Elsevier

Tetrahedron

Volume 74, Issue 43, 25 October 2018, Pages 6221-6261
Tetrahedron

Tetrahedron report 1174
Ozone, chemical reactivity and biological functions

https://doi.org/10.1016/j.tet.2018.09.023Get rights and content

Abstract

Various aspects of the structure, the reactivity in organic synthesis, in the atmosphere, in environment, in biology of ozone are described. Emphasis is placed on the relation with singlet oxygen and dihydrotrioxide.

Graphical abstract

Ozone structure; Reactions with alkenes; Ozonation of heteroatoms and carbon radicals; Ozonolyse in gas phase; in the atmosphere; Ozonation of C–H bonds; Hydrogen trioxide; Peroxone; Ozone in biology; Natural ozonides.

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Section snippets

Introduction [1]

The chemical reactivity of ozone is very difficult to study as the products obtained are usually unstable and the physicochemical methods to determine their structure poorly adapted. Further, theoretical calculations, sophisticated as they may be, could not even settle on electronic parity (i.e., biradical triplet/ singulet).

Ozone O3 (CAS Number 10028-15-6) is an allotrope of oxygen [2]. It is formed from molecular oxygen by the action of electrical discharges. In 1789, Martin Van Marum

Ozone structure

The molecular geometry of O3 was determined by rotational [17] and IR spectroscopy techniques [18,19]. It is a bent structure of C2v symmetry (Scheme 3), the O–O bond having a considerable double-bond character (O–O bond distance in HOOH, 1.49 Å, Odouble bondO bond distance in O2, 1.21 Å).

The distance between the terminal oxygen atoms is 2.18 Å. It is shorter from that expected from the sum of the van der Waals radii (i.e., 2.80 Å), which suggests that they somehow bonded. The dipolar moment of O3 (0.54

General mechanism in solution

Ozonolysis is a useful reaction in which the double bond of an alkene is oxidatively cleaved and replaced by two carbonyl groups [2,56].

The mechanism formulated by Criegee is now generally accepted, at least for simple alkenes [57,58]. The first step involves a suprafacial 1,3-dipolar cycloaddition of ozone to the double bond leading to a primary ozonide (1,2,3-trioxolane) [59]. The reacting centre of ozone is comprised of 4 π electrons and that of the alkene consists of 2 π electrons so that

Ozonation of heteroatoms and carbon radicals

When ozone reacts by O-atom transfer, one O-atom from O3 is incorporated into the oxidized product while two O-atoms are released as singlet oxygen 1O2. More than 50 compounds were tested for their ability to produce singlet oxygen when reacted with ozone. It turned out that nearly quantitative yields of 1O2 were achieved from ozonation of methionine, methanesulfinic acid and nitrite to give methionine sulfoxide, methanesulfonic acid and nitrate, respectively [200].

Ozonation of aliphatic

Ozonolyse in the gas phase – ozone reactivity in the atmosphere

Ozone plays a dual role. In the stratosphere, it prevents harmful UV radiation from reaching the Earth's surface, thus protecting living organisms. In contrast, in the troposphere, it acts as a pollutant, having an oxidizing effect.

The large amount of ozone in the stratosphere is referred to as the “ozone layer.” Without a protective ozone layer in the atmosphere, animals and plants could not exist, at least upon land. About 10% of ozone is in the troposphere, the remaining (90%) resides in the

Formation and structure of hydrogen trioxide [280].

Several review articles on the subject have been published [[281], [282], [283]].

Hydrogen polyoxides (H2On), first postulated by Berthelot in 1880 [284], have been theoretically studied in the gas phase. Aggregates up to n = 4 have been detected experimentally. Larger systems are still speculative but, nevertheless, predicted to be stable. The dissociation energy of H2O6 into two HO3 radicals would be 6.4 kcal mol−1 [285]. On the basis of theoretical considerations, Benson postulated, in 1960,

Formation and reactivity of ozone and hydrogen peroxide mixture (peroxone)

The reaction of ozone with H2O2, commonly termed the “peroxone process”, was discovered by Hoigné and Staehelin [350]. It represents one of the Advanced Oxidation Processes (AOPs) that produces highly reactive HOradical dot radicals for pollutant abatement at relatively low cost when compared to other AOPs. Ozone decomposition in “pure water” obeys first order kinetics with respect to O3 and HO(−) concentrations. For instance, a solution of ozone 1.6 10−3 mol l−1 in perchloric acid (0.2 N) loses only 5%

Ozone in biology

In a series of fascinating papers in the early 2000s, Wentworth and co-workers suggested that ozone should be produced by antibody-catalyzed oxidation of water by singlet oxygen [364] and, as such, play a key role in immunology [365]. They also postulated that H2O3 was the first intermediate in a reaction cascade that eventually leads to H2O2.

Antibodies are a family of glycoproteins that share a common functional structure (Fig. 8). It has been estimated that a human should make of the order of

Natural ozonides

Surprisingly, some natural ozonides have been discovered in higher plant species. Thus, Gilvanol is a new triterpene isolated from Quercus gilva BLUME. It originates from the ozonolysis of hop-17(21)-en-3β-ol and its structure has been elucidated by chemical and x-ray analysis (Scheme 172) [394].

The ozonide of the adian-5-ene has been isolated from Adiantum monochlamys Eaton (Pteridaceae), a Japanese fern, and from Oleandra wallichii (Davalliaceae). This ozonide represents 0.12% by weight of

Conclusion

Ozone is one of the most reactive oxidant known.

It is of considerable interest in organic chemistry, largely because of its reactivity toward double bond which provides a reliable access to a range of oxygenated functions. The main mechanism of double bonds ozonolysis, known as the Criegee mechanism, is complex but well understood.

A growing body of work deals with the reactions of ozone and carbon-hydrogen bonds. Ozonation of saturated organic substrates leads to organic hydrotrioxides and

Acknowledgements

M.S. warmly thanks Dr. Bernard Vacher (Pierre Fabre Médicaments, Castres, France) for his aid, helpful comments and encouragement.

Maurice Santelli is graduated in chemistry from Ecole Supérieure de Chimie de Marseille (1961) become recently Ecole Centrale Marseille. He received his Ph.D. in chemistry working with Prof. M. Bertrand (homoallenylic participation, non-classical ions). He had a post-doctoral position at the University of Cambridge (U. K.) in 1973 (Prof. R. A. Raphael). After an appointment at the University of Oran (Algeria) (1975–77), he is presently emeritus Prof. of Chemistry at the Aix-Marseille

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    Maurice Santelli is graduated in chemistry from Ecole Supérieure de Chimie de Marseille (1961) become recently Ecole Centrale Marseille. He received his Ph.D. in chemistry working with Prof. M. Bertrand (homoallenylic participation, non-classical ions). He had a post-doctoral position at the University of Cambridge (U. K.) in 1973 (Prof. R. A. Raphael). After an appointment at the University of Oran (Algeria) (1975–77), he is presently emeritus Prof. of Chemistry at the Aix-Marseille University. His main research areas are physical organic chemistry, electrophilic activation, allylsilane chemistry (Bistro …), palladium-chemistry with new ligands (Tedicyp …), radical chemistry and the synthesis of bioactive products (polyunsaturated fatty acids, Prelog–Djerassi lactone, non-natural steroids …).

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