Page 245 - Arrow Pushing in Inorganic Chemistry A Logical Approach to the Chemistry of the Main Group Elements

6.8 OZONE 225
According to a recent hypothesis by researchers at the Scripps Research Institute,
California, antibodies generate ozone by oxidizing water with singlet oxygen, with
trioxidane (H O ) as an intermediate:
2
3
H O + O=O → H O (6.82)
2 2 3
Oxidation of H O to ozone would then involve a second molecule of singlet oxygen, a
2 3
possible mechanistic picture being as follows:

− +
O O
O O
O
H O + (6.83)
H
O H
H
O O O
The researchers also showed that atherosclerotic plaque contains carbonyl compounds, con-
sistent with the ozonolysis of cholesterol (see, e.g., Wentworth, P., et al. Science 2003, 302,
1053–1056). The carbonyl compounds were derivatized to the arylhydrazones, as shown
below, followed by mass spectroscopic characterization:

H H
Ozonolysis
H H H H
O
HO HO O
Cholesterol
Aldolization
Derivatization

H
H H
H O (6.84)
HO
OH
H H
N
HO O NH Derivatization
O 2 N
Arylhydrazone

NO 2
H
H H
N
HO NH
OH
O 2 N
Arylhydrazone
NO 2