 CH3

Ph H

O O O

CH3 + H+ CH3

Ph H

H Ph H O O O H H Ph H O O + O H CH3 O CH3 H
+ H+

CH3 O CH3 H

+ H+

Ph H

O O O H

CH3 O CH3 H

Ph H

O O + O H H CH3 CH3

CH3 CH3

O H

H H O O + CH3 O CH3 H

H H O O +O H

Ph O H

CH3 O CH3

continued ...

HYDROGEN PEROXIDE IS A PRODUCT OF THE OXIDATIVE WORKUP

Aldehydes are easily oxidized by the H2O2 that is produced.

Ph O H +

H H O O

Ph O O H

oxidizing agent

Ketones are not oxidized by hydrogen peroxide.

OXIDATIVE METHODS DESTROY FORMALDEHYDE

If formaldehyde is produced, it is oxidized to CO2 and H2O.

H H H H H C O + O O O
two moles

gas

H C O H O + C O O H CO2 + H2O

Carbonic acid is unstable and decomposes to CO2 and H2O.

REDUCTIVE WORKUP

REDUCTIVE WORKUP
There are two methods of reductive workup.

METHOD A METHOD B

Add Zn and H2O (or acetic acid) Reduce the ozonide with Pd / H2 , and then add acid ( H3O+ ).

With either method, aldehydes survive intact and are not oxidized.

REDUCTIVE WORKUP - METHOD A

With the REDUCTIVE WORKUPS, no H2O2 is produced. The zinc scavenges the peroxide before it can act.
H H CH3 CH3 O O O CH3 + Zn + H2O CH3 CH3 CH3 O O O CH3 + ZnO2 CH3

Notice that the O-O bond is broken so that no H2O2 is formed during the subsequent hydrolysis.

REDUCTIVE WORKUP - METHOD B

With the REDUCTIVE WORKUPS, no H2O2 is produced. The hydrogenation step cleaves the O-O bond.

H H CH3 CH3 O O O CH3 CH3

H2 Pd

CH3 CH3

O O O

CH3 CH3

Since the O-O bond is broken, no H2O2 is formed during the hydrolysis.

EXAMPLES
CH2
O3 Zn / H2O OR O3 1) O3 2) H3O+ 1) Pd/H2 2) H3O+

H C O O

aldehyde survives

REDUCTIVE WORKUP

O
OXIDATIVE WORKUP

+ CO2
formaldehyde CO2

USING OZONOLYSIS FOR STRUCTURE PROOF

AT ONE TIME OZONOLYSIS WAS WIDELY USED FOR STRUCTURE PROOF BY DEGRADATION
Simpler Known Compounds

O
O3 CH2Cl2 H3O+

+ O

+ CH3 O

O CH3

Unknown compound At one time = before spectroscopy.

Broken apart ( or degraded ) to simpler pieces that are easier to identify. The original structure can be deduced by reassembling the pieces.

PROBLEM TO SOLVE
1) O3 / CH2Cl2

6-ketoheptanoic acid or 6-oxoheptanoic acid

C7H12
Pd / H2

2) H3O+

H3C C CH2CH2CH2CH2 C OH

CH3 CH3 H OH
answer

C7H14

O O C

WHAT WAS THE ORIGINAL STRUCTURE ?

C8H12
H2 Pd O3 H3O+

O HO C

O C O + OH O C OH

C8H16

oxidative workup

HO CH3

CH3

HO
oxidized during work-up

C O O

C OH O O C OH CH3 CH3

HO CH3

CH3

OXIDATION OF ACETYLENES

ACETYLENES
Ph C C CH2 Ph
KMnO4 or 1) O3, CH2Cl2 2) H3O+

O C O H H O

O C CH2

Oxidation of acetylenes, whether by KMnO4 or ozone, normally yields carboxylic acids.

OZONE AND SMOG

FORMATION OF SMOG - OZONE IS A COMPONENT

temperature inversion traps pollutants

WARMER AIR

CO2

SO2

COOLER AIR H2O

O3

reacts with unburned hydrocarbons

NO2 NO
incompletely burned hydrocarbons

R-CH=CH2

Temperature Inversion:

Air above land is cooler than air above.

NATURAL SOURCES
temperature inversion traps bioemissions

reacts with terpenes

Terpenes

O3

Spruce, Cedar, Fir or Pine Forest

OXIDATION OF SIDE CHAINS ON AROMATIC RINGS

BENZENE RINGS
Under normal conditions of ozonolysis, or treatment by KMnO4, benzene rings are not oxidized. They are quite resistant to reaction due to the presence of aromatic ring resonance. When using KMnO4 on a benzene ring that has a side chain, the side chain is oxidized before the ring is affected.
KMnO4 / 50o C /2 hours
CH2 CH2 CH3 O O H

The exception is rings with -OH, -OCH3, -NH2 and similar O/N groups, which oxidize quite readily.

BENZENE RINGS
Ozone, will not attack the saturated side chain.
O3 / CH2Cl2 /0o
CH2 CH2 CH3 O O H

O3 / CH2Cl2 /20o long time

O
5 CO2 +

HO

C CH2 CH2 CH3

However, under more vigorous conditions the benzene ring can be ozonized.

SELECTIVITY

SELECTIVITY
CH CH CHO

H2O2
oxidizes aldehyde
CH CH COOH
cinnamic acid

cinnamaldehyde

more vigorous ozonolysis :

O3 / 20o/ CH2Cl2 2 hours 1) 2) O3 / CH2Cl2 /0o H3O+

O C COOH HO HOOC
oxalic acid

COOH

benzoic acid

COOH HOOC COOH

cleaves benzene ring cleaves double bond oxidizes aldehydes

cleaves double bond oxidizes aldehydes (oxidative work-up)

MORE SELECTIVITY
RCO3H
CH CH CHO

O CH CH CHO

epoxidation

1) OsO4 2) NaHSO3 H2O

cinnamaldehyde

KMnO4 30 min H2SO4 1) O3 / CH2Cl2 / 0o 2) Zn / CH3COOH

CH CH CHO OH OH

COOH HOOC COOH

aldehyde survives (OsO4 is mild)

benzaldehyde

CHO OHC CHO

aldehydes are oxidized by KMnO4

aldehydes survive (reductive work-up)